Gibbs Ensemble Simulations of the Solvent Swelling of Polymer Films

NASA Astrophysics Data System (ADS)

Gartner, Thomas; Epps, Thomas, III; Jayaraman, Arthi

Solvent vapor annealing (SVA) is a useful technique to tune the morphology of block polymer, polymer blend, and polymer nanocomposite films. Despite SVA's utility, standardized SVA protocols have not been established, partly due to a lack of fundamental knowledge regarding the interplay between the polymer(s), solvent, substrate, and free-surface during solvent annealing and evaporation. An understanding of how to tune polymer film properties in a controllable manner through SVA processes is needed. Herein, the thermodynamic implications of the presence of solvent in the swollen polymer film is explored through two alternative Gibbs ensemble simulation methods that we have developed and extended: Gibbs ensemble molecular dynamics (GEMD) and hybrid Monte Carlo (MC)/molecular dynamics (MD). In this poster, we will describe these simulation methods and demonstrate their application to polystyrene films swollen by toluene and n-hexane. Polymer film swelling experiments, Gibbs ensemble molecular simulations, and polymer reference interaction site model (PRISM) theory are combined to calculate an effective Flory-Huggins χ (χeff) for polymer-solvent mixtures. The effects of solvent chemistry, solvent content, polymer molecular weight, and polymer architecture on χeff are examined, providing a platform to control and understand the thermodynamics of polymer film swelling.

Direct comparisons of X-ray scattering and atomistic molecular dynamics simulations for precise acid copolymers and ionomers

DOE PAGES

Buitrago, C. Francisco; Bolintineanu, Dan; Seitz, Michelle E.; ...

2015-02-09

Designing acid- and ion-containing polymers for optimal proton, ion, or water transport would benefit profoundly from predictive models or theories that relate polymer structures with ionomer morphologies. Recently, atomistic molecular dynamics (MD) simulations were performed to study the morphologies of precise poly(ethylene-co-acrylic acid) copolymer and ionomer melts. Here, we present the first direct comparisons between scattering profiles, I(q), calculated from these atomistic MD simulations and experimental X-ray data for 11 materials. This set of precise polymers has spacers of exactly 9, 15, or 21 carbons between acid groups and has been partially neutralized with Li, Na, Cs, or Zn. Inmore » these polymers, the simulations at 120 °C reveal ionic aggregates with a range of morphologies, from compact, isolated aggregates (type 1) to branched, stringy aggregates (type 2) to branched, stringy aggregates that percolate through the simulation box (type 3). Excellent agreement is found between the simulated and experimental scattering peak positions across all polymer types and aggregate morphologies. The shape of the amorphous halo in the simulated I(q) profile is in excellent agreement with experimental I(q). We found that the modified hard-sphere scattering model fits both the simulation and experimental I(q) data for type 1 aggregate morphologies, and the aggregate sizes and separations are in agreement. Given the stringy structure in types 2 and 3, we develop a scattering model based on cylindrical aggregates. Both the spherical and cylindrical scattering models fit I(q) data from the polymers with type 2 and 3 aggregates equally well, and the extracted aggregate radii and inter- and intra-aggregate spacings are in agreement between simulation and experiment. Furthermore, these dimensions are consistent with real-space analyses of the atomistic MD simulations. By combining simulations and experiments, the ionomer scattering peak can be associated with the average distance between branches of type 2 or 3 aggregates. Furthermore, this direct comparison of X-ray scattering data to the atomistic MD simulations is a substantive step toward providing a comprehensive, predictive model for ionomer morphology, gives substantial support for this atomistic MD model, and provides new credibility to the presence of stringy, branched, and percolated ionic aggregates in precise ionomer melts.« less

A Functional Monomer Is Not Enough: Principal Component Analysis of the Influence of Template Complexation in Pre-Polymerization Mixtures on Imprinted Polymer Recognition and Morphology

PubMed Central

Golker, Kerstin; Karlsson, Björn C. G.; Rosengren, Annika M.; Nicholls, Ian A.

2014-01-01

In this report, principal component analysis (PCA) has been used to explore the influence of template complexation in the pre-polymerization phase on template molecularly imprinted polymer (MIP) recognition and polymer morphology. A series of 16 bupivacaine MIPs were studied. The ethylene glycol dimethacrylate (EGDMA)-crosslinked polymers had either methacrylic acid (MAA) or methyl methacrylate (MMA) as the functional monomer, and the stoichiometry between template, functional monomer and crosslinker was varied. The polymers were characterized using radioligand equilibrium binding experiments, gas sorption measurements, swelling studies and data extracted from molecular dynamics (MD) simulations of all-component pre-polymerization mixtures. The molar fraction of the functional monomer in the MAA-polymers contributed to describing both the binding, surface area and pore volume. Interestingly, weak positive correlations between the swelling behavior and the rebinding characteristics of the MAA-MIPs were exposed. Polymers prepared with MMA as a functional monomer and a polymer prepared with only EGDMA were found to share the same characteristics, such as poor rebinding capacities, as well as similar surface area and pore volume, independent of the molar fraction MMA used in synthesis. The use of PCA for interpreting relationships between MD-derived descriptions of events in the pre-polymerization mixture, recognition properties and morphologies of the corresponding polymers illustrates the potential of PCA as a tool for better understanding these complex materials and for their rational design. PMID:25391043

A functional monomer is not enough: principal component analysis of the influence of template complexation in pre-polymerization mixtures on imprinted polymer recognition and morphology.

PubMed

Golker, Kerstin; Karlsson, Björn C G; Rosengren, Annika M; Nicholls, Ian A

2014-11-10

In this report, principal component analysis (PCA) has been used to explore the influence of template complexation in the pre-polymerization phase on template molecularly imprinted polymer (MIP) recognition and polymer morphology. A series of 16 bupivacaine MIPs were studied. The ethylene glycol dimethacrylate (EGDMA)-crosslinked polymers had either methacrylic acid (MAA) or methyl methacrylate (MMA) as the functional monomer, and the stoichiometry between template, functional monomer and crosslinker was varied. The polymers were characterized using radioligand equilibrium binding experiments, gas sorption measurements, swelling studies and data extracted from molecular dynamics (MD) simulations of all-component pre-polymerization mixtures. The molar fraction of the functional monomer in the MAA-polymers contributed to describing both the binding, surface area and pore volume. Interestingly, weak positive correlations between the swelling behavior and the rebinding characteristics of the MAA-MIPs were exposed. Polymers prepared with MMA as a functional monomer and a polymer prepared with only EGDMA were found to share the same characteristics, such as poor rebinding capacities, as well as similar surface area and pore volume, independent of the molar fraction MMA used in synthesis. The use of PCA for interpreting relationships between MD-derived descriptions of events in the pre-polymerization mixture, recognition properties and morphologies of the corresponding polymers illustrates the potential of PCA as a tool for better understanding these complex materials and for their rational design.

Final report for the DOE Early Career Award #DE-SC0003912

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jayaraman, Arthi

This DoE supported early career project was aimed at developing computational models, theory and simulation methods that would be then be used to predict assembly and morphology in polymer nanocomposites. In particular, the focus was on composites in active layers of devices, containing conducting polymers that act as electron donors and nanoscale additives that act as electron acceptors. During the course this work, we developed the first of its kind molecular models to represent conducting polymers enabling simulations at the experimentally relevant length and time scales. By comparison with experimentally observed morphologies we validated these models. Furthermore, using these modelsmore » and molecular dynamics simulations on graphical processing units (GPUs) we predicted the molecular level design features in polymers and additive that lead to morphologies with optimal features for charge carrier behavior in solar cells. Additionally, we also predicted computationally new design rules for better dispersion of additives in polymers that have been confirmed through experiments. Achieving dispersion in polymer nanocomposites is valuable to achieve controlled macroscopic properties of the composite. The results obtained during the course of this DOE funded project enables optimal design of higher efficiency organic electronic and photovoltaic devices and improve every day life with engineering of these higher efficiency devices.« less

Material and morphology parameter sensitivity analysis in particulate composite materials

NASA Astrophysics Data System (ADS)

Zhang, Xiaoyu; Oskay, Caglar

2017-12-01

This manuscript presents a novel parameter sensitivity analysis framework for damage and failure modeling of particulate composite materials subjected to dynamic loading. The proposed framework employs global sensitivity analysis to study the variance in the failure response as a function of model parameters. In view of the computational complexity of performing thousands of detailed microstructural simulations to characterize sensitivities, Gaussian process (GP) surrogate modeling is incorporated into the framework. In order to capture the discontinuity in response surfaces, the GP models are integrated with a support vector machine classification algorithm that identifies the discontinuities within response surfaces. The proposed framework is employed to quantify variability and sensitivities in the failure response of polymer bonded particulate energetic materials under dynamic loads to material properties and morphological parameters that define the material microstructure. Particular emphasis is placed on the identification of sensitivity to interfaces between the polymer binder and the energetic particles. The proposed framework has been demonstrated to identify the most consequential material and morphological parameters under vibrational and impact loads.

Understanding morphology-mobility dependence in PEDOT:Tos

NASA Astrophysics Data System (ADS)

Rolland, Nicolas; Franco-Gonzalez, Juan Felipe; Volpi, Riccardo; Linares, Mathieu; Zozoulenko, Igor V.

2018-04-01

The potential of conjugated polymers to compete with inorganic materials in the field of semiconductor is conditional on fine-tuning of the charge carriers mobility. The latter is closely related to the material morphology, and various studies have shown that the bottleneck for charge transport is the connectivity between well-ordered crystallites, with a high degree of π -π stacking, dispersed into a disordered matrix. However, at this time there is a lack of theoretical descriptions accounting for this link between morphology and mobility, hindering the development of systematic material designs. Here we propose a computational model to predict charge carriers mobility in conducting polymer PEDOT depending on the physicochemical properties of the system. We start by calculating the morphology using molecular dynamics simulations. Based on the calculated morphology we perform quantum mechanical calculation of the transfer integrals between states in polymer chains and calculate corresponding hopping rates using the Miller-Abrahams formalism. We then construct a transport resistive network, calculate the mobility using a mean-field approach, and analyze the calculated mobility in terms of transfer integrals distributions and percolation thresholds. Our results provide theoretical support for the recent study [Noriega et al., Nat. Mater. 12, 1038 (2013), 10.1038/nmat3722] explaining why the mobility in polymers rapidly increases as the chain length is increased and then saturates for sufficiently long chains. Our study also provides the answer to the long-standing question whether the enhancement of the crystallinity is the key to designing high-mobility polymers. We demonstrate, that it is the effective π -π stacking, not the long-range order that is essential for the material design for the enhanced electrical performance. This generic model can compare the mobility of a polymer thin film with different solvent contents, solvent additives, dopant species or polymer characteristics, providing a general framework to design new high mobility conjugated polymer materials.

Polymer-mediated nanorod self-assembly predicted by dissipative particle dynamics simulations.

PubMed

Khani, Shaghayegh; Jamali, Safa; Boromand, Arman; Hore, Michael J A; Maia, Joao

2015-09-14

Self-assembly of nanoparticles in polymer matrices is an interesting and growing subject in the field of nanoscience and technology. We report herein on modelling studies of the self-assembly and phase behavior of nanorods in a homopolymer matrix, with the specific goal of evaluating the role of deterministic entropic and enthalpic factors that control the aggregation/dispersion in such systems. Grafting polymer brushes from the nanorods is one approach to control/impact their self-assembly capabilities within a polymer matrix. From an energetic point of view, miscible interactions between the brush and the matrix are required for achieving a better dispersibility; however, grafting density and brush length are the two important parameters in dictating the morphology. Unlike in previous computational studies, the present Dissipative Particle Dynamics (DPD) simulation framework is able to both predict dispersion or aggregation of nanorods and determine the self-assembled structure, allowing for the determination of a phase diagram, which takes all of these factors into account. Three types of morphologies are predicted: dispersion, aggregation and partial aggregation. Moreover, favorable enthalpic interactions between the brush and the matrix are found to be essential for expanding the window for achieving a well-dispersed morphology. A three-dimensional phase diagram is mapped on which all the afore-mentioned parameters are taken into account. Additionally, in the case of immiscibility between brushes and the matrix, simulations predict the formation of some new and tunable structures.

Stability and dewetting of metal nanoparticle filled thin polymer films: control of instability length scale and dynamics.

PubMed

Mukherjee, Rabibrata; Das, Soma; Das, Anindya; Sharma, Satinder K; Raychaudhuri, Arup K; Sharma, Ashutosh

2010-07-27

We investigate the influence of gold nanoparticle addition on the stability, dewetting, and pattern formation in ultrathin polymer-nanoparticle (NP) composite films by examining the length and time scales of instability, morphology, and dynamics of dewetting. For these 10-50 nm thick (h) polystyrene (PS) thin films containing uncapped gold nanoparticles (diameter approximately 3-4 nm), transitions from complete dewetting to arrested dewetting to absolute stability were observed depending on the concentration of the particles. Experiments show the existence of three distinct stability regimes: regime 1, complete dewetting leading to droplet formation for nanoparticle concentration of 2% (w/w) or below; regime 2, partial dewetting leading to formation of arrested holes for NP concentrations in the range of 3-6%; and regime 3, complete inhibition of dewetting for NP concentrations of 7% and above. Major results are (a) length scale of instability, where lambdaH approximately hn remains unchanged with NP concentration in regime 1 (n approximately 2) but increases in regime 2 with a change in the scaling relation (n approximately 3-3.5); (b) dynamics of instability and dewetting becomes progressively sluggish with an increase in the NP concentration; (c) there are distinct regimes of dewetting velocity at low NP concentrations; (d) force modulation AFM, as well as micro-Raman analysis, shows phase separation and aggregation of the gold nanoparticles within each dewetted polymer droplet leading to the formation of a metal core-polymer shell morphology. The polymer shell could be removed by washing in a selective solvent, thus exposing an array of bare gold nanoparticle aggregates.

Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

DOE PAGES

Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; ...

2016-07-19

Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporatingmore » them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.« less

Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe

Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporatingmore » them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.« less

Structural dependence of MEH-PPV chromism in solution.

PubMed

de Magalhães, Carlos E T; Savedra, Ranylson M L; Dias, Karina S; Ramos, Rodrigo; Siqueira, Melissa F

2017-03-01

The chromism observed in the MEH-PPV polymer in tetrahydrofuran (THF) solution is discussed as a function of the structural morphology of the backbone chains. To evaluate this phenomenon, we carried out simulations employing a hybrid methodology using molecular dynamics and quantum mechanical approaches. Our results support the hypothesis that the morphological order-disorder transition is related to the change from red to blue phase observed experimentally. The morphological disorder is associated with total or partial twisted arrangements in the polymer backbone, which induces an electronic conjugation length more confined to shorter segments. In addition, the main band of the MEH-PPV UV-Vis spectrum at the lower wavelength is related to the blue phase, in contrast to the red phase found for the more planar backbone chains.

Development of Simulation Methods in the Gibbs Ensemble to Predict Polymer-Solvent Phase Equilibria

NASA Astrophysics Data System (ADS)

Gartner, Thomas; Epps, Thomas; Jayaraman, Arthi

Solvent vapor annealing (SVA) of polymer thin films is a promising method for post-deposition polymer film morphology control. The large number of important parameters relevant to SVA (polymer, solvent, and substrate chemistries, incoming film condition, annealing and solvent evaporation conditions) makes systematic experimental study of SVA a time-consuming endeavor, motivating the application of simulation and theory to the SVA system to provide both mechanistic insight and scans of this wide parameter space. However, to rigorously treat the phase equilibrium between polymer film and solvent vapor while still probing the dynamics of SVA, new simulation methods must be developed. In this presentation, we compare two methods to study polymer-solvent phase equilibrium-Gibbs Ensemble Molecular Dynamics (GEMD) and Hybrid Monte Carlo/Molecular Dynamics (Hybrid MC/MD). Liquid-vapor equilibrium results are presented for the Lennard Jones fluid and for coarse-grained polymer-solvent systems relevant to SVA. We found that the Hybrid MC/MD method is more stable and consistent than GEMD, but GEMD has significant advantages in computational efficiency. We propose that Hybrid MC/MD simulations be used for unfamiliar systems in certain choice conditions, followed by much faster GEMD simulations to map out the remainder of the phase window.

Effect of simulation conditions on friction in polytetrafluoroethylene (PTFE)

NASA Astrophysics Data System (ADS)

Barry, Peter R.; Jang, Inkook; Perry, Scott S.; Sawyer, W. Gregory; Sinnott, Susan B.; Phillpot, Simon R.

2007-12-01

We report the results of molecular-dynamics simulations of friction at polytetrafluoroethylene (PTFE) interfaces and show that the calculated tribological properties are robust against significant changes in the sliding speed and the morphology of the polymer.

Structure and Dynamics of Ionic Block Copolymer Melts: Computational Study

DOE PAGES

Aryal, Dipak; Agrawal, Anupriya; Perahia, Dvora; ...

2017-09-06

Structure and dynamics of melts of copolymers with an ABCBA topology, where C is an ionizable block, have been studied by fully atomistic molecular dynamics (MD) simulations. Introducing an ionizable block for functionality adds a significant element to the coupled set of interactions that determine the structure and dynamics of the macromolecule. The polymer consists of a randomly sulfonated polystyrene C block tethered to a flexible poly(ethylene-r-propylene) bridge B and end-capped with poly(tert-butylstyrene) A. The chemical structure and topology of these polymers constitute a model for incorporation of ionic blocks within a framework that provides tactility and mechanical stability. Heremore » in this paper we resolve the structure and dynamics of a structured polymer on the nanoscale constrained by ionic clusters. We find that the melts form intertwined networks of the A and C blocks independent of the degree of sulfonation of the C block with no long-range order. The cluster cohesiveness and morphology affect both macroscopic translational motion and segmental dynamics of all the blocks.« less

Structure and Dynamics of Ionic Block Copolymer Melts: Computational Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aryal, Dipak; Agrawal, Anupriya; Perahia, Dvora

Structure and dynamics of melts of copolymers with an ABCBA topology, where C is an ionizable block, have been studied by fully atomistic molecular dynamics (MD) simulations. Introducing an ionizable block for functionality adds a significant element to the coupled set of interactions that determine the structure and dynamics of the macromolecule. The polymer consists of a randomly sulfonated polystyrene C block tethered to a flexible poly(ethylene-r-propylene) bridge B and end-capped with poly(tert-butylstyrene) A. The chemical structure and topology of these polymers constitute a model for incorporation of ionic blocks within a framework that provides tactility and mechanical stability. Heremore » in this paper we resolve the structure and dynamics of a structured polymer on the nanoscale constrained by ionic clusters. We find that the melts form intertwined networks of the A and C blocks independent of the degree of sulfonation of the C block with no long-range order. The cluster cohesiveness and morphology affect both macroscopic translational motion and segmental dynamics of all the blocks.« less

Porous fiber formation in polymer-solvent system undergoing solvent evaporation

NASA Astrophysics Data System (ADS)

Dayal, Pratyush; Kyu, Thein

2006-08-01

Temporal evolution of the fiber morphology during dry spinning has been investigated in the framework of Cahn-Hilliard equation [J. Chem. Phys. 28, 258 (1958)] pertaining to the concentration order parameter or volume fraction given by the Flory-Huggins free energy of mixing [P. J. Flory, Principles of Polymer Chemistry (Cornell University Press, Ithaca, NY, 1953), p. 672] in conjunction with the solvent evaporation rate. To guide the solvent evaporation induced phase separation, equilibrium phase diagram of the starting polymer solution was established on the basis of the Flory-Huggins free energy of mixing. The quasi-steady-state approximation has been adopted to account for the nonconserved nature of the concentration field caused by the solvent loss. The process of solvent evaporation across the fiber skin-air interface was treated in accordance with the classical Fick's law [R. B. Bird et al., Transport Phenomena (J. Wiley, New York, 1960), p. 780]. The simulated morphologies include gradient type, hollow fiber type, bicontinuous type, and host-guest type. The development of these diverse fiber morphologies is explicable in terms of the phase diagram of the polymer solution in a manner dependent on the competition between the phase separation dynamics and rate of solvent evaporation.

Inter-Fullerene Electronic Coupling Controls the Efficiency of Photoinduced Charge Generation in Organic Bulk Heterojunctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larson, Bryon W.; Reid, Obadiah G.; Coffey, David C.

2016-09-26

Photoinduced charge generation (PCG) dynamics are notoriously difficult to correlate with specific molecular properties in device relevant polymer:fullerene organic photovoltaic blend films due to the highly complex nature of the solid state blend morphology. Here, this study uses six judiciously selected trifluoromethylfullerenes blended with the prototypical polymer poly(3-hexylthiophene) and measure the PCG dynamics in 50 fs-500 ns time scales with time-resolved microwave conductivity and femtosecond transient absorption spectroscopy. The isomeric purity and thorough chemical characterization of the fullerenes used in this study allow for a detailed correlation between molecular properties, driving force, local intermolecular electronic coupling and, ultimately, the efficiencymore » of PCG yield. The findings show that the molecular design of the fullerene not only determines inter-fullerene electronic coupling, but also influences the decay dynamics of free holes in the donor phase even when the polymer microstructure remains unchanged.« less

Atomic Origins of the Self-Healing Function in Cement–Polymer Composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Manh-Thuong; Wang, Zheming; Rod, Kenton A.

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized towards defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement/polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties ofmore » these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG spectroscopy.« less

Atomic Origins of the Self-Healing Function in Cement-Polymer Composites.

PubMed

Nguyen, Manh-Thuong; Wang, Zheming; Rod, Kenton A; Childers, M Ian; Fernandez, Carlos; Koech, Phillip K; Bennett, Wendy D; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

2018-01-24

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) vibrational spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized toward defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement-polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties of these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG vibrational spectroscopy.

Solution-Phase Conformation and Dynamics of Conjugated Isoindigo-Based Donor–Acceptor Polymer Single Chains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Franklin L.; Farimani, Amir Barati; Gu, Kevin L.

Conjugated polymers are the key material in thin-film organic optoelectronic devices due to the versatility of these molecules combined with their semiconducting properties. A molecular-scale understanding of conjugated polymers is important to the optimization of the thin-film morphology. We examine the solution-phase behavior of conjugated isoindigo-based donor–acceptor polymer single chains of various chain lengths using atomistic molecular dynamics simulations. Our simulations elucidate the transition from a rod-like to a coil-like conformation from an analysis of normal modes and persistence length. In addition, we find another transition based on the solvent environment, contrasting the coil-like conformation in a good solvent withmore » a globule-like conformation in a poor solvent. Altogether, our results provide valuable insights into the transition between conformational regimes for conjugated polymers as a function of both the chain length and the solvent environment, which will help to accurately parametrize higher level models.« less

Solution-Phase Conformation and Dynamics of Conjugated Isoindigo-Based Donor–Acceptor Polymer Single Chains

DOE PAGES

Lee, Franklin L.; Farimani, Amir Barati; Gu, Kevin L.; ...

2017-10-25

Conjugated polymers are the key material in thin-film organic optoelectronic devices due to the versatility of these molecules combined with their semiconducting properties. A molecular-scale understanding of conjugated polymers is important to the optimization of the thin-film morphology. We examine the solution-phase behavior of conjugated isoindigo-based donor–acceptor polymer single chains of various chain lengths using atomistic molecular dynamics simulations. Our simulations elucidate the transition from a rod-like to a coil-like conformation from an analysis of normal modes and persistence length. In addition, we find another transition based on the solvent environment, contrasting the coil-like conformation in a good solvent withmore » a globule-like conformation in a poor solvent. Altogether, our results provide valuable insights into the transition between conformational regimes for conjugated polymers as a function of both the chain length and the solvent environment, which will help to accurately parametrize higher level models.« less

Volume effect of non-polar solvent towards the synthesis of hydrophilic polymer nanoparticles prepares via inverse miniemulsion polymerization

NASA Astrophysics Data System (ADS)

Kamaruddin, Nur Nasyita; Kassim, Syara; Harun, Noor Aniza

2017-09-01

Polymeric nanoparticles have drawn tremendous attention to researchers and have utilized in diverse fields especially in biomedical applications. Nevertheless, question has raised about the safety and hydrophilicity of the nanoparticles to be utilized in medical and biological applications. One promising solution to this problem is to develop biodegradable polymeric nanoparticles with improve hydrophilicity. This study is focusing to develop safer and "greener" polymeric nanoparticles via inverse miniemulsion polymerization techniques, a robust and convenient method to produce water-soluble polymer nanoparticles. Acrylamide (Am), acrylic acid (AA) and methacrylic acid (MAA) monomers have chosen, as they are biocompatible, non-toxic and ecological. The effect of different volumes of cyclohexane towards the formation of polymer nanoparticles, particle size, particle size distribution and morphology of polymer nanoparticles are investigated. The formation and morphology of polymer nanoparticles are determined using FTIR and SEM respectively. The mean diameters of the polymer nanoparticles were in a range of 80 - 250 nm and with broad particle size distributions as determined by dynamic light scattering (DLS). Hydrophilic polyacrylamide (pAm), poly(acrylic acid) (pAA) and poly(methacrylic acid) (pMAA) nanoparticles were successfully achieved by inverse miniemulsion polymerization and have potentiality to be further utilized in the fabrication of hybrid polymer composite nanoparticles especially in biological and medical applications.

Morphological Study of Langmuir Polymer Films by means of Atomic Force Microscopy and MD Simulations

NASA Astrophysics Data System (ADS)

Reiter, Renate; Knecht, Volker; Chandran, Sivasurender; Reiter, Günter

In general it is difficult to reproduce well defined morphologies of Langmuir polymer films (LPFs) because they have a high propensity to form non-equilibrium states. We present a systematic study based on different compression protocols designed to allow for relaxations of LPFs under well defined conditions. The homo peptide poly-?-benzyl-L-glutamate (PBLG) was chosen for this study because it is a well investigated system that represents the relaxational behaviour of rod-like molecules which is expected to show less complexity than coiled polymer molecules. Our results demonstrate that experimentally manipulating the course of relaxations in LPFs has tremendous impact on the ordering of the molecules. Coarse grain molecular dynamics simulations were performed under comparable conditions. The results match the experimental observations reasonably well and allow to zoom into molecular details which are not resolved experimentally.

Effect of flexibility of grafted polymer on the morphology and property of nanosilica/PVC composites

NASA Astrophysics Data System (ADS)

Zhu, Aiping; Cai, Aiyun; Zhou, Weidong; Shi, Zhehua

2008-04-01

In this study, poly(methyl methacrylate)-grafted-nanosilica (PMMA-g-silica) and a copolymer of styrene (St), n-butyl acrylate (BA) and acrylic acid (AA)-grafted-nanosilica (PSBA-g-silica) hybrid nanoparticles were prepared by using a heterophase polymerization technique in an aqueous system. The grafted polymers made up approximately 50 wt.% of the resulted hybrid nanoparticles which showed a spherical and well-dispersed morphology. The silica hybrid nanoparticles were subsequently used as fillers in a poly(vinyl chloride) (PVC) matrix to fabricate PVC nanocomposite. Morphology study of PVC nanocomposites revealed that both PMMA- and PSBA-grafted-silica had an adhesive interface between the silica and PVC. The tensile strength and elongation to break were found to be improved significantly in comparison with that of untreated nanosilica/PVC composites. Finally our results clearly demonstrated that the properties (e.g. chain flexibility, composition) of the grafted polymer in the hybrid nanoparticles could significantly affect the dispersion behavior of hybrid nanoparticles in PVC matrix, dynamic mechanical thermal properties and mechanical properties of the resulted PVC composites.

Kinetic factors determining conducting filament formation in solid polymer electrolyte based planar devices

NASA Astrophysics Data System (ADS)

Krishnan, Karthik; Aono, Masakazu; Tsuruoka, Tohru

2016-07-01

Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength, and the reduction sites for precipitation. Different filament formations, resulting from unidirectional and dendritic growth behaviours, can be controlled by tuning specified parameters, which in turn improves the stability and performance of SPE-based devices.Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength, and the reduction sites for precipitation. Different filament formations, resulting from unidirectional and dendritic growth behaviours, can be controlled by tuning specified parameters, which in turn improves the stability and performance of SPE-based devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00569a

Heterogeneous chain dynamics and aggregate lifetimes in precise acid-containing polyethylenes: Experiments and simulations

DOE PAGES

Middleton, L. Robert; Tarver, Jacob D.; Cordaro, Joseph; ...

2016-11-10

Melt state dynamics for a series of strictly linear polyethylenes with precisely spaced associating functional groups were investigated. The periodic pendant acrylic acid groups form hydrogen-bonded acid aggregates within the polyethylene (PE) matrix. The dynamics of these nanoscale heterogeneous morphologies were investigated from picosecond to nanosecond timescales by both quasi-elastic neutron scattering (QENS) measurements and fully atomistic molecular dynamics (MD) simulations. Two dynamic processes were observed. The faster dynamic processes which occur at the picosecond timescales are compositionally insensitive and indicative of spatially restricted local motions. The slower dynamic processes are highly composition dependent and indicate the structural relaxation ofmore » the polymer backbone. Higher acid contents, or shorter PE spacers between pendant acid groups, slow the structural relaxation timescale and increase the stretching parameter (β) of the structural relaxation. Additionally, the dynamics of specific hydrogen atom positions along the backbone correlate structural heterogeneity imposed by the associating acid groups with a mobility gradient along the polymer backbone. At time intervals (<2 ns), the mean-squared displacements for the four methylene groups closest to the acid groups are up to 10 times smaller than those of methylene groups further from the acid groups. At longer timescales acid aggregates rearrange and the chain dynamics of the slow, near-aggregate regions and the faster bridge regions converge, implying a characteristic timescale for the passage of chains between aggregates. As a result, the characterization of the nanoscale chain dynamics in these associating polymer systems both provides validation of simulation force fields and provides understanding of heterogeneous chain dynamics in associating polymers.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buitrago, C. Francisco; Bolintineanu, Dan; Seitz, Michelle E.

Designing acid- and ion-containing polymers for optimal proton, ion, or water transport would benefit profoundly from predictive models or theories that relate polymer structures with ionomer morphologies. Recently, atomistic molecular dynamics (MD) simulations were performed to study the morphologies of precise poly(ethylene-co-acrylic acid) copolymer and ionomer melts. Here, we present the first direct comparisons between scattering profiles, I(q), calculated from these atomistic MD simulations and experimental X-ray data for 11 materials. This set of precise polymers has spacers of exactly 9, 15, or 21 carbons between acid groups and has been partially neutralized with Li, Na, Cs, or Zn. Inmore » these polymers, the simulations at 120 °C reveal ionic aggregates with a range of morphologies, from compact, isolated aggregates (type 1) to branched, stringy aggregates (type 2) to branched, stringy aggregates that percolate through the simulation box (type 3). Excellent agreement is found between the simulated and experimental scattering peak positions across all polymer types and aggregate morphologies. The shape of the amorphous halo in the simulated I(q) profile is in excellent agreement with experimental I(q). We found that the modified hard-sphere scattering model fits both the simulation and experimental I(q) data for type 1 aggregate morphologies, and the aggregate sizes and separations are in agreement. Given the stringy structure in types 2 and 3, we develop a scattering model based on cylindrical aggregates. Both the spherical and cylindrical scattering models fit I(q) data from the polymers with type 2 and 3 aggregates equally well, and the extracted aggregate radii and inter- and intra-aggregate spacings are in agreement between simulation and experiment. Furthermore, these dimensions are consistent with real-space analyses of the atomistic MD simulations. By combining simulations and experiments, the ionomer scattering peak can be associated with the average distance between branches of type 2 or 3 aggregates. Furthermore, this direct comparison of X-ray scattering data to the atomistic MD simulations is a substantive step toward providing a comprehensive, predictive model for ionomer morphology, gives substantial support for this atomistic MD model, and provides new credibility to the presence of stringy, branched, and percolated ionic aggregates in precise ionomer melts.« less

From precision polymers to complex materials and systems

NASA Astrophysics Data System (ADS)

Lutz, Jean-François; Lehn, Jean-Marie; Meijer, E. W.; Matyjaszewski, Krzysztof

2016-05-01

Complex chemical systems, such as living biological matter, are highly organized structures based on discrete molecules in constant dynamic interactions. These natural materials can evolve and adapt to their environment. By contrast, man-made materials exhibit simpler properties. In this Review, we highlight that most of the necessary elements for the development of more complex synthetic matter are available today. Using modern strategies, such as controlled radical polymerizations, supramolecular polymerizations or stepwise synthesis, polymers with precisely controlled molecular structures can be synthesized. Moreover, such tailored polymers can be folded or self-assembled into defined nanoscale morphologies. These self-organized macromolecular objects can be at thermal equilibrium or can be driven out of equilibrium. Recently, in the latter case, interesting dynamic materials have been developed. However, this is just a start, and more complex adaptive materials are anticipated.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Middleton, L. Robert; Tarver, Jacob D.; Cordaro, Joseph

Melt state dynamics for a series of strictly linear polyethylenes with precisely spaced associating functional groups were investigated. The periodic pendant acrylic acid groups form hydrogen-bonded acid aggregates within the polyethylene (PE) matrix. The dynamics of these nanoscale heterogeneous morphologies were investigated from picosecond to nanosecond timescales by both quasi-elastic neutron scattering (QENS) measurements and fully atomistic molecular dynamics (MD) simulations. Two dynamic processes were observed. The faster dynamic processes which occur at the picosecond timescales are compositionally insensitive and indicative of spatially restricted local motions. The slower dynamic processes are highly composition dependent and indicate the structural relaxation ofmore » the polymer backbone. Higher acid contents, or shorter PE spacers between pendant acid groups, slow the structural relaxation timescale and increase the stretching parameter (β) of the structural relaxation. Additionally, the dynamics of specific hydrogen atom positions along the backbone correlate structural heterogeneity imposed by the associating acid groups with a mobility gradient along the polymer backbone. At time intervals (<2 ns), the mean-squared displacements for the four methylene groups closest to the acid groups are up to 10 times smaller than those of methylene groups further from the acid groups. At longer timescales acid aggregates rearrange and the chain dynamics of the slow, near-aggregate regions and the faster bridge regions converge, implying a characteristic timescale for the passage of chains between aggregates. As a result, the characterization of the nanoscale chain dynamics in these associating polymer systems both provides validation of simulation force fields and provides understanding of heterogeneous chain dynamics in associating polymers.« less

Controlled release of tocopherols from polymer blend films

NASA Astrophysics Data System (ADS)

Obinata, Noe

Controlled release packaging has great potential to increase storage stability of foods by releasing active compounds into foods continuously over time. However, a major limitation in development of this technology is the inability to control the release and provide rates useful for long term storage of foods. Better understanding of the factors affecting active compound release is needed to overcome this limitation. The objective of this research was to investigate the relationship between polymer composition, polymer processing method, polymer morphology, and release properties of active compounds, and to provide proof of principle that compound release is controlled by film morphology. A natural antioxidant, tocopherol was used as a model active compound because it is natural, effective, heat stable, and soluble in most packaging polymers. Polymer blend films were produced from combination of linear low density polyethylene (LLDPE) and high density polyethylene (HDPE), polypropylene (PP), or polystyrene (PS) with 3000 ppm mixed tocopherols using conventional blending method and innovative blending method, smart blending with a novel mixer using chaotic advection. Film morphologies were visualized with scanning electron microscopy (SEM). Release of tocopherols into 95% ethanol as a food simulant was measured by UV/Visible spectrophotometry or HPLC, and diffusivity of tocopherols in the polymers was estimated from this data. Polymer composition (blend proportions) and processing methods have major effects on film morphology. Four different types of morphologies, dispersed, co-continuous, fiber, and multilayer structures were developed by either conventional extrusion or smart blending. With smart blending of fixed polymer compositions, different morphologies were progressively developed with fixed polymer composition as the number of rod rotations increased, providing a way to separate effects of polymer composition and morphology. The different morphologies obtained using conventional and smart blending greatly affected tocopherol release. Strong correlation was observed between morphology and release rate: multilayer, slow release; co-continuous and fiber, moderate; disperse: fast release. Results indicate that morphology can be manipulated by polymer composition and processing method, and release rates of tocopherols are varied with polymer morphology. Manipulating polymer compositions and film morphologies may provide a means to control the release of tocopherols from food contact films.

Self-Assembly and Responsiveness of Polypeptide-Based Star and Triblock Copolymers

NASA Astrophysics Data System (ADS)

Savin, Daniel

This study involves the bottom-up design and tunability of responsive, peptide-based block polymers. The self-assembly of amphiphilic block polymers is dictated primarily by the balance between the hydrophobic core volume and the hydrophilic corona. In these studies, amphiphilic triblock and star copolymers containing poly(lysine) (PK), poly(leucine) (PL) and poly(glutamic acid) (PE) were synthesized and their solution properties studied using dynamic light scattering, circular dichroism spectroscopy and transmission electron microscopy. The peptide block in these structures can serve to introduce pH responsiveness (in the case of PK and PE), or can facilitate the formation of elongated or kinetically-trapped structures (in the case of PL.) This talk will present some recent studies in solution morphology transitions that occur in these materials under varying solution conditions. As the topological complexity of the polymers increases from diblock to linear triblock or star polymers, the solution morphology and response becomes much more complex. We present a systematic series of structures, with increasing complexity, that have applications as passive and active delivery vehicles, hydrogels, and responsive viscosity modifiers. NSF CHE-1539347.

Styrene-butadiene-styrene copolymer compatibilized carbon black/polypropylene/polystyrene composites with tunable morphology, electrical conduction and rheological stabilities.

PubMed

Song, Yihu; Xu, Chunfeng; Zheng, Qiang

2014-04-21

We report a facile kinetic strategy in combination with styrene-butadiene-styrene (SBS) copolymer compatibilizers for preparing carbon black (CB) filled immiscible polypropylene (PP)/polystyrene (PS) (1/1) blends with finely tuned morphologies and show the important role of location and migration of CB nanoparticles in determining the electrical conductivity and rheological behaviour of the composites. A novel method of mixing a SBS/CB (5/3) masterbatch with the polymers allowed producing composites with CB aggregates dispersed partially in the unfavorable PP phase and partially in the PP side of the interface to exhibit diverse phase connectivity and electrical conductivity depending on the compounding sequences. A cocontinuous morphology with CB enrichment along the interface was formed in the composite prepared by mixing the SBS/CB masterbatch with the premixed PP/PS blend, giving rise to a highest electrical conductivity and dynamic moduli at low frequencies. On the other hand, mixing the masterbatch with one and then with another polymer yielded droplet (PS)-in-matrix (filled PP) composites. The composites underwent phase coalescence and CB redistribution accompanied by marked dynamic electrical conduction and modulus percolations as a function of time during thermal annealing at 180 °C. The composites with the initial droplet-in-matrix morphology progressed anomalously into the cocontinuous morphology, reflecting a common mechanism being fairly nonspecific for understanding the processing of filled multicomponent composites with tailored performances of general concern.

Mechanisms of Morphology Development and Control in Polymer- Polymer Blends

NASA Astrophysics Data System (ADS)

Macosko, Christopher W.

1998-03-01

Polymer-polymer blends continue to be the most important method for achieving optimization of properties in plastics products. Over 30 percent of all plastics are blends. While miscible blends generally give average properties between the components, immiscible blends offer synergistic possibilities such as high modulus with high toughness; high flow with high impact strength or diffusion barriers with good mechanical properties and low cost. The key to performance of these immiscible blends is their morphology. There are several important types of morphology which can lead to valuable property improvement: emulsion - small polymer spheres well dispersed in a polymer matrix. double emulsion - spheres inside spheres which are dispersed in another matrix. microlayer - thin, parallel layers of one polymer in a matrix. cocontinuous - two (or more) continuous, interpenetrating polymer phases. To be economical it is desirable to create these morphologies via melt mixing of powder or pellets in conventional compounding equipment. The melting stage during compounding is very important for morphology development. This presentation will demonstrate the role of melting or softening of each phase as well as their viscosity, elasticity and interfacial tension in morphology development. Interfacial modification with premade block copolymers or reactively formed copolymers can greatly alter morphology formation and stability. Experimental results will be presented which quantify the role of these additives. References to recent work in this area by our group are listed below: DeBrule, M. B., L. Levitt and C.W. Macosko, "The Rheology and Morphology of Layered Polymer Melts in Shear," Soc. Plastics Eng. Tech Papers (ANTEC), 84-89 (1996). Guegan, P., C. W. Macosko, T. Ishizone, A. Hirao and S. Nakahama, "Kinetics of Chain Coupling at Melt Interfaces, Macromol. 27, 4993-4997 (1994). Lee, M. S., T.P. Lodge, and C. W. Macosko, "Can Random Copolymers Serve as Effective Polymeric Compatibilizers?" accepted for publication by Journal of Polymer Science, Polymer Physics Edition, 1997. Levitt, L. and C. W. Macosko, "Extensional Rheometry of Polymer Multilayers: A Sensitive Probe of Interfaces," J. Rheol, 41, 3, 671-685, (1997). Levitt, L., C.W. Macosko and S.D. Pearson, "Influence of Normal Stress Difference on Polymer Drop Deformation," Polym. Eng. Sci., 36, Part 12, 1647-1655 (1996). Nakayama, A., T. Inoue, A. Hirao, P. Guegan, A. Khandpur, and C. W. Macosko, "Compatibilization of Blends: Effect of Reaction Rate," PPS Proceedings, Sorrento, May 1996. Levitt, L., "Microlayer Morphology Via Polymer Melt Processing, Ph.D. Thesis, Department of Chemical Engineering & Materials Science, University of Minnesota, 1997. Orr, C. A., A. Adedeji, A. Hirao, F. S. Bates, and C. W. Macosko, "Flow-Induced Reactive Self-Assembly", Macromolecules, 30, 4, 1243-1246, (1997). Orr, C. A., "Reactive Compatibilization of Polymer Blends," Ph.D. Thesis, Department of Chemical Engineering & Materials Science, University of Minnesota, 1997. Scott, C. E., and C. W. Macosko, "Morphology Development During the Initial Stages of Polymer-Polymer Blending," Polymer, 36, 461-470 (1995). Scott, C. E. and C. W. Macosko, "Model Experiments Concerning Morphology Development During the Initial Stages of Polymer Blending," Polymer Bulletin 26, 341- 348 (1991). Sundararaj, U., C. K. Shih, and C. W. Macosko, "Evidence For Inversion of Phase Continuity During Morphology Development in Polymer Blending," Polymer Eng. and Sci., 36, 1769-1781 (1996). Sundararaj, U., and C. W. Macosko, "Drop Breakup and Coalescence in Polymer Blends: The Effects of Concentration and Compatibilization, Macromolecules, 28, 2647-2657 (1995). Sundararaj, U., Y. Dori and C. W. Macosko, "Sheet Formation in Immiscible Polymer Blends: Model Experiments on Initial Blend Morphology," Polymer, 36, 1957-1968 (1995). Sundararaj, U., C. W. Macosko, A. Nakayama, and T. Inoue, "Milligrams to Kilograms: An Evaluation of Mixers for Reactive Polymer Blending," Polym. Eng. Sci. 35, 100-114 (1995). Sundararaj, U, R. J. Rolando, H. T. Chan and C. W. Macosko, "Morphology Development in Polymer Blends," Polymer Eng. Sci. 32, 1814-1823 (1992). Utracki, L., Polymer Alloys and Blends; Hanser: New York, 1989.

Chemical degradation and morphological instabilities during focused ion beam prototyping of polymers.

PubMed

Orthacker, A; Schmied, R; Chernev, B; Fröch, J E; Winkler, R; Hobisch, J; Trimmel, G; Plank, H

2014-01-28

Focused ion beam processing of low melting materials, such as polymers or biological samples, often leads to chemical and morphological instabilities which prevent the straight-forward application of this versatile direct-write structuring method. In this study the behaviour of different polymer classes under ion beam exposure is investigated using different patterning parameters and strategies with the aim of (i) correlating local temperatures with the polymers' chemistry and its morphological consequences; and (ii) finding a way of processing sensitive polymers with lowest chemical degradation while maintaining structuring times. It is found that during processing of polymers three temperature regimes can be observed: (1) at low temperatures all polymers investigated show stable chemical and morphological behaviour; (2) very high temperatures lead to strong chemical degradation which entails unpredictable morphologies; and (3) in the intermediate temperature regime the behaviour is found to be strongly material dependent. A detailed look reveals that polymers which rather cross-link in the proximity of the beam show stable morphologies in this intermediate regime, while polymers that rather undergo chain scission show tendencies to develop a creeping phase, where material follows the ion beam movement leading to instable and unpredictable morphologies. Finally a simple, alternative patterning strategy is suggested, which allows stable processing conditions with lowest chemical damage even for challenging polymers undergoing chain scission.

Characterization of ethyl cellulose polymer.

PubMed

Mahnaj, Tazin; Ahmed, Salah U; Plakogiannis, Fotios M

2013-01-01

Ethyl cellulose (EC) polymer was characterized for its property before considering the interactions with the plasicizer. Ethocel Std.10 FP Premium from Dow chemical company USA was tested for its solubility, morphology and thermal properties. Seven percentage of EC solution in ethanol was found to be the right viscosity used to prepare the film. The EC polymer and EC film without any plasticizers showed almost identical thermal behavior, but in X-ray diffraction showed different arrangements of crystallites and amorphous region. Dynamic mechanical analysis of film showed that without a plasticizer, EC film was not flexible and had very low elongation with high applied force. The aim of the work was to avoid using the commercially available EC dispersions Surelease® and Aquacoat®; both already have additives on it. Instead, Ethocel EC polymer (powder) was characterized in our laboratory in order to find out the properties of polymer before considering the interactions of the polymer with various plasticizers.

Non-covalent nanodiamond-polymer dispersions and electrostatic immobilization of bovine serum albumin protein

NASA Astrophysics Data System (ADS)

Skaltsas, T.; Pispas, S.; Tagmatarchis, N.

2015-11-01

Nanodiamonds (NDs) lack efficient dispersion, not only in solvents but also in aqueous media. The latter is of great importance, considering the inherent biocompatibility of NDs and the plethora of suitable strategies for immobilizing functional biomolecules. In this work, a series of polymers was non-covalently interacted with NDs, forming ND-polymer ensembles, and their dispersibility and stability was examined. Dynamic light scattering gave valuable information regarding the size of the ensembles in liquid phase, while their morphology was further examined by high-resolution transmission electron microscopy imaging. In addition, thermal analysis measurements were applied to collect information on the thermal behavior of NDs and their ensembles and to calculate the amount of polymer interacting with the NDs, as well as the dispersibility values of the ND-polymer ensembles. Finally, the bovine serum albumin protein was electrostatically bound to a ND-polymer ensemble in which the polymeric moiety was carrying quaternized pyridine units.

The Characterization of Material Properties and Structural Dynamics of the Manduca Sexta Forewing for Application to Flapping Wing Micro Air Vehicle Design

DTIC Science & Technology

2012-09-13

2.1.1 Wing Morphology. Insect wings are formed from a complex makeup of polymer based chains, Chitin , that form the Cuticle, which provides the strong... Chitin , a long-chain polymer and a deriva- tive of glucose, is the main component of the exoskeletons and wings of insects . Due to the ability of the...biological specimen to vary the bonding chains, assemblage of nanofibers, and crystalline structure, the material properties of chitin can vary over a

A systematic examination of the morphogenesis of calcium carbonate in the presence of a double-hydrophilic block copolymer.

PubMed

Cölfen, H; Qi, L

2001-01-05

In this paper, a systematic study of the influence of various experimental parameters on the morphology and size of CaCO3 crystals after room-temperature crystallization from water in the presence of poly(ethylene glycol)-block-poly(methacrylic acid) (PEG-b-PMAA) is presented. The pH of the solution, the block copolymer concentration, and the ratio [polymer]/[CaCO3] turned out to be important parameters for the morphogenesis of CaCO3, whereas a moderate increase of the ionic strength (0.016 M) had no influence. Depending on the experimental conditions, the crystal morphologies can be tuned from calcite rhombohedra via rods, ellipsoids or dumbbells to spheres. A morphology map is presented which allows the prediction of the crystal morphology from a combination of pH, and CaCO3 and polymer concentration. Morphologies reported in literature for the same system but under different crystallization conditions agree well with the predictions from the morphology map. A closer examination of the growth of polycrystalline macroscopic CaCO3 spheres by TEM and time-resolved dynamic light scattering showed that CaCO3 macrocrystals are formed from strings of aggregated amorphous nanoparticles and then recrystallize as dumbbell-shaped or spherical calcite macrocrystal.

Clustering Effects on Dynamics in Ionomer Solutions: A Neutron Spin Echo Insight

NASA Astrophysics Data System (ADS)

Perahia, Dvora; Wijesinghe, Sidath; Senanayake, Manjula; Wickramasinghe, Anuradhi; Mohottalalage, Supun S.; Ohl, Michael

Ionizable blocks in ionomers associate into aggregates serving as physical cross-links and concurrently form transport pathways. The dynamics of ionomers underline their functionality. Incorporating small numbers of ionic groups into polymers significantly constraint their dynamics. Recent computational studies demonstrated a direct correlation between ionic cluster morphology and polymer dynamics. Here using neutron spin echo, we probe the segmental dynamics of polystyrene sulfonate (PSS) as the degree of sulfonation of the PSS and the solution dielectrics are varied. Specifically, 20Wt% PSS of 11,000 g/mol with polydispersity of 1.02 with 3% and 9% sulfonation were studies in toluene (dielectric constant ɛ = 2.8), a good solvent for polystyrene, and with 5Wt% of ethanol (ɛ = 24.3l) added. The dynamic structure factor S(q,t) was analyzed with a single exponential except for a limited q range where two time constants associated with constraint and mobile segments were detected. S(q,t) exhibits several distinctive time and length scales for the dynamics with a crossover appearing at the length scale of the ionic clusters. NSF DMR 1611136.

Effectiveness of External Electric Field Treatment of Conjugated Polymers in Bulk-Heterojunction Solar Cells.

PubMed

Solanki, Ankur; Bagui, Anirban; Long, Guankui; Wu, Bo; Salim, Teddy; Chen, Yongsheng; Lam, Yeng Ming; Sum, Tze Chien

2016-11-30

External electric field treatment (EFT) on P3HT:PCBM bulk heterojunction (BHJ) devices was recently found to be a viable approach for improving the power conversion efficiencies (PCEs) through modulating the blend nanomorphology. However, its effectiveness over the broad family of polymer-fullerene blends remains unclear. Herein, we investigate the effects of external EFT on various polymer-fullerene blends with distinct morphologies stemming from the difference in molecular structure of the polymers (i.e., semicrystalline vs amorphous) in a bid to establish a clear morphology-function-charge dynamics relationship to the photovoltaic performance. Our findings reveal that EFT promotes self-organization of the semicrystalline thiophene-based conjugated polymers (i.e., P3HT and P3BT) while it was ineffective for the amorphous polymers (i.e., PTB7 and PCPDTBT) even at the maximum applied E-field of 8 kV cm -1 . Transient absorption spectroscopy shows an improvement in the initial charge-carrier and polaron formation from delocalized excitons in the E-field treated semicrystalline blends compared to their untreated reference samples. Interfacial trap-assisted monomolecular and trap-free bimolecular recombination at nanosecond-microsecond time scale in the E-field treated P3BT:PC60BM devices are significantly suppressed. Importantly, our findings shed new light and provide guidelines on the effectiveness of utilizing external EFT to enhance the PCEs of a larger family of conjugated polymer-based BHJ OSCs.

Interfacial crowding of nanoplatelets in co-continuous polymer blends: assembly, elasticity and structure of the interfacial nanoparticle network.

PubMed

Altobelli, R; Salzano de Luna, M; Filippone, G

2017-09-27

The sequence of events which leads to the interfacial crowding of plate-like nanoparticles in co-continuous polymer blends is investigated through a combination of morphological and rheological analyses. Very low amounts (∼0.2 vol%) of organo-modified clay are sufficient to suppress phase coarsening in a co-continuous polystyrene/poly(methyl methacrylate) blend, while lower particle loading allows for a tuning of the characteristic size of the polymer phases at the μm-scale. In any case, an interfacial network of nanoparticles eventually forms, which is driven by the preferred polymer-polymer interface. The elastic features and stress-bearing ability of this peculiar nanoparticle assembly are studied in detail by means of a descriptive two-phase viscoelastic model, which allows isolation of the contribution of the filler network. The role of the co-continuous matrix in driving the space arrangement of the nanoparticles is emphasized by means of comparative analysis with systems based on the same polymers and nanoparticles, but in which the matrix is either a pure polymer or a blend with drop-in-matrix morphology. The relaxation dynamics of the interfacial network was found not to depend on the matrix microstructure, which instead substantially affects the assembly of the nanoplatelets. When the host medium is co-continuous, the particles align along the preferred polymer-polymer interface, percolating at a very low amount (∼0.17 vol%) and prevalently interacting edge-to-edge. The stress bearing ability of such a network is much higher than that in the case of matrix based on a homogeneous polymer or a drop-in-matrix blend, but its elasticity shows low sensitivity to the filler content.

Application of mesoscale simulation to explore the aggregate morphology of pH-sensitive nanoparticles used as the oral drug delivery carriers under different conditions.

PubMed

Wang, Yan; Chen, Bo Zhi; Liu, Yue Jin; Wu, Zhi Min; Guo, Xin Dong

2017-03-01

The pH-sensitive nanoparticles are selected as the potentially promising oral protein and peptide drug carriers due to their excellent performance. With the poly (lactic-co-glycolic acid)/hydroxypropyl methylcellulose phthalate (PLGA/HP55) nanoparticle as a model nanoparticle, the structure-property relationship of nanoparticles with different conditions is investigated by dissipative particle dynamics (DPD) simulations in our work. In the oral drug delivery system, the poly (lactic-co-glycolic acid) (PLGA) is hydrophobic polymer, hydroxypropyl methylcellulose phthalate (HP55) is pH-sensitive enteric polymer which used to protect the nanoparticles through the stomach and polyvinyl alcohol (PVA) is hydrophilic polymer as the stabilizer. It can be seen from DPD simulations that all polymer molecules form spherical core-shell nanoparticles with stabilizer PVA molecules adsorbed on the outer surface of the PLGA/HP55 matrix at certain compositions. The DPD simulation study can provide microscopic insight into the formation and morphological changes of pH-sensitive nanoparticles which is useful for the design of new materials for high-efficacy oral drug delivery. Copyright © 2016 Elsevier B.V. All rights reserved.

Wetting-Dewetting and Dispersion-Aggregation Transitions Are Distinct for Polymer Grafted Nanoparticles in Chemically Dissimilar Polymer Matrix.

PubMed

Martin, Tyler B; Mongcopa, Katrina Irene S; Ashkar, Rana; Butler, Paul; Krishnamoorti, Ramanan; Jayaraman, Arthi

2015-08-26

Simulations and experiments are conducted on mixtures containing polymer grafted nanoparticles in a chemically distinct polymer matrix, where the graft and matrix polymers exhibit attractive enthalpic interactions at low temperatures that become progressively repulsive as temperature is increased. Both coarse-grained molecular dynamics simulations, and X-ray scattering and neutron scattering experiments with deuterated polystyrene (dPS) grafted silica and poly(vinyl methyl ether) PVME matrix show that the sharp phase transition from (mixed) dispersed to (demixed) aggregated morphologies due to the increasingly repulsive effective interactions between the blend components is distinct from the continuous wetting-dewetting transition. Strikingly, this is unlike the extensively studied chemically identical graft-matrix composites, where the two transitions have been considered to be synonymous, and is also unlike the free (ungrafted) blends of the same graft and matrix homopolymers, where the wetting-dewetting is a sharp transition coinciding with the macrophase separation.

Morphology and Performance of Polymer Solar Cell Characterized by DPD Simulation and Graph Theory.

PubMed

Du, Chunmiao; Ji, Yujin; Xue, Junwei; Hou, Tingjun; Tang, Jianxin; Lee, Shuit-Tong; Li, Youyong

2015-11-19

The morphology of active layers in the bulk heterojunction (BHJ) solar cells is critical to the performance of organic photovoltaics (OPV). Currently, there is limited information for the morphology from transmission electron microscopy (TEM) techniques. Meanwhile, there are limited approaches to predict the morphology /efficiency of OPV. Here we use Dissipative Particle Dynamics (DPD) to determine 3D morphology of BHJ solar cells and show DPD to be an efficient approach to predict the 3D morphology. Based on the 3D morphology, we estimate the performance indicator of BHJ solar cells by using graph theory. Specifically, we study poly (3-hexylthiophene)/[6, 6]-phenyl-C61butyric acid methyl ester (P3HT/PCBM) BHJ solar cells. We find that, when the volume fraction of PCBM is in the region 0.4 ∼ 0.5, P3HT/PCBM will show bi-continuous morphology and optimum performance, consistent with experimental results. Further, the optimum temperature (413 K) for the morphology and performance of P3HT/PCBM is in accord with annealing results. We find that solvent additive plays a critical role in the desolvation process of P3HT/PCBM BHJ solar cell. Our approach provides a direct method to predict dynamic 3D morphology and performance indicator for BHJ solar cells.

Transition state analogue imprinted polymers as artificial amidases for amino acid p-nitroanilides: morphological effects of polymer network on catalytic efficiency.

PubMed

Mathew, Divya; Thomas, Benny; Devaky, K S

2017-11-13

The morphology of the polymer network - porous/less porous - plays predominant role in the amidase activities of the polymer catalysts in the hydrolytic reactions of amino acid p-nitroanilides. Polymers with the imprints of stable phosphonate analogue of the intermediate of hydrolytic reactions were synthesized as enzyme mimics. Molecular imprinting was carried out in thermodynamically stable porogen dimethyl sulphoxide and unstable porogen chloroform, to investigate the morphological effects of polymers on catalytic amidolysis. It was found that the medium of polymerization has vital influence in the amidase activities of the enzyme mimics. The morphological studies of the polymer catalysts were carried out by scanning electron microscopy and Bruner-Emmett-Teller analysis. The morphology of the polymer catalysts and their amidase activities are found to be dependent on the composition of reaction medium. The polymer catalyst prepared in dimethyl sulphoxide is observed to be efficient in 1:9 acetonitrile (ACN)-Tris HCl buffer and that prepared in chloroform is noticed to be stereo specifically and shape-selectively effective in 9:1 ACN-Tris HCl buffer. The solvent memory effect in catalytic amidolysis was investigated using the polymer prepared in acetonitrile.

Highly temperature responsive core-shell magnetic particles: synthesis, characterization and colloidal properties.

PubMed

Rahman, Md Mahbubor; Chehimi, Mohamed M; Fessi, Hatem; Elaissari, Abdelhamid

2011-08-15

Temperature responsive magnetic polymer submicron particles were prepared by two step seed emulsion polymerization process. First, magnetic seed polymer particles were obtained by emulsion polymerization of styrene using potassium persulfate (KPS) as an initiator and divinylbenzne (DVB) as a cross-linker in the presence of oil-in-water magnetic emulsion (organic ferrofluid droplets). Thereafter, DVB cross-linked magnetic polymer particles were used as seed in the precipitation polymerization of N-isopropylacrylamide (NIPAM) to induce thermosensitive PNIPAM shell onto the hydrophobic polymer surface of the cross-linked magnetic polymer particles. To impart cationic functional groups in the thermosensitive PNIPAM backbone, the functional monomer aminoethylmethacrylate hydrochloride (AEMH) was used to polymerize with NIPAM while N,N'-methylenebisacrylamide (MBA) and 2, 2'-azobis (2-methylpropionamidine) dihydrochloride (V-50) were used as a cross-linker and as an initiator respectively. The effect of seed to monomer (w/w) ratio along with seed nature on the final particle morphology was investigated. Dynamic light scattering (DLS) results demonstrated particles swelling at below volume phase transition temperature (VPTT) and deswelling above the VPTT. The perfect core (magnetic) shell (polymer) structure of the particles prepared was confirmed by Transmission Electron Microscopy (TEM). The chemical composition of the particles were determined by thermogravimetric analysis (TGA). The effect of temperature, pH, ionic strength on the colloidal properties such as size and zeta potential of the micron sized thermo-sensitive magnetic particles were also studied. In addition, a short mechanistic discussion on the formation of core-shell morphology of magnetic polymer particles has also been discussed. Copyright © 2011 Elsevier Inc. All rights reserved.

Molecular dynamics simulation of diffusion of gases in a carbon-nanotube-polymer composite

NASA Astrophysics Data System (ADS)

Lim, Seong Y.; Sahimi, Muhammad; Tsotsis, Theodore T.; Kim, Nayong

2007-07-01

Extensive molecular dynamics (MD) simulations were carried out to compute the solubilities and self-diffusivities of CO2 and CH4 in amorphous polyetherimide (PEI) and mixed-matrix PEI generated by inserting single-walled carbon nanotubes into the polymer. Atomistic models of PEI and its composites were generated using energy minimizations, MD simulations, and the polymer-consistent force field. Two types of polymer composite were generated by inserting (7,0) and (12,0) zigzag carbon nanotubes into the PEI structure. The morphologies of PEI and its composites were characterized by their densities, radial distribution functions, and the accessible free volumes, which were computed with probe molecules of different sizes. The distributions of the cavity volumes were computed using the Voronoi tessellation method. The computed self-diffusivities of the gases in the polymer composites are much larger than those in pure PEI. We find, however, that the increase is not due to diffusion of the gases through the nanotubes which have smooth energy surfaces and, therefore, provide fast transport paths. Instead, the MD simulations indicate a squeezing effect of the nanotubes on the polymer matrix that changes the composite polymers’ free-volume distributions and makes them more sharply peaked. The presence of nanotubes also creates several cavities with large volumes that give rise to larger diffusivities in the polymer composites. This effect is due to the repulsive interactions between the polymer and the nanotubes. The solubilities of the gases in the polymer composites are also larger than those in pure PEI, hence indicating larger gas permeabilities for mixed-matrix PEI than PEI itself.

Low density microcellular foams

DOEpatents

Aubert, J.H.; Clough, R.L.; Curro, J.G.; Quintana, C.A.; Russick, E.M.; Shaw, M.T.

1985-10-02

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the reusltant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 ..mu..m and a volume such that the foams have a length greater than 1 cm are provided.

Electrostatic effects on clustering and ion dynamics in ionomer melts

NASA Astrophysics Data System (ADS)

Ma, Boran; Nguyen, Trung; Pryamitsyn, Victor; Olvera de La Cruz, Monica

An understanding of the relationships between ionomer chain morphology, dynamics and counter-ion mobility is a key factor in the design of ion conducting membranes for battery applications. In this study, we investigate the influence of electrostatic coupling between randomly charged copolymers (ionomers) and counter ions on the structural and dynamic features of a model system of ionomer melts. Using coarse-grained molecular dynamics (CGMD) simulations, we found that variations in electrostatic coupling strength (Γ) remarkably affect the formation of ion-counter ion clusters, ion mobility, and polymer dynamics for a range of charged monomer fractions. Specifically, an increase in Γ leads to larger ionic cluster sizes and reduced polymer and ion mobility. Analysis of the distribution of the radius of gyration of the clusters further reveals that the fractal dimension of the ion clusters is nearly independent from Γ for all the cases studied. Finally, at sufficiently high values of Γ, we observed arrested heterogeneous ions mobility, which is correlated with an increase in ion cluster size. These findings provide insight into the role of electrostatics in governing the nanostructures formed by ionomers.

Relating dynamics of model unentangled, crystallizable polymeric liquids to their local structure

NASA Astrophysics Data System (ADS)

Nguyen, Hong T.; Hoy, Robert S.

We study the liquid-state dynamics of a recently developed, crystallizable bead-spring polymer model. The model possesses a single ground state (NCP, wherein monomers close-pack and chains are nematically aligned) for all finite bending stiffnesses kb, but the solid morphologies formed under cooling vary strongly with kb, varying from NCP to amorphous. We find that systems with kb producing amorphous order are good glass-formers exhibiting the classic Vogel-Fulcher slowdown with decreasing temperature T. In contrast, systems with kb producing crystalline solids exhibit a simpler dynamics when kb is small. Larger kb produce more complex dynamics, but these are associated with the existence of an intermediate nematic liquid rather than glassy slowdown. We relate these differences to local, cluster-level structure measured via TCC analyses. Formation propensities and lifetimes of various clusters (associated with amorphous or crystalline order) vary strongly with kb and T. We relate these differences to those measured by the self-intermediate scattering function and other macroscopic measures of dynamics. Our results should aid in understanding the competition between crystallization and glass-formation in synthetic polymers.

Synthesis of metronidazole-imprinted molecularly imprinted polymers by distillation precipitation polymerization and their use as a solid-phase adsorbent and chromatographic filler.

PubMed

Liu, Jiang; Zhang, Lu; Li Han Song, Le; Liu, Yuan; Tang, Hui; Li, Yingchun

2015-04-01

Metronidazole-imprinted polymers with superior recognition properties were prepared by a novel strategy called distillation-precipitation polymerization. The as-obtained polymers were characterized by Fourier-transform infrared spectroscopy, laser particle size determination and scanning electron microscopy, and their binding performances were evaluated in detail by static, kinetic and dynamic rebinding tests, and Scatchard analysis. The results showed that when the fraction of the monomers was 5 vol% in the whole reaction system, the prepared polymers afforded good morphology, monodispersity, and high adsorption capacity and excellent selectivity to the target molecule, metronidazole. The optimal binding performance is 12.41 mg/g for metronidazole just before leakage occurred and 38.51 mg/g at saturation in dynamic rebinding tests. Metronidazole-imprinted polymers were further applied as packing agents in solid-phase extraction and as chromatographic filler, both of which served for the detection of metronidazole in fish tissue. The results illustrated the recoveries of spiked samples ranged from 82.97 to 87.83% by using molecularly imprinted solid-phase extraction combined with a C18 commercial column and 93.7 to 101.2% by directly using the polymer-packed chromatographic column. The relative standard deviation of both methods was less than 6%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Chan Yi, E-mail: vicchanyiwei@hotmail.com; Ongkudon, Clarence M., E-mail: clarence@ums.edu.my; Kansil, Tamar, E-mail: tamarkansil87@gmail.com

Modern day synthesis protocols of methacrylate monolithic polymer adsorbent are based on existing polymerization blueprint without a thorough understanding of the dynamics of pore structure and formation. This has resulted in unproductiveness of polymer adsorbent consequently affecting purity and recovery of final product, productivity, retention time and cost effectiveness of the whole process. The problems magnified in monolith scaling-up where internal heat buildup resulting from external heating and high exothermic polymerization reaction was reflected in cracking of the adsorbent. We believe that through careful and precise control of the polymerization kinetics and parameters, it is possible to prepare macroporous methacrylatemore » monolithic adsorbents with controlled pore structures despite being carried out in an unstirred mould. This research involved the study of the effect of scaling-up on pore morphology of monolith, in other words, porous polymethacrylate adsorbents that were prepared via bulk free radical polymerization process by imaging the porous morphology of polymethacrylate with scanning electron microscope.« less

Time-Resolved Transient Optical Absorption Study of Bis(terpyridyl)oligothiophenes and Their Metallo-Supramolecular Polymers with Zn(II) Ion Couplers.

PubMed

Rais, David; Menšík, Miroslav; Štenclová-Bláhová, Pavla; Svoboda, Jan; Vohlídal, Jiří; Pfleger, Jiří

2015-06-18

α,ω-Bis(terpyridyl)oligothiophenes spontaneously assemble with Zn(II) ions giving conjugated constitutional dynamic polymers (dynamers) of the metallo-supramolecular class, which potentially might be utilized in optoelectronics. Their photophysical properties, which are of great importance in this field of application, are strongly influenced by the dynamic morphology. It was assessed in this study by using ultrafast pump-probe optical absorption spectroscopy. We identified and characterized relaxation processes running in photoexcited molecules of these oligomers and dynamers and show impacts of disturbed coplanarity of adjacent rings (twisting the thiophene-thiophene and thiophene-terpyridyl bonds by attached hexyl side groups) and Zn(II) ion couplers on these processes. Major effects are seen in the time constants of rotational relaxation, intersystem crossing, and de-excitation lifetimes. The photoexcited states formed on different repeating units within the same dynamer chain do not interact with each other even at very high excitation density. The method is presented that allows determining the equilibrium fraction of unbound oligothiophene species in a dynamer solution, from which otherwise hardly accessible values of the average degree of polymerization of constitutionally dynamic chains in solution can be estimated.

Transferable coarse-grained model for perfluorosulfonic acid polymer membranes

NASA Astrophysics Data System (ADS)

Kuo, An-Tsung; Okazaki, Susumu; Shinoda, Wataru

2017-09-01

Perfluorosulfonic acid (PFSA) polymer membranes are widely used as proton exchange membranes. Because the structure of the aqueous domain within the PFSA membrane is expected to directly influence proton conductance, many coarse-grained (CG) simulation studies have been performed to investigate the membrane morphology; these studies mostly used phenomenological models, such as dissipative particle dynamics. However, a chemically accurate CG model is required to investigate the morphology in realistic membranes and to provide a concrete molecular design. Here, we attempt to construct a predictive CG model for the structure and morphology of PFSA membranes that is compatible with the Sinoda-DeVane-Klein (SDK) CG water model [Shinoda et al., Mol. Simul. 33, 27 (2007)]. First, we extended the parameter set for the SDK CG force field to examine a hydrated PFSA membrane based on thermodynamic and structural data from experiments and all-atom (AA) molecular dynamics (MD) simulations. However, a noticeable degradation of the morphology motivated us to improve the structural properties by using the iterative Boltzmann inversion (IBI) approach. Thus, we explored a possible combination of the SDK and IBI approaches to describe the nonbonded interaction. The hybrid SDK/IBI model improved the structural issues of SDK, showing a better agreement with AA-MD in the radial distribution functions. The hybrid SDK/IBI model was determined to reasonably reproduce both the thermodynamic and structural properties of the PFSA membrane for all examined water contents. In addition, the model demonstrated good transferability and has considerable potential for application to realistic long-chained PFSA membranes.

Study of structural morphologies of thermoresponsive diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene)

NASA Astrophysics Data System (ADS)

Rodríguez-Hidalgo, María del Rosario; Soto-Figueroa, César; Vicente, Luis

2018-03-01

Structural morphologies of diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene) in aqueous environment have been investigated by dissipative particle dynamics (DPD). In triblock copolymers insoluble PS blocks contract while soluble pNIPAM blocks stay at the periphery forming looped chains as corona. As the temperature is increased there is a continuous morphological transition and micelles form ellipsoidal structures with segregated polymer zones. The phase transition of looped pNIPAM chains occurs at lower temperature than for linear chains and within broader temperature range. It is discussed how the chain topology of pNIPAM affects the phase transition.

Dynamics of direct X-ray detection processes in high-Z Bi2O3 nanoparticles-loaded PFO polymer-based diodes

NASA Astrophysics Data System (ADS)

Ciavatti, A.; Cramer, T.; Carroli, M.; Basiricò, L.; Fuhrer, R.; De Leeuw, D. M.; Fraboni, B.

2017-10-01

Semiconducting polymer based X-ray detectors doped with high-Z nanoparticles hold the promise to combine mechanical flexibility and large-area processing with a high X-ray stopping power and sensitivity. Currently, a lack of understanding of how nanoparticle doping impacts the detector dynamics impedes the optimization of such detectors. Here, we study direct X-ray radiation detectors based on the semiconducting polymer poly(9,9-dioctyfluorene) blended with Bismuth(III)oxide (Bi2O3) nanoparticles (NPs). Pure polymer diodes show a high mobility of 1.3 × 10-5 cm2/V s, a low leakage current of 200 nA/cm2 at -80 V, and a high rectifying factor up to 3 × 105 that allow us to compare the X-ray response of a polymer detector in charge-injection conditions (forward bias) and in charge-collection conditions (reverse bias), together with the impact of NP-loading in the two operation regimes. When operated in reverse bias, the detectors reach the state of the art sensitivity of 24 μC/Gy cm2, providing a fast photoresponse. In forward operation, a slower detection dynamics but improved sensitivity (up to 450 ± 150 nC/Gy) due to conductive gain is observed. High-Z NP doping increases the X-ray absorption, but higher NP loadings lead to a strong reduction of charge-carrier injection and transport due to a strong impact on the semiconductor morphology. Finally, the time response of optimized detectors showed a cut-off frequency up to 200 Hz. Taking advantage of such a fast dynamic response, we demonstrate an X-ray based velocity tracking system.

Ultrafast Transient Absorption Spectroscopy Investigation of Photoinduced Dynamics in POLY(3-HEXYLTHIOPHENE)-BLOCK-OLIGO(ANTHRACENE-9,10-DIYL)

NASA Astrophysics Data System (ADS)

Strain, Jacob; Rathnayake, Hemali; Liu, Jinjun

2017-06-01

Semiconducting polymer nanostructures featuring bulk heterojunction (BHJ) architecture are promising light harvesters in photovoltaic (PV) devices because they allow control of individual domain sizes, internal structure and ordering, as well as well-defined contact between the electron donor and acceptor. Power conversion efficiency (PCE) of PV devices strongly depends on photoinduced dynamics. Understanding and optimizing photoinduced charge transfer processes in BHJ's hence help improve the performance of PV devices and increase their PCE in particular. We have investigated the photoinduced dynamics of a block polymer containing moieties of poly-3-hexylthiophene (P3HT) and polyanthracene (PANT) in solution and in solid state with femtosecond transient absorption (TA) spectroscopy. The dynamics of the polymer PANT alone are also studied as a control. The TA spectra of PANT includes a strong excited state absorption centered at 610 (nm) along with a stimulated emission signal stretching past the detection limit into the UV region which is absent in the monomer's spectra in the detection window. The block polymer's TA spectra strongly resembles that of P3HT but a noticeable positive pull on P3HT's stimulated emission signal residing at 575-620 (nm) is indicative of the excited state absorption of PANT in the adjacent spectral region. The doubling of the lifetime exciton delocalization on the block polymer versus P3HT alone have alluded that the lifetime of P3HT is extended by the covalent addition of PANT. The current spectroscopic investigation represents an interesting example of photoinduced processes in systems with complex energy level structure. Studies of dependence of change generation and separation on composition, dimension, and morphology of the heterojunctions are in process.

Development of toughened epoxy polymers for high performance composite and ablative applications

NASA Technical Reports Server (NTRS)

Allen, V. R.

1982-01-01

A survey of current procedures for the assessment of state of cure in epoxy polymers and for the evaluation of polymer toughness as related to nature of the crosslinking agent was made to facilitate a cause-effect study of the chemical modification of epoxy polymers. Various conformations of sample morphology were examined to identify testing variables and to establish optimum conditions for the selected physical test methods. Dynamic viscoelasticity testing was examined in conjunction with chemical analyses to allow observation of the extent of the curing reaction with size of the crosslinking agent the primary variable. Specifically the aims of the project were twofold: (1) to consider the experimental variables associated with development of "extent of cure" analysis, and (2) to assess methodology of fracture energy determination and to prescribe a meaningful and reproducible procedure. The following is separated into two categories for ease of presentation.

[Preparation and evaluation of novel mesoporous molecular sieve of baicalin surface molecularly imprinted polymers].

PubMed

Gu, Xia-li; He, Hong-liang; Shi, Li-ying; Gao, Yan-kun; Chen, Li-na

2015-05-01

Taking mesoporous molecular sieve MCM-41 as a substrate, baicalin (BA) as template, acrylamide (AM) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, ethanol as solvent, under thermal polymerization initiator of azobis isobutyronitrilo (AIBN) , a kind of selective recognition of baicalin surface molecularly imprinted polymer was synthesized. The surface morphologies and characteristics of the MIPs were characterized by infrared spectroscopy (IR) and transmission electron microscope (TEM). The adsorption properties of polymer microsphere for the template were tested by the dynamic adsorption equilibrium experiments and static adsorption equilibrium experiments. The experiment showed that the imprinting process was successfully and the well-ordered one-dimensional pore structure of MCM-41 was still preserved. Furthermore, molecularly imprinted polymers had higher selective ability for BA, then provided a new method for the efficient separation and enrichment of baicalin active ingredients from medicinal plants Scutellaria baicalensis.

Low density microcellular foams

DOEpatents

Aubert, James H.; Clough, Roger L.; Curro, John G.; Quintana, Carlos A.; Russick, Edward M.; Shaw, Montgomery T.

1987-01-01

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the resultant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Means for subjecting such a solvent to one-dimensional cooling are also provided. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 .mu.m and a volume such that the foams have a length greater than 1 cm are provided.

Pattern interpolation in thin films of lamellar, symmetric copolymers on nano-patterned substrates

NASA Astrophysics Data System (ADS)

Detcheverry, Francois; Nagpal, Umang; Liu, Guoliang; Nealey, Paul; de Pablo, Juan

2009-03-01

A molecular model of block copolymer systems is used to conduct a systematic study of the morphologies that arise when thin films of symmetric, lamellar forming block copolymer materials are deposited on nanopatterned surfaces. Over 500 distinct cases are considered. It is found that, in general, three distinct morphologies can arise depending on the strength of the substrate-polymer interactions, the film thickness, and the period of the substrate pattern. The relative stability of those morphologies is determined by direct calculation of the free energy differences. The dynamic propensity of those morphologies to emerge is examined by careful analysis of simulated trajectories. The results of this systematic study are used to interpret recent experimental data for films of polystyrene-PMMA copolymers on chemically nanopatterned surfaces.

Nanowires and Nanostructures That Grow Like Polymer Molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shaw, Santosh; Cademartiri, Ludovico

Unique properties (e.g., rubber elasticity, viscoelasticity, folding, reptation) determine the utility of polymer molecules and derive from their morphology (i.e., one-dimensional connectivity and large aspect ratios) and flexibility. Crystals do not display similar properties because they have smaller aspect ratios, they are rigid, and they are often too large and heavy to be colloidally stable. We argue, with the support of recent experimental studies, that these limitations are not fundamental and that they might be overcome by growth processes that mimic polymerization. Furthermore, we (i) discuss the similarities between crystallization and polymerization, (ii) critically review the existing experimental evidence ofmore » polymer-like growth kinetic and behavior in crystals and nanostructures, and (iii) propose heuristic guidelines for the synthesis of “polymer-like” crystals and assemblies. Understanding these anisotropic materials at the boundary between molecules and solids will determine whether we can confer the unique properties of polymer molecules to crystals, expanding them with topology, dynamics, and information and not just tuning them with size.« less

Liquid crystal Janus emulsion droplets: preparation, tumbling, and swimming.

PubMed

Jeong, Joonwoo; Gross, Adam; Wei, Wei-Shao; Tu, Fuquan; Lee, Daeyeon; Collings, Peter J; Yodh, A G

2015-09-14

This study introduces liquid crystal (LC) Janus droplets. We describe a process for the preparation of these droplets, which consist of nematic LC and polymer compartments. The process employs solvent-induced phase separation in emulsion droplets generated by microfluidics. The droplet morphology was systematically investigated and demonstrated to be sensitive to the surfactant concentration in the background phase, the compartment volume ratio, and the possible coalescence of multiple Janus droplets. Interestingly, the combination of a polymer and an anisotropic LC introduces new functionalities into Janus droplets, and these properties lead to unusual dynamical behaviors. The different densities and solubilities of the two compartments produce gravity-induced alignment, tumbling, and directional self-propelled motion of Janus droplets. LC Janus droplets with remarkable optical properties and dynamical behaviors thus offer new avenues for applications of Janus colloids and active soft matter.

Behavior of grafted polymers on nanofillers and their influence on polymer nanocomposite properties

NASA Astrophysics Data System (ADS)

Dukes, Douglas Michael

Polymer nanocomposites continue to receive wide-spread acclaim for their potential to improve composite materials beyond conventional macroscale fillers. The improvement lies both in the altered properties of the particle itself and in the interaction region surrounding the filler. As the surface area of the filler increases, a greater volume fraction of this interphase region is present in the composite. However, simply minimizing the particle size to maximize surface area introduces additional problems; the larger specific surface area promotes aggregation to reduce the surface energy. Since the composite's properties are largely tied to the morphology, aggregation prevents control over the dispersion state of the filler, and thus the properties. Therefore, disaggregation and morphology control are vital to achieving designable nanocomposites. To accomplish both tasks, this thesis focuses on the behavior of grafted polymer coatings on nanoparticles and their in uence on the macroscopic properties. Grafted chains play an integral role in both morphology control and reinforcement. To investigate the behavior of polymer brushes on nanoparticles, polystyrene was grafted on 15 nm silica particles at varying graft densities and molecular weights. Dynamic light scattering studies in dilute solution were performed to obtain the brush height as a function of both graft density and molecular weight. Three distinct regimes of behavior exist, the "mushroom", the semi-dilute polymer brush (SDPB), and the concentrated polymer brush (CPB) regimes. In the CPB regime, which is an extraordinary configuration of highly-stretched chains on densely grafted surfaces, the brush height h was found to scale as h ∝ N4/5, where N is the degree of polymerization. This result is contrary to the observed scaling of the CPB in flat interface systems, where h ∝ N1. To explore the behavior of grafted chains in the melt, molecular dynamics simulations were performed on grafted nanoparticles grafted with varying amounts of polymer chains at different curvatures. Particles as small as 15 monomers in size were found to already be in the large particle limit, a result that has many implications regarding the dispersibility of grafted fillers in composites. At low graft densities, melt chains were found to form entanglements with the brush all the way to the particle surface, implying the particle is not effectively screened by the grafted chains. The mechanical properties of these grafted silica composites were studied as a function of matrix polymer fraction. As more matrix polymer is introduced, the dominant contribution to the behavior shifts from the grafted chains to the matrix chains. This elucidates the role of grafted chains on the mechanical properties of grafted nanoparticle composites. As the graft density is increased, the wettability of grafted chains was shown to decrease, causing fewer entanglements between grafted chains and matrix chains, resulting in poorer reinforcement. Interesting behavior was observed at low graft densities; a pronounced shape memory effect occurred at high particle concentrations. It is proposed that the grafted chains entangle with adjacent grafted chains, forming a three-dimensional network of entangled brushes attached to silica cores. This structure effectively forms "cross-links" as in elastomeric systems, giving an entropic restorative force to stretched chains. Thus, above Tg, when chains have a higher degree of mobility, the composites can be stretched to over 800%. When cooled to below Tg, they retain the deformed geometry. Upon reheating above Tg, the composite is restored to its original dimensions. This work has identified means of improving theoretical models to better guide future experiments and lead to predictability in polymer composite design. Grafted chains have the demonstrated ability to control the morphology and reinforcement in polymer composites. The behavior of grafted chains were shown to demonstrate drastically different properties from their bulk polymer counterparts.

Synthesis and supramolecular assembly of biomimetic polymers

NASA Astrophysics Data System (ADS)

Marciel, Amanda Brittany

A grand challenge in materials chemistry is the synthesis of macromolecules and polymers with precise shapes and architectures. Polymer microstructure and architecture strongly affect the resulting functionality of advanced materials, yet understanding the static and dynamic properties of these complex macromolecules in bulk has been difficult due to their inherit polydispersity. Single molecule studies have provided a wealth of information on linear flexible and semi-flexible polymers in dilute solutions. However, few investigations have focused on industrially relevant complex topologies (e.g., star, comb, hyperbranched polymers) in industrially relevant solution conditions (e.g., semi-dilute, concentrated). Therefore, from this perspective there is a strong need to synthesize precision complex architectures for bulk studies as well as complex architectures compatible with current single molecule techniques to study static and dynamic polymer properties. In this way, we developed a hybrid synthetic strategy to produce branched polymer architectures based on chemically modified DNA. Overall, this approach enables control of backbone length and flexibility, as well as branch grafting density and chemical identity. We utilized a two-step scheme based on enzymatic incorporation of non-natural nucleotides containing bioorthogonal dibenzocyclooctyne (DBCO) functional groups along the main polymer backbone, followed by copper-free "click" chemistry to graft synthetic polymer branches or oligonucleotide branches to the DNA backbone, thereby allowing for the synthesis of a variety of polymer architectures, including three-arm stars, H-polymers, graft block copolymers, and comb polymers for materials assembly and single molecule studies. Bulk materials properties are also affected by industrial processing conditions that alter polymer morphology. Therefore, in an alternative strategy we developed a microfluidic-based approach to assemble highly aligned synthetic oligopeptides nanostructures using microscale extensional flows. This strategy enabled reproducible, reliable fabrication of aligned hierarchical constructs that do not form spontaneously in solution. In this way, fluidic-directed assembly of supramolecular structures allows for unprecedented manipulation at the nano- and mesoscale, which has the potential to provide rapid and efficient control of functional materials properties.

Elucidating the correlation between morphology and ion dynamics in polymerized ionic liquids.

NASA Astrophysics Data System (ADS)

Heres, Maximilian; Cosby, Tyler; Iacob, Ciprian; Runt, James; Benson, Roberto; Liu, Hongjun; Paddison, Stephen; Sangoro, Joshua

Charge transport and dynamics are investigated for a series of poly-ammonium and poly-imidazolium-based polymerized ionic liquids (polyIL) with a common bis(trifluoromethylsulfonyl)imide anion using broadband dielectric spectroscopy and temperature modulated differential scanning calorimetry. A significant enhancement of the Tg independent ionic conductivity is observed for ammonium based polyIL with shorter pendant groups, in comparison to imidazolium based systems. These results emphasize the importance of polymer backbone spacing as well as counter-ion size on ionic conductivity in polymerized ionic liquids. NSF DMR 1508394.

Nonequilibrium Simulations of Ion Dynamics in Ionomer Melts

NASA Astrophysics Data System (ADS)

Frischknecht, Amalie

Ionomers, polymers containing a small fraction of covalently bound ionic groups, are of interest as possible electrolytes in batteries. However, to date ionomers do not have sufficiently high conductivities for practical application, most likely because the ions tend to form aggregates, leading to slow ion transport. To build a better understanding of the relationships among ionomer chemistry, morphology, and ion transport, we have performed a series of molecular dynamics simulations and connected aspects of these simulations with experiment. In previous work using both atomistic and coarse-grained models, we showed that precise ionomers (with a fixed spacing between ionic groups along the polymer backbone) exhibit a range of ionic aggregate morphologies, from discrete clusters to percolated aggregates. In this talk I will describe recent simulations of our coarse-grained ionomer melts in an applied electric field. From a constant applied field, we are able to extract the ion mobilities and hence conductivities. We find that ionomers with percolated ionic aggregate morphologies have higher ion mobilities and hence higher conductivities. Application of an oscillating electric field enables us to calculate the frequency-dependent conductivity of the model ionomer melts. The real part of the conductivity has a high frequency peak associated with plasma oscillations, and a very broad low frequency peak associated with ion motions in ionic aggregates. I will end with comments on the connections to atomistic simulations and to experimental probes of ion dynamics. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Linking Silica Support Morphology to the Dynamics of Aminopolymers in Composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carrillo, Jan-Michael Y.; Potter, Matthew E.; Sakwa-Novak, Miles A.

A combined computational and experimental approach is used to elucidate the effect of silica support morphology on polymer dynamics and CO 2 adsorption capacities in aminopolymer/silica composites. Furthermore, simulations are based on coarse-grained molecular dynamics simulations of aminopolymer composites where a branched aminopolymer, representing poly(ethylenimine) (PEI), is impregnated into different silica mesoporous supports. The morphology of the mesoporous supports varies from hexagonally packed cylindrical pores representing SBA-15, double gyroids representing KIT-6 and MCM-48, and cagelike structures representing SBA-16. In parallel, composites of PEI and the silica supports SBA-15, KIT-6, MCM-48, and SBA-16 are synthesized and characterized, including measuring their COmore » 2 uptake. Simulations predict that a 3D pore morphology, such as those of KIT-6, MCM-48, and SBA-16, will have faster segmental mobility and have lower probability of primary amine and surface silanol associations, which should translate to higher CO 2 uptake in comparison to a 2D pore morphology such as that of SBA-15. We found that KIT-6 has higher CO 2 uptake than SBA-15 at equivalent PEI loading, even though both supports have similar surface area and pore volume. But, this is not the case for the MCM-48 support, which has smaller pores, and SBA-16, whose pore structure rapidly degrades after PEI impregnation.« less

Fluoropolymer Microstructure and Dynamics: Influence of Molecular Orientation Induced by Uniaxial Drawing

NASA Astrophysics Data System (ADS)

Miranda, Daniel; Yin, Chaoqing; Runt, James

Fluorinated semi-crystalline polymer films are attractive for dielectric film applications due to their chemical inertness, heat resistance, and high thermal stability. In the present investigation we explore the influence of orientation induced by uniaxial drawing on the crystalline microstructure and relaxation processes of poly(ethylene-tetrafluoroethylene) (ETFE), in order to ascertain how morphological control can benefit polymer dielectric design. When drawn below or near the Tg, the crystallinity of the drawn films is unchanged, and oriented amorphous structures and crystalline microfibrils form at high draw ratios. This orientation slows segmental relaxation, reflected by an increase in the dynamic Tg, and also delays the transition to the high temperature crystalline form of ETFE. When drawing above the Tg, the films undergo strain-induced crystallization at high draw ratios. For these films an increase in the dynamic Tg is also observed, in addition to a second segmental relaxation process, appearing as a shoulder on the primary process. We propose that this represents a contribution from a rigid amorphous fraction, having slowed chain dynamics. Supported by Office of Naval Research.

Spectroscopic study of excitations in pi-conjugated polymers

NASA Astrophysics Data System (ADS)

Yang, Cungeng

This dissertation deals with spin-physics of photo excitations in pi-conjugated polymers. Optical and magneto-optical spectroscopies, including continuous wave and time-resolved photo-induced absorption, photoluminescence, electroluminescence, and their optically detected magnetic resonance, were used to study steady state and transient photogeneration, energy transfer, spin relaxation, and spin dependent recombination process in the time domain from tens of nanoseconds to tens of milliseconds in polymer materials including regio-random poly (3-hexyl-thiophene-2,5-diyl), regio-regular poly (3-hexyl-thiophene-2,5-diyl), poly (9,9-dioctyl-fluorenyl-2,7-diyl), poly (poly (2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene) of various morphologies, and transition metal complex poly (Pt-quinoxene). Our studies provided the tools to clarify the physical pictures regarding two types of long-lived photoexcitations, namely polarons (both germinate polaron-pairs, and unpaired polarons) and triplet excitons, which are the major excitations in these exotic semiconductors in electrical and optical related applications. From measurements of transient fluorescence and transient fluorescence detected magnetic resonance we show that photogenerated geminate polaron pairs live up to hundreds of microseconds following laser pulsed excitation. This conclusion is in agreement with the delayed formation of triplet excitons that we measured by transient photoinduced absorption. It also agrees with the weak spin-lattice relaxation rate in polymers that we measured using the optically detected magnetic resonance dynamic in thin films and organic light emitting devices. Randomly captured nongeminate polaron pairs were shown to be the major source of optically detected magnetic resonance signal at steady, state. We found that the dynamics and magnitude of the signal depend on the spin-relaxation rate, generation rate and decay rate of the geminate pairs and nongeminate pairs. Importantly we found that the spin-relaxation rate depends weakly on temperature and strongly on coupled heavy atom orbital and magnetic momentum dipole induced by dopants or high intensity excitation. Also the polaron generation rate is excitation energy and nano-morphology dependent; whereas the polaron decay rate is morphology and spin dependent.

Aggregation and morphology control enables multiple cases of high-efficiency polymer solar cells

PubMed Central

Liu, Yuhang; Zhao, Jingbo; Li, Zhengke; Mu, Cheng; Hu, Huawei; Jiang, Kui; Lin, Haoran; Ade, Harald; Yan, He

2014-01-01

Although the field of polymer solar cell has seen much progress in device performance in the past few years, several limitations are holding back its further development. For instance, current high-efficiency (>9.0%) cells are restricted to material combinations that are based on limited donor polymers and only one specific fullerene acceptor. Here we report the achievement of high-performance (efficiencies up to 10.8%, fill factors up to 77%) thick-film polymer solar cells for multiple polymer:fullerene combinations via the formation of a near-ideal polymer:fullerene morphology that contains highly crystalline yet reasonably small polymer domains. This morphology is controlled by the temperature-dependent aggregation behaviour of the donor polymers and is insensitive to the choice of fullerenes. The uncovered aggregation and design rules yield three high-efficiency (>10%) donor polymers and will allow further synthetic advances and matching of both the polymer and fullerene materials, potentially leading to significantly improved performance and increased design flexibility. PMID:25382026

Construction of dual-functional polymer nanomaterials with near-infrared fluorescence imaging and polymer prodrug by RAFT-mediated aqueous dispersion polymerization.

PubMed

Tian, Chun; Niu, Jinyun; Wei, Xuerui; Xu, Yujie; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2018-05-31

The performance of functional polymer nanomaterials is a vigorously discussed topic in polymer science. We devoted ourselves to investigating polymer nanomaterials based on near-infrared (NIR) fluorescence imaging and polymer prodrug in this study. Aza-boron dipyrromethene (BODIPY) is an important organic dye, having characteristics such as environmental resistance, light resistance, high molar extinction coefficient, and fluorescence quantum yield. We incorporated it into our target monomer, which can be polymerized without changing its parent structure in a polar solvent and copolymerized with water-soluble monomer to improve the solubility of the dye in an aqueous solution. At the same time, the hydrophobic drug camptothecin (CPT) was designed as a prodrug monomer, and the polymeric nanoparticles (NPs) with NIR fluorescence imaging and prodrug were synthesized in situ in reversible addition-fragmentation chain transfer (RAFT)-mediated aqueous dispersion polymerization. The dynamic light scattering (DLS) and transmission electron microscopy (TEM) revealed the final uniform size of the dual-functional polymeric NPs morphology. The dual-functional polymeric NPs had a strong absorption and emission signal in the NIR region (>650 nm) based on the fluorescence tests. In consideration of the long-term biological toxicity, confocal laser scanning microscopy (CLSM) results indicated that the dual-functional NPs with controlled drug content exhibited effective capability of killing HeLa cells. In addition, in vivo imaging of the dual-functional NPs was observed in real time, and the fluorescent signals clearly demonstrated the dynamic process of prodrug transfer.

Drug-polymer interactions at water-crystal interfaces and implications for crystallization inhibition: molecular dynamics simulations of amphiphilic block copolymer interactions with tolazamide crystals.

PubMed

Gao, Yi; Olsen, Kenneth W

2015-07-01

A diblock copolymer, poly(ethylene glycol)-block-poly(lactic acid) (PEG-b-PLA), modulates the crystal growth of tolazamide (TLZ), resulting in a crystal morphology change from needles to plates in aqueous media. To understand this crystal surface drug-polymer interaction, we conducted molecular dynamics simulations on crystal surfaces of TLZ in water containing PEG-b-PLA. A 130-ns simulation of the polymer in a large water box was run before initiating 50 ns simulations with each of the crystal surfaces. The simulations demonstrated differentiated drug-polymer interactions that are consistent with experimental studies. Interaction of PEG-b-PLA with the (001) face occurred more rapidly (≤10 ns) and strongly (total interaction energy of -121.1 kJ/mol/monomer) than that with the (010) face (∼35 ns, -85.4 kJ/mol/monomer). There was little interaction with the (100) face. Hydrophobic and van der Waals (VDW) interactions were the dominant forces, accounting for more than 90% of total interaction energies. It suggests that polymers capable of forming strong hydrophobic and VDW interactions might be more effective in inhibiting crystallization of poorly water-soluble and hydrophobic drugs in aqueous media (such as gastrointestinal fluid) than those with hydrogen-bonding capacities. Such in-depth analysis and understanding facilitate the rational selection of polymers in designing supersaturation-based enabling formulations. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Polymer blends made of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and epoxidized natural rubber: Thermal and mechanical response

NASA Astrophysics Data System (ADS)

Salim, Yoga Sugama; Han, Chan Chin; Kammer, Hans-Werner; Kumar, Sudesh; Neon, Gan Seng

2015-08-01

The ever-increasing demand of biodegradable over conventional polymers places microbial polyhydroxyalkanoates (PHA) as an ideal choice of research material for specific applications. In this study, polymer blends made of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(3HB-co-3HHx) and epoxidized natural rubber (ENR) were prepared using solution casting technique. The influence of ENR on thermal, morphological and mechanical properties of P(3HB-co-3HHx) was investigated. There are two glass transition (Tg) temperatures observed using differential scanning calorimeter. This indicates that P(3HB-co-3HHx) and ENR are immiscible at macroscopic level. Although the Tg of P(3HB-co-3HHx) is seen to shift toward ENR in the least manner, infrared analysis suggests that the crystal structure of P(3HB-co-3HHx) retains its conformational structure. In terms of morphology, ENR exists as droplets in P(3HB-co-3HHx)-rich phase, e.g. at ENR weight fraction (wENR) of 0.3. In dynamic mechanical analysis, all blend compositions exhibit solid-like behavior, with storage moduli larger than loss moduli, across the frequency sweep at room temperature.

Effect of chain stiffness on the competition between crystallization and glass-formation in model unentangled polymers

NASA Astrophysics Data System (ADS)

Nguyen, Hong T.; Smith, Tyler B.; Hoy, Robert S.; Karayiannis, Nikos Ch.

2015-10-01

We map out the solid-state morphologies formed by model soft-pearl-necklace polymers as a function of chain stiffness, spanning the range from fully flexible to rodlike chains. The ratio of Kuhn length to bead diameter (lK/r0) increases monotonically with increasing bending stiffness kb and yields a one-parameter model that relates chain shape to bulk morphology. In the flexible limit, monomers occupy the sites of close-packed crystallites while chains retain random-walk-like order. In the rodlike limit, nematic chain ordering typical of lamellar precursors coexists with close-packing. At intermediate values of bending stiffness, the competition between random-walk-like and nematic chain ordering produces glass-formation; the range of kb over which this occurs increases with the thermal cooling rate | T ˙ | implemented in our molecular dynamics simulations. Finally, values of kb between the glass-forming and rodlike ranges produce complex ordered phases such as close-packed spirals. Our results should provide a useful initial step in a coarse-grained modeling approach to systematically determining the effect of chain stiffness on the crystallization-vs-glass-formation competition in both synthetic and colloidal polymers.

Polyethersulfone/polyacrylonitrile blended ultrafiltration membranes: preparation, morphology and filtration properties.

PubMed

Pasaoglu, Mehmet Emin; Guclu, Serkan; Koyuncu, Ismail

Polyethersulfone (PES)/polyacrylonitrile (PAN) membranes have been paid attention among membrane research subjects. However, very few studies are included in the literature. In our study, asymmetric ultrafiltration (UF) membranes were prepared from blends of PES/PAN with phase inversion method using water as coagulation bath. Polyvinylpyrrolidone (PVP) with Mw of 10,000 Da was used as pore former agent. N,N-dimethylformamide was used as solvent. The effects of different percentage of PVP and PES/PAN composition on morphology and water filtration properties were investigated. Membrane performances were examined using pure water and lake water filtration studies. Performances of pure water were less with the addition of PAN into the PES polymer casting solutions. However, long-term water filtration tests showed that PES/PAN blend membranes anti-fouling properties were much higher than the neat PES membranes. The contact angles of PES/PAN membranes were lower than neat PES membranes because of PAN addition in PES polymer casting solutions. Furthermore, it was found that PES/PAN blend UF membranes' dynamic mechanical analysis properties in terms of Young's modules were less than neat PES membrane because of decreasing amount of PES polymer.

Vertical and lateral morphology effects on solar cell performance for a thiophene–quinoxaline copolymer:PC 70BM blend

DOE PAGES

Hansson, Rickard; Ericsson, Leif K. E.; Holmes, Natalie P.; ...

2015-02-13

The distribution of electron donor and acceptor in the active layer is known to strongly influence the electrical performance of polymer solar cells for most of the high performance polymer:fullerene systems. The formulation of the solution from which the active layer is spincoated plays an important role in the quest for morphology control. We have studied how the choice of solvent and the use of small amounts of a low vapour pressure additive in the coating solution influence the film morphology and the solar cell performance for blends of poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1) and [6,6]-phenyl C 71-butyric acid methyl ester (PC 70BM).more » We have investigated the lateral morphology using atomic force microscopy (AFM) and scanning transmission X-ray microscopy (STXM), the vertical morphology using dynamic secondary ion mass spectrometry (d-SIMS) and variable-angle spectroscopic ellipsometry (VASE), and the surface composition using near-edge X-ray absorption fine structure (NEXAFS). The lateral phase-separated domains observed in films spincoated from single solvents, increase in size with increasing solvent vapour pressure and decreasing PC 70BM solubility, but are not observed when 1-chloronaphthalene (CN) is added. A strongly TQ1-enriched surface layer is formed in all TQ1:PC 70BM blend films and rationalized by surface energy differences. The photocurrent and power conversion efficiency strongly increased upon the addition of CN, while the leakage current decreased by one to two orders of magnitude. The higher photocurrent correlates with the finer lateral structure and stronger TQ1-enrichment at the interface with the electron-collecting electrode. This indicates that the charge transport and collection are not hindered by this polymer-enriched surface layer. Neither the open-circuit voltage nor the series resistance of the devices are sensitive to the differences in morphology.« less

Polymer Nanocomposites: Insights from Theory and Molecular Simulations

NASA Astrophysics Data System (ADS)

Pani, Rakhee

Advantages of polymer nanocomposites have attracted great industrial attention due to their multifunctionality and innovative technological properties. Addition of small amount of nanoparticle (nanospheres, nanotubes, nanorods, nanoplatelets, or sheets) to polymer matrix cause dramatic improvement in structural and functional properties, which is difficult to attain from those of individual components. The interaction between polymer and nanoparticle create bulk materials dominated by solid state physics at the nanoscale. Furthermore, morphology of nanocomposites depends on structural arrangements of nanoparticles. Thus, for achievement of optimized functionality like electrical, optical, mechanical and thermal properties control over the dispersion of the nanoparticle is essential. However, properties of polymer nanocomposites depend on morphology control and nature of interfacial interactions. In order to control the morphology it is necessary to understand how the processing conditions, shape and size of nanoparticle influence the structure of composite. Molecular simulations can help us to predict the parameters that control the structural changes and we could design polymer nanocomposite entailing their end-use. In this work, we addressed the following research questions: (1) the dependence of nanoparticle ligand corona structure on solvent quality and (2) the role of interfacial energy and interactions on the dispersion of molecules and nanoparticles. Specifically, this research assessed the effect of solvent interactions on the structure of nanoparticles on the example of redox core encapsulating dendrimer and ligand functionalized gold nanoparticles, role of chemical interaction on solubility of glucose in ionic liquids, diffusion of fullerene nanoparticles in polymer matrix and influence of solubility parameters on the compatibility of gold nanoparticles with diblock copolymers. Computational methods allow quantifying the structure and flexibility of the polymer chains, how energetics and surface tension change with chemical composition of the polymer/dendrimer blocks, influence of nanoparticle on structural properties of polymer and factors which may contribute to the phase separation of the polymer from nanoparticle. Interfacial characteristics are not only determined by the size-induced properties, but also the surface chemistry of the particles. Presence of solvent and the resultant interactions with the solvent are known to influence the morphology and prevent or induce aggregation of nanoparticles in polymers. We found that surface chemistry can induce change in the structure of dendrimers encapsulating a redox active core and change the solubility of the nanoparticles. The interactions between nanoparticles and polymers can also influence the morphology. We performed investigation on the role of orientation of fullerene derivatives and surface energy of polymer surface which may induce the aggregation of the fullerene nanoparticles. Furthermore, we used quantitative measurements like cluster analysis to understand the most probable orientation of the fullerene derivative with respect to the polymer chains and the diffusion of the fullerene nanoparticle, which is related to the efficiency of solar cells, can change on presence of regiorandom and regioregular polymer chains. Furthermore, we have also used different solvents based on their Hildebrand solubility parameters to investigate factors governing the morphology of polymer nanocomposite via solvent interactions. We showed that change in solvent interactions affect the compatibility, aggregation/dispersion of the gold nanoparticles, which will directly affect the morphology of polymer matrix and structural aspects which can impact their functionality. Overall, our research indicated that solvent interaction play a role in controlling the morphology of polymer nanocomposite and solubility parameter can help us to predict the resulting morphology.

Processing Solvent Dependent Morphology of Diketopyrrolopyrrole (DPP) based Low Band Gap Polymer and PCBM Blends

NASA Astrophysics Data System (ADS)

Ferdous, Sunzida; Liu, Feng; Russell, Thomas

2013-03-01

Solution processing of polymer semiconductors is widely used for fabrication of low cost organic solar cells. Recently, mixed solvent systems or additive based systems for fabricating polymer solar cells have proven to be beneficial for obtaining high performance devices with multi-length scale morphologies. To control the morphology during the processing step, one needs to understand the effect of solvent as it evaporates to form the final thin film structure. In this study, we used diketopyrrolopyrrole (DPP) based low band gap polymer and phenyl-C71-butyric acid methyl ester (PCBM) blend in a series of mixed solvent systems consisting of a good solvent for both of the active material components, as well as different solvents that are good solvents for PCBM, but poor solvents for the polymer. Different evaporation times of the poor solvents during the drying process, and different solubility of the polymer in these poor solvents as well as their interaction with the substrate play an important role in the final morphology. In-situ GIWAXS studies were performed to observe the evolution of the structure as the solvent evaporates. The final morphologies of the thin film devices were also characterized by AFM, TEM, and various x-ray scattering techniques to correlate the morphology with the obtained device performances.

Semi-flexible polymer engendered aggregation/dispersion of fullerene (C60) nano-particles: An atomistic investigation

NASA Astrophysics Data System (ADS)

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.

Reprint of: Combining theory and experiment for X-ray absorption spectroscopy and resonant X-ray scattering characterization of polymers

DOE PAGES

Su, Gregory M.; Cordova, Isvar A.; Brady, Michael A.; ...

2016-11-01

An improved understanding of fundamental chemistry, electronic structure, morphology, and dynamics in polymers and soft materials requires advanced characterization techniques that are amenable to in situ and operando studies. Soft X-ray methods are especially useful in their ability to non-destructively provide information on specific materials or chemical moieties. Analysis of these experiments, which can be very dependent on X-ray energy and polarization, can quickly become complex. Complementary modeling and predictive capabilities are required to properly probe these critical features. Here in this paper, we present relevant background on this emerging suite of techniques. We focus on how the combination ofmore » theory and experiment has been applied and can be further developed to drive our understanding of how these methods probe relevant chemistry, structure, and dynamics in soft materials.« less

Combining theory and experiment for X-ray absorption spectroscopy and resonant X-ray scattering characterization of polymers

DOE PAGES

Su, Gregory M.; Cordova, Isvar A.; Brady, Michael A.; ...

2016-07-04

We present that an improved understanding of fundamental chemistry, electronic structure, morphology, and dynamics in polymers and soft materials requires advanced characterization techniques that are amenable to in situ and operando studies. Soft X-ray methods are especially useful in their ability to non-destructively provide information on specific materials or chemical moieties. Analysis of these experiments, which can be very dependent on X-ray energy and polarization, can quickly become complex. Complementary modeling and predictive capabilities are required to properly probe these critical features. Here, we present relevant background on this emerging suite of techniques. Finally, we focus on how the combinationmore » of theory and experiment has been applied and can be further developed to drive our understanding of how these methods probe relevant chemistry, structure, and dynamics in soft materials.« less

Development of Biomimetic and Functionally Responsive Surfaces

NASA Astrophysics Data System (ADS)

Anastasiadis, Spiros H.

2010-03-01

Controlling the surface morphology of solids and manufacturing of functional surfaces with special responsive properties has been the subject of intense research. We report a methodology for creating multifunctionally responsive surfaces by irradiating silicon wafers with femtosecond laser pulses and subsequently coating them with different types of functional conformal coatings. Such surfaces exhibit controlled dual-scale roughness at the micro- and the nano-scale, which mimics the hierarchical morphology of water repellent natural surfaces. When a simple alkylsilane coating is utilized, highly water repellent surfaces are produced that quantitatively compare to those of the Lotus leaf. When a polymer brush is ``grafted from" these surfaces based on a pH-sensitive polymer, the surfaces can alter their behavior from super-hydrophilic (after immersion in a low pH buffer) to super-hydrophobic and water-repellent (following immersion to a high pH buffer). We quantify the water repellency of such responsive systems by drop elasticity measurements whereas we demonstrate that the water repellent state of such surface requires appropriate hydrophobicity of the functionalizing polymer. When a photo-responsive azobenzene-type polymer is deposited, a dynamic optical control of the wetting properties is obtained and the surface can be switched from super-hydrophilic (following UV irradiation) to hydrophobic (following green irradiation). In all the above cases we show that the principal effect of roughness is to cause amplification of the response to the different external stimuli.

Nanoparticles in Mesostructured Polymers: Stabilizations and Morphology Selection

NASA Astrophysics Data System (ADS)

Kim, Jaeup; O'Shaughnessy, Ben

2002-03-01

A major challenge in the rapidly developing field of nano-materials is finding ways to create delicate spatial arrangements of nano-sized particles. Nanostructured polymer phases and ultrathin polymer films offer potential templates to spontaneously generate this spatial organization. Here we present theory of such systems. Our conclusions are as follows. (1) Nanoparticles tending to aggregate into clusters under van der Waals attractions may be stabilized in a stretched polymer environment as offered by tethered thin film brushes or lamellar diblock phases. By extending the hydrodynamic analogy of Williams and Pincus to the real case of the end-annealed Semenov brush, we show cluster formation is strongly influenced: disc-shaped clusters are suppressed in favor of extended cylindrical forms. (2) The final morphology of extended nanoparticle aggregates depends on the polymer environment. If the nanoparticle/air/polymer surface tensions and the degree of chain stretching satisfy certain conditions, the polymer media selects the length scale of nanoparticle clusters. This offers the possibility of tuning nanoparticle aggregate morphology by suitable choice of polymeric media. Our predictions are consistent with experiments at Columbia by Levicky, Durning, Cerise and Liu demonstrating nanoparticle stabilization and morphology selection in ultrathin end-tethered polymer films.

Static and Dynamic Mechanical Characteristics of Ionic Liquid Modified MWCNT-SBR Composites: Theoretical Perspectives for the Nanoscale Reinforcement Mechanism.

PubMed

Abraham, Jiji; Thomas, Jince; Kalarikkal, Nandakumar; George, Soney C; Thomas, Sabu

2018-02-01

Well-dispersed, robust, mechanicaly long-term stable functionalized multiwalled carbon nanotube (f-MWCNT)-styrene butadiene rubber (SBR) nanocomposites were fabricated via a melt mixing route with the assistance of ionic liquid as a dispersing agent. The mechanical properties of f-MWCNT/SBR vulcanizates were compared over a range of loadings, and it was found that the network morphology was highly favorable for mechanical performance with enlarged stiffness. A comparative investigation of composite models found that modified Kelly-Tyson theory gave an excellent fit to tensile strength data of the composites considering the effect of the interphase between polymer and f-MWCNT. Dynamic mechanical analysis highlighted the mechanical reinforcement due to the improved filler-polymer interactions which were the consequence of proper dispersion of the nanotubes in the SBR matrix. Effectiveness of filler, entanglement density, and adhesion factor were evaluated to get an in depth understanding of the reinforcing mechanism of modified MWCNT. The amount of polymer chains immobilized by the filler surface computed from dynamic mechanical analysis further supports a substantial boost up in mechanics. The Cole-Cole plot shows an imperfect semicircular curve representing the heterogeneity of the system and moderately worthy filler polymer bonding. The combined results of structural characterizatrion by Raman spectroscopy, cure characteristics, mechanical properties, and scanning and transmission electron microscopy (SEM, TEM) confirm the role of ionic liquid modified MWCNT as a reinforcing agent in the present system.

Effects of cross-linking on partitioning of nanoparticles into a polymer brush: Coarse-grained simulations test simple approximate theories

NASA Astrophysics Data System (ADS)

Ozmaian, Masoumeh; Jasnow, David; Eskandari Nasrabad, Afshin; Zilman, Anton; Coalson, Rob D.

2018-01-01

The effect of cohesive contacts or, equivalently, dynamical cross-linking on the equilibrium morphology of a polymer brush infiltrated by nanoparticles that are attracted to the polymer strands is studied for plane-grafted brushes using coarse-grained molecular dynamics and approximate statistical mechanical models. In particular, the Alexander-de Gennes (AdG) and Strong Stretching Theory (SST) mean-field theory (MFT) models are considered. It is found that for values of the MFT cross-link strength interaction parameter beyond a certain threshold, both AdG and SST models predict that the polymer brush will be in a compact state of nearly uniform density packed next to the grafting surface over a wide range of solution phase nanoparticle concentrations. Coarse grained molecular dynamics simulations confirm this prediction, for both small nanoparticles (nanoparticle volume = monomer volume) and large nanoparticles (nanoparticle volume = 27 × monomer volume). Simulation results for these cross-linked systems are compared with analogous results for systems with no cross-linking. At the same solution phase nanoparticle concentration, strong cross-linking results in additional compression of the brush relative to the non-crosslinked analog and, at all but the lowest concentrations, to a lesser degree of infiltration by nanoparticles. For large nanoparticles, the monomer density profiles show clear oscillations moving outwards from the grafting surface, corresponding to a degree of layering of the absorbed nanoparticles in the brush as they pack against the grafting surface.

Photobleaching dynamics in small molecule vs.  polymer organic photovoltaic blends with 1,7-bis-trifluoromethylfullerene

DOE PAGES

Garner, Logan E.; Nellissery Viswanathan, Vinila; Arias, Dylan H.; ...

2018-02-27

Two organic photovoltaic (OPV) donor materials (one polymer and one small molecule) are synthesized from the same constituent building blocks, namely thiophene units, cyclopentathiophene dione (CTD), and cyclopentadithiophene (CPDT). Photobleaching dynamics of these donor materials are then studied under white light illumination in air with blends of PC 70BM and the bistrifluoromethylfullerene 1,7-C 60(CF 3) 2. For both the polymer and small molecule blends, C 60(CF 3) 2 stabilizes the initial rate of photobleaching by a factor of 15 relative to PC70BM. However, once the small molecule:C 60(CF 3) 2 blend bleaches to ~80% of its initial optical density, themore » rate of photobleaching dramatically accelerates, which is not observed in the analagous polymer blend. We probe that phenomenon using time-resovled photoluminescence (TRPL) to measure PL quenching efficiencies at defined intervals during the photobleaching experiments. The data indicates the small molecule donor and C 60(CF 3) 2 acceptor significantly de-mix with time, after which the blend begins to bleach at approximately the same rate as the neat donor sample. The work suggests that perfluoroalkylfullerenes have great potential to stabilize certain OPV active layers toward photodegradation, provided their morphology is stable.« less

Photobleaching dynamics in small molecule vs.  polymer organic photovoltaic blends with 1,7-bis-trifluoromethylfullerene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garner, Logan E.; Nellissery Viswanathan, Vinila; Arias, Dylan H.

Two organic photovoltaic (OPV) donor materials (one polymer and one small molecule) are synthesized from the same constituent building blocks, namely thiophene units, cyclopentathiophene dione (CTD), and cyclopentadithiophene (CPDT). Photobleaching dynamics of these donor materials are then studied under white light illumination in air with blends of PC 70BM and the bistrifluoromethylfullerene 1,7-C 60(CF 3) 2. For both the polymer and small molecule blends, C 60(CF 3) 2 stabilizes the initial rate of photobleaching by a factor of 15 relative to PC70BM. However, once the small molecule:C 60(CF 3) 2 blend bleaches to ~80% of its initial optical density, themore » rate of photobleaching dramatically accelerates, which is not observed in the analagous polymer blend. We probe that phenomenon using time-resovled photoluminescence (TRPL) to measure PL quenching efficiencies at defined intervals during the photobleaching experiments. The data indicates the small molecule donor and C 60(CF 3) 2 acceptor significantly de-mix with time, after which the blend begins to bleach at approximately the same rate as the neat donor sample. The work suggests that perfluoroalkylfullerenes have great potential to stabilize certain OPV active layers toward photodegradation, provided their morphology is stable.« less

Lithium secondary batteries: Role of polymer cathode morphology

NASA Astrophysics Data System (ADS)

Naoi, Katsuhiko; Osaka, Tetsuya; Owens, Boone B.

1988-06-01

Electrically conducting polymers have been utilized both as the cathode and as the electrolyte element of Li secondary cells. Polymer cathodes were limited in their suitability for batteries because of the low energy content associated with low levels of doping and the inclusion of complex ionic species in the cathode. Recent studies have indicated that doping levels up to 100 percent can be achieved in polyanilene. High doping levels in combination with controlled morphologies have been found to improve the energy and rate capabilities of polymer cathodes. A morphology-modifying technique was utilized to enhance the charge/discharge characteristics of Li/liquid electrolyte polypyrrole cells. The polymer is electropolymerized in a preferred orientation morphology when the substrate is first precoated with an insulating film of nitrile butadiene rubber (NBR). Modification of the kinetic behavior of the electrode results from variations in the chemical composition of the NBR.

Evolved phase separation toward balanced charge transport and high efficiency in polymer solar cells.

PubMed

Fan, Haijun; Zhang, Maojie; Guo, Xia; Li, Yongfang; Zhan, Xiaowei

2011-09-01

Understanding effect of morphology on charge carrier transport within polymer/fullerene bulk heterojunction is necessary to develop high-performance polymer solar cells. In this work, we synthesized a new benzodithiophene-based polymer with good self-organization behavior as well as favorable morphology evolution of its blend films with PC(71)BM under improved processing conditions. Charge carrier transport behavior of blend films was characterized by space charge limited current method. Evolved blend film morphology by controlling blend composition and additive content gradually reaches an optimized state, featured with nanoscale fibrilla polymer phase in moderate size and balanced mobility ratio close to 1:1 for hole and electron. This optimized morphology toward more balanced charge carrier transport accounts for the best power conversion efficiency of 3.2%, measured under simulated AM 1.5 solar irradiation 100 mW/cm(2), through enhancing short circuit current and reducing geminate recombination loss.

Solid Rocket Fuel Constitutive Theory and Polymer Cure

NASA Technical Reports Server (NTRS)

Ream, Robert

2006-01-01

Solid Rocket Fuel is a complex composite material for which no general constitutive theory, based on first principles, has been developed. One of the principles such a relation would depend on is the morphology of the binder. A theory of polymer curing is required to determine this morphology. During work on such a theory an algorithm was developed for counting the number of ways a polymer chain could assemble. The methods used to develop and check this algorithm led to an analytic solution to the problem. This solution is used in a probability distribution function which characterizes the morphology of the polymer.

Thin Film Mediated Phase Change Phenomena: Crystallization, Evaporation and Wetting

NASA Technical Reports Server (NTRS)

Wettlaufer, John S.

1998-01-01

We focus on two distinct materials science problems that arise in two distinct microgravity environments: In space and within the space of a polymeric network. In the former environment, we consider a near eutectic alloy film in contact with its vapor which, when evaporating on earth, will experience compositionally induced buoyancy driven convection. The latter will significantly influence the morphology of the crystallized end member. In the absence of gravity, the morphology will be dominated by molecular diffusion and Marangoni driven viscous flow, and we study these phenomena theoretically and experimentally. The second microgravity environment exists in liquids, gels, and other soft materials where the small mass of individual molecules makes the effect of gravity negligible next to the relatively strong forces of intermolecular collisions. In such materials, an essential question concerns how to relate the molecular dynamics to the bulk rheological behavior. Here, we observe experimentally the diffusive motion of a single molecule in a single polymer filament, embedded within a polymer network and find anomalous diffusive behavior.

Fly ash reinforced thermoplastic vulcanizates obtained from waste tire powder.

PubMed

Sridhar, V; Xiu, Zhang Zhen; Xu, Deng; Lee, Sung Hyo; Kim, Jin Kuk; Kang, Dong Jin; Bang, Dae-Suk

2009-03-01

Novel thermoplastic composites made from two major industrial and consumer wastes, fly ash and waste tire powder, have been developed. The effect of increasing fly ash loadings on performance characteristics such as tensile strength, thermal, dynamic mechanical and magnetic properties has been investigated. The morphology of the blends shows that fly ash particles have more affinity and adhesion towards the rubbery phase when compared to the plastic phase. The fracture surface of the composites shows extensive debonding of fly ash particles. Thermal analysis of the composites shows a progressive increase in activation energy with increase in fly ash loadings. Additionally, morphological studies of the ash residue after 90% thermal degradation shows extensive changes occurring in both the polymer and filler phases. The processing ability of the thermoplastics has been carried out in a Monsanto processability testing machine as a function of shear rate and temperature. Shear thinning behavior, typical of particulate polymer systems, has been observed irrespective of the testing temperatures. Magnetic properties and percolation behavior of the composites have also been evaluated.

Polymeric Thin Films for Organic Electronics: Properties and Adaptive Structures

PubMed Central

Cataldo, Sebastiano; Pignataro, Bruno

2013-01-01

This review deals with the correlation between morphology, structure and performance of organic electronic devices including thin film transistors and solar cells. In particular, we report on solution processed devices going into the role of the 3D supramolecular organization in determining their electronic properties. A selection of case studies from recent literature are reviewed, relying on solution methods for organic thin-film deposition which allow fine control of the supramolecular aggregation of polymers confined at surfaces in nanoscopic layers. A special focus is given to issues exploiting morphological structures stemming from the intrinsic polymeric dynamic adaptation under non-equilibrium conditions. PMID:28809362

Preparation of polycaprolactone nanoparticles via supercritical carbon dioxide extraction of emulsions.

PubMed

Ajiboye, Adejumoke Lara; Trivedi, Vivek; Mitchell, John C

2017-08-21

Polycaprolactone (PCL) nanoparticles were produced via supercritical fluid extraction of emulsions (SFEE) using supercritical carbon dioxide (scCO 2 ). The efficiency of the scCO 2 extraction was investigated and compared to that of solvent extraction at atmospheric pressure. The effects of process parameters including polymer concentration (0.6-10% w/w in acetone), surfactant concentration (0.07 and 0.14% w/w) and polymer-to-surfactant weight ratio (1:1-16:1 w/w) on the particle size and surface morphology were also investigated. Spherical PCL nanoparticles with mean particle sizes between 190 and 350 nm were obtained depending on the polymer concentration, which was the most important factor where increase in the particle size was directly related to total polymer content in the formulation. Nanoparticles produced were analysed using dynamic light scattering and scanning electron microscopy. The results indicated that SFEE can be applied for the preparation of PCL nanoparticles without agglomeration and in a comparatively short duration of only 1 h.

Dynamic Relaxational Behaviour of Hyperbranched Polyether Polyols

NASA Astrophysics Data System (ADS)

Navarro-Gorris, A.; Garcia-Bernabé, A.; Stiriba, S.-E.

2008-08-01

Hyperbranched polymers are highly cascade branched polymers easily accessible via one-pot procedure from ABm type monomers. A key property of hyperbranched polymers is their molecular architecture, which allows core-shell morphology to be manipulated for further specific applications in material and medical sciences. Since the discovery of hyperbranched polymer materials, an increasing number of reports have been published describing synthetic procedures and technological applications of such materials, but their physical properties have remained less studied until the last decade. In the present work, different esterified hyperbranched polyglycerols have been prepared starting from polyglycerol precursors in presence of acetic acid, thus generating functionalization degree with range from 0 to 94%. Thermal analysis of the obtained samples has been studied by Differential Scanning Calorimetry (DSC). Dielectric Spectroscopy measurements have been analyzed by combining loss spectra deconvolution with the modulus formalism. In this regard, all acetylated polyglycerols exhibited a main relaxation related to the glass transition (α process) and two sub-glassy relaxations (β and γ processes) which vanish at high functionalization degrees.

Morphology and transport in biodegradable polymer compositions based on poly(3-hydroxybutyrate) and polyamide 54C

NASA Astrophysics Data System (ADS)

Zhul'Kina, A. L.; Ivantsova, E. L.; Filatova, A. G.; Kosenko, R. Yu.; Gumargalieva, K. Z.; Iordanskii, A. L.

2009-05-01

Complex investigation of the equilibrium sorption of water, diffusive transport of antiseptic, and morphology of mixed compositions based on polyoxybutirate and polyamide resin 54C has been performed to develop and analyze new biodegradable polymer compositions for controlled release of medicinal substances. Samples of mixtures were prepared by two methods: pressing under pressure and solvent evaporation from a polymer solution. The samples were compared and their morphology was analyzed by scanning electron microscopy. It is shown that the component ratio in the obtained mixtures affects their morphological, transport, and sorption characteristics.

Morphology and transport in biodegradable polymer compositions based on poly(3-hydroxybutyrate) and polyamide 54C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhul'kina, A. L.; Ivantsova, E. L.; Filatova, A. G.

2009-05-15

Complex investigation of the equilibrium sorption of water, diffusive transport of antiseptic, and morphology of mixed compositions based on polyoxybutirate and polyamide resin 54C has been performed to develop and analyze new biodegradable polymer compositions for controlled release of medicinal substances. Samples of mixtures were prepared by two methods: pressing under pressure and solvent evaporation from a polymer solution. The samples were compared and their morphology was analyzed by scanning electron microscopy. It is shown that the component ratio in the obtained mixtures affects their morphological, transport, and sorption characteristics.

Morphological study on small molecule acceptor-based organic solar cells with efficiencies beyond 7% (Presentation Recording)

NASA Astrophysics Data System (ADS)

Ma, Wei; Yan, He

2015-10-01

Despite the essential role of fullerenes in achieving best-performance organic solar cells (OSCs), fullerene acceptors have several drawbacks including poor light absorption, high-cost production and purification. For this reason, small molecule acceptor (SMA)-based OSCs have attracted much attention due to the easy tunability of electronic and optical properties of SMA materials. In this study, polymers with temperature dependent aggregation behaviors are combined with various small molecule acceptor materials, which lead to impressive power conversion efficiencies of up to 7.3%. The morphological and aggregation properties of the polymer:small molecule blends are studied in details. It is found that the temperature-dependent aggregation behavior of polymers allows for the processing of the polymer solutions at moderately elevated temperature, and more importantly, controlled aggregation and strong crystallization of the polymer during the film cooling and drying process. This results in a well-controlled and near-ideal polymer:small molecule morphology that is controlled by polymer aggregation during warm casting and thus insensitive to the choice of small molecules. As a result, several cases of highly efficient (PCE between 6-7.3%) SMA OSCs are achieved. The second part of this presentation will describe the morphology of a new small molecule acceptor with a unique 3D structure. The relationship between molecular structure and morphology is revealed.

Controlled assembly of nanoparticle structures: spherical and toroidal superlattices and nanoparticle-coated polymeric beads.

PubMed

Isojima, Tatsushi; Suh, Su Kyung; Vander Sande, John B; Hatton, T Alan

2009-07-21

The emulsion droplet solvent evaporation method has been used to prepare nanoclusters of monodisperse magnetite nanoparticles of varying morphologies depending on the temperature and rate of solvent evaporation and on the composition (solvent, presence of polymer, nanoparticle concentration, etc.) of the emulsion droplets. In the absence of a polymer, and with increasing solvent evaporation temperatures, the nanoparticles formed single- or multidomain crystalline superlattices, amorphous spherical aggregates, or toroidal clusters, as determined by the energetics and dynamics of the solvent evaporation process. When polymers that are incompatible with the nanoparticle coatings were included in the emulsion formulation, monolayer- and multilayer-coated polymer beads and partially coated Janus beads were prepared; the nanoparticles were expelled by the polymer as its concentration increased on evaporation of the solvent and accumulated on the surfaces of the beads in a well-ordered structure. The precise number of nanoparticle layers depended on the polymer/magnetic nanoparticle ratio in the oil droplet phase parent emulsion. The magnetic nanoparticle superstructures responded to the application of a modest magnetic field by forming regular chains with alignment of nonuniform structures (e.g., toroids and Janus beads) that are in accord with theoretical predictions and with observations in other systems.

Influence of polymer coating morphology on microsensor response

NASA Astrophysics Data System (ADS)

Levit, Natalia; Pestov, Dmitry; Tepper, Gary C.

2004-03-01

Nanoscale polymeric coatings are used in a variety of sensor systems. The influence of polymer coating morphology on sensor response was investigated and it was determined that coating morphology plays a particularly important role in transducers based on optical or acoustic resonance such as surface acoustic wave (SAW) or surface plasmon resonance (SPR) devices. Nanoscale polymeric coatings were deposited onto a number of miniature devices using a "solvent-free" deposition technique known as Rapid Expansion of Supercritical Solutions (RESS). In RESS, the supercritical solvent goes into the vapor phase upon fast depressurization and separates from the polymer. Therefore, dry polymer particles are deposited from the gas phase. The average diameter of RESS precipitates is about two orders of magnitude smaller than the minimum droplet size achievable by the air-brush method. For rubbery polymers, such as PIB and PDMS, the nanoscale solute droplets produced by RESS agglomerate on the surface forming a highly-uniform continuous nanoscale film. For glassy and crstalline polymers, the RESS droplets produce uniform particulate coatings exhibiting high surface-to-volume ratio. The coating morphology can be changed by controlling the RESS processing conditions.

Robust solid polymer electrolyte for conducting IPN actuators

NASA Astrophysics Data System (ADS)

Festin, Nicolas; Maziz, Ali; Plesse, Cédric; Teyssié, Dominique; Chevrot, Claude; Vidal, Frédéric

2013-10-01

Interpenetrating polymer networks (IPNs) based on nitrile butadiene rubber (NBR) as first component and poly(ethylene oxide) (PEO) as second component were synthesized and used as a solid polymer electrolyte film in the design of a mechanically robust conducting IPN actuator. IPN mechanical properties and morphologies were mainly investigated by dynamic mechanical analysis and transmission electron microscopy. For 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide (EMITFSI) swollen IPNs, conductivity values are close to 1 × 10-3 S cm-1 at 25 ° C. Conducting IPN actuators have been synthesized by chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) within the PEO/NBR IPN. A pseudo-trilayer configuration has been obtained with PEO/NBR IPN sandwiched between two interpenetrated PEDOT electrodes. The robust conducting IPN actuators showed a free strain of 2.4% and a blocking force of 30 mN for a low applied potential of ±2 V.

Modeling the formation of ordered nano-assemblies comprised by dendrimers and linear polyelectrolytes: The role of Coulombic interactions

NASA Astrophysics Data System (ADS)

Eleftheriou, E.; Karatasos, K.

2012-10-01

Models of mixtures of peripherally charged dendrimers with oppositely charged linear polyelectrolytes in the presence of explicit solvent are studied by means of molecular dynamics simulations. Under the influence of varying strength of electrostatic interactions, these systems appear to form dynamically arrested film-like interconnected structures in the polymer-rich phase. Acting like a pseudo-thermodynamic inverse temperature, the increase of the strength of the Coulombic interactions drive the polymeric constituents of the mixture to a gradual dynamic freezing-in. The timescale of the average density fluctuations of the formed complexes initially increases in the weak electrostatic regime reaching a finite limit as the strength of electrostatic interactions grow. Although the models are overall electrically neutral, during this process the dendrimer/linear complexes develop a polar character with an excess charge mainly close to the periphery of the dendrimers. The morphological characteristics of the resulted pattern are found to depend on the size of the polymer chains on account of the distinct conformational features assumed by the complexed linear polyelectrolytes of different length. In addition, the length of the polymer chain appears to affect the dynamics of the counterions, thus affecting the ionic transport properties of the system. It appears, therefore, that the strength of electrostatic interactions together with the length of the linear polyelectrolytes are parameters to which these systems are particularly responsive, offering thus the possibility for a better control of the resulted structure and the electric properties of these soft-colloidal systems.

Comparison of Coarse-Grained Approaches in Predicting Polymer Nanocomposite Phase Behavior

DOE PAGES

Koski, Jason P.; Ferrier, Robert C.; Krook, Nadia M.; ...

2017-11-02

Because of the considerable parameter space, efficient theoretical and simulation methods are required to predict the morphology and guide experiments in polymer nanocomposites (PNCs). Unfortunately, theoretical and simulation methods are restricted in their ability to accurately map to experiments based on necessary approximations and numerical limitations. In this study, we provide direct comparisons of two recently developed coarse-grained approaches for modeling polymer nanocomposites (PNCs): polymer nanocomposite field theory (PNC-FT) and dynamic mean-field theory (DMFT). These methods are uniquely suited to efficiently capture mesoscale phase behavior of PNCs in comparison to other theoretical and simulation frameworks. We demonstrate the ability ofmore » both methods to capture macrophase separation and describe the thermodynamics of PNCs. We systematically test how the nanoparticle morphology in PNCs is affected by a uniform probability distribution of grafting sites, common in field-based methods, versus random discrete grafting sites on the nanoparticle surface. We also analyze the accuracy of the mean-field approximation in capturing the phase behavior of PNCs. Moreover, the DMFT method introduces the ability to describe nonequilibrium phase behavior while the PNC-FT method is strictly an equilibrium method. With the DMFT method we are able to show the evolution of nonequilibrium states toward their equilibrium state and a qualitative assessment of the dynamics in these systems. These simulations are compared to experiments consisting of polystyrene grafted gold nanorods in a poly(methyl methacrylate) matrix to ensure the model gives results that qualitatively agree with the experiments. This study reveals that nanoparticles in a relatively high matrix molecular weight are trapped in a nonequilibrium state and demonstrates the utility of the DMFT framework in capturing nonequilibrium phase behavior of PNCs. In conclusion, both the PNC-FT and DMFT framework are promising methods to describe the thermodynamic and nonequilibrium phase behavior of PNCs.« less

Comparison of Coarse-Grained Approaches in Predicting Polymer Nanocomposite Phase Behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koski, Jason P.; Ferrier, Robert C.; Krook, Nadia M.

Because of the considerable parameter space, efficient theoretical and simulation methods are required to predict the morphology and guide experiments in polymer nanocomposites (PNCs). Unfortunately, theoretical and simulation methods are restricted in their ability to accurately map to experiments based on necessary approximations and numerical limitations. In this study, we provide direct comparisons of two recently developed coarse-grained approaches for modeling polymer nanocomposites (PNCs): polymer nanocomposite field theory (PNC-FT) and dynamic mean-field theory (DMFT). These methods are uniquely suited to efficiently capture mesoscale phase behavior of PNCs in comparison to other theoretical and simulation frameworks. We demonstrate the ability ofmore » both methods to capture macrophase separation and describe the thermodynamics of PNCs. We systematically test how the nanoparticle morphology in PNCs is affected by a uniform probability distribution of grafting sites, common in field-based methods, versus random discrete grafting sites on the nanoparticle surface. We also analyze the accuracy of the mean-field approximation in capturing the phase behavior of PNCs. Moreover, the DMFT method introduces the ability to describe nonequilibrium phase behavior while the PNC-FT method is strictly an equilibrium method. With the DMFT method we are able to show the evolution of nonequilibrium states toward their equilibrium state and a qualitative assessment of the dynamics in these systems. These simulations are compared to experiments consisting of polystyrene grafted gold nanorods in a poly(methyl methacrylate) matrix to ensure the model gives results that qualitatively agree with the experiments. This study reveals that nanoparticles in a relatively high matrix molecular weight are trapped in a nonequilibrium state and demonstrates the utility of the DMFT framework in capturing nonequilibrium phase behavior of PNCs. In conclusion, both the PNC-FT and DMFT framework are promising methods to describe the thermodynamic and nonequilibrium phase behavior of PNCs.« less

Molecular and Nanoscale Engineering of High Efficiency Excitonic Solar Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jenekhe, Samson A.; Ginger, David S.; Cao, Guozhong

We combined the synthesis of new polymers and organic-inorganic hybrid materials with new experimental characterization tools to investigate bulk heterojunction (BHJ) polymer solar cells and hybrid organic-inorganic solar cells during the 2007-2010 period (phase I) of this project. We showed that the bulk morphology of polymer/fullerene blend solar cells could be controlled by using either self-assembled polymer semiconductor nanowires or diblock poly(3-alkylthiophenes) as the light-absorbing and hole transport component. We developed new characterization tools in-house, including photoinduced absorption (PIA) spectroscopy, time-resolved electrostatic force microscopy (TR-EFM) and conductive and photoconductive atomic force microscopy (c-AFM and pc-AFM), and used them to investigatemore » charge transfer and recombination dynamics in polymer/fullerene BHJ solar cells, hybrid polymer-nanocrystal (PbSe) devices, and dye-sensitized solar cells (DSSCs); we thus showed in detail how the bulk photovoltaic properties are connected to the nanoscale structure of the BHJ polymer solar cells. We created various oxide semiconductor (ZnO, TiO 2) nanostructures by solution processing routes, including hierarchical aggregates and nanorods/nanotubes, and showed that the nanostructured photoanodes resulted in substantially enhanced light-harvesting and charge transport, leading to enhanced power conversion efficiency of dye-sensitized solar cells.« less

Comprehensive Computational and Experimental Analysis of Biomaterial toward the Behavior of Imidazolium-Based Ionic Liquids: An Interplay between Hydrophilic and Hydrophobic Interactions.

PubMed

Umapathi, Reddicherla; Vepuri, Suresh B; Venkatesu, Pannuru; Soliman, Mahmoud E

2017-05-11

To provide insights into the aggregation behavior, hydration tendency and variation in phase transition temperature produced by the addition of ionic liquids (ILs) to poly(N-isopropylacrylamide) (PNIPAM) aqueous solution, systematic physicochemical studies, and molecular dynamic simulations were carried out. The influence of ILs possessing the same [Cl] - anion and a set of cations [C n mim] + with increasing alkyl chain length such as 1-ethyl-3-methylimidazolium ([Emim] + ), 1-allyl-3-methylimidazolium ([Amim] + ), 1-butyl-3-methylimidazolium ([Bmim] + ), 1-hexyl-3-methylimidazolium ([Hmim] + ), 1-benzyl-3-methylimidazolium ([Bzmim] + ), and 1-decyl-3-methylimidazolium ([Dmim] + ) on the phase transition of PNIPAM was monitored by the aid of UV-visible absorption spectra, fluorescence intensity spectra, viscosity (η), dynamic light scattering (DLS), and Fourier transform infrared (FTIR) spectroscopy. Furthermore, to interpret the direct images and surface morphologies of the PNIPAM-IL aggregates, we performed field emission scanning electron microscopy (FESEM). The overall specific ranking of ILs in preserving the hydration layer around the PNIPAM aqueous solution was [Emim][Cl] > [Amim][Cl] > [Bmim][Cl] > [Hmim][Cl] > [Bzmim][Cl] > [Dmim][Cl]. Moreover, to investigate the molecular mechanism behind the change in the lower critical solution temperature (LCST) of the polymer in the presence of the ILs, a molecular dynamics (MD) study was performed. The MD simulation has clearly shown the reduction in hydration shell of the polymer after interacting with the ILs at their respective LCST. MD study revealed significant changes in polymer conformation because of IL interactions and strongly supports the experimental observation of polymer phase transition at a temperature lower than typical LCST for all the studied ILs. The driving force for concomitant sharp configurational transition has been attributed to the displacement of water molecules on the polymer surface by the ILs because of their hydrophobic interaction with the polymer.

Structural characterization of semicrystalline polymer morphologies by imaging-SANS

NASA Astrophysics Data System (ADS)

Radulescu, A.; Fetters, L. J.; Richter, D.

2012-02-01

Control and optimization of polymer properties require the global knowledge of the constitutive microstructures of polymer morphologies in various conditions. The microstructural features can be typically explored over a wide length scale by combining pinhole-, focusing- and ultra-small-angle neutron scattering (SANS) techniques. Though it proved to be a successful approach, this involves major efforts related to the use of various scattering instruments and large amount of samples and the need to ensure the same crystallization kinetics for the samples investigated at various facilities, in different sample cell geometries and at different time intervals. With the installation and commissioning of the MgF2 neutron lenses at the KWS-2 SANS diffractometer installed at the Heinz Maier-Leibnitz neutron source (FRMII reactor) in Garching, a wide Q-range, between 10-4Å-1 and 0.5Å-1, can be covered at a single instrument. This enables investigation of polymer microstructures over a length scale from lnm up to 1μm, while the overall polymer morphology can be further examined up to 100μm by optical microscopy (including crossed polarizers). The study of different semi-crystalline polypropylene-based polymers in solution is discussed and the new imaging-SANS approach allowing for an unambiguous and complete structural characterization of polymer morphologies is presented.

Morphology control in polymer blend fibers—a high throughput computing approach

NASA Astrophysics Data System (ADS)

Sesha Sarath Pokuri, Balaji; Ganapathysubramanian, Baskar

2016-08-01

Fibers made from polymer blends have conventionally enjoyed wide use, particularly in textiles. This wide applicability is primarily aided by the ease of manufacturing such fibers. More recently, the ability to tailor the internal morphology of polymer blend fibers by carefully designing processing conditions has enabled such fibers to be used in technologically relevant applications. Some examples include anisotropic insulating properties for heat and anisotropic wicking of moisture, coaxial morphologies for optical applications as well as fibers with high internal surface area for filtration and catalysis applications. However, identifying the appropriate processing conditions from the large space of possibilities using conventional trial-and-error approaches is a tedious and resource-intensive process. Here, we illustrate a high throughput computational approach to rapidly explore and characterize how processing conditions (specifically blend ratio and evaporation rates) affect the internal morphology of polymer blends during solvent based fabrication. We focus on a PS: PMMA system and identify two distinct classes of morphologies formed due to variations in the processing conditions. We subsequently map the processing conditions to the morphology class, thus constructing a ‘phase diagram’ that enables rapid identification of processing parameters for specific morphology class. We finally demonstrate the potential for time dependent processing conditions to get desired features of the morphology. This opens up the possibility of rational stage-wise design of processing pathways for tailored fiber morphology using high throughput computing.

Buckling Instabilities in Polymer Brush Surfaces via Postpolymerization Modification

DOE PAGES

Guo, Wei; Reese, Cassandra M.; Xiong, Li; ...

2017-10-30

We report a simple route to engineer ultrathin polymer brush surfaces with wrinkled morphologies using postpolymerization modification (PPM), where the length scale of the buckled features can be tuned using PPM reaction time. Here, we show that partial crosslinking of the outer layer of the polymer brush under poor solvent conditions is critical to obtain wrinkled morphologies upon swelling.

Morphological study of polymer surfaces exposed to non-thermal plasma based on contact angle and the use of scaling laws

NASA Astrophysics Data System (ADS)

Felix, T.; Cassini, F. A.; Benetoli, L. O. B.; Dotto, M. E. R.; Debacher, N. A.

2017-05-01

The experiments presented in this communication have the purpose to elaborate an explanation for the morphological evolution of the growth of polymeric surfaces provided by the treatment of non-thermal plasma. According to the roughness analysis and the model proposed by scaling laws it is possible relate to a predictable or merely random effect. Polyethylene terephthalate (PET) and poly(etherether)ketone (PEEK) samples were exposed to a non-thermal plasma discharge and the resulting surfaces roughness were analyzed based on the measurements from contact angle, scanning electron microscopy and atomic force microscopy coupled with scaling laws analysis which can help to describe and understand the dynamic of formation of a wide variety of rough surfaces. The roughness, RRMS (RMS- Root Mean Square) values for polymer surface range between 19.8 nm and 110.9 nm. The contact angle and the AFM (Atomic Force Microscopy) measurements as a function of the plasma exposure time were in agreement with both polar and dispersive components according to the surface roughness and also with the morphology evaluated described by Wolf-Villain model, with proximate values of α between 0.91(PET) and 0.88(PEEK), β = 0.25(PET) and z = 3,64(PET).

Hydrocarbon-Based Polymer Electrolyte Membranes: Importance of Morphology on Ion Transport and Membrane Stability.

PubMed

Shin, Dong Won; Guiver, Michael D; Lee, Young Moo

2017-03-22

A fundamental understanding of polymer microstructure is important in order to design novel polymer electrolyte membranes (PEMs) with excellent electrochemical performance and stabilities. Hydrocarbon-based polymers have distinct microstructure according to their chemical structure. The ionic clusters and/or channels play a critical role in PEMs, affecting ion conductivity and water transport, especially at medium temperature and low relative humidity (RH). In addition, physical properties such as water uptake and dimensional swelling behavior depend strongly on polymer morphology. Over the past few decades, much research has focused on the synthetic development and microstructural characterization of hydrocarbon-based PEM materials. Furthermore, blends, composites, pressing, shear field, electrical field, surface modification, and cross-linking have also been shown to be effective approaches to obtain/maintain well-defined PEM microstructure. This review summarizes recent work on developments in advanced PEMs with various chemical structures and architecture and the resulting polymer microstructures and morphologies that arise for potential application in fuel cell, lithium ion battery, redox flow battery, actuators, and electrodialysis.

Semi-crystalline morphologies of linear and cyclic poly(ɛ-caprolactones) in the diffusion-limited film thickness regime

NASA Astrophysics Data System (ADS)

Kelly, Giovanni; Bergeson, Amelia; Haque, Farihah; Grayson, Scott; Albert, Julie

Thin and ultrathin films of semi-crystalline polymers have been studied for decades due to their far-reaching applications including opto-electronic materials and biological studies of drug delivery and cell adhesion. This body of work has focused on every aspect of crystallization, from the fundamental thermodynamics and kinetics of crystal growth to methods for affecting crystalline morphologies via blending with other polymers. Due to significant synthetic challenges, one area where progress has lagged behind is the study of non-linear architectures, especially ring polymers. However, pioneering work by polymer chemists around the world has closed that gap, and we are beginning to observe important differences between ring and linear polymers in bulk materials. As a complement to those advances, this work aims to compare the morphologies of linear and cyclic poly(ɛ-caprolactones) (PCL) observed in heavily-confined ultrathin films where crystal growth is diffusion-limited. Understanding how confinement effects alter morphology will provide invaluable insight into differences in crystal growth as a function of molecular architecture.

Morphology evolution in high-performance polymer solar cells processed from nonhalogenated solvent

DOE PAGES

Cai, Wanzhu; Liu, Peng; Jin, Yaocheng; ...

2015-05-26

A new processing protocol based on non-halogenated solvent and additive is developed to produce polymer solar cells with power conversion efficiencies better than those processed from commonly used halogenated solvent-additive pair. Morphology studies show that good performance correlates with a finely distributed nanomorphology with a well-defined polymer fibril network structure, which leads to balanced charge transport in device operation.

Characterization of proton exchange membrane materials for fuel cells by solid state nuclear magnetic resonance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kong, Zueqian

2010-01-01

Solid-state nuclear magnetic resonance (NMR) has been used to explore the nanometer-scale structure of Nafion, the widely used fuel cell membrane, and its composites. We have shown that solid-state NMR can characterize chemical structure and composition, domain size and morphology, internuclear distances, molecular dynamics, etc. The newly-developed water channel model of Nafion has been confirmed, and important characteristic length-scales established. Nafion-based organic and inorganic composites with special properties have also been characterized and their structures elucidated. The morphology of Nafion varies with hydration level, and is reflected in the changes in surface-to-volume (S/V) ratio of the polymer obtained by small-anglemore » X-ray scattering (SAXS). The S/V ratios of different Nafion models have been evaluated numerically. It has been found that only the water channel model gives the measured S/V ratios in the normal hydration range of a working fuel cell, while dispersed water molecules and polymer ribbons account for the structures at low and high hydration levels, respectively.« less

Elongated phase separation domains in spin-cast polymer blend thin films characterized using a panoramic image.

PubMed

Zhang, Hong; Okamura, Yosuke

2018-02-14

Polymer thin films with micro/nano-structures can be prepared by a solvent evaporation induced phase separation process via spin-casting a polymer blend, where the elongated phase separation domains are always inevitable. The striation defect, as a thickness nonunifomity in spin-cast films, is generally coexistent with the elongated domains. Herein, the morphologies of polymer blend thin films are recorded from the spin-cast center to the edge in a panoramic view. The elongated domains are inclined to appear at the ridge regions of striations with increasing radial distance and align radially, exhibiting a coupling between the phase separation morphology and the striation defect that may exist. We demonstrate that the formation of elongated domains is not attributed to shape deformation, but is accomplished in situ. A possible model to describe the initiation and evolution of the polymer blend phase separation morphology during spin-casting is proposed.

Dynamic covalent polymers

PubMed Central

García, Fátima

2016-01-01

ABSTRACT This Highlight presents an overview of the rapidly growing field of dynamic covalent polymers. This class of polymers combines intrinsic reversibility with the robustness of covalent bonds, thus enabling formation of mechanically stable, polymer‐based materials that are responsive to external stimuli. It will be discussed how the inherent dynamic nature of the dynamic covalent bonds on the molecular level can be translated to the macroscopic level of the polymer, giving access to a range of applications, such as stimuli‐responsive or self‐healing materials. A primary distinction will be made based on the type of dynamic covalent bond employed, while a secondary distinction will be based on the consideration whether the dynamic covalent bond is used in the main chain of the polymer or whether it is used to allow side chain modification of the polymer. Emphasis will be on the chemistry of the dynamic covalent bonds present in the polymer, in particular in relation to how the specific (dynamic) features of the bond impart functionality to the polymer material, and to the conditions under which this dynamic behavior is manifested. © 2016 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3551–3577. PMID:27917019

Interplay between dewetting and layer inversion in poly(4-vinylpyridine)/polystyrene bilayers.

PubMed

Thickett, Stuart C; Harris, Andrew; Neto, Chiara

2010-10-19

We investigated the morphology and dynamics of the dewetting of metastable poly(4-vinylpyridine) (P4VP) thin films situated on top of polystyrene (PS) thin films as a function of the molecular weight and thickness of both films. We focused on the competition between the dewetting process, occurring as a result of unfavorable intermolecular interactions at the P4VP/PS interface, and layer inversion due to the lower surface energy of PS. By means of optical and atomic force microscopy (AFM), we observed how both the dynamics of the instability and the morphology of the emerging patterns depend on the ratio of the molecular weights of the polymer films. When the bottom PS layer was less viscous than the top P4VP layer (liquid-liquid dewetting), nucleated holes in the P4VP film typically stopped growing at long annealing times because of a combination of viscous dissipation in the bottom layer and partial layer inversion. Full layer inversion was achieved when the viscosity of the top P4VP layer was significantly greater (>10⁴) than the viscosity of the PS layer underneath, which is attributed to strongly different mobilities of the two layers. The density of holes produced by nucleation dewetting was observed for the first time to depend on the thickness of the top film as well as the polymer molecular weight. The final (completely dewetted) morphology of isolated droplets could be achieved only if the time frame of layer inversion was significantly slower than that of dewetting, which was characteristic of high-viscosity PS underlayers that allowed dewetting to fall into a liquid-solid regime. Assuming a simple reptation model for layer inversion occurring at the dewetting front, the observed surface morphologies could be predicted on the basis of the relative rates of dewetting and layer inversion.

Structure and Dynamics of Interacting Nanoparticles in Semidilute Polymer Solutions

DOE PAGES

Pollng-Skutvik, Ryan; Mongcopa, Katrina Irene S.; Faraone, Antonio; ...

2016-08-17

We investigate the structure and dynamics of silica nanoparticles and polymer chains in semidilute solutions of high molecular weight polystyrene in 2-butanone to determine the effect of long-range interparticle interactions on the coupling between particle and polymer dynamics. Particles at concentrations of 1–10 wt % are well dispersed in the semidilute polymer solutions and exhibit long-range electrostatic repulsions between particles. Because the particles are comparably sized to the radius of gyration of the polymer, the particle dynamics is predicted to couple to that of the polymer. We verify that the polymer structure and dynamics are not significantly affected by themore » particles, indicating that the particle–polymer coupling does not change with increasing particle loading. We find that the coupling between the dynamics of comparably sized particles and polymer results in subdiffusive particle dynamics, as expected. Over the interparticle distance, however, the particle dynamics is hindered and not fully described by the relaxation of the surrounding polymer chains. Instead, the particle dynamics is inversely related to the structure factor, suggesting that physical particle–polymer coupling on short length scales and interparticle interactions on long length scales both present energetic barriers to particle motion that lead to subdiffusive dynamics and de Gennes narrowing, respectively.« less

Effects of polymer surface energy on morphology and properties of silver nanowire fabricated via nanoimprint and E-beam evaporation

NASA Astrophysics Data System (ADS)

Zhao, Zhi-Jun; Hwang, Soon Hyoung; Jeon, Sohee; Jung, Joo-Yun; Lee, Jihye; Choi, Dae-Geun; Choi, Jun-Hyuk; Park, Sang-Hu; Jeong, Jun-Ho

2017-10-01

In this paper, we demonstrate that use of different nanoimprint resins as a polymer pattern has a significant effect on the morphology of silver (Ag) nanowires deposited via an E-beam evaporator. RM-311 and Ormo-stamp resins are chosen as a polymer pattern to form a line with dimensions of width (100 nm) × space (100 nm) × height (120 nm) by using nanoimprint lithography (NIL). Their contact angles are then measured to evaluate their surface energies. In order to compare the properties of the Ag nanowires deposited on the various polymer patterns with different surface energies, hydrophobic surface treatment of the polymer pattern surface is implemented using self-assembled monolayers. In addition, gold and aluminum nanowires are fabricated for comparison with the Ag nanowires, with the differences in the nanowire morphologies being determined by the different atomic properties. The monocrystalline and polycrystalline structures of the various Ag nanowire formations are observed using transmission electron microscopy. In addition, the melting temperatures and optical properties of four kinds of Ag nanowire morphologies deposited on various polymer patterns are evaluated using a hot plate and an ultraviolet-visible (UV-vis) spectrometer, respectively. The results indicate that the morphology of the Ag nanowire determines the melting temperature and the transmission. We believe that these findings will greatly aid the development of NIL, along with physical evaporation and chemical deposition techniques, and will be widely employed in optics, biology, and surface wettability applications.

Characterization of Polymer Blends: Optical Microscopy (*Polarized, Interference and Phase Contrast Microscopy*) and Confocal Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramanathan, Nathan Muruganathan; Darling, Seth B.

2015-01-01

Chapter 15 surveys the characterization of macro, micro and meso morphologies of polymer blends by optical microscopy. Confocal Microscopy offers the ability to view the three dimensional morphology of polymer blends, popular in characterization of biological systems. Confocal microscopy uses point illumination and a spatial pinhole to eliminate out-of focus light in samples that are thicker than the focal plane.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Kyle J.; Glynos, Emmanouil; Maroulas, Serafeim-Dionysios

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 PNCmore » 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.« less

Ion Correlation Effects in Salt-Doped Block Copolymers

NASA Astrophysics Data System (ADS)

Brown, Jonathan R.; Seo, Youngmi; Hall, Lisa M.

2018-03-01

We apply classical density functional theory to study how salt changes the microphase morphology of diblock copolymers. Polymers are freely jointed and one monomer type favorably interacts with ions, to account for the selective solvation that arises from different dielectric constants of the microphases. By including correlations from liquid state theory of an unbound reference fluid, the theory can treat chain behavior, microphase separation, ion correlations, and preferential solvation, at the same coarse-grained level. We show good agreement with molecular dynamics simulations.

Morphology Evolution of Polymer Blends under Intense Shear During High Speed Thin-Wall Injection Molding.

PubMed

Zhou, Yi; Yu, Feilong; Deng, Hua; Huang, Yajiang; Li, Guangxian; Fu, Qiang

2017-06-29

The morphology evolution under shear during different processing is indeed an important issue regarding the phase morphology control as well as final physical properties of immiscible polymer blends. High-speed thin wall injection molding (HSTWIM) has recently been demonstrated as an effective method to prepare alternating multilayered structure. To understand the formation mechanism better and explore possible phase morphology for different blends under HSTWIM, the relationship between the morphology evolution of polymer blends based on polypropylene (PP) under HSTWIM and some intrinsic properties of polymer blends, including viscosity ratio, interfacial tension, and melt elasticity, is systematically investigated in this study. Blends based on PP containing polyethylene (PE), ethylene vinyl alcohol copolymer (EVOH), and polylactic acid (PLA) are used as examples. Compatibilizer has also been added into respective blends to alter their interfacial interaction. It is demonstrated that dispersed phase can be deformed into a layered-like structure if interfacial tension, viscosity ratio, and melt elasticity are relatively small. While some of these values are relatively large, these dispersed droplets are not easily deformed under HSTWIM, forming ellipsoidal or fiber-like structure. The addition of a moderate amount of compatibilizer into these blends is shown to be able to reduce interfacial tension and the size of dispersed phase, thus, allowing more deformation on the dispersed phase. Such a study could provide some guidelines on phase morphology control of immiscible polymer blends under shear during various processing methods.

Coordination Polymer Gels with Modular Nanomorphologies, Tunable Emissions, and Stimuli-Responsive Behavior Based on an Amphiphilic Tripodal Gelator.

PubMed

Sutar, Papri; Maji, Tapas Kumar

2017-08-21

The recent upsurge in research on coordination polymer gels (CPGs) stems from their synthetic modularity, nanoscale processability, and versatile functionalities. Here we report self-assembly of an amphiphilic, tripodal low-molecular weight gelator (L) that consists of 4,4',4-[1,3,5-phenyl-tri(methoxy)]-tris-benzene core and 2,2':6',2″-terpyridyl termini, with different metal ions toward the formation of CPGs that show controllable nanomorphologies, tunable emission, and stimuli-responsive behaviors. L can also act as a selective chemosensor for Zn II with very low limit of detection (0.18 ppm) in aqueous medium. Coordination-driven self-assembly of L with Zn II in H 2 O/MeOH solvent mixture results in a coordination polymer hydrogel (ZnL) that exhibits sheet like morphology and charge-transfer emission. On the other hand, coordination of L with Tb III and Eu III in CHCl 3 /tetrahydrofuran solvent mixture results in green- and red-emissive CPGs, respectively, with nanotubular morphology. Moreover, precise stoichiometric control of L/Eu III /Tb III ratio leads to the formation of bimetallic CPGs that show emissions over a broad spectral range, including white-light-emission. We also explore the multistimuli responsive properties of the white-light-emitting CPG by exploiting the dynamics of Ln III -tpy coordination.

Physical properties of sequential interpenetrating polymer networks produced from canola oil-based polyurethane and poly(methyl methacrylate).

PubMed

Kong, Xiaohua; Narine, Suresh S

2008-05-01

Sequential interpenetrating polymer networks (IPNs) were prepared using polyurethane (PUR) synthesized from canola oil-based polyol with terminal primary functional groups and poly(methyl methacrylate) (PMMA). The properties of the material were evaluated by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and modulated differential scanning calorimetry (MDSC), as well as tensile properties measurements. The morphology of the IPNs was investigated using scanning electron microscopy (SEM) and MDSC. A five-phase morphology, that is, sol phase, PUR-rich phase, PUR-rich interphase, PMMA-rich interphase, and PMMA-rich phase, was observed for all the IPNs by applying a new quantitative method based on the measurement of the differential of reversing heat capacity versus temperature from MDSC, although not confirmed by SEM, most likely due to resolution restrictions. NCO/OH molar ratios (cross-linking density) and compositional variations of PUR/PMMA both affected the thermal properties and phase behaviors of the IPNs. Higher degrees of mixing occurred for the IPN with higher NCO/OH molar ratio (2.0/1.0) at PUR concentration of 25 wt %, whereas for the IPN with lower NCO/OH molar ratio (1.6/1.0), higher degrees of mixing occurred at PUR concentration of 35 wt %. The mechanical properties of the IPNs were superior to those of the constituent polymers due to the finely divided rubber and plastic combination structures in these IPNs.

Coarse-grained molecular dynamics simulations of polymerization with forward and backward reactions.

PubMed

Krajniak, Jakub; Zhang, Zidan; Pandiyan, Sudharsan; Nies, Eric; Samaey, Giovanni

2018-06-11

We develop novel parallel algorithms that allow molecular dynamics simulations in which byproduct molecules are created and removed because of the chemical reactions during the molecular dynamics simulation. To prevent large increases in the potential energy, we introduce the byproduct molecules smoothly by changing the non-bonded interactions gradually. To simulate complete equilibrium reactions, we allow the byproduct molecules attack and destroy created bonds. Modeling of such reactions are, for instance, important to study the pore formation due to the presence of e.g. water molecules or development of polymer morphology during the process of splitting off byproduct molecules. Another concept that could be studied is the degradation of polymeric materials, a very important topic in a recycling of polymer waste. We illustrate the method by simulating the polymerization of polyethylene terephthalate (PET) at the coarse-grained level as an example of a polycondensation reaction with water as a byproduct. The algorithms are implemented in a publicly available software package and are easily accessible using a domain-specific language that describes chemical reactions in an input configuration file. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Effect of Polymer Electrode Morphology on Performance of a Lithium/Polypyrrole Battery. M.S. Thesis

NASA Technical Reports Server (NTRS)

Nicholson, Marjorie Anne

1991-01-01

A variety of conducting polymer batteries were described in the recent literature. In this work, a Li/Polypyrrole secondary battery is described. The effect of controlling the morphology of the polymer on enhancement of counterion diffusion in the polymer phase is explored. A method of preparing conducting polymers was developed which yields high surface area per unit volume of electrode material. A porous membrane is used as a template in which to electrochemically polymerize pyrrole, then the membrane is dissolved, leaving the polymer in a fibrillar form. Conventionally, the polymer is electrochemically polymerized as a dense polymer film on a smooth Pt disk electrode. Previous work has shown that when the polymer is electrochemically polymerized in fribrillar form, charge transport rates are faster and charge capacities are greater than for dense, conventionally grown films containing the same amount of polymer. The purpose is to expand previous work by further investigating the possibilities of the optimization of transport rates in polypyrrole films by controlling the morphology of the films. The utility of fibrillar polypyrrole as a cathode material in a lithium/polymer secondary battery is then assessed. The performance of the fibrillar battery is compared to the performance of an analogous battery which employed a conventionally grown polypyrrole film. The study includes a comparison of cyclic voltammetry, shape of charge/discharge curves, discharge time and voltage, cycle life, coulombic efficiencies, charge capacities, energy densities, and energy efficiencies.

Recognition-Mediated Assembly of Quantum Dot Polymer Conjugates with Controlled Morphology

PubMed Central

Nandwana, Vikas; Subramani, Chandramouleeswaran; Eymur, Serkan; Yeh, Yi-Cheun; Tonga, Gulen Yesilbag; Tonga, Murat; Jeong, Youngdo; Yang, Boqian; Barnes, Michael D.; Cooke, Graeme; Rotello, Vincent M.

2011-01-01

We have demonstrated a polymer mediated “bricks and mortar” method for the self-assembly of quantum dots (QDs). This strategy allows QDs to self-assemble into structured aggregates using complementary three-point hydrogen bonding. The resulting nanocomposites have distinct morphologies and inter-particle distances based on the ratio between QDs and polymer. Time resolved photoluminescence measurements showed that the optical properties of the QDs were retained after self-assembly. PMID:22016664

Controlling Film Morphology in Conjugated Polymer

PubMed Central

Park, Lee Y.; Munro, Andrea M.; Ginger, David S.

2009-01-01

We study the effects of patterned surface chemistry on the microscale and nanoscale morphology of solution-processed donor/acceptor polymer-blend films. Focusing on combinations of interest in polymer solar cells, we demonstrate that patterned surface chemistry can be used to tailor the film morphology of blends of semiconducting polymers such as poly-[2-(3,7-dimethyloctyloxy)-5-methoxy-p-phenylenevinylene] (MDMO-PPV), poly-3-hexylthiophene (P3HT), poly[(9,9-dioctylflorenyl-2,7-diyl)-co-benzothiadiazole)] (F8BT), and poly(9,9-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-1,4-phenylendiamine) (PFB) with the fullerene derivative, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). We present a method for generating patterned, fullerene-terminated monolayers on gold surfaces, and use microcontact printing and Dip-Pen Nanolithography (DPN) to pattern alkanethiols with both micro- and nanoscale features. After patterning with fullerenes and other functional groups, we backfill the rest of the surface with a variety of thiols to prepare substrates with periodic variations in surface chemistry. Spin coating polymer:PCBM films onto these substrates, followed by thermal annealing under nitrogen, leads to the formation of structured polymer films. We characterize these films with Atomic Force Microscopy (AFM), Raman spectroscopy, and fluorescence microscopy. The surface patterns are effective in guiding phase separation in all of the polymer:PCBM systems investigated, and lead to a rich variety of film morphologies that are inaccessible with unpatterned substrates. We demonstrate our ability to guide pattern formation in films thick enough of be of interest for actual device applications (up to 200 nm in thickness) using feature sizes as small as 100 nm. Finally, we show that the surface chemistry can lead to variations in film morphology on length scales significantly smaller than those used in generating the original surface patterns. The variety of behaviors observed and the wide range of control over polymer morphology achieved at a variety of different length scales have important implications for the development of bulk heterojunction solar cells. PMID:18983150

Evaluation of superporous hydrogel (SPH) and SPH composite in porcine intestine ex-vivo: assessment of drug transport, morphology effect, and mechanical fixation to intestinal wall.

PubMed

Dorkoosh, Farid A; Borchard, Gerrit; Rafiee-Tehrani, Morteza; Verhoef, J Coos; Junginger, Hans E

2002-03-01

The objective of this study was to investigate the potential of superporous hydrogel (SPH) and SPH composite (SPHC) polymers to enhance the transport of N-alpha-benzoyl-L-arginine ethylester (BAEE) and fluorescein isothiocyanate-dextran 4400 (FD4) across porcine intestinal epithelium ex-vivo, and to study any possible morphological damage to the epithelium by applying these polymers. In addition, the ability of these polymers to attach to the gut wall by mechanical pressure was examined by using a specifically designed centrifuge model. The transport of BAEE and FD4 across the intestinal mucosa was enhanced 2- to 3-fold by applying SPHC polymer in comparison to negative control. No significant morphological damage was observed by applying these polymers inside the intestinal lumen. Moreover, the SPH and SPHC polymers were able to attach mechanically to the intestinal wall by swelling and did not move in the intestinal lumen even when a horizontal force of 13 gms(-2) was applied. In conclusion, these polymers are appropriate vehicles for enhancing the intestinal absorption of peptide and protein drugs.

Core–Shell Structure and Aggregation Number of Micelles Composed of Amphiphilic Block Copolymers and Amphiphilic Heterografted Polymer Brushes Determined by Small-Angle X-ray Scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szymusiak, Magdalena; Kalkowski, Joseph; Luo, Hanying

2017-08-31

A large group of functional nanomaterials employed in biomedical applications, including targeted drug delivery, relies on amphiphilic polymers to encapsulate therapeutic payloads via self-assembly processes. Knowledge of the micelle structures will provide critical insights into design of polymeric drug delivery systems. Core–shell micelles composed of linear diblock copolymers poly(ethylene glycol)-b-poly(caprolactone) (PEG-b-PCL), poly(ethylene oxide)-b-poly(lactic acid) (PEG-b-PLA), as well as a heterografted brush consisting of a poly(glycidyl methacrylate) backbone with PEG and PLA branches (PGMA-g-PEG/PLA) were characterized by dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) measurements to gain structural information regarding the particle morphology, core–shell size, and aggregation number. Themore » structural information at this quasi-equilibrium state can also be used as a reference when studying the kinetics of polymer micellization.« less

Core–Shell Structure and Aggregation Number of Micelles Composed of Amphiphilic Block Copolymers and Amphiphilic Heterografted Polymer Brushes Determined by Small-Angle X-ray Scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szymusiak, Magdalena; Kalkowski, Joseph; Luo, Hanying

2017-08-16

A large group of functional nanomaterials employed in biomedical applications, including targeted drug delivery, relies on amphiphilic polymers to encapsulate therapeutic payloads via self-assembly processes. Knowledge of the micelle structures will provide critical insights into design of polymeric drug delivery systems. Core–shell micelles composed of linear diblock copolymers poly(ethylene glycol)-b-poly(caprolactone) (PEG-b-PCL), poly(ethylene oxide)-b-poly(lactic acid) (PEG-b-PLA), as well as a heterografted brush consisting of a poly(glycidyl methacrylate) backbone with PEG and PLA branches (PGMA-g-PEG/PLA) were characterized by dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) measurements to gain structural information regarding the particle morphology, core–shell size, and aggregation number. Themore » structural information at this quasi-equilibrium state can also be used as a reference when studying the kinetics of polymer micellization.« less

Development and Modeling of a Novel Self-Assembly Process for Polymer and Polymeric Composite Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sumpter, Bobby G.; Carrillo, Jan-Michael Y.; Ahn, Suk-Kyun

Extensive computational simulations and experiments have been used to investigate the structure, dynamics and resulting photophysical properties of a number para-phenylenevinylene (PPV) based polymers and oligomers. These studies have shown how the morphology and structure are controlled to a large extent by the nature of the solute-solvent interactions in the initial solution phase preparation. A good solvent such as dichloromethane generates non-compact structures with more of a defect-extended chain like morphology while a bad solvent such as toluene leads to compact organized and folded structures with rod-like morphologies. Secondary structural organization is induced by using the solution phase structures tomore » generate solvent-free single molecule nanoparticles. These nanoparticles are very compact and rod shaped, consisting of near-cofacial ordering of the conjugated PPV chain backbones between folds located at tetrahedral defects (sp3 C-C bonds). The resulting photophysical properties exhibit a significant enhancement in the photoluminescence quantum yield, lifetime, and stability. In addition, the single molecule nanoparticles have Gaussian-like emission spectra with discrete center frequencies that are correlated to a conjugation length, allowing the design of nanoparticles which luminesces at a particular frequency. We followed a similar approach and applied a comparable methodology in our recent work on polythiophenes in order to study the effect of polymer architecture on nanoscale assembly. Unlike linear chains of comparable size, we observed aggregation of the bottlebrush architecture of poly(norbornene)-g-poly(3-hexylthiophene) (PNB-g-P3HT) after the freeze-drying and dissolution processes. The behavior can be attributed to a significant enhancement in the number of π-π interactions between grafted P3HT side chains.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Min, Ji Won; Kalathil, Abdul Kareem; Yim, Chul Jin

Li-rich Li{sub 1.2}Ni{sub 0.17}Co{sub 0.17}Mn{sub 0.5}O{sub 2} cathode materials were synthesized by electrospinning technique with different polymers, and their structural, morphological, and electrochemical performances were investigated. It was found that the electrospinning process leads to the formation of a fiber and flower-like morphology, by using different polymers and heat treatment conditions. The nanostructured morphology provided these materials with high initial discharge capacity. The cycling stability was improved with agglomerated nano-particles, as compared with porous materials. - Highlights: • Fiber and flower-like Li-rich cathode was synthesized by simple electrospinning. • Polymer dependent morphology and electrochemical performance was investigated. • Well-organized porousmore » structure facilitates the diffusion of lithium ions. • Technique could be applicable to other cathode materials as well.« less

Strategy for good dispersion of well-defined tetrapods in semiconducting polymer matrices.

PubMed

Lim, Jaehoon; Borg, Lisa zur; Dolezel, Stefan; Schmid, Friederike; Char, Kookheon; Zentel, Rudolf

2014-10-01

The morphology or dispersion control in inorganic/organic hybrid systems is studied, which consist of monodisperse CdSe tetrapods (TPs) with grafted semiconducting block copolymers with excess polymers of the same type. Tetrapod arm-length and amount of polymer loading are varied in order to find the ideal morphology for hybrid solar cells. Additionally, polymers without anchor groups are mixed with the TPs to study the effect of such anchor groups on the hybrid morphology. A numerical model is developed and Monte Carlo simulations to study the basis of compatibility or dispersibility of TPs in polymer matrices are performed. The simulations show that bare TPs tend to form clusters in the matrix of excess polymers. The clustering is significantly reduced after grafting polymer chains to the TPs, which is confirmed experimentally. Transmission electron microscopy reveals that the block copolymer-TP mixtures ("hybrids") show much better film qualities and TP distributions within the films when compared with the homopolymer-TP mixtures ("blends"), representing massive aggregations and cracks in the films. This grafting-to approach for the modification of TPs significantly improves the dispersion of the TPs in matrices of "excess" polymers up to the arm length of 100 nm. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of solvents and supercritical CO2 drying on the morphology and structure of polymer-based biofilms

NASA Astrophysics Data System (ADS)

Causa, Andrea; Salerno, Aurelio; Domingo, Concepción; Acierno, Domenico; Filippone, Giovanni

2014-05-01

In the present work, two-dimensional systems based on biodegradable polymers such as poly(ɛ-caprolactone) (PCL), poly(ethylene oxide) (PEO) and polylactic acid (PLA) are fabricated by means of a sustainable approach which consists in inducing phase separation in solutions of such polymers and "green" solvents, namely ethyl lactate (EL) and ethyl acetate (EA). The extraction of the solvent is promoted by a controlled drying process, which is performed in either air or supercritical CO2. The latter can indeed act as both an antisolvent, which favors the deposition of the polymer by forming a mixture with EL and EA, and a plasticizing agent, whose solvation and transport properties may considerably affect the microstructure and crystallinity of the polymer films. The morphological, topographical and crystalline properties of the films are tailored through a judicial selection of the materials and the processing conditions and assessed by means of thermal analyses, polarized optical microscopy, scanning electron microscopy and confocal interferometric microscopy. The results show that the morphological and crystalline properties of the films are strongly dependent on the choice of both the polymer/solvent system and the operating conditions during the drying step. In particular, the morphological, topographical and thermal properties of films prepared starting from highly crystalline polymers, namely PCL and PEO, are greatly affected by the crystallization of the material. Conversely, the less crystalline PLA forms almost completely amorphous films.

High Energy Density in Azobenzene-based Materials for Photo-Thermal Batteries via Controlled Polymer Architecture and Polymer-Solvent Interactions.

PubMed

Jeong, Seung Pyo; Renna, Lawrence A; Boyle, Connor J; Kwak, Hyunwook S; Harder, Edward; Damm, Wolfgang; Venkataraman, Dhandapani

2017-12-19

Energy densities of ~510 J/g (max: 698 J/g) have been achieved in azobenzene-based syndiotactic-rich poly(methacrylate) polymers. The processing solvent and polymer-solvent interactions are important to achieve morphologically optimal structures for high-energy density materials. This work shows that morphological changes of solid-state syndiotactic polymers, driven by different solvent processings play an important role in controlling the activation energy of Z-E isomerization as well as the shape of the DSC exotherm. Thus, this study shows the crucial role of processing solvents and thin film structure in achieving higher energy densities.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Wei; Reese, Cassandra M.; Xiong, Li

We report a simple route to engineer ultrathin polymer brush surfaces with wrinkled morphologies using postpolymerization modification (PPM), where the length scale of the buckled features can be tuned using PPM reaction time. Here, we show that partial crosslinking of the outer layer of the polymer brush under poor solvent conditions is critical to obtain wrinkled morphologies upon swelling.

Photoinduced Reversible Morphological Transformation of Azobenzene-Containing Pseudo-2D Polymers.

PubMed

Li, Zili; Tang, Miao; Jiang, Chen; Bai, Ruke; Bai, Wei

2018-05-02

2D polymer sheets containing azobenzene are successfully prepared by a facile strategy of "2D self-assembly polymerization (2DSP)" via free radical polymerization in solution. A bola amphiphile containing azobenzene as a novel monomer is designed and synthesized. The results indicate that single-layer covalent pseudo-2D polymers on a micrometer scale are obtained after polymerization with vinyl monomers. Moreover, the 2D polymer sheets are highly sensitive to UV light due to incorporation of azobenzene groups into the polymer. Upon alternative irradiation with UV and visible light, the morphological transformation between sheets and rolled-up nanotubes can be achieved based on the reversible trans-to-cis photoisomerization of azobenzene units in the 2D polymer sheets. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

On-command on/off switching of progenitor cell and cancer cell polarized motility and aligned morphology via a cytocompatible shape memory polymer scaffold.

PubMed

Wang, Jing; Quach, Andy; Brasch, Megan E; Turner, Christopher E; Henderson, James H

2017-09-01

In vitro biomaterial models have enabled advances in understanding the role of extracellular matrix (ECM) architecture in the control of cell motility and polarity. Most models are, however, static and cannot mimic dynamic aspects of in vivo ECM remodeling and function. To address this limitation, we present an electrospun shape memory polymer scaffold that can change fiber alignment on command under cytocompatible conditions. Cellular response was studied using the human fibrosarcoma cell line HT-1080 and the murine mesenchymal stem cell line C3H/10T1/2. The results demonstrate successful on-command on/off switching of cell polarized motility and alignment. Decrease in fiber alignment causes a change from polarized motility along the direction of fiber alignment to non-polarized motility and from aligned to unaligned morphology, while increase in fiber alignment causes a change from non-polarized to polarized motility along the direction of fiber alignment and from unaligned to aligned morphology. In addition, the findings are consistent with the hypothesis that increased fiber alignment causes increased cell velocity, while decreased fiber alignment causes decreased cell velocity. On-command on/off switching of cell polarized motility and alignment is anticipated to enable new study of directed cell motility in tumor metastasis, in cell homing, and in tissue engineering. Copyright © 2017 Elsevier Ltd. All rights reserved.

Simplified Models for Accelerated Structural Prediction of Conjugated Semiconducting Polymers

DOE PAGES

Henry, Michael M.; Jones, Matthew L.; Oosterhout, Stefan D.; ...

2017-11-08

We perform molecular dynamics simulations of poly(benzodithiophene-thienopyrrolodione) (BDT-TPD) oligomers in order to evaluate the accuracy with which unoptimized molecular models can predict experimentally characterized morphologies. The predicted morphologies are characterized using simulated grazing-incidence X-ray scattering (GIXS) and compared to the experimental scattering patterns. We find that approximating the aromatic rings in BDT-TPD with rigid bodies, rather than combinations of bond, angle, and dihedral constraints, results in 14% lower computational cost and provides nearly equivalent structural predictions compared to the flexible model case. The predicted glass transition temperature of BDT-TPD (410 +/- 32 K) is found to be in agreement withmore » experiments. Predicted morphologies demonstrate short-range structural order due to stacking of the chain backbones (p-p stacking around 3.9 A), and long-range spatial correlations due to the self-organization of backbone stacks into 'ribbons' (lamellar ordering around 20.9 A), representing the best-to-date computational predictions of structure of complex conjugated oligomers. We find that expensive simulated annealing schedules are not needed to predict experimental structures here, with instantaneous quenches providing nearly equivalent predictions at a fraction of the computational cost of annealing. We therefore suggest utilizing rigid bodies and fast cooling schedules for high-throughput screening studies of semiflexible polymers and oligomers to utilize their significant computational benefits where appropriate.« less

Simplified Models for Accelerated Structural Prediction of Conjugated Semiconducting Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henry, Michael M.; Jones, Matthew L.; Oosterhout, Stefan D.

We perform molecular dynamics simulations of poly(benzodithiophene-thienopyrrolodione) (BDT-TPD) oligomers in order to evaluate the accuracy with which unoptimized molecular models can predict experimentally characterized morphologies. The predicted morphologies are characterized using simulated grazing-incidence X-ray scattering (GIXS) and compared to the experimental scattering patterns. We find that approximating the aromatic rings in BDT-TPD with rigid bodies, rather than combinations of bond, angle, and dihedral constraints, results in 14% lower computational cost and provides nearly equivalent structural predictions compared to the flexible model case. The predicted glass transition temperature of BDT-TPD (410 +/- 32 K) is found to be in agreement withmore » experiments. Predicted morphologies demonstrate short-range structural order due to stacking of the chain backbones (p-p stacking around 3.9 A), and long-range spatial correlations due to the self-organization of backbone stacks into 'ribbons' (lamellar ordering around 20.9 A), representing the best-to-date computational predictions of structure of complex conjugated oligomers. We find that expensive simulated annealing schedules are not needed to predict experimental structures here, with instantaneous quenches providing nearly equivalent predictions at a fraction of the computational cost of annealing. We therefore suggest utilizing rigid bodies and fast cooling schedules for high-throughput screening studies of semiflexible polymers and oligomers to utilize their significant computational benefits where appropriate.« less

Nanoscale control of the network morphology of high efficiency polymer fullerene solar cells by the use of high material concentration in the liquid phase

NASA Astrophysics Data System (ADS)

Radbeh, R.; Parbaile, E.; Bouclé, J.; Di Bin, C.; Moliton, A.; Coudert, V.; Rossignol, F.; Ratier, B.

2010-01-01

Despite the constant improvement of their power conversion efficiencies, organic solar cells based on an interpenetrating network of a conjugated polymer as donor and fullerene derivatives as acceptor materials still need to be improved for commercial use. In this context, we present a study on the optimization of solar cells based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) by varying a specific cell parameter, namely the concentration of the active layer components in the liquid phase before blend film deposition, in order to improve device performance and to better understand the relation between morphology and device operation. Our study shows a significant increase of the short-circuit current, open-circuit voltage and cell efficiency by properly choosing the formulation of the initial blend before film deposition. We demonstrate that the active layer morphology, which is strongly dependent on the initial material concentrations and the processing conditions, can greatly impact the electronic characteristics of the device, especially regarding charge recombination dynamics at the donor-acceptor interface. Our optimized P3HT:PCBM device exhibits both slow recombination and high photocurrent generation associated with an overall power conversion efficiency of 4.25% under 100 mW cm-2 illumination (AM1.5G).

Predicting the Highly Nonlinear Mechanical Properties of Polymeric Materials

NASA Astrophysics Data System (ADS)

Porter, David

2009-06-01

Over the past few years, we have developed models that calculate the highly nonlinear mechanical properties of polymers as a function of temperature, strain and strain rate from their molecular and morphological structure. A review of these models is presented here, with emphasis on combining the fundamental aspects of molecular physics that dictate these properties and the pragmatic need to make realistic predictions for our customers; the designer of new materials and the engineers who use these materials. The models calculate the highly nonlinear mechanical properties of polymers as a function of temperature, strain and strain rate from their molecular structure. The model is based upon the premise that mechanical properties are a direct consequence of energy stored and energy dissipated during deformation of a material. This premise is transformed into a consistent set of structure-property relations for the equation of state, EoS, and the engineering constitutive relations in a polymer by quantifying energy storage and loss at the molecular level of interactions between characteristic groups of atoms in a polymer. These relations are derived from a simple volumetric mean field Lennard-Jones potential function for the potential energy of intermolecular interactions in a polymer. First, properties such as temperature-volume relations and glass transition temperature are calculated directly from the potential function. Then, the `shock' EoS is derived simply by differentiating the potential function with respect to volume, assuming that the molecules cannot relax in the time scales of the deformation. The energy components are then used to predict the dynamic mechanical spectrum of a polymer in terms of temperature and rate. This can be transformed directly into the highly nonlinear stress-strain relations through yield. The constitutive relations are formulated as a set of analytical equations that predict properties directly in terms of a small set of structural parameters that can be calculated directly and independently from the chemical composition and morphology of a polymer. A number of examples are given to illustrate the model and also to show that the method can be applied, with appropriate modifications, to other materials.

Design of Donor Polymers with Strong Temperature-Dependent Aggregation Property for Efficient Organic Photovoltaics.

PubMed

Hu, Huawei; Chow, Philip C Y; Zhang, Guangye; Ma, Tingxuan; Liu, Jing; Yang, Guofang; Yan, He

2017-10-17

Bulk heterojunction (BHJ) organic solar cells (OSCs) have attracted intensive research attention over the past two decades owing to their unique advantages including mechanical flexibility, light weight, large area, and low-cost fabrications. To date, OSC devices have achieved power conversion efficiencies (PCEs) exceeding 12%. Much of the progress was enabled by the development of high-performance donor polymers with favorable morphological, electronic, and optical properties. A key problem in morphology control of OSCs is the trade-off between achieving small domain size and high polymer crystallinity, which is especially important for the realization of efficient thick-film devices with high fill factors. For example, the thickness of OSC blends containing state-of-the-art PTB7 family donor polymers are restricted to ∼100 nm due to their relatively low hole mobility and impure polymer domains. To further improve the device performance and promote commercialization of OSCs, there is a strong demand for the design of new donor polymers that can achieve an optimal blend morphology containing highly crystalline yet reasonably small domains. In this Account, we highlight recent progress on a new family of conjugated polymers with strong temperature-dependent aggregation (TDA) property. These polymers are mostly disaggregated and can be easily dissolved in solution at high temperatures, yet they can strongly aggregate when the solution is cooled to room temperature. This unique aggregation property allows us to control the disorder-order transition of the polymer during solution processing. By preheating the solution to high temperature (∼100 °C), the polymer chains are mostly disaggregated before spin coating; as the temperature of the solution drops during the spin coating process, the polymer can strongly aggregate and form crystalline domains yet that are not excessivelylarge. The overall blend morphology can be optimized by various processing conditions (e.g., temperature, spin-rates, concentration, etc.). This well-controlled and near-optimal BHJ morphology produced over a dozen cases of efficient OSCs with an active layer nearly 300 nm thick that can still achieve high FFs (70-77%) and efficiencies (10-11.7%). By studying the structure-property relationships of the donor polymers, we show that the second position branched alkyl chains and the fluorination on the polymer backbone are two key structural features that enable the strong TDA property. Our comparative studies also show that the TDA polymer family can be used to match with non-fullerene acceptors yielding OSCs with low voltage losses. The key difference between the empirical matching rules for fullerene and non-fullerene OSCs is that TDA polymers with slightly reduced crystallinity appear to match better with small molecular acceptors and yield higher OSC performances.

Internal dynamics of semiflexible polymers with active noise

NASA Astrophysics Data System (ADS)

Eisenstecken, Thomas; Gompper, Gerhard; Winkler, Roland G.

2017-04-01

The intramolecular dynamics of flexible and semiflexible polymers in response to active noise is studied theoretically. The active noise may either originate from interactions of a passive polymer with a bath of active Brownian particles or the polymer itself is comprised of active Brownian particles. We describe the polymer by the continuous Gaussian semiflexible-polymer model, taking into account the finite polymer extensibility. Our analytical calculations predict a strong dependence of the polymer dynamics on the activity. In particular, active semiflexible polymers exhibit a crossover from a bending elasticity-dominated dynamics at weak activity to that of flexible polymers at strong activity. The end-to-end vector correlation function decays exponentially for times longer than the longest polymer relaxation time. Thereby, the polymer relaxation determines the decay of the correlation function for long and flexible polymers. For shorter and stiffer polymers, the relaxation behavior of individual active Brownian particles dominates the decay above a certain activity. The diffusive dynamics of a polymer is substantially enhanced by the activity. Three regimes can be identified in the mean square displacement for sufficiently strong activities: an activity-induced ballistic regime at short times, followed by a Rouse-type polymer-specific regime for any polymer stiffness, and free diffusion at long times, again determined by the activity.

Model systems for single molecule polymer dynamics

PubMed Central

Latinwo, Folarin

2012-01-01

Double stranded DNA (dsDNA) has long served as a model system for single molecule polymer dynamics. However, dsDNA is a semiflexible polymer, and the structural rigidity of the DNA double helix gives rise to local molecular properties and chain dynamics that differ from flexible chains, including synthetic organic polymers. Recently, we developed single stranded DNA (ssDNA) as a new model system for single molecule studies of flexible polymer chains. In this work, we discuss model polymer systems in the context of “ideal” and “real” chain behavior considering thermal blobs, tension blobs, hydrodynamic drag and force–extension relations. In addition, we present monomer aspect ratio as a key parameter describing chain conformation and dynamics, and we derive dynamical scaling relations in terms of this molecular-level parameter. We show that asymmetric Kuhn segments can suppress monomer–monomer interactions, thereby altering global chain dynamics. Finally, we discuss ssDNA in the context of a new model system for single molecule polymer dynamics. Overall, we anticipate that future single polymer studies of flexible chains will reveal new insight into the dynamic behavior of “real” polymers, which will highlight the importance of molecular individualism and the prevalence of non-linear phenomena. PMID:22956980

Advanced Polymer Network Structures

DTIC Science & Technology

2016-02-01

double networks in a single step was identified from coarse-grained molecular dynamics simulations of polymer solvents bearing rigid side chains dissolved...in a polymer network. Coarse-grained molecular dynamics simulations also explored the mechanical behavior of traditional double networks and...DRI), polymer networks, polymer gels, molecular dynamics simulations , double networks 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF

Simulation of Ionic Aggregation and Ion Dynamics in Model Ionomers

NASA Astrophysics Data System (ADS)

Frischknecht, Amalie L.

2012-02-01

Ionomers, polymers containing a small fraction of covalently bound ionic groups, are of interest as possible electrolytes in batteries. A single-ion conducting polymer electrolyte would be safer and have higher efficiency than the currently-used liquid electrolytes. However, to date ionomeric materials do not have sufficiently high conductivities for practical application. This is most likely because the ions tend to form aggregates, leading to slow ion transport. A key question is therefore how molecular structure affects the ionic aggregation and ion dynamics. To probe these structure-property relationships, we have performed molecular simulations of a set of recently synthesized poly(ethylene-co-acrylic acid) copolymers and ionomers, with a focus on the morphology of the ionic aggregates. The ionomers have a precise, constant spacing of charged groups, making them ideal for direct comparisons with simulations. Ab initio calculations give insight into the expected coordination of cations with fragments of the ionomers. All-atom molecular dynamics (MD) simulations of the ionomer melt show aggregation of the ionic groups into extended string-like clusters. An extensive set of coarse-grained molecular dynamics simulations extend the results to longer times and larger length scales. The structure factors calculated from the MD simulations compare favorably with x-ray scattering data. Furthermore, the simulations give a detailed picture of the sizes, shapes, and composition of the ionic aggregates, and how they depend on polymer architecture. Implications for ion transport will be discussed. [Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Advancing Renewable Materials by Integrated Light and X-ray Scattering - Final Technical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akpalu, Yvonne A.

Polyhydroxyalkanotes (PHAs), a group of newly developed, commercially available biopolymers, and their composites have the potential to replace petroleum-based amorphous and semicrystalline polymers currently in use for consumer packaging, adhesives, and coating applications and to have significant advantages in medical applications such as tissue engineering. While the potential of PHAs is recognized in the literature and has even been realized in some cases, knowledge of these systems is decades behind that of synthetic polymers. Composites based on PHAs, furthermore, are just emerging in the research community. We argue that widespread adoption of nano-enhanced PHA materials can only be achieved throughmore » a proper characterization of the nanofiller morphology and its impact on the polymer matrix. Our goal is to build a robust understanding of the structure-processing relationships of PHAs to make it possible to achieve fundamental control over the final properties of these biopolymers and their bionanocomposites and to develop cost-effective manufacturing technologies for them. With the ultimate goal to design PHA polymer nanocomposites with tailored properties, we have performed a systematic study of the influence of cooling rate on the thermal properties and morphology of linear PHAs (PHB Mw = 690,000 g/mol; PHBV Mw = 407,000 g/mol, 8 mol % HV) and branched (PHBHx, Mw = 903, 000 g/mol, 7.2 mol % Hx) copolymers. Structure-property relations for silica/PHBHx nanocomposites were also investigated. Our studies show that simple two-phase composite models do not account for the molecular weight dependent enhancement in the modulus. Although improvement of the mechanical properties (stiffness/modulus and toughness) must be due to alteration of the matrix by the nanoparticle filler, the observed improvement was not caused by the change of crystallinity or spherulitic morphology. Since the mechanical properties of polymer nanocomposites can be affected by many factors, such as the interaction between particles and a polymer matrix, crystallinity of the polymer, spherulitic morphology, molecular weight of the polymer matrix, the PHA system studied can serve as a model system for determining the unique influence of particle characteristics on the morphology and mechanical properties of renewable polymer matrices. Motivated by our promising results, we have initiated a systematic morphology characterization studies on a series of branched PHA polymers to uncover conceptual models that predict reinforcement and toughening in renewable polymer nanocomposites as a function particle characteristics, molecular weight and polymer backbone structure. Thus how enhancement in the mechanical properties occurs in PHAs is the focus of our work. In March 2010, the PI discovered a process that will allow better control of particle dispersion in PHA matrices. A graduate student (Sandip Argekar) was added to the project to help test this discovery and the scale up potential for the low-cost manufacture of renewable polymer nanocomposite films. If successful, the PI and co-PI will submit an SBIR proposal to facilitate technology transfer of the discoveries under this award.« less

Evaluation of the morphology of metal particles in intrinsic conductive polymer dispersions

NASA Astrophysics Data System (ADS)

Lempa, E.; Graßmann, C.; Rabe, M.; Schwarz-Pfeiffer, A.; van Langenhove, L.

2017-10-01

For the production of smart textiles the resistivity of prints and coatings with intrinsic conductive polymers is often too high and the performance properties not sufficient. The addition of metal components enhances many characteristics, however the choice of type of metal, morphology and application method influence results to great extend.

Poly(terphenylene) Anion Exchange Membranes: The Effect of Backbone Structure on Morphology and Membrane Property

DOE PAGES

Lee, Woo-Hyung; Park, Eun Joo; Han, Junyoung; ...

2017-05-05

A new design concept for ion-conducting polymers in anion exchange membranes (AEMs) fuel cells is proposed based on structural studies and conformational analysis of polymers and their effect on the properties of AEMs. Thermally, chemically, and mechanically stable terphenyl-based polymers with pendant quaternary ammonium alkyl groups were synthesized to investigate the effect of varying the arrangement of the polymer backbone and cation-tethered alkyl chains. The results demonstrate that the microstructure and morphology of these polymeric membranes significantly influence ion conductivity and fuel cell performance. Finally, the results of this study provide new insights that will guide the molecular design ofmore » polymer electrolyte materials to improve fuel cell performance.« less

Experiment Research on Hot-Rolling Processing of Nonsmooth Pit Surface.

PubMed

Gu, Yun-Qing; Fan, Tian-Xing; Mou, Jie-Gang; Yu, Wei-Bo; Zhao, Gang; Wang, Evan

2016-01-01

In order to achieve the nonsmooth surface drag reduction structure on the inner polymer coating of oil and gas pipelines and improve the efficiency of pipeline transport, a structural model of the machining robot on the pipe inner coating is established. Based on machining robot, an experimental technique is applied to research embossing and coating problems of rolling-head, and then the molding process rules under different conditions of rolling temperatures speeds and depth are analyzed. Also, an orthogonal experiment analysis method is employed to analyze the different effects of hot-rolling process apparatus on the embossed pits morphology and quality of rolling. The results also reveal that elevating the rolling temperature or decreasing the rolling speed can also improve the pit structure replication rates of the polymer coating surface, and the rolling feed has little effect on replication rates. After the rolling-head separates from the polymer coating, phenomenon of rebounding and refluxing of the polymer coating occurs, which is the reason of inability of the process. A continuous hot-rolling method for processing is used in the robot and the hot-rolling process of the processing apparatus is put in a dynamics analysis.

Experiment Research on Hot-Rolling Processing of Nonsmooth Pit Surface

PubMed Central

Gu, Yun-qing; Fan, Tian-xing; Mou, Jie-gang; Yu, Wei-bo; Zhao, Gang; Wang, Evan

2016-01-01

In order to achieve the nonsmooth surface drag reduction structure on the inner polymer coating of oil and gas pipelines and improve the efficiency of pipeline transport, a structural model of the machining robot on the pipe inner coating is established. Based on machining robot, an experimental technique is applied to research embossing and coating problems of rolling-head, and then the molding process rules under different conditions of rolling temperatures speeds and depth are analyzed. Also, an orthogonal experiment analysis method is employed to analyze the different effects of hot-rolling process apparatus on the embossed pits morphology and quality of rolling. The results also reveal that elevating the rolling temperature or decreasing the rolling speed can also improve the pit structure replication rates of the polymer coating surface, and the rolling feed has little effect on replication rates. After the rolling-head separates from the polymer coating, phenomenon of rebounding and refluxing of the polymer coating occurs, which is the reason of inability of the process. A continuous hot-rolling method for processing is used in the robot and the hot-rolling process of the processing apparatus is put in a dynamics analysis. PMID:27022235

Facile control of nanoporosity in Cellulose Acetate using Nickel(II) nitrate additive and water pressure treatment for highly efficient battery gel separators.

PubMed

Lee, Woong Gi; Kim, Do Hyeong; Jeon, Woo Cheol; Kwak, Sang Kyu; Kang, Seok Ju; Kang, Sang Wook

2017-04-28

We succeed in fabricating nearly straight nanopores in cellulose acetate (CA) polymers for use as battery gel separators by utilizing an inorganic hexahydrate (Ni(NO 3 ) 2 ·6H 2 O) complex and isostatic water pressure treatment. The continuous nanopores are generated when the polymer film is exposed to isostatic water pressure after complexing the nickel(II) nitrate hexahydrate (Ni(NO 3 ) 2 ·6H 2 O) with the CA. These results can be attributed to the manner in which the polymer chains are weakened because of the plasticization effect of the Ni(NO 3 ) 2 ·6H 2 O that is incorporated into the CA. Furthermore, we performed extensive molecular dynamics simulation for confirming the interaction between electrolyte and CA separator. The well controlled CA membrane after water pressure treatment enables fabrication of highly reliable cell by utilizing 2032-type coin cell structure. The resulting cell performance exhibits not only the effect of the physical morphology of CA separator, but also the chemical interaction of electrolyte with CA polymer which facilitates the Li-ion in the cell.

Embedded Gold Nanorods as Microscale Thermochromic Temperature Sensors

NASA Astrophysics Data System (ADS)

Kennedy, W. Joshua; Slinker, Keith; Koerner, Hilmar; Ehlert, Gregory; Baur, Jeffery

2015-03-01

Gold nanorods (AuNRs) are known to undergo a shape transformation via surface melting at temperatures far below the bulk melting temperature of gold. Because the optical scattering by the AuNRs depends on both particle morphology and the surrounding local dielectric constant the opto-thermal properties of polymer-AuNR nanocomposites depend strongly on the chemical and mechanical characteristics of the polymer host. We have measured the optical absorption of polymer nanocomposites consisting of AuNRs in a variety of polymer systems as a function of temperature, time, molecular weight, and crosslink density. Our results show that the shape transformation of the AuNRs is not well described by a simple kinetic model, and that multiple contributors to the surface energy play significant roles in the process. We show that the dynamics of the shape transformation may be calibrated in a nanocomposite such that the optical absorption spectrum of the material may be used as a local sensor of both temperature history and degree of cure. We demonstrate the usefulness of this technique by measuring (ex situ) the temperature of an internally heated epoxy resin with a lateral spatial resolution of < 10 μm. Principal Investigator.

Smart membranes: Hydroxypropyl cellulose for flavor delivery

NASA Astrophysics Data System (ADS)

Heitfeld, Kevin A.

2007-12-01

This work focuses on the use of temperature responsive gels (TRGs) (polymeric hydrogels with a large temperature-dependent change in volume) for flavor retention at cooking temperatures. Specifically, we have studied a gel with a lower critical solution temperature (LCST) that swells at low temperatures and collapses at high temperatures. In the collapsed state, the polymer acts as a transport barrier, keeping the volatile flavors inside. An encapsulation system was designed to utilize the solution (phase separation) behavior of a temperature responsive gel. The gel morphology was understood and diffusive properties were tailored through morphology manipulation. Heterogeneous and homogeneous gels were processed by understanding the effect of temperature on gel morphology. A morphology model was developed linking bulk diffusive properties to molecular morphology. Flavor was encapsulated within the gel and the emulsifying capability was determined. The capsules responded to temperature similarly to the pure polymer. The release kinetcs were compared to commercial gelatin capsules and the temperature responsive polymer took longer to release.

Preparation and application of conducting polymer/Ag/clay composite nanoparticles formed by in situ UV-induced dispersion polymerization

PubMed Central

Zang, Limin; Qiu, Jianhui; Yang, Chao; Sakai, Eiichi

2016-01-01

In this work, composite nanoparticles containing polypyrrole, silver and attapulgite (PPy/Ag/ATP) were prepared via UV-induced dispersion polymerization of pyrrole using ATP clay as a templet and silver nitrate as photoinitiator. The effects of ATP concentration on morphology, structure and electrical conductivity were studied. The obtained composite nanoparticles with an interesting beads-on-a-string morphology can be obtained in a short time (10 min), which indicates the preparation method is facile and feasible. To explore the potential applications of the prepared PPy/Ag/ATP composite nanoparticles, they were served as multifunctional filler and blended with poly(butylene succinate) (PBS) matrix to prepare biodegradable composite material. The distribution of fillers in polymer matrix and the interfacial interaction between fillers and PBS were confirmed by scanning electron microscope, elemental mapping and dynamic mechanical analysis. The well dispersed fillers in PBS matrix impart outstanding antibacterial property to the biodegradable composite material as well as enhanced storage modulus due to Ag nanoparticles and ATP clay. The biodegradable composite material also possesses modest surface resistivity (106 ~ 109 Ω/◻). PMID:26839126

Plasma Modification of Poly Lactic Acid Solutions to Generate High Quality Electrospun PLA Nanofibers.

PubMed

Rezaei, Fatemeh; Nikiforov, Anton; Morent, Rino; De Geyter, Nathalie

2018-02-02

Physical properties of pre-electrospinning polymer solutions play a key role in electrospinning as they strongly determine the morphology of the obtained electrospun nanofibers. In this work, an atmospheric-pressure argon plasma directly submerged in the liquid-phase was used to modify the physical properties of poly lactic acid (PLA) spinning solutions in an effort to improve their electrospinnability. The electrical characteristics of the plasma were investigated by two methods; V-I waveforms and Q-V Lissajous plots while the optical emission characteristics of the plasma were also determined using optical emission spectroscopy (OES). To perform a complete physical characterization of the plasma-modified polymer solutions, measurements of viscosity, surface tension, and electrical conductivity were performed for various PLA concentrations, plasma exposure times, gas flow rates, and applied voltages. Moreover, a fast intensified charge-couple device (ICCD) camera was used to image the bubble dynamics during the plasma treatments. In addition, morphological changes of PLA nanofibers generated from plasma-treated PLA solutions were observed by scanning electron microscopy (SEM). The performed plasma treatments were found to induce significant changes to the main physical properties of the PLA solutions, leading to an enhancement of electrospinnability and an improvement of PLA nanofiber formation.

Preparation and application of conducting polymer/Ag/clay composite nanoparticles formed by in situ UV-induced dispersion polymerization.

PubMed

Zang, Limin; Qiu, Jianhui; Yang, Chao; Sakai, Eiichi

2016-02-03

In this work, composite nanoparticles containing polypyrrole, silver and attapulgite (PPy/Ag/ATP) were prepared via UV-induced dispersion polymerization of pyrrole using ATP clay as a templet and silver nitrate as photoinitiator. The effects of ATP concentration on morphology, structure and electrical conductivity were studied. The obtained composite nanoparticles with an interesting beads-on-a-string morphology can be obtained in a short time (10 min), which indicates the preparation method is facile and feasible. To explore the potential applications of the prepared PPy/Ag/ATP composite nanoparticles, they were served as multifunctional filler and blended with poly(butylene succinate) (PBS) matrix to prepare biodegradable composite material. The distribution of fillers in polymer matrix and the interfacial interaction between fillers and PBS were confirmed by scanning electron microscope, elemental mapping and dynamic mechanical analysis. The well dispersed fillers in PBS matrix impart outstanding antibacterial property to the biodegradable composite material as well as enhanced storage modulus due to Ag nanoparticles and ATP clay. The biodegradable composite material also possesses modest surface resistivity (10(6)~ 10(9) Ω/◻).

Multiple dynamic regimes in colloid-polymer dispersions: New insight using X-ray photon correlation spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Srivastava, Sunita; Kishore, Suhasini; Narayanan, Suresh

We present an X-ray photon correlation spectros- copy (XPCS) study of dynamic transitions in an anisotropic colloid-polymer dispersion with multiple arrested states. The results provide insight into the mechanism for formation of repulsive glasses, attractive glasses, and networked gels of col- loids with weakly adsorbing polymer chains. In the presence of adsorbing polymer chains, we observe three distinct regimes: a state with slow dynamics consisting of finite particles and clusters, for which interparticle interactions are predominantly repulsive; a second dynamic regime occurring above the satu- ration concentration of added polymer, in which small clusters of nanoparticles form via a short-rangemore » depletion attraction; and a third regime above the overlap concentration in which dynamics of clusters are independent of polymer chain length. The observed complex dynamic state diagram is primarily gov- erned by the structural reorganization of a nanoparticle cluster and polymer chains at the nanoparticle-polymer surface and in the concentrated medium, which in turn controls the dynamics of the dispersion« less

Elastin-like-recombinamers multilayered nanofibrous scaffolds for cardiovascular applications.

PubMed

Putzu, M; Causa, F; Nele, V; de Torre, I González; Rodriguez-Cabello, J C; Netti, P A

2016-11-15

Coronary angioplasty is the most widely used technique for removing atherosclerotic plaques in blood vessels. The regeneration of the damaged intima layer after this treatment is still one of the major challenges in the field of cardiovascular tissue engineering. Different polymers have been used in scaffold manufacturing in order to improve tissue regeneration. Elastin-mimetic polymers are a new class of molecules that have been synthesized and used to obtain small diameter fibers with specific morphological characteristics. Elastin-like polymers produced by recombinant techniques and called elastin-like recombinamers (ELRs) are particularly promising due to their high degree of functionalization. Generally speaking, ELRs can show more complex molecular designs and a tighter control of their sequence than other chemically synthetized polymers Rodriguez Cabello et al (2009 Polymer 50 5159-69, 2011 Nanomedicine 6 111-22). For the fabrication of small diameter fibers, different ELRs were dissolved in 2,2,2-fluoroethanol (TFE). Dynamic light scattering was used to identify the transition temperature and get a deep characterization of the transition behavior of the recombinamers. In this work, we describe the use of electrospinning technique for the manufacturing of an elastic fibrous scaffold; the obtained fibers were characterized and their cytocompatibility was tested in vitro. A thorough study of the influence of voltage, flow rate and distance was carried out in order to determine the appropriate parameters to obtain fibrous mats without beads and defects. Moreover, using a rotating mandrel, we fabricated a tubular scaffold in which ELRs containing different cell adhesion sequences (mainly REDV and RGD) were collected. The stability of the scaffold was improved by using genipin as a crosslinking agent. Genipin-ELRs crosslinked scaffolds  show a good stability and fiber morphology. Human umbilical vein endothelial cells  were used to assess the in vitro bioactivity of the cell adhesion domains within the backbone of the ELRs.

Phase stability and dynamics of entangled polymer-nanoparticle composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mangal, Rahul; Srivastava, Samanvaya; Archer, Lynden A.

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,more » 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.« less

Structure and Dynamics of Polymer/Polymer grafted nanoparticle composite

NASA Astrophysics Data System (ADS)

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.

Linear rheology and structure of molecular bottlebrushes with short side chains

DOE Office of Scientific and Technical Information (OSTI.GOV)

López-Barrón, Carlos R., E-mail: carlos.r.lopez-barron@exxonmobil.com; Brant, Patrick; Crowther, Donna J.

We investigate the microstructure and linear viscoelasticity of model molecular bottlebrushes (BBs) using rheological and small-angle X-ray and neutron scattering measurements. Our polymers have short atactic polypropylene (aPP) side chains of molecular weight ranging from 119 g/mol to 259 g/mol and narrow molecular weight distribution (M{sub w}/M{sub n} 1.02–1.05). The side chain molecular weights are a small fraction of the entanglement molecular weight of the corresponding linear polymer (M{sub e,aPP}= 7.05 kg/mol), and as such, they are unentangled. The morphology of the aPP BBs is characterized as semiflexible thick chains with small side chain interdigitation. Their dynamic master curves, obtained by time-temperature superposition,more » reveal two sequential relaxation processes corresponding to the segmental relaxation and the relaxation of the BB backbone. Due to the short length of the side chains, their fast relaxation could not be distinguished from the glassy relaxation. The fractional free volume is an increasing function of the side chain length (N{sub SC}). Therefore, the glassy behavior of these polymers as well as their molecular friction and dynamic properties are influenced by their N{sub SC} values. The apparent flow activation energies are a decreasing function of N{sub SC}, and their values explain the differences in zero-shear viscosity measured at different temperatures.« less

Dynamic photopatterning of cells in situ by Q-switched neodymium-doped yttrium ortho-vanadate laser.

PubMed

Deka, Gitanjal; Okano, Kazunori; Kao, Fu-Jen

2014-01-01

Cellular micropattering has been increasingly adopted in quantitative biological experiments. A Q-switched pulsed neodymium-doped yttrium ortho-vanadate (Nd∶YVO4) laser directed in-situ microfabrication technique for cell patterning is presented. A platform is designed uniquely to achieve laser ablation. The platform is comprised of thin gold coating over a glass surface that functions as a thermal transducer and is over-layered by a cell repellant polymer layer. Micropatterns are engraved on the platform, subsequently exposing specific cell adhesive micro-domains by ablating the gold-polymer coating photothermally. Experimental results indicate that the proposed approach is applicable under culture conditions, viable toward cells, and has a higher engraving speed. Possible uses in arraying isolated single cells on the platform are also shown. Additionally, based on those micro-patterns, dynamic cellular morphological changes and migrational speed in response to geometrical barriers are studied to demonstrate the potential applications of the proposed approach. Our results further demonstrate that cells in narrower geometry had elongated shapes and higher migrational speed than those in wider geometry. Importantly, the proposed approach will provide a valuable reference for efforts to study single cell dynamics and cellular migration related processes for areas such as cell division, wound healing, and cancer invasion.

Molecular Dynamics Simulations of Ion Transport and Mechanisms in Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Mogurampelly, Santosh; Ganesan, Venkat

2015-03-01

Using all atom molecular dynamics and trajectory-extending kinetic Monte Carlo simulations, we study the influence of Al2O3 nanoparticles on the transport properties of Li+ ions in polymer electrolytes consisting of polyethylene oxide (PEO) melt solvated with LiBF4 salt. We observe that the nanoparticles have a strong influence on polymer segmental dynamics which in turn correlates with the mobility of Li+ ions. Explicitly, polymer segmental relaxation times and Li+ ion residence times around polymer were found to increase with the addition of nanoparticles. We also observe that increasing short range repulsive interactions between nanoparticles and polymer membrane leads to increasing polymer dynamics and ion mobility. Overall, our simulation results suggest that nanoparticle induced changes in conformational and dynamic properties of the polymer influences the ion mobilities in polymer electrolytes and suggests possible directions for using such findings to improve the polymer matrix conductivity. The authors acknowledge the Texas Advanced Computing Center (TACC) at The University of Texas at Austin for providing computing resources that have contributed to the research.

Morphology and vulcanizate properties of ethylene-propylene-diene rubber/ styrene-butadiene rubber blends.

PubMed

Park, Gayoung; Kim, Yun Hee; Kim, Dong Soo; Ko, Young Chun

2010-05-01

Morphology and vulcanizate properties of EPDM/SBR blends were investigated. AAHR (a mixture of aliphatic and aromatic hydrocarbon resins) was used as a compatibilizer and bis(3-triethoxysilylpropyl)tetrasulfide (TESPT) was used as a coupling agent. The vulcanizate properties and the morphological studies revealed that EPDM and SBR were incompatible, and the addition of AAHR was very effective to enhance the compatibility between EPDM and SBR. The weight percent of bound rubbers was increased with increasing SBR contents. The addition of an AAHR increased the amounts of bound rubbers, and hence the vulcanizate properties such as tear strength and fatigue resistance of the EPDM/SBR blends were improved. The dynamic mechanical analysis and the morphological studies revealed that the addition of TESPT increased the weight of bound rubbers and provided better dispersion of carbon black, resulting in good mechanical properties such as tear strength and fatigue resistance of the vulcanized EPDM/SBR blends. The smaller particle of zinc oxide (i.e., 50 nm > 100 nm > 1000 nm) yielded to the better blending properties of the polymer blend.

Precise control of polymer coated nanopores by nanoparticle additives: Insights from computational modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eskandari Nasrabad, Afshin; Coalson, Rob D.; Jasnow, David

Polymer-nanoparticle composites are a promising new class of materials for creation of controllable nano-patterned surfaces and nanopores. We use coarse-grained molecular dynamics simulations augmented with analytical theory to study the structural transitions of surface grafted polymer layers (brushes) induced by infiltration of nanoparticles that are attracted to the polymers in the layer. We systematically compare two different polymer brush geometries: one where the polymer chains are grafted to a planar surface and the other where the chains are grafted to the inside of a cylindrical nanochannel. We perform a comprehensive study of the effects of the material parameters such asmore » the polymer chain length, chain grafting density, nanoparticle size, strength of attraction between nanoparticles and polymer monomers, and, in the case of the cylindrically grafted brush, the radius of the cylinder. We find a very general behavioral motif for all geometries and parameter values: the height of the polymer brush is non-monotonic in the nanoparticle concentration in solution. As the nanoparticle concentration increases, the brush height first decreases and after passing through a minimum value begins to increase, resulting in the swelling of the nanoparticle infused brush. These morphological features may be useful for devising tunable “smart” nano-devices whose effective dimensions can be reversibly and precisely adjusted by changing the nanoparticle concentration in solution. The results of approximate Self-Consistent Field Theory (SCFT) calculations, applicable in the regime of strong brush stretching, are compared to the simulation results. The SCFT calculations are found to be qualitatively, even semi-quantitatively, accurate when applied within their intended regime of validity, and provide a useful and efficient tool for modeling such materials.« less

Dynamic peptide libraries for the discovery of supramolecular nanomaterials

NASA Astrophysics Data System (ADS)

Pappas, Charalampos G.; Shafi, Ramim; Sasselli, Ivan R.; Siccardi, Henry; Wang, Tong; Narang, Vishal; Abzalimov, Rinat; Wijerathne, Nadeesha; Ulijn, Rein V.

2016-11-01

Sequence-specific polymers, such as oligonucleotides and peptides, can be used as building blocks for functional supramolecular nanomaterials. The design and selection of suitable self-assembling sequences is, however, challenging because of the vast combinatorial space available. Here we report a methodology that allows the peptide sequence space to be searched for self-assembling structures. In this approach, unprotected homo- and heterodipeptides (including aromatic, aliphatic, polar and charged amino acids) are subjected to continuous enzymatic condensation, hydrolysis and sequence exchange to create a dynamic combinatorial peptide library. The free-energy change associated with the assembly process itself gives rise to selective amplification of self-assembling candidates. By changing the environmental conditions during the selection process, different sequences and consequent nanoscale morphologies are selected.

Dynamic peptide libraries for the discovery of supramolecular nanomaterials.

PubMed

Pappas, Charalampos G; Shafi, Ramim; Sasselli, Ivan R; Siccardi, Henry; Wang, Tong; Narang, Vishal; Abzalimov, Rinat; Wijerathne, Nadeesha; Ulijn, Rein V

2016-11-01

Sequence-specific polymers, such as oligonucleotides and peptides, can be used as building blocks for functional supramolecular nanomaterials. The design and selection of suitable self-assembling sequences is, however, challenging because of the vast combinatorial space available. Here we report a methodology that allows the peptide sequence space to be searched for self-assembling structures. In this approach, unprotected homo- and heterodipeptides (including aromatic, aliphatic, polar and charged amino acids) are subjected to continuous enzymatic condensation, hydrolysis and sequence exchange to create a dynamic combinatorial peptide library. The free-energy change associated with the assembly process itself gives rise to selective amplification of self-assembling candidates. By changing the environmental conditions during the selection process, different sequences and consequent nanoscale morphologies are selected.

Solvent Effects of Model Polymeric Corrosion Control Coatings on Water Transport and Corrosion Rate

NASA Astrophysics Data System (ADS)

Konecki, Christina

Industrial coating formulations are often made for volatile organic content compliance and ease of application, with little regard for the solvent impact on resultant performance characteristics. Our research objective was to understand the effect of both solvent retention and chemical structure on water transport through polymer films and resultant corrosion area growth of coated steel substrates. A clear, unpigmented Phenoxy(TM) thermoplastic polymer (PKHH) was formulated into resin solutions with three separate solvent blends selected by Hansen solubility parameter (HSP), boiling point, and ability to solubilize PKHH. Polymer films cast from MEK/PGME (methyl ethyl ketone/ propylene glycol methyl ether), dried under ambient conditions (AMB, > 6wt.% residual solvent) produced a porous morphology, which resulted in a corrosion area greater than 50%. We attributed this to the water-soluble solvent used in film preparation, which enabled residual PGME to be extracted by water. The resin solution prepared with CYCOH/DXL (Cyclohexanol/ 1,3 dioxolane) was selected because CYCOH is a solid at room temperature which acts as a pigment in the final film. Therefore, increasing the tortuosity of water transport, as well as a high hydrogen bonding character, which caused more interactions with water, slowing diffusion, producing a nodular morphology, and 37% less corrosion area than MEK/PGME AMB. The HSP of PKHH and EEP (ethyl 3-ethoxypropionate) are within 5% of each other, which produced a homogeneous morphology and resulted in comparable corrosion rates regardless of residual solvent content. We utilized electrochemical techniques and attenuated total reflectance- Fourier transform infrared spectroscopy to elucidate dynamic water absorption and solvent extraction in the exposed model formulations. We found that water absorption resulted in a loss of barrier properties, and increased corrosion due to the voids formed by solvent extraction. The polymer films were rejuvenated (removal of water) as an attempt to decrease the number of water transport pathways during exposure. Results found that samples rejuvenated at temperatures above the glass transition temperature of the samples achieved lower moisture content and consequently, lower corrosion growth rates. In commercial systems, rejuvenation lowered the corrosion rate up to 60% indicating better coating formulations and maintenance cycles would control the corrosion rate.

Atomic Oxygen Textured Polymers

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Rutledge, Sharon K.; Hunt, Jason D.; Drobotij, Erin; Cales, Michael R.; Cantrell, Gidget

1995-01-01

Atomic oxygen can be used to microscopically alter the surface morphology of polymeric materials in space or in ground laboratory facilities. For polymeric materials whose sole oxidation products are volatile species, directed atomic oxygen reactions produce surfaces of microscopic cones. However, isotropic atomic oxygen exposure results in polymer surfaces covered with lower aspect ratio sharp-edged craters. Isotropic atomic oxygen plasma exposure of polymers typically causes a significant decrease in water contact angle as well as altered coefficient of static friction. Such surface alterations may be of benefit for industrial and biomedical applications. The results of atomic oxygen plasma exposure of thirty-three (33) different polymers are presented, including typical morphology changes, effects on water contact angle, and coefficient of static friction.

Anomalous charge transport in conjugated polymers reveals underlying mechanisms of trapping and percolation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mollinger, Sonya A.; Salleo, Alberto; Spakowitz, Andrew J.

While transport in conjugated polymers has many similarities to that in crystalline inorganic materials, several key differences reveal the unique relationship between the morphology of polymer films and the charge mobility. We develop a model that directly incorporates the molecular properties of the polymer film and correctly predicts these unique transport features. At low degree of polymerization, the increase of the mobility with the polymer chain length reveals trapping at chain ends, and saturation of the mobility at high degree of polymerization results from conformational traps within the chains. Similarly, the inverse field dependence of the mobility reveals that transportmore » on single polymer chains is characterized by the ability of the charge to navigate around kinks and loops in the chain. Lastly, these insights emphasize the connection between the polymer conformations and the transport and thereby offer a route to designing improved device morphologies through molecular design and materials processing.« less

Anomalous charge transport in conjugated polymers reveals underlying mechanisms of trapping and percolation

DOE PAGES

Mollinger, Sonya A.; Salleo, Alberto; Spakowitz, Andrew J.

2016-11-10

While transport in conjugated polymers has many similarities to that in crystalline inorganic materials, several key differences reveal the unique relationship between the morphology of polymer films and the charge mobility. We develop a model that directly incorporates the molecular properties of the polymer film and correctly predicts these unique transport features. At low degree of polymerization, the increase of the mobility with the polymer chain length reveals trapping at chain ends, and saturation of the mobility at high degree of polymerization results from conformational traps within the chains. Similarly, the inverse field dependence of the mobility reveals that transportmore » on single polymer chains is characterized by the ability of the charge to navigate around kinks and loops in the chain. Lastly, these insights emphasize the connection between the polymer conformations and the transport and thereby offer a route to designing improved device morphologies through molecular design and materials processing.« less

Distinguishing the importance of fullerene phase separation from polymer ordering in the performance of low band gap polymer: Bis-fullerene heterojunctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Huipeng; Hsiao, Yu -Che; Chen, Jihua

2014-09-16

It is known, one way to improve power conversion efficiency (PCE) of polymer based bulk-heterojunction (BHJ) photovoltaic cells is to increase the open circuit voltage (V oc). Replacing PCBM with bis-adduct fullerenes significantly improves V oc and the PCE in devices based on the conjugated polymer poly(3-hexyl thiophene) (P3HT). However, for the most promising low band-gap polymer (LBP) system, replacing PCBM with ICBA results in poor short-circuit current (J sc) and PCE although V oc is significantly improved. The optimization of the morphology of as-cast LBP/bis-fullerene BHJ photovoltaics is attempted by adding a co-solvent to the polymer/fullerene solution prior tomore » film deposition. Varying the solubility of polymer and fullerene in the co-solvent, bulk heterojunctions are fabricated with no change of polymer ordering, but with changes in fullerene phase separation. The morphologies of the as-cast samples are characterized by small angle neutron scattering and neutron reflectometry. A homogenous dispersion of ICBA in LBP is found in the samples where the co-solvent is selective to the polymer, giving poor device performance. Aggregates of ICBA are formed in samples where the co-solvent is selective to ICBA. Furthermore, the resultant morphology improves PCE by up to 246%. Finally, a quantitative analysis of the neutron data shows that the interfacial area between ICBA aggregates and its surrounding matrix is improved, facilitating charge transport and improving the PCE.« less

Hydration-Induced Phase Separation in Amphiphilic Polymer Matrices and its Influence on Voclosporin Release

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khan, I. John; Murthy, N. Sanjeeva; Kohn, Joachim

2015-10-30

Voclosporin is a highly potent, new cyclosporine -- a derivative that is currently in Phase 3 clinical trials in the USA as a potential treatment for inflammatory diseases of the eye. Voclosporin represents a number of very sparingly soluble drugs that are difficult to administer. It was selected as a model drug that is dispersed within amphiphilic polymer matrices, and investigated the changing morphology of the matrices using neutron and x-ray scattering during voclosporin release and polymer resorption. The hydrophobic segments of the amphiphilic polymer chain are comprised of desaminotyrosyl-tyrosine ethyl ester (DTE) and desaminotyrosyl-tyrosine (DT), and the hydrophilic componentmore » is poly(ethylene glycol) (PEG). Water uptake in these matrices resulted in the phase separation of hydrophobic and hydrophilic domains that are a few hundred Angstroms apart. These water-driven morphological changes influenced the release profile of voclosporin and facilitated a burst-free release from the polymer. No such morphological reorganization was observed in poly(lactide-co-glycolide) (PLGA), which exhibits an extended lag period, followed by a burst-like release of voclosporin when the polymer was degraded. An understanding of the effect of polymer composition on the hydration behavior is central to understanding and controlling the phase behavior and resorption characteristics of the matrix for achieving long-term controlled release of hydrophobic drugs such as voclosporin.« less

Neutrophils establish rapid and robust WAVE complex polarity in an actin-dependent fashion.

PubMed

Millius, Arthur; Dandekar, Sheel N; Houk, Andrew R; Weiner, Orion D

2009-02-10

Asymmetric intracellular signals enable cells to migrate in response to external cues. The multiprotein WAVE (also known as SCAR or WASF) complex activates the actin-nucleating Arp2/3 complex [1-4] and localizes to propagating "waves," which direct actin assembly during neutrophil migration [5, 6]. Here, we observe similar WAVE complex dynamics in other mammalian cells and analyze WAVE complex dynamics during establishment of neutrophil polarity. Earlier models proposed that spatially biased generation [7] or selection of protrusions [8] enables chemotaxis. These models require existing morphological polarity to control protrusions. We show that spatially biased generation and selection of WAVE complex recruitment also occur in morphologically unpolarized neutrophils during development of their first protrusions. Additionally, several mechanisms limit WAVE complex recruitment during polarization and movement: Intrinsic cues restrict WAVE complex distribution during establishment of polarity, and asymmetric intracellular signals constrain it in morphologically polarized cells. External gradients can overcome both intrinsic biases and control WAVE complex localization. After latrunculin-mediated inhibition of actin polymerization, addition and removal of agonist gradients globally recruits and releases the WAVE complex from the membrane. Under these conditions, the WAVE complex no longer polarizes, despite the presence of strong external gradients. Thus, actin polymer and the WAVE complex reciprocally interact during polarization.

Zirconium tungstate/epoxy nanocomposites: effect of nanoparticle morphology and negative thermal expansivity.

PubMed

Wu, Hongchao; Rogalski, Mark; Kessler, Michael R

2013-10-09

The ability to tailor the coefficient of thermal expansion (CTE) of a polymer is essential for mitigating thermal residual stress and reducing microcracks caused by CTE mismatch of different components in electronic applications. This work studies the effect of morphology and thermal expansivity of zirconium tungstate nanoparticles on the rheological, thermo-mechanical, dynamic-mechanical, and dielectric properties of ZrW2O8/epoxy nanocomposites. Three types of ZrW2O8 nanoparticles were synthesized under different hydrothermal conditions and their distinct properties were characterized, including morphology, particle size, aspect ratio, surface area, and CTE. Nanoparticles with a smaller particle size and larger surface area led to a more significant reduction in gel-time and glass transition temperature of the epoxy nanocomposites, while a higher initial viscosity and significant shear thinning behavior was found in prepolymer suspensions containing ZrW2O8 with larger particle sizes and aspect ratios. The thermo- and dynamic-mechanical properties of epoxy-based nanocomposites improved with increasing loadings of the three types of ZrW2O8 nanoparticles. In addition, the introduced ZrW2O8 nanoparticles did not negatively affect the dielectric constant or the breakdown strength of the epoxy resin, suggesting potential applications of ZrW2O8/epoxy nanocomposites in the microelectronic insulation industry.

Comparison of the Morphology Development of Polymer-Fullerene and Polymer-Polymer Solar Cells during Solution-Shearing Blade Coating

DOE PAGES

Gu, Xiaodan; Yan, Hongping; Kurosawa, Tadanori; ...

2016-08-22

Here in this work, the detailed morphology studies of polymer poly(3-hexylthiophene-2,5-diyl) (P3HT):fullerene(PCBM) and polymer(P3HT):polymer naphthalene diimide thiophene (PNDIT) solar cell are presented to understand the challenge for getting high performance all-polymer solar cells. The in situ X-ray scattering and optical interferometry and ex situ hard and soft X-ray scattering and imaging techniques are used to characterize the bulk heterojunction (BHJ) ink during drying and in dried state. The crystallization of P3HT polymers in P3HT:PCBM bulk heterojunction shows very different behavior compared to that of P3HT:PNDIT BHJ due to different mobilities of P3HT in the donor:acceptor glass. Supplemented by the exmore » situ grazing incidence X-ray diffraction and soft X-ray scattering, PNDIT has a lower tendency to form a mixed phase with P3HT than PCBM, which may be the key to inhibit the donor polymer crystallization process, thus creating preferred small phase separation between the donor and acceptor polymer.« less

Characterization and modeling of viscoelastic behavior of carbon nanotube reinforced polymers: The influence of interphase and nanotube morphology

NASA Astrophysics Data System (ADS)

Liu, Hua

The addition of nanoparticles into polymer materials has been observed to dramatically change the mechanical, thermal, electrical, and diffusion properties of the host polymers, promising a novel class of polymer matrix composite materials with superior properties and added functionalities that are ideal candidates in many applications, including aerospace, automobile, medical devices, and sporting goods. Understanding the behavior and underlying mechanisms of these polymer nanocomposites is critical. The research work presented in this dissertation represents one of the initial efforts in the long journey pursuing the ultimate understanding of nanoparticle reinforced polymer systems. Particular focal points are experimental evaluation and the development of appropriate modeling methods to capture the influence of the interphase on the overall viscoelastic behavior of carbon nanotube reinforced polymer nanocomposites. The first portion of this dissertation study investigates the viscoelastic behavior of MWCNT based PMMA nanocomposites, which complements our previous study of SWCNT/PMMA systems to confirm functionalization of nanotubes as an effective way to manipulate the interaction between nanotube and polymers and control the properties of the interphase region forming around the nanotubes and consequently change the overall performance of nanotube based polymer nanocomposites. In the second portion of this dissertation, we present a novel hybrid numerical-analytical modeling method that is capable of predicting viscoelastic behavior of multiphase polymer nanocomposites, in which the nanoscopic fillers can assume complex configurations. By combining the finite element technique and a micromechanical approach (particularly, the Mori-Tanaka method) with local phase properties, this method operates at low computational cost and effectively accounts for the influence of the interphase as well as in situ nanoparticle morphology. This modeling method is implemented two-dimensionally on nanotube and nanoplatelet based polymer nanocomposites. Given the experimentally measured frequency domain response of the bulk polymer, the viscoelastic behavior of the nanocomposites in both frequency and temperature domains can be calculated. The predicted pattern of influence of the interphase on the overall performance of the nanocomposites is consistent with the experimental observation. 3D parametric studies utilizing this modeling technique reveal that the nanotube morphology "modifies" the effect of interphase and hence profoundly influences the overall viscoelastic behavior. The findings help explain some experimental observations and furthermore, draw attention to the importance of morphology control through appropriate synthesis and processing techniques to further tune the thermomechanical behavior of the nanocomposites.

Structural and Interfacial Properties of Hyperbranched-Linear Polymer Surfactant.

PubMed

Qiang, Taotao; Bu, Qiaoqiao; Huang, Zhaofeng; Wang, Xuechuan

2014-01-01

With oleic acid grafting modification, a series of hyperbranched-linear polymer surfactants (HLPS) were prepared by hydroxyl-terminated hyperbranched polymer (HBP), which was gained through a step synthesis method using trimethylolpropane and AB 2 monomer. The AB 2 monomers were obtained through the Michael addition reaction of methyl acrylate and diethanol amine. The structures of HLPS were characterised by Fourier transform infrared spectrophotometer and nuclear magnetic resonance (NMR), which indicated that HBP was successfully modified by oleic acid. Furthermore, the properties of surface tension and critical micelle concentration of HLPS solution showed that HLPS can significantly reduce the surface tension of water. The morphology of the HLPS solution was characterised by dynamic light scattering, which revealed that HLPS exhibited a nonmonotonic appearance in particle size at different scattering angles owing to the different replaced linear portions. The relationships of the surface pressure to monolayer area and time were measured using the Langmuir-Blodgett instrument, which showed that the surface tension of monolayer molecules increased with the increasing of hydrophobic groups. In addition, the interface conditions of different replaced HLPS solutions were simulated.

Template-directed control of crystal morphologies.

PubMed

Meldrum, Fiona C; Ludwigs, Sabine

2007-02-12

Biominerals are characterised by unique morphologies, and it is a long-term synthetic goal to reproduce these synthetically. We here apply a range of templating routes to investigate whether a fascinating category of biominerals, the single crystals with complex forms, can be produced using simple synthetic methods. Macroporous crystals with sponge-like morphologies identical to that of sea urchin skeletal plates were produced on templating with a sponge-like polymer membrane. Similarly, patterning of individual crystal faces was achieved from the micrometer to nanometer scale through crystallisation on colloidal particle monolayers and patterned polymer thin films. These experiments demonstrate the versatility of a templating approach to producing single crystals with unique morphologies.

Mineralized polymer composites as biogenic bone substitute material

NASA Astrophysics Data System (ADS)

Shah, Rushita; Saha, Nabanita; Kitano, Takeshi; Saha, Petr

2015-05-01

Mineralized polymer composites (MPC) are recognized as potential fillers of bone defects. Though bioceramics exhibits quite a good bone-bonding and vascularization, it is considered to be too stiff and brittle for using alone. Thus, the use of polymer scaffold instead of bioceramics has several advantages including combining the osteoconductivity and bone-bonding potential of the inorganic phase with the porosity and interconnectivity of the three-dimensional construction. Aiming the advantages of ceramic-polymer composite scaffolds, the calcium carbonate (CaCO3) based biomineralized scaffold was prepared, where the PVP-CMC hydrogel was used as an extracellular matrix. This paper is reported about the morphology, swelling trend (in physiological solution) and viscoelastic behavior of (90 min mineralized) MPC. The dry MPC are off-white, coarse in texture, comparatively less flexible than the original PVP-CMC based hydrogel film, and the deposition of granular structures on the surface of the hydrogel film confirms about the development of biomineralized scaffold/polymer composites. Irrespective of thickness, the dry MPC shows higher values of swelling ratio within 30 min, which varies between 200-250 approximately. The dynamic viscoelastic nature of freshly prepared MPC was investigated applying 1% and 10% strain. At higher strain the viscoelastic moduli (G' and G") show significant change, and the nature of MPC turns from elastic to viscous. Based on the observed basic properties, the MPC (calcite based polymer composites) can be recommended for the treatment of adyanamic bone disorder.

Nanoscale morphogenesis of nylon-sputtered plasma polymer particles

NASA Astrophysics Data System (ADS)

Choukourov, Andrei; Shelemin, Artem; Pleskunov, Pavel; Nikitin, Daniil; Khalakhan, Ivan; Hanuš, Jan

2018-05-01

Sub-micron polymer particles are highly important in various fields including astrophysics, thermonuclear fusion and nanomedicine. Plasma polymerization offers the possibility to produce particles with tailor-made size, crosslink density and chemical composition to meet the requirements of a particular application. However, the mechanism of nucleation and growth of plasma polymer particles as well as diversity of their morphology remain far from being clear. Here, we prepared nitrogen-containing plasma polymer particles by rf magnetron sputtering of nylon in a gas aggregation cluster source with variable length. The method allowed the production of particles with roughly constant chemical composition and number density but with the mean size changing from 80 to 320 nm. Atomic Force Microscopy with super-sharp probes was applied to study the evolution of the particle surface topography as they grow in size. Height–height correlation and power spectral density functions were obtained to quantify the roughness exponent α  =  0.78, the growth exponent β  =  0.35, and the dynamic exponent 1/z  =  0.50. The set of critical exponents indicates that the particle surface evolves in a self-affine mode and the overall particle growth is caused by the accretion of polymer-forming species from the gas phase and not by coagulation. Redistribution of the incoming material over the surface coupled with the inhomogeneous distribution of inner stress is suggested as the main factor that determines the morphogenesis of the plasma polymer particles.

Nanostructural self-organization and dynamic adaptation of metal-polymer tribosystems

NASA Astrophysics Data System (ADS)

Mashkov, Yu. K.

2017-02-01

The results of investigating the effect of nanosize modifiers of a polymer matrix on the nanostructural self-organization of polymer composites and dynamic adaptation of metal-polymer tribosystems, which considerably affect the wear resistance of polymer composite materials, have been analyzed. It has been shown that the physicochemical nanostructural self-organization processes are developed in metal-polymer tribosystems with the formation of thermotropic liquid-crystal structures of the polymer matrix, followed by the transition of the system to the stationary state with a negative feedback that ensures dynamic adaptation of the tribosystem to given operating conditions.

Dynamics of Nanoparticles in Entangled Polymer Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nath, Pooja; Mangal, Rahul; Kohle, Ferdinand

The mean square displacement < r 2 > of nanoparticle probes dispersed in simple isotropic liquids and in polymer solutions is interrogated using fluorescence correlation spectroscopy and single-particle tracking (SPT) experiments. Probe dynamics in different regimes of particle diameter (d), relative to characteristic polymer length scales, including the correlation length (ξ), the entanglement mesh size (a), and the radius of gyration (R g), are investigated. In simple fluids and for polymer solutions in which d >> R g, long-time particle dynamics obey random-walk statistics < r 2 >:t, with the bulk zero-shear viscosity of the polymer solution determining the frictionalmore » resistance to particle motion. In contrast, in polymer solutions with d < R g, polymer molecules in solution exert noncontinuum resistances to particle motion and nanoparticle probes appear to interact hydrodynamically only with a local fluid medium with effective drag comparable to that of a solution of polymer chain segments with sizes similar to those of the nanoparticle probes. Under these conditions, the nanoparticles exhibit orders of magnitude faster dynamics than those expected from continuum predictions based on the Stokes–Einstein relation. SPT measurements further show that when d > a, nanoparticle dynamics transition from diffusive to subdiffusive on long timescales, reminiscent of particle transport in a field with obstructions. This last finding is in stark contrast to the nanoparticle dynamics observed in entangled polymer melts, where X-ray photon correlation spectroscopy measurements reveal faster but hyperdiffusive dynamics. As a result, we analyze these results with the help of the hopping model for particle dynamics in polymers proposed by Cai et al. and, on that basis, discuss the physical origins of the local drag experienced by the nanoparticles in entangled polymer solutions.« less

Dynamics of Nanoparticles in Entangled Polymer Solutions

DOE PAGES

Nath, Pooja; Mangal, Rahul; Kohle, Ferdinand; ...

2017-12-01

The mean square displacement < r 2 > of nanoparticle probes dispersed in simple isotropic liquids and in polymer solutions is interrogated using fluorescence correlation spectroscopy and single-particle tracking (SPT) experiments. Probe dynamics in different regimes of particle diameter (d), relative to characteristic polymer length scales, including the correlation length (ξ), the entanglement mesh size (a), and the radius of gyration (R g), are investigated. In simple fluids and for polymer solutions in which d >> R g, long-time particle dynamics obey random-walk statistics < r 2 >:t, with the bulk zero-shear viscosity of the polymer solution determining the frictionalmore » resistance to particle motion. In contrast, in polymer solutions with d < R g, polymer molecules in solution exert noncontinuum resistances to particle motion and nanoparticle probes appear to interact hydrodynamically only with a local fluid medium with effective drag comparable to that of a solution of polymer chain segments with sizes similar to those of the nanoparticle probes. Under these conditions, the nanoparticles exhibit orders of magnitude faster dynamics than those expected from continuum predictions based on the Stokes–Einstein relation. SPT measurements further show that when d > a, nanoparticle dynamics transition from diffusive to subdiffusive on long timescales, reminiscent of particle transport in a field with obstructions. This last finding is in stark contrast to the nanoparticle dynamics observed in entangled polymer melts, where X-ray photon correlation spectroscopy measurements reveal faster but hyperdiffusive dynamics. As a result, we analyze these results with the help of the hopping model for particle dynamics in polymers proposed by Cai et al. and, on that basis, discuss the physical origins of the local drag experienced by the nanoparticles in entangled polymer solutions.« less

TOPICAL REVIEW: Monitoring of polymer melt processing

NASA Astrophysics Data System (ADS)

Alig, Ingo; Steinhoff, Bernd; Lellinger, Dirk

2010-06-01

The paper reviews the state-of-the-art of in-line and on-line monitoring during polymer melt processing by compounding, extrusion and injection moulding. Different spectroscopic and scattering techniques as well as conductivity and viscosity measurements are reviewed and compared concerning their potential for different process applications. In addition to information on chemical composition and state of the process, the in situ detection of morphology, which is of specific interest for multiphase polymer systems such as polymer composites and polymer blends, is described in detail. For these systems, the product properties strongly depend on the phase or filler morphology created during processing. Examples for optical (UV/vis, NIR) and ultrasonic attenuation spectra recorded during extrusion are given, which were found to be sensitive to the chemical composition as well as to size and degree of dispersion of micro or nanofillers in the polymer matrix. By small-angle light scattering experiments, process-induced structures were detected in blends of incompatible polymers during compounding. Using conductivity measurements during extrusion, the influence of processing conditions on the electrical conductivity of polymer melts with conductive fillers (carbon black or carbon nanotubes) was monitored.

H-aggregate analysis of P3HT thin films-Capability and limitation of photoluminescence and UV/Vis spectroscopy.

PubMed

Ehrenreich, Philipp; Birkhold, Susanne T; Zimmermann, Eugen; Hu, Hao; Kim, Kwang-Dae; Weickert, Jonas; Pfadler, Thomas; Schmidt-Mende, Lukas

2016-09-01

Polymer morphology and aggregation play an essential role for efficient charge carrier transport and charge separation in polymer-based electronic devices. It is a common method to apply the H-aggregate model to UV/Vis or photoluminescence spectra in order to analyze polymer aggregation. In this work we present strategies to obtain reliable and conclusive information on polymer aggregation and morphology based on the application of an H-aggregate analysis on UV/Vis and photoluminescence spectra. We demonstrate, with P3HT as model system, that thickness dependent reflection behavior can lead to misinterpretation of UV/Vis spectra within the H-aggregate model. Values for the exciton bandwidth can deviate by a factor of two for polymer thicknesses below 150 nm. In contrast, photoluminescence spectra are found to be a reliable basis for characterization of polymer aggregation due to their weaker dependence on the wavelength dependent refractive index of the polymer. We demonstrate this by studying the influence of surface characteristics on polymer aggregation for spin-coated thin-films that are commonly used in organic and hybrid solar cells.

Morphology of Block Copolymer Electrolytes: A Numerical Self-Consistent Field Theory Study

NASA Astrophysics Data System (ADS)

Hou, Kevin; Qin, Jian

Engineering the morphology of ion-containing block copolymers is imperative for the optimization of their charge-transport and mechanical properties. Existing experiments have demonstrated that the addition of ions has a dramatic effect on the morphology and thermodynamic behavior of these structured electrolytes. We have developed an efficient, symmetry-adapted algorithm to calculate the ionic interactions in the SCFT for ion-containing polymers. We present the results of a numerical SCFT study examining how dielectric heterogeneity, ion concentration, and ion solvation affect morphology, domain spacing, ion distribution, and polymer density profiles. Particular attention is given to the detailed morphological analysis of the bicontinuous gyroidal phase, as well as the relevance of the aforementioned results to ionic conductivity.

Assessment of femtosecond laser induced periodic surface structures on polymer films.

PubMed

Rebollar, Esther; Vázquez de Aldana, Javier R; Martín-Fabiani, Ignacio; Hernández, Margarita; Rueda, Daniel R; Ezquerra, Tiberio A; Domingo, Concepción; Moreno, Pablo; Castillejo, Marta

2013-07-21

In this work we present the formation of laser induced periodic surface structures (LIPSS) on spin-coated thin films of several model aromatic polymers including poly(ethylene terephthalate), poly(trimethylene terephthalate) and poly carbonate bis-phenol A upon irradiation with femtosecond pulses of 795 and 265 nm at fluences well below the ablation threshold. LIPSS are formed with period lengths similar to the laser wavelength and parallel to the direction of the laser polarization vector. Formation of LIPSS upon IR irradiation at 795 nm, a wavelength at which the polymers absorb weakly, contrasts with the absence of LIPSS in this spectral range upon irradiation with nanosecond pulses. Real and reciprocal space characterization of LIPSS obtained by Atomic Force Microscopy (AFM) and Grazing Incidence Small Angle X-ray Scattering (GISAXS), respectively, yields well correlated morphological information. Comparison of experimental and simulated GISAXS patterns suggests that LIPSS can be suitably described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice. Fluorescence measurements, after laser irradiation, provide indirect information about dynamics and structure of the polymer at the molecular level. Our results indicate that the LIPSS are formed by interference of the incident and surface scattered waves. As a result of this process, heating of the polymer surface above its glass transition temperature takes place enabling LIPSS formation.

Optical, thermal and morphological study of ZnS doped PVA polymer nano composites

NASA Astrophysics Data System (ADS)

Guruswamy, B.; Ravindrachary, V.; Shruthi, C.; Sagar, Rohan N.; Hegde, Shreedatta

2018-05-01

The effect of ZnS nano particle doping on optical, thermal properties and morphological study of the PVA polymer has been investigated using FTIR, UV-Visible and TGA, FESEM techniques. Nano sized ZnS particles were synthesized by a simple wet chemical route. Pure and ZnS/PVA nano composites were prepared using solution casting technique. The FTIR study confirms that the ZnS nano particles interacts with the OH group of PVA polymer and forms the complex. The formation of these complexes affects the optical and thermal properties of the composite. The changes in optical properties were studied using UV-Vis absorption method. The variation in thermal property was analysed using TGA results. The modified surface morphology analysis was carried out using FESEM.

Dynamers: Polyacylhydrazone reversible covalent polymers, component exchange, and constitutional diversity

PubMed Central

Skene, Williams G.; Lehn, Jean-Marie P.

2004-01-01

Component exchange in reversible polymers allows the generation of dynamic constitutional diversity. The polycondensation of dihydrazides with dialdehydes generates polyacylhydrazones, to which the acylhydrazone functionality formed confers both hydrogen-bonding and reversibility features through the amide and imine groups, respectively. Polyacylhydrazones are thus dynamic polyamides. They are able to reversibly exchange either one or both of their repeating monomer units in the presence of different monomers, thus presenting constitutional dynamic diversity. The polymers subjected to monomer exchange/interchange may be brought to exhibit physical properties vastly different from those of the original polymer. The principle may be extended to other important classes of polymers, giving access, for instance, to dynamic polyureas or polycarbamates. These reversible polymers are therefore able to incorporate, decorporate, or reshuffle their constituting monomers, namely in response to environmental physical or chemical factors, an adaptability feature central to constitutional dynamic chemistry. PMID:15150411

Integration of motor proteins - towards an ATP fueled soft actuator.

PubMed

Kakugo, Akira; Shikinaka, Kazuhiro; Gong, Jian Ping

2008-09-01

We present a soft bio-machine constructed from biological motors (actin/myosin). We have found that chemically cross-linked polymer-actin complex gel filaments can move on myosin coated surfaces with a velocity as high as that of native F-actin, by coupling to ATP hydrolysis. Additionally, it is shown that the velocity of polymer-actin complex gel depends on the species of polycations binding to the F-actins. Since the design of functional actuators of well-defined size and morphology is important, the structural behavior of polymer-actin complexes has been investigated. Our results show that the morphology and growth size of polymer-actin complex can be controlled by changes in the electrostatic interactions between F-actins and polycations. Our results indicate that bio actuators with desired shapes can be created by using a polymer-actin complex.

Influence of electron beam irradiation on the microrheology of incompatible polymer blends: Thread break-up and coalescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Gisbergen, J.G.M.; Meijer, H.E.H.

1991-01-01

The microrheology of polymer blends as influenced by crosslinks induced in the dispersed phase via electron beam irradiation, is systematically investigated for the model system polystyrene/low density polyethylene (PS/LDPE). Both break-up of threads and coalescence of particles are delayed to a large extent, but are not inhibited completely and occur faster than would be expected for a nonirradiated material with a comparable viscosity. Small amplitude, dynamic rheological measurements indicated that in the irradiated materials a yield stress could exist. In contrast, direct microrheological measurements showed that this yield stress, which would prevent both break-up and coalescence, could not be realizedmore » by EB irradiation. Apparently, the direct study of the microrheology of a blend system is important for the prediction of the development of its morphology and it is not possible to rely only on rheological data obtained via other methods.« less

Charged triblock copolymer self-assembly into charged micelles

NASA Astrophysics Data System (ADS)

Chen, Yingchao; Zhang, Ke; Zhu, Jiahua; Wooley, Karen; Pochan, Darrin; Department of Material Science; Engineering University of Delaware Team; Department of Chemistry Texas A&M University Collaboration

2011-03-01

Micelles were formed through the self-assembly of amphiphlic block copolymer poly(acrylic acid)-block-poly(methyl acrylate)-block-polystyrene (PAA-PMA-PS). ~Importantly, the polymer is complexed with diamine molecules in pure THF solution prior to water titration solvent processing-a critical aspect in the control of final micelle geometry. The addition of diamine triggers acid-base complexation ~between the carboxylic acid PAA side chains and amines. ~Remarkably uniform spheres were found to form close-packed patterns when forced into dried films and thin, solvated films when an excess of amine was used in the polymer assembly process. Surface properties and structural features of these hexagonal-packed spherical micelles with charged corona have been explored by various characterization methods including Transmission Electron Microscopy (TEM), cryogenic TEM, z-potential analysis and Dynamic Light Scattering. The forming mechanism for this pattern and morphology changes against external stimulate such as salt will be discussed.

Experimental mixture design as a tool for the synthesis of antimicrobial selective molecularly imprinted monodisperse microbeads.

PubMed

Benito-Peña, Elena; Navarro-Villoslada, Fernando; Carrasco, Sergio; Jockusch, Steffen; Ottaviani, M Francesca; Moreno-Bondi, Maria C

2015-05-27

The effect of the cross-linker on the shape and size of molecular imprinted polymer (MIP) beads prepared by precipitation polymerization has been evaluated using a chemometric approach. Molecularly imprinted microspheres for the selective recognition of fluoroquinolone antimicrobials were prepared in a one-step precipitation polymerization procedure using enrofloxacin (ENR) as the template molecule, methacrylic acid as functional monomer, 2-hydroxyethyl methacrylate as hydrophilic comonomer, and acetonitrile as the porogen. The type and amount of cross-linker, namely ethylene glycol dimethacrylate, divinylbenzene or trimethylolpropane trimethacrylate, to obtain monodispersed MIP spherical beads in the micrometer range was optimized using a simplex lattice design. Particle size and morphology were assessed by scanning electron microscopy, dynamic light scattering, and nitrogen adsorption measurements. Electron paramagnetic resonance spectroscopy in conjunction with a nitroxide as spin probe revealed information about the microviscosity and polarity of the binding sites in imprinted and nonimprinted polymer beads.

Responsive Guest Encapsulation of Dynamic Conjugated Microporous Polymers.

PubMed

Xu, Lai; Li, Youyong

2016-06-30

The host-guest complexes of conjugated microporous polymers encapsulating C60 and dye molecules have been investigated systematically. The orientation of guest molecules inside the cavities, have different terms: inside the open cavities of the polymer, or inside the cavities formed by packing different polymers. The host backbone shows responsive dynamic behavior in order to accommodate the size and shape of incoming guest molecule or guest aggregates. Simulations show that the host-guest binding of conjugated polymers is stronger than that of non-conjugated polymers. This detailed study could provide a clear picture for the host-guest interaction for dynamic conjugated microporous polymers. The mechanism obtained could guide designing new conjugated microporous polymers.

Microscopic mechanism for the effect of adding salt on electrospinning by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Wang, Bing-Bing; Wang, Xiao-Dong; Wang, Tian-Hu

2014-09-01

Adding salts into polymer solution has been found to modulate the fiber structure and significantly improve the solution spinnability in electrospinning. However, the mechanisms have not been fully understood. This work adopted molecular dynamics method to investigate the dynamic behavior of poly(ethylene oxide) (PEO)/water droplet with or without dissolved NaCl salt under high-voltage electric field. Our simulation results agreed with the previous experimental reports well. We observed that some daughter droplets detach from the mother droplet due to the ions evaporation and hydration effect, which significantly accelerates the water evaporation and hence improves the solution spinnability. We also observed that some sodium ions are always coordinated with the ether oxygen group in the PEO chain. When these ions are accelerated by the electric field, the PEO chain segments follow the motion of the ions, inevitably stretching the chain and improving the fiber morphology.

Microchannel fabrication on cyclic olefin polymer substrates via 1064 nm Nd:YAG laser ablation

NASA Astrophysics Data System (ADS)

McCann, Ronán; Bagga, Komal; Groarke, Robert; Stalcup, Apryll; Vázquez, Mercedes; Brabazon, Dermot

2016-11-01

This paper presents a method for fabrication of microchannels on cyclic olefin polymer films that have application in the field of microfluidics and chemical sensing. Continuous microchannels were fabricated on 188-μm-thick cyclic olefin polymer substrates using a picosecond pulsed 1064 nm Nd:YAG laser. The effect of laser fluence on the microchannel morphology and dimensions was analysed via scanning electron microscopy and optical profilometry. Single laser passes were found to produce v-shaped microchannels with depths ranging from 12 μm to 47 μm and widths from 44 μm to 154 μm. The ablation rate during processing was lower than predicted theoretically. Multiple laser passes were applied to examine the ability for finer control over microchannel morphology with channel depths ranging from 22 μm to 77 μm and channel widths from 59 μm to 155 μm. For up to five repeat passes, acceptable reproducibility was found in the produced microchannel morphology. Infrared spectroscopy revealed oxidation and dehydrogenation of the polymer surface following laser ablation. These results were compared to other work conducted on cyclic olefin polymers.

Thermo-reversible morphology and conductivity of a conjugated polymer network embedded in polymeric self-assembly

NASA Astrophysics Data System (ADS)

Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; Li, Yunchao; Hong, Kunlun; Sumpter, Bobby G.; Ohl, Michael; Paranthaman, Mariappan Parans; Smith, Gregory S.; Do, Changwoo

Self-assembly of block copolymers provides opportunities to create nano hybrid materials, utilizing self-assembled micro-domains with a variety of morphology and periodic architectures as templates for functional nano-fillers. Here we report new progress towards the fabrication of a thermally responsive conducting polymer self-assembly made from a water-soluble poly(thiophene) derivative with short PEO side chains and Pluronic L62 solution in water. The structural and electrical properties of conjugated polymer-embedded nanostructures were investigated by combining SANS, SAXS, CGMD simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellar-to-lamellar phase transition defines the embedded conjugated polymer network. The conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. The research was sponsored by the Scientific User Facilities Division, Office of BES, U.S. DOE and Laboratory Directed Research and Development Program of ORNL, managed by UT-Battelle, LLC.

Alternative Thieno[3,2-b][1]benzothiophene Isoindigo Polymers for Solar Cell Applications.

PubMed

Neophytou, Marios; Bryant, Daniel; Lopatin, Sergei; Chen, Hu; Hallani, Rawad K; Cater, Lewis; McCulloch, Iain; Yue, Wan

2018-03-05

This work reports the synthesis, characterization, photophysical, and photovoltaic properties of five new thieno[3,2-b][1]benzothiophene isoindigo (TBTI)-containing low bandgap donor-acceptor conjugated polymers with a series of comonomers and different side chains. When TBTI is combined with different electron-rich moieties, even small structural variations can have significant impact on thin film morphology of the polymer:phenyl C70 butyric acid methyl ester (PCBM) blends. More importantly, high-resolution electron energy loss spectroscopy is used to investigate the phase-separated bulk heterojunction domains, which can be accurately and precisely resolved, enabling an enhanced correlation between polymer chemical structure, photovoltaic device performance, and morphology. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Morphology and conductivity of PEO-based polymers having various end functional groups

NASA Astrophysics Data System (ADS)

Jung, Ha Young; Mandal, Prithwiraj; Park, Moon Jeong

Poly(ethylene oxide) (PEO)-based polymers have been considered most promising candidates of polymer electrolytes for lithium batteries owing to the high ionic conductivity of PEO/lithium salt complexes. This positive aspect prompted researchers to investigate PEO-containing block copolymers prepared by linking mechanically robust block to PEO covalently. Given that the microphase separation of block copolymers can affect both mechanical properties and ion transport properties, various strategies have been reported to tune the morphology of PEO-containing block copolymers. In the present study, we describe a simple means for modulating the morphologies of PEO-based block copolymers with an aim to improve ion transport properties. By varying terminal groups of PEO in block copolymers, the disordered morphology can be readily transformed into ordered lamellae or gyroid phases, depending on the type and number density of end group. In particular, the existence of terminal groups resulted in a large reduction in crystallinity of PEO chains and thereby increasing room temperature ionic conductivity.

Studies on the relation between the size and dispersion of metallic silver nanoparticles and morphologies of initial silver(I) coordination polymer precursor

NASA Astrophysics Data System (ADS)

Moradi, Zhaleh; Akhbari, Kamran; Phuruangrat, Anukorn; Costantino, Ferdinando

2017-04-01

Micro and nano-structures of [Ag2(μ2-dcpa)2]n (1), [Hdcpa = 2,4-dichlorophenoxyacetic acid] which is a one-dimensional coordination polymer with corrugated tape chains, were synthesized as the bulk sample (1B), by sonochemical process (1S) and from mechanochemical reaction (1M). These three samples have been used as new precursors for fabricating silver nanoparticles via direct calcination at 300 °C and also thermal decomposition in oleic acid (OA) as a surfactant at 180 °C. In the presence of OA less agglomerated nanostructures were formed. It seems that the size, dispersion, morphology and agglomeration of initial precursor have direct influence on size, dispersion, morphology and agglomeration of metallic silver. This coordination polymer with various micro and nano morphologies were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Thermal stability of these samples were studied and compared with each other, too.

Dynamic-template-directed multiscale assembly for large-area coating of highly-aligned conjugated polymer thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohammadi, Erfan; Zhao, Chuankai; Meng, Yifei

Solution processable semiconducting polymers have been under intense investigations due to their diverse applications from printed electronics to biomedical devices. However, controlling the macromolecular assembly across length scales during solution coating remains a key challenge, largely due to the disparity in timescales of polymer assembly and high-throughput printing/coating. Herein we propose the concept of dynamic templating to expedite polymer nucleation and the ensuing assembly process, inspired by biomineralization templates capable of surface reconfiguration. Molecular dynamic simulations reveal that surface reconfigurability is key to promoting template–polymer interactions, thereby lowering polymer nucleation barrier. Employing ionic-liquid-based dynamic template during meniscus-guided coating results inmore » highly aligned, highly crystalline donor-acceptor polymer thin films over large area (41cm 2) and promoted charge transport along both the polymer backbone and the π-π stacking direction in field-effect transistors. We further demonstrate that the charge transport anisotropy can be reversed by tuning the degree of polymer backbone alignment.« less

Dynamic-template-directed multiscale assembly for large-area coating of highly-aligned conjugated polymer thin films

PubMed Central

Mohammadi, Erfan; Zhao, Chuankai; Meng, Yifei; Qu, Ge; Zhang, Fengjiao; Zhao, Xikang; Mei, Jianguo; Zuo, Jian-Min; Shukla, Diwakar; Diao, Ying

2017-01-01

Solution processable semiconducting polymers have been under intense investigations due to their diverse applications from printed electronics to biomedical devices. However, controlling the macromolecular assembly across length scales during solution coating remains a key challenge, largely due to the disparity in timescales of polymer assembly and high-throughput printing/coating. Herein we propose the concept of dynamic templating to expedite polymer nucleation and the ensuing assembly process, inspired by biomineralization templates capable of surface reconfiguration. Molecular dynamic simulations reveal that surface reconfigurability is key to promoting template–polymer interactions, thereby lowering polymer nucleation barrier. Employing ionic-liquid-based dynamic template during meniscus-guided coating results in highly aligned, highly crystalline donor–acceptor polymer thin films over large area (>1 cm2) and promoted charge transport along both the polymer backbone and the π–π stacking direction in field-effect transistors. We further demonstrate that the charge transport anisotropy can be reversed by tuning the degree of polymer backbone alignment. PMID:28703136

Dynamic-template-directed multiscale assembly for large-area coating of highly-aligned conjugated polymer thin films

DOE PAGES

Mohammadi, Erfan; Zhao, Chuankai; Meng, Yifei; ...

2017-07-13

Solution processable semiconducting polymers have been under intense investigations due to their diverse applications from printed electronics to biomedical devices. However, controlling the macromolecular assembly across length scales during solution coating remains a key challenge, largely due to the disparity in timescales of polymer assembly and high-throughput printing/coating. Herein we propose the concept of dynamic templating to expedite polymer nucleation and the ensuing assembly process, inspired by biomineralization templates capable of surface reconfiguration. Molecular dynamic simulations reveal that surface reconfigurability is key to promoting template–polymer interactions, thereby lowering polymer nucleation barrier. Employing ionic-liquid-based dynamic template during meniscus-guided coating results inmore » highly aligned, highly crystalline donor-acceptor polymer thin films over large area (41cm 2) and promoted charge transport along both the polymer backbone and the π-π stacking direction in field-effect transistors. We further demonstrate that the charge transport anisotropy can be reversed by tuning the degree of polymer backbone alignment.« less

Long conducting polymer nanonecklaces with a `beads-on-a-string' morphology: DNA nanotube-template synthesis and electrical properties

NASA Astrophysics Data System (ADS)

Chen, Guofang; Mao, Chengde

2016-05-01

Complex and functional nanostructures are always desired. Herein, we present the synthesis of novel long conducting polymer nanonecklaces with a `beads-on-a-string' morphology by the DNA nanotube-template approach and in situ oxidative polymerization of the 3-methylthiophene monomer with FeCl3 as the oxidant/catalyst. The length of the nanonecklaces is up to 60 μm, and the polymer beads of around 20-25 nm in diameter are closely packed along the axis of the DNA nanotube template with a density of ca. 45 particles per μm. The formation of porous DNA nanotubes impregnated with FeCl3 was also demonstrated as intermediate nanostructures. The mechanisms for the formation of both the porous DNA nanotubes and the conducting polymer nanonecklaces are discussed in detail. The as-synthesized polymer/DNA nanonecklaces exhibit good electrical properties.Complex and functional nanostructures are always desired. Herein, we present the synthesis of novel long conducting polymer nanonecklaces with a `beads-on-a-string' morphology by the DNA nanotube-template approach and in situ oxidative polymerization of the 3-methylthiophene monomer with FeCl3 as the oxidant/catalyst. The length of the nanonecklaces is up to 60 μm, and the polymer beads of around 20-25 nm in diameter are closely packed along the axis of the DNA nanotube template with a density of ca. 45 particles per μm. The formation of porous DNA nanotubes impregnated with FeCl3 was also demonstrated as intermediate nanostructures. The mechanisms for the formation of both the porous DNA nanotubes and the conducting polymer nanonecklaces are discussed in detail. The as-synthesized polymer/DNA nanonecklaces exhibit good electrical properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01603k

Precise Side-Chain Engineering of Thienylenevinylene-Benzotriazole-Based Conjugated Polymers with Coplanar Backbone for Organic Field Effect Transistors and CMOS-like Inverters.

PubMed

Lee, Min-Hye; Kim, Juhwan; Kang, Minji; Kim, Jihong; Kang, Boseok; Hwang, Hansu; Cho, Kilwon; Kim, Dong-Yu

2017-01-25

Two donor-acceptor (D-A) alternating conjugated polymers based on thienylenevinylene-benzotriazole (TV-BTz), PTV6B with a linear side chain and PTVEhB with a branched side chain, were synthesized and characterized for organic field effect transistors (OFETs) and complementary metal-oxide-semiconductor (CMOS)-like inverters. According to density functional theory (DFT), polymers based on TV-BTz exhibit a coplanar and rigid structure with no significant twists, which could cause to an increase in charge-carrier mobility in OFETs. Alternating alkyl side chains of the polymers impacted neither the band gap nor the energy level. However, it significantly affected the morphology and crystallinity when the polymer films were thermally annealed. To investigate the effect of thermal annealing on the morphology and crystallinity, we characterized the polymer films using atomic force microscopy (AFM) and 2D-grazing incidence X-ray diffraction (2D-GIWAXD). Fibrillary morphologies with larger domains and increased crystallinity were observed in the polymer films after thermal annealing. These polymers exhibited improved charge-carrier mobilities in annealed films at 200 °C and demonstrated optimal OFET device performance with p-type transport characteristics with charge-carrier mobilities of 1.51 cm 2 /(V s) (PTV6B) and 2.58 cm 2 /(V s) (PTVEhB). Furthermore, CMOS-like inorganic (ZnO)-organic (PTVEhB) hybrid bilayer inverter showed that the inverting voltage (V inv ) was positioned near the ideal switching point at half (1/2) of supplied voltage (V DD ) due to fairly balanced p- and n-channels.

Effect of silica nanoparticle filler on microscopic polymer α-relaxation dynamics

NASA Astrophysics Data System (ADS)

Saito, Makina; Mashita, Ryo; Kishimoto, Hiroyuki; Masuda, Ryo; Yoda, Yoshitaka; Seto, Makoto

2017-11-01

Tyre rubber has been continuously developed to improve its performance, but the microscopic mechanisms behind these improvements, e.g. by adding nanoparticles to the rubber, are still not fully understood. We study the microscopic polymer dynamics of a rubber nanocomposite system consisting of polymer polybutadiene with 20 volume% of silica nanoparticles with diameters of 100 nm via quasi-elastic scattering experiments using gamma-ray time-domain interferometry. The result shows that the presence of silica nanoparticles caused the inter-chain α-relaxation dynamics to slow down in a shallowly supercooled state suggesting that the presence of the nanoparticles that came in contact with the polymer controlled the timescale of the polymer's α-relaxation dynamics. Conversely, the presence of nanoparticles less affects the dynamics in a lower temperature region near T g. It is consistent with the result of the differential scanning calorimetry study showing negligible T g difference among the pure polymer and the nanocomposite system. It also shows that the quasi-elastic scattering experiment can be used to reveal the polymer dynamics in nanocomposites and is appropriate for characterising their microscopic dynamics for the purpose of improving tyre performance.

Breaking the barriers of all-polymer solar cells: Solving electron transporter and morphology problems

NASA Astrophysics Data System (ADS)

Gavvalapalli, Nagarjuna

All-polymer solar cells (APSC) are a class of organic solar cells in which hole and electron transporting phases are made of conjugated polymers. Unlike polymer/fullerene solar cell, photoactive material of APSC can be designed to have hole and electron transporting polymers with complementary absorption range and proper frontier energy level offset. However, the highest reported PCE of APSC is 5 times less than that of polymer/fullerene solar cell. The low PCE of APSC is mainly due to: i) low charge separation efficiency; and ii) lack of optimal morphology to facilitate charge transfer and transport; and iii) lack of control over the exciton and charge transport in each phase. My research work is focused towards addressing these issues. The charge separation efficiency of APSC can be enhanced by designing novel electron transporting polymers with: i) broad absorption range; ii) high electron mobility; and iii) high dielectric constant. In addition to with the above parameters chemical and electronic structure of the repeating unit of conjugated polymer also plays a role in charge separation efficiency. So far only three classes of electron transporting polymers, CN substituted PPV, 2,1,3-benzothiadiazole derived polymers and rylene diimide derived polymers, are used in APSC. Thus to enhance the charge separation efficiency new classes of electron transporting polymers with the above characteristics need to be synthesized. I have developed a new straightforward synthetic strategy to rapidly generate new classes of electron transporting polymers with different chemical and electronic structure, broad absorption range, and high electron mobility from readily available electron deficient monomers. In APSCs due to low entropy of mixing, polymers tend to micro-phase segregate rather than forming the more useful nano-phase segregation. Optimizing the polymer blend morphology to obtain nano-phase segregation is specific to the system under study, time consuming, and not trivial. Thus to avoid micro-phase segregation, nanoparticles of hole and electron transporters are synthesized and blended. But the PCE of nanoparticle blends are far less than those of polymer blends. This is mainly due to the: i) lack of optimal assembly of nanoparticles to facilitate charge transfer and transport processes; and ii) lack of control over the exciton and charge transport properties within the nanoparticles. Polymer packing within the nanoparticle controls the optoelectronic and charge transport properties of the nanoparticle. In this work I have shown that the solvent used to synthesize nanoparticles plays a crucial role in determining the assembly of polymer chains inside the nanoparticle there by affecting its exciton and charge transport processes. To obtain the optimal morphology for better charge transfer and transport, we have also synthesized nanoparticles of different radius with surfactants of opposite charge. We propose that depending on the radius and/or Coulombic interactions these nanoparticles can be assembled into mineral structure-types that are useful for photovoltaic devices.

Analysis of Crushing Response of Composite Crashworthy Structures

NASA Astrophysics Data System (ADS)

David, Matthew; Johnson, Alastair F.; Voggenreiter, H.

2013-10-01

The paper describes quasi-static and dynamic tests to characterise the energy absorption properties of polymer composite crash energy absorbing segment elements under axial loads. Detailed computer tomography scans of failed specimens are used to identify local compression crush failure mechanisms at the crush front. The varied crushing morphology between the compression strain rates identified in this paper is observed to be due to the differences in the response modes and mechanical properties of the strain dependent epoxy matrix. The importance of understanding the role of strain rate effects in composite crash energy absorbing structures is highlighted in this paper.

Electrochemical and morphological studies of ionic polymer metal composites as stress sensors

DOE PAGES

Hong, Wangyujue; Almomani, Abdallah; Montazami, Reza

2016-10-04

Ionic polymer metal composites (IPMCs) are the backbone of a wide range of ionic devices. IPMC mechanoelectric sensors are advanced nanostructured transducers capable of converting mechanical strain into easily detectable electric signal. Such attribute is realized by ion mobilization in and through IPMC nanostructure. In this study we have investigated electrochemical and morphological characteristics of IPMCs by varying the morphology of their metal composite component (conductive network composite (CNC)). We have demonstrated the dependence of electrochemical properties on CNC nanostructure as well as mechanoelectrical performance of IPMC sensors as a function of CNC morphology. Lastly, it is shown that themore » morphology of CNC can be used as a means to improve sensitivity of IPMC sensors by 3–4 folds.« less

Interaction of polyhedral oligomeric silsesquioxanes and dipalmitoylphosphatidylcholine at the air/water interface: Thermodynamic and rheological study.

PubMed

Skrzypiec, M; Georgiev, G As; Rojewska, M; Prochaska, K

2017-10-01

Polyhedral oligomeric silsesquioxanes (POSS) derivatives containing open silsesquioxane cage bear great potential for biomedical applications and therefore their lateral interactions with phospholipids, major biomembranes and drug vehicles constituent, should be studied in detail. That is why the properties of surface films by two POSS-derivatives, POSS-polyethylene glycol (POSS-PEG) and POSS-perfluoroalkyl (POSS-OFP), pure and in presence of 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC) were studied using Langmuir surface balance. Side chains of opposite nature (PEG is hydrophilic; OFP is hydrophobic) were selected, so that to evaluate their impact on polymers' surface properties. Two types of measurements were performed: (i) the miscibility of POSS-derivatives with DPPC was evaluated via thermodynamic analysis of the surface pressure (π)-area (A) isotherms and (ii) the dilatational rheology of selected POSS-polymer containing films was studied by the stress relaxation method. Fourier transformation analysis of the relaxation transients allows to access films' dynamic interfacial properties in broad frequency range (10 -5 -1Hz). Film morphology was monitored with Brewster Angle Microscopy. PEG moiety enabled POSS-PEG to stably incorporate in DPPC films, modifying their equilibrium and dynamic properties. In contrast OFP chains excluded from interactions with other molecules and diminished PEG-OFP amphiphilicity. Therefore at high packing densities (π≥25mN/m) PEG-OFP was expelled from the air/water interface in DPPC/PEG-OFP mixtures, and the binary films equilibrium and dynamic surface properties were determined primarily by DPPC. Thus the choice of POSS side chains can play key role in biomedical applications depending on whether strong or weak incorporation of POSS-polymers in lipid environment is aimed for. Copyright © 2017 Elsevier B.V. All rights reserved.

Control of morphology and function of low band gap polymer–bis-fullerene mixed heterojunctions in organic photovoltaics with selective solvent vapor annealing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Huipeng; Hsiao, Yu-Che; Hu, Bin

2014-05-07

We reported how by replacing PCBM with a bis-adduct fullerene (i.e. ICBA) we significantly improve the open circuit voltage (VOC) and power conversion efficiency (PCE) in P3HT bulk heterojunctions. But, for the most promising low band-gap polymer (LBP) systems, replacing PCBM with ICBA results in very poor shortcircuit current (JSC) and PCE although the VOC is significantly improved. Therefore, in this work, we have completed small angle neutron scattering and neutron reflectometry experiments to study the impact of post-deposition solvent annealing (SA) with control of solvent quality on the morphology and performance of LBP bis-fullerene BHJ photovoltaics. Our results showmore » that SA in a solvent that is selective for the LBP results in a depletion of bis-fullerene near the air surface, which limits device performance. SA in a solvent vapor which has similar solubility for polymer and bis-fullerene results in a higher degree of polymer ordering, bis-fullerene phase separation, and segregation of the bis-fullerene to the air surface, which facilitates charge transport and increases power conversion efficiency (PCE) by 100%. The highest degree of polymer ordering combined with significant bis-fullerene phase separation and segregation of bis-fullerene to the air surface is obtained by SA in a solvent vapor that is selective for the bis-fullerene. The resultant morphology increases PCE by 190%. These results indicate that solvent annealing with judicious solvent choice provides a unique tool to tune the morphology of LBP bisfullerene BHJ system, providing sufficient polymer ordering, formation of a bis-fullerene pure phase, and segregation of bis-fullerene to the air surface to optimize the morphology of the active layer. Furthermore, this process is broadly applicable to improving current disappointing LBP bis-fullerene systems to optimize their morphology and OPV performance post-deposition, including higher VOC and power conversion efficiency.« less

Towards seamlessly-integrated textile electronics: methods to coat fabrics and fibers with conducting polymers for electronic applications.

PubMed

Allison, Linden; Hoxie, Steven; Andrew, Trisha L

2017-06-29

Traditional textile materials can be transformed into functional electronic components upon being dyed or coated with films of intrinsically conducting polymers, such as poly(aniline), poly(pyrrole) and poly(3,4-ethylenedioxythiophene). A variety of textile electronic devices are built from the conductive fibers and fabrics thus obtained, including: physiochemical sensors, thermoelectric fibers/fabrics, heated garments, artificial muscles and textile supercapacitors. In all these cases, electrical performance and device ruggedness is determined by the morphology of the conducting polymer active layer on the fiber or fabric substrate. Tremendous variation in active layer morphology can be observed with different coating or dyeing conditions. Here, we summarize various methods used to create fiber- and fabric-based devices and highlight the influence of the coating method on active layer morphology and device stability.

Dynamics of Poly(methyl methacrylate) and Polystyrene Thin Films on Hydrophobic and Hydrophilic Surfaces

NASA Astrophysics Data System (ADS)

Tsige, Mesfin

While an extensive literature dealing with the structure and dynamics of polymers at surfaces and interfaces exist, there has been a paucity of information regarding the length scale of the influence of the surface on polymer mobility and its dependence on polymer-surface interaction. To address this issue, we have investigated using molecular dynamics simulations the dynamics of PMMA and PS films of similar system sizes on two different surfaces as a function of film thickness, polymer molecular weight, and temperature. The dynamics of the polymer chains in the film on two different surfaces will be discussed in the context of a three-layer model. This work was supported by NSF Grant DMR1410290.

Simple green approach to reinforce natural rubber with bacterial cellulose nanofibers.

PubMed

Trovatti, Eliane; Carvalho, Antonio J F; Ribeiro, Sidney J L; Gandini, Alessandro

2013-08-12

Natural rubber (NR) is a renewable polymer with a wide range of applications, which is constantly tailored, further increasing its utilizations. The tensile strength is one of its most important properties susceptible of being enhanced by the simple incorporation of nanofibers. The preparation and characterization of natural-rubber based nanocomposites reinforced with bacterial cellulose (BC) and bacterial cellulose coated with polystyrene (BCPS), yielded high performance materials. The nanocomposites were prepared by a simple and green process, and characterized by tensile tests, dynamical mechanical analysis (DMA), scanning electron microscopy (SEM), and swelling experiments. The effect of the nanofiber content on morphology, static, and dynamic mechanical properties was also investigated. The results showed an increase in the mechanical properties, such as Young's modulus and tensile strength, even with modest nanofiber loadings.

Molecular Strategies for Morphology Control in Semiconducting Polymers for Optoelectronics.

PubMed

Rahmanudin, Aiman; Sivula, Kevin

2017-06-28

Solution-processable semiconducting polymers have been explored over the last decades for their potential applications in inexpensively fabricated transistors, diodes and photovoltaic cells. However, a remaining challenge in the field is to control the solid-state self-assembly of polymer chains in thin films devices, as the aspects of (semi)crystallinity, grain boundaries, and chain entanglement can drastically affect intra-and inter-molecular charge transport/transfer and thus device performance. In this short review we examine how the aspects of molecular weight and chain rigidity affect solid-state self-assembly and highlight molecular engineering strategies to tune thin film morphology. Side chain engineering, flexibly linking conjugation segments, and block co-polymer strategies are specifically discussed with respect to their effect on field effect charge carrier mobility in transistors and power conversion efficiency in solar cells. Example systems are taken from recent literature including work from our laboratories to illustrate the potential of molecular engineering semiconducting polymers.

Computational approach to the study of morphological properties of polymer/fullerene blends in photovoltaics

NASA Astrophysics Data System (ADS)

Gaitho, Francis M.; Mola, Genene T.; Pellicane, Giuseppe

2018-02-01

Organic solar cells have the ability to transform solar energy efficiently and have a promising energy balance. Producing these cells is economical and makes use of methods of printing using inks built on solvents that are well-matched with a variety of cheap materials like flexible plastic or paper. The primary materials used to manufacture organic solar cells include carbon-based semiconductors, which are good light absorbers and efficient charge generators. In this article, we review previous research of interest based on morphology of polymer blends used in bulk heterojunction (BHJ) solar cells and introduce their basic principles. We further review computational models used in the analysis of surface behavior of polymer blends in BHJ as well as the trends in the field of polymer surface science as applied to BHJ photovoltaics. We also give in brief, the opportunities and challenges in the area of polymer blends on BHJ organic solar cells.

Translocation of polymers into crowded media with dynamic attractive nanoparticles.

PubMed

Cao, Wei-Ping; Ren, Qing-Bao; Luo, Meng-Bo

2015-07-01

The translocation of polymers through a small pore into crowded media with dynamic attractive nanoparticles is simulated. Results show that the nanoparticles at the trans side can affect the translocation by influencing the free-energy landscape and the diffusion of polymers. Thus the translocation time τ is dependent on the polymer-nanoparticle attraction strength ɛ and the mobility of nanoparticles V. We observe a power-law relation of τ with V, but the exponent is dependent on ɛ and nanoparticle concentration. In addition, we find that the effect of attractive dynamic nanoparticles on the dynamics of polymers is dependent on the time scale. At a short time scale, subnormal diffusion is observed at strong attraction and the diffusion is slowed down by the dynamic nanoparticles. However, the diffusion of polymers is normal at a long time scale and the diffusion constant increases with the increase in V.

Microscopic Chain Motion in Polymer Nanocomposites with Dynamically Asymmetric Interphases

PubMed Central

Senses, Erkan; Faraone, Antonio; Akcora, Pinar

2016-01-01

Dynamics of the interphase region between matrix and bound polymers on nanoparticles is important to understand the macroscopic rheological properties of nanocomposites. Here, we present neutron scattering investigations on nanocomposites with dynamically asymmetric interphases formed by a high-glass transition temperature polymer, poly(methyl methacrylate), adsorbed on nanoparticles and a low-glass transition temperature miscible matrix, poly(ethylene oxide). By taking advantage of selective isotope labeling of the chains, we studied the role of interfacial polymer on segmental and collective dynamics of the matrix chains from subnanoseconds to 100 nanoseconds. Our results show that the Rouse relaxation remains unchanged in a weakly attractive composite system while the dynamics significantly slows down in a strongly attractive composite. More importantly, the chains disentangle with a remarkable increase of the reptation tube size when the bound polymer is vitreous. The glassy and rubbery states of the bound polymer as temperature changes underpin the macroscopic stiffening of nanocomposites. PMID:27457056

Acceptor Percolation Determines How Electron-Accepting Additives Modify Transport of Ambipolar Polymer Organic Field-Effect Transistors.

PubMed

Ford, Michael J; Wang, Ming; Bustillo, Karen C; Yuan, Jianyu; Nguyen, Thuc-Quyen; Bazan, Guillermo C

2018-06-18

Organic field-effect transistors (OFETs) that utilize ambipolar polymer semiconductors can benefit from the ability of both electron and hole conduction, which is necessary for complementary circuits. However, simultaneous hole and electron transport in organic field-effect transistors result in poor ON/OFF ratios, limiting potential applications. Solution processing methods have been developed to control charge transport properties and transform ambipolar conduction to hole-only conduction. The electron-acceptor phenyl-C61-butyric acid methyl ester (PC 61 BM), when mixed in solution with an ambipolar semiconducting polymer, can reduce electron conduction. Unipolar p-type OFETs with high, well-defined ON/OFF ratios and without detrimental effects on hole conduction are achieved for a wide range of blend compositions, from 95:5 to 5:95 wt % semiconductor polymer:PC 61 BM. When introducing the alternative acceptor N, N'-bis(1-ethylpropyl)-3,4:9,10-perylenediimide (PDI), high ON/OFF ratios are achieved for 95:5 wt % semiconductor polymer:PDI; however, electron conduction increases for 50:50 and 5:95 wt % semiconductor polymer:PDI. As described within, we show that electron conduction is practically eliminated when additive domains do not percolate across the OFET channel, that is, electrons are "morphologically trapped". Morphologies were characterized by optical, electron, and atomic force microscopy as well as X-ray scattering techniques. PC 61 BM was substituted with an endohedral Lu 3 N fullerene, which enhanced contrast in electron microscopy and allowed for more detailed insight into the blend morphologies. Blends with alternative, nonfullerene acceptors further emphasize the importance of morphology and acceptor percolation, providing insights for such blends that control ambipolar transport and ON/OFF ratios.

Unraveling the Solution-State Supramolecular Structures of Donor-Acceptor Polymers and their Influence on Solid-State Morphology and Charge-Transport Properties.

PubMed

Zheng, Yu-Qing; Yao, Ze-Fan; Lei, Ting; Dou, Jin-Hu; Yang, Chi-Yuan; Zou, Lin; Meng, Xiangyi; Ma, Wei; Wang, Jie-Yu; Pei, Jian

2017-11-01

Polymer self-assembly in solution prior to film fabrication makes solution-state structures critical for their solid-state packing and optoelectronic properties. However, unraveling the solution-state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution-state structure and the charge-transport properties in field-effect transistors. Here, for the first time, it is revealed that the thin-film morphology of a conjugated polymer inherits the features of its solution-state supramolecular structures. A "solution-state supramolecular structure control" strategy is proposed to increase the electron mobility of a benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)-based polymer. It is shown that the solution-state structures of the BDOPV-based conjugated polymer can be tuned such that it forms a 1D rod-like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution-state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V -1 s -1 . This work demonstrates that "solution-state supramolecular structure" control is critical for understanding and optimization of the thin-film morphology and charge-transport properties of conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computer simulation of heterogeneous polymer photovoltaic devices

NASA Astrophysics Data System (ADS)

Kodali, Hari K.; Ganapathysubramanian, Baskar

2012-04-01

Polymer-based photovoltaic devices have the potential for widespread usage due to their low cost per watt and mechanical flexibility. Efficiencies close to 9.0% have been achieved recently in conjugated polymer based organic solar cells (OSCs). These devices were fabricated using solvent-based processing of electron-donating and electron-accepting materials into the so-called bulk heterojunction (BHJ) architecture. Experimental evidence suggests that a key property determining the power-conversion efficiency of such devices is the final morphological distribution of the donor and acceptor constituents. In order to understand the role of morphology on device performance, we develop a scalable computational framework that efficiently interrogates OSCs to investigate relationships between the morphology at the nano-scale with the device performance. In this work, we extend the Buxton and Clarke model (2007 Modelling Simul. Mater. Sci. Eng. 15 13-26) to simulate realistic devices with complex active layer morphologies using a dimensionally independent, scalable, finite-element method. We incorporate all stages involved in current generation, namely (1) exciton generation and diffusion, (2) charge generation and (3) charge transport in a modular fashion. The numerical challenges encountered during interrogation of realistic microstructures are detailed. We compare each stage of the photovoltaic process for two microstructures: a BHJ morphology and an idealized sawtooth morphology. The results are presented for both two- and three-dimensional structures.

Hole-Transfer Dependence on Blend Morphology and Energy Level Alignment in Polymer: ITIC Photovoltaic Materials.

PubMed

Eastham, Nicholas D; Logsdon, Jenna L; Manley, Eric F; Aldrich, Thomas J; Leonardi, Matthew J; Wang, Gang; Powers-Riggs, Natalia E; Young, Ryan M; Chen, Lin X; Wasielewski, Michael R; Melkonyan, Ferdinand S; Chang, Robert P H; Marks, Tobin J

2018-01-01

Bulk-heterojunction organic photovoltaic materials containing nonfullerene acceptors (NFAs) have seen remarkable advances in the past year, finally surpassing fullerenes in performance. Indeed, acceptors based on indacenodithiophene (IDT) have become synonymous with high power conversion efficiencies (PCEs). Nevertheless, NFAs have yet to achieve fill factors (FFs) comparable to those of the highest-performing fullerene-based materials. To address this seeming anomaly, this study examines a high efficiency IDT-based acceptor, ITIC, paired with three donor polymers known to achieve high FFs with fullerenes, PTPD3T, PBTI3T, and PBTSA3T. Excellent PCEs up to 8.43% are achieved from PTPD3T:ITIC blends, reflecting good charge transport, optimal morphology, and efficient ITIC to PTPD3T hole-transfer, as observed by femtosecond transient absorption spectroscopy. Hole-transfer is observed from ITIC to PBTI3T and PBTSA3T, but less efficiently, reflecting measurably inferior morphology and nonoptimal energy level alignment, resulting in PCEs of 5.34% and 4.65%, respectively. This work demonstrates the importance of proper morphology and kinetics of ITIC → donor polymer hole-transfer in boosting the performance of polymer:ITIC photovoltaic bulk heterojunction blends. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micellar Self-Assembly of Recombinant Resilin-/Elastin-Like Block Copolypeptides.

PubMed

Weitzhandler, Isaac; Dzuricky, Michael; Hoffmann, Ingo; Garcia Quiroz, Felipe; Gradzielski, Michael; Chilkoti, Ashutosh

2017-08-14

Reported here is the synthesis of perfectly sequence defined, monodisperse diblock copolypeptides of hydrophilic elastin-like and hydrophobic resilin-like polypeptide blocks and characterization of their self-assembly as a function of structural parameters by light scattering, cryo-TEM, and small-angle neutron scattering. A subset of these diblock copolypeptides exhibit lower critical solution temperature and upper critical solution temperature phase behavior and self-assemble into spherical or cylindrical micelles. Their morphologies are dictated by their chain length, degree of hydrophilicity, and hydrophilic weight fraction of the ELP block. We find that (1) independent of the length of the corona-forming ELP block there is a minimum threshold in the length of the RLP block below which self-assembly does not occur, but that once that threshold is crossed, (2) the RLP block length is a unique molecular parameter to independently tune self-assembly and (3) increasing the hydrophobicity of the corona-forming ELP drives a transition from spherical to cylindrical morphology. Unlike the self-assembly of purely ELP-based block copolymers, the self-assembly of RLP-ELPs can be understood by simple principles of polymer physics relating hydrophilic weight fraction and polymer-polymer and polymer-solvent interactions to micellar morphology, which is important as it provides a route for the de novo design of desired nanoscale morphologies from first principles.

Morphological Consequences of Frustration in ABC Triblock Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Radlauer, Madalyn R.; Sinturel, Christophe; Asai, Yusuke

2016-12-19

Three poly(styrene)-block-poly(isoprene)-block-poly(lactide) (PS-b-PI-b-PLA, SIL) triblock terpolymers were synthesized and characterized in the bulk and as thin films. The pronounced incompatibility of the covalently connected PI and PLA led to significant frustration and the tendency to minimize their intermaterial dividing surface area. This resulted in the formation of a core–shell cylinder morphology with exaggerated nonconstant mean curvature from triblock polymers with equal block volume fractions rather than the more typical lamellar morphology. The effect of frustration was magnified in thin films by both confinement and interfacial interactions such that the PI domains became discontinuous. Self-consistent field theory (SCFT) calculations emphasize thatmore » the marked difference in the PS/PI and PI/PLA interaction parameters promotes the formation of nonlamellar morphologies. However, SCFT predicts that lamellar morphology is more stable than the observed cylindrical morphology, demonstrating a limitation that arises from the underlying assumptions.« less

Assembly of P3HT/CdSe nanowire networks in an insulating polymer host.

PubMed

Heo, Kyuyoung; Miesch, Caroline; Na, Jun-Hee; Emrick, Todd; Hayward, Ryan C

2018-06-27

Nanoparticles may act as compatibilizing agents for blending of immiscible polymers, leading to changes in blend morphology through a variety of mechanisms including interfacial adsorption, aggregation, and nucleation of polymer crystals. Herein, we report an approach to define highly structured donor/acceptor networks based on poly(3-hexylthiophene) (P3HT) and CdSe quantum dots (QDs) by demixing from an insulating polystyrene (PS) matrix. The incorporation of QDs led to laterally phase-separated co-continuous structures with sub-micrometer dimensions, and promoted crystallization of P3HT, yielding highly interconnected P3HT/QD hybrid nanowires embedded in the polymer matrix. These nanohybrid materials formed by controlling phase separation, interfacial activity, and crystallization within ternary donor/acceptor/insulator blends, offer attractive morphologies for potential use in optoelectronics.

Electrochemical Deposition of Nanostructured Conducting Polymer Coatings on Neural Prosthetic Devices

NASA Astrophysics Data System (ADS)

Yang, Junyan; Martin, David

2003-03-01

Micromachined neural prosthetic devices facilitate the functional stimulation of and recording from the central nervous system (CNS). These devices have been fabricated to consist of silicon shanks that have gold or iridium sites along their surface. Our goal is to improve the biocompatibility and long-term performance of the neural prosthetic probes when they are implanted chronically in the brain. In our most recent efforts we have established that electrochemical polymerization can be used to deposit fuzzy coatings of conducting polymers specifically on the electrode sites. For neural prosthetic devices that are intended for long term implantation, we need to develop surfaces that provide intimate contact and promote efficient signal transport at the interface of the microelectrode array and brain tissue. We have developed methods to rapidly and reliably fabricate nanostructured conducting polymer coatings on the electrode probes using templated and surfactant-mediated techniques. Conducting polymer nanomushrooms and nanohairs of polypyrrole (PPy) were electrochemically polymerized onto the functional sites of neural probes by using either nanoporous block copolymers thin films, "track-etched" polycarbonate films or anodic aluminium oxide membranes as templates. Nanofibers of conducting polymers have also been successfully obtained by polymerizations in the presence of surfactants. The influence of current density, monomer concentration, surfactant concentration, and deposition charge on the thickness and morphology of the nanostructured conducting polymer coatings has been studied by optical, scanned probe, scanning electron and transmission electron microscopy. As compared with the normal nodular morphology of polypyrrole, the nanostructured morphologies grown from the neural electrode result in fuzzy coatings with extremely high surface area. The electrical properties of the polymer coatings were studied by Impedance Spectroscopy (IS) and Cyclic Voltammetry (CV). The significant drop in impedance in magnitude and phase angle is consistent with an increase of the surface area due to the roughened surface morphology.

Study of fracture and stress-induced morphological instabilities in polymeric materials

NASA Astrophysics Data System (ADS)

Sabouri-Ghomi, Mohsen

We study the phenomena of fracture in polymers at the molecular and continuum level. At a molecular level, we study the failure of polymer/polymer interfaces. Our main focus is on a specific mode of failure known as chain pull-out fracture, which is common to weak adhesive junctions, and polymer blends and mixtures. In the case of the interface between incompatible polymers, reinforcement is achieved by adding a block copolymer to the interface. We introduce a microscopic model based on Brownian dynamics to investigate the effect of the polymerization index N, of the block connector chain, on fracture toughness of such reinforced polymeric junctions. We consider the mushroom regime, where connector chains are grafted with low surface density, for the case of large pulling velocity. We find that for short chains the interface fracture toughness depends linearly on the polymerization index N of the connector chains, while for longer chains the dependence becomes N 3/2. We propose a scaling argument, based on the geometry of the initial configuration, that accounts for both short and long chains and the crossover between them. At the continuum level, we study the pattern selection mechanism of finger-like crack growth phenomena in gradient driven growth problems in general, and the structure of stress-induced morphological instabilities in crazing of polymer glasses in particular. We simulate solidification in a narrow channel through the use of a phase-field model with an adaptive grid. By tuning a dimensionless parameter, the Peclet number, we show a continuous crossover from a free dendrite at high Peclet numbers to anisotropic viscous fingering at low Peclet numbers. At low Peclet numbers we find good agreement between our results, theoretical predictions, and experiment, providing the first quantitative test of solvability theory for anisotropic viscous fingers. For high undercoolings, we find new phenomena, a solid forger which satisfies stability and thermodynamic criterion. We further provide an analytical form for the shape of these fingers, based on local models of solidification, which fits our numerical results from simulation. Later we study the growth of crazes in polymer glasses by deriving the equations of motion of plastic flow at the craze tip, and the steady-state velocity profile of this flow. By developing a phenomenological model, we solve the full time-dependent equations of motion of this highly non-linear phenomena. Our simulation produces the steady-state cellular pattern observed in experiments. We further show that polymer glasses with lower yield stress produce cellular patterns with sharper tips and more cells, indicating instabilities with smaller wavelengths.

Optical and Morphological Properties of P3HT and P3HT: PCBM Thin Films Used in Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Hrostea, L.; Girtan, M.; Mallet, R.; Leontie, L.

2018-06-01

This work is focused on the study of some physical properties of poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly(e-hexylthiophene-2,5-diyl): Methanolfullerene Phenyl-C61-Butyric-Accid-Methyl-Ester (PCBM) blend thin films. Knowing the polymer advantages, such as ease of processing, high thermal stability, strong interaction with light, its properties have captured the attention regarding the changes that can occur in a polymer:fullerene blend in term of them. Polymer and polymer:fullerene blend (1:0.1, 1:0.2, 1:0.4 and 1:0.8 ratios) were deposited by spin coating on glass and SnO2:F (FTO) coated glass. The optical properties were emphasized using spectrophotometry (300 – 2200 nm wavelength range) and spectroscopic ellipsometry models, to obtain the refractive index, extinction coefficient and the transmission (found higher than 80%). According to X-ray diffraction analysis, as-obtained films are amorphous. Investigation of the surface morphology of thin-film samples using Atomic Force Microscopy revealed a crystallite-like surface morphology with crystallite size in the nanometer range.

Generation of conductivity through transfer charge properties, for polyesters and polyamides with characteristic functional groups

NASA Astrophysics Data System (ADS)

Gonzalez, Carmen; Tagle, Luis Hernan; Terraza, Claudio A.; Barriga, Andres; Cabrera, A. L.; Volkmann, Ulrich G.

2011-03-01

Electro-optic properties of σ -conjugated polymers, as polysilylene; are associated with electron conjugation in the silicon atom, which allows a significant delocalization of electrons along of the chain. Thus, the conductivity is intimately connected to the mobility of charge carriers, which in turn depends on the structure and morphology of the system. We report the characterization of polyesters (PEFs) and polyamides (PAFs). Film thicknesses were obtained by ellipsometry. The vibration frequencies of the groups were determined by FT-IR and corroborated by Raman spectroscopy. Structural information was obtained from X-Ray diffraction (XRD). The structural and surface morphology were studied by scanning electron microscope (SEM). Electrical conductivity of the polymers was measured before and after exposure to iodine vapor, for films of different thicknesses. Morphological differentiation was studied by energy dispersive microscopy (EDX), showing a regular distribution of iodine within the polymer. Preliminary conductivity measurements showed adverse effects when oxidation of the polymer films is induced These effects are related to a certain grade of disorder within the system

How morphology influences relaxivity - comparative study of superparamagnetic iron oxide-polymer hybrid nanostructures.

PubMed

Ebert, Sandro; Bannwarth, Markus B; Musyanovych, Anna; Landfester, Katharina; Münnemann, Kerstin

2015-01-01

Superparamagnetic iron oxides (SPIOs) are widely used in MRI as T2 contrast agents, and interest is still growing. Here, the T2 relaxivity of three different SPIO-polymer hybrid morphologies, i.e. homogeneously distributed iron oxide within a polymer matrix, Janus-like nanoparticles and polymer nanocapsules containing iron oxides, is studied. Making use of calculations based on theory for agglomerated systems, the obtained T2 values could be predicted for all different morphologies, except for nanocapsules. Nanocapsules, in contrast to full spheres, allow for water exchange between encapsulated water and bulk water, and thus have two contributions to relaxivity. One originates from the capsules acting as a weakly magnetized cluster and the other stems from the individual SPIOs inside the capsule. Therefore, the relaxivities were also computed using an empirical equation found in the literature, which considers water exchange, resulting in a better T2 forecast for the nanocapsules. The presented study is the first example of a comparison between measured and calculated relaxivities of nanocapsules. Copyright © 2015 John Wiley & Sons, Ltd.

Polymer Fluid Dynamics.

ERIC Educational Resources Information Center

Bird, R. Byron

1980-01-01

Problems in polymer fluid dynamics are described, including development of constitutive equations, rheometry, kinetic theory, flow visualization, heat transfer studies, flows with phase change, two-phase flow, polymer unit operations, and drag reduction. (JN)

Ultra-sensitive ROS-responsive tellurium-containing polymers.

PubMed

Cao, Wei; Gu, Yuwei; Li, Tianyu; Xu, Huaping

2015-04-25

A novel tellurium-containing polymer micelle system is reported to be responsive to 100 μM H2O2 and can undergo a series of morphological changes. The polymer micelles also respond to 2 Gy gamma radiation, which is the exact dosage a patient receives per day for clinical radiation therapy.

Morphological, mechanical properties and biodegradability of biocomposite thermoplastic starch and polycaprolactone reinforced with sisal fibers

USDA-ARS?s Scientific Manuscript database

The incorporation of fibers as reinforcements in polymer composites has increased due to their renewability, low cost and biodegradability. In this study, sisal fibers were added to a polymer matrix of thermoplastic starch and polycaprolactone, both biodegradable polymers. Sisal fibers (5% and 10%) ...

Four-Dimensional Printing Hierarchy Scaffolds with Highly Biocompatible Smart Polymers for Tissue Engineering Applications.

PubMed

Miao, Shida; Zhu, Wei; Castro, Nathan J; Leng, Jinsong; Zhang, Lijie Grace

2016-10-01

The objective of this study was to four-dimensional (4D) print novel biomimetic gradient tissue scaffolds with highly biocompatible naturally derived smart polymers. The term "4D printing" refers to the inherent smart shape transformation of fabricated constructs when implanted minimally invasively for seamless and dynamic integration. For this purpose, a series of novel shape memory polymers with excellent biocompatibility and tunable shape changing effects were synthesized and cured in the presence of three-dimensional printed sacrificial molds, which were subsequently dissolved to create controllable and graded porosity within the scaffold. Surface morphology, thermal, mechanical, and biocompatible properties as well as shape memory effects of the synthesized smart polymers and resultant porous scaffolds were characterized. Fourier transform infrared spectroscopy and gel content analysis confirmed the formation of chemical crosslinking by reacting polycaprolactone triol and castor oil with multi-isocyanate groups. Differential scanning calorimetry revealed an adjustable glass transition temperature in a range from -8°C to 35°C. Uniaxial compression testing indicated that the obtained polymers, possessing a highly crosslinked interpenetrating polymeric networks, have similar compressive modulus to polycaprolactone. Shape memory tests revealed that the smart polymers display finely tunable recovery speed and exhibit greater than 92% shape fixing at -18°C or 0°C and full shape recovery at physiological temperature. Scanning electron microscopy analysis of fabricated scaffolds revealed a graded microporous structure, which mimics the nonuniform distribution of porosity found within natural tissues. With polycaprolactone serving as a control, human bone marrow-derived mesenchymal stem cell adhesion, proliferation, and differentiation greatly increased on our novel smart polymers. The current work will significantly advance the future design and development of novel and functional biomedical scaffolds with advanced 4D printing technology and highly biocompatible smart biomaterials.

Four-Dimensional Printing Hierarchy Scaffolds with Highly Biocompatible Smart Polymers for Tissue Engineering Applications

PubMed Central

Miao, Shida; Zhu, Wei; Castro, Nathan J.; Leng, Jinsong

2016-01-01

The objective of this study was to four-dimensional (4D) print novel biomimetic gradient tissue scaffolds with highly biocompatible naturally derived smart polymers. The term “4D printing” refers to the inherent smart shape transformation of fabricated constructs when implanted minimally invasively for seamless and dynamic integration. For this purpose, a series of novel shape memory polymers with excellent biocompatibility and tunable shape changing effects were synthesized and cured in the presence of three-dimensional printed sacrificial molds, which were subsequently dissolved to create controllable and graded porosity within the scaffold. Surface morphology, thermal, mechanical, and biocompatible properties as well as shape memory effects of the synthesized smart polymers and resultant porous scaffolds were characterized. Fourier transform infrared spectroscopy and gel content analysis confirmed the formation of chemical crosslinking by reacting polycaprolactone triol and castor oil with multi-isocyanate groups. Differential scanning calorimetry revealed an adjustable glass transition temperature in a range from −8°C to 35°C. Uniaxial compression testing indicated that the obtained polymers, possessing a highly crosslinked interpenetrating polymeric networks, have similar compressive modulus to polycaprolactone. Shape memory tests revealed that the smart polymers display finely tunable recovery speed and exhibit greater than 92% shape fixing at −18°C or 0°C and full shape recovery at physiological temperature. Scanning electron microscopy analysis of fabricated scaffolds revealed a graded microporous structure, which mimics the nonuniform distribution of porosity found within natural tissues. With polycaprolactone serving as a control, human bone marrow-derived mesenchymal stem cell adhesion, proliferation, and differentiation greatly increased on our novel smart polymers. The current work will significantly advance the future design and development of novel and functional biomedical scaffolds with advanced 4D printing technology and highly biocompatible smart biomaterials. PMID:28195832

Nanostructures and nanosecond dynamics at the polymer/filler interface

NASA Astrophysics Data System (ADS)

Koga, Tad; Barkley, Deborah; Endoh, Maya; Masui, Tomomi; Kishimoto, Hiroyuki; Nagao, Michihiro; Taniguchi, Takashi

We report in-situ nanostructures and nanosecond dynamics of polybutadiene (PB) chains bound to carbon black (CB) fillers (the so-called ``bound polymer layer (BPL)'') in polymer solutions (from dilute to concentrated solutions). The BPL on the CB fillers were extracted by solvent leaching of a CB-filled PB compound and subsequently dispersed in deuterated toluene (a good solvent) to label the BPL for ``contrast-matching'' small-angle neutron scattering (SANS) and neutron spin echo (NSE) techniques. The SANS results demonstrate that the BPL is composed of two regions regardless of molecular weights of PB: the inner unswollen region of 0.5 nm thick and outer swollen region where the polymer chains display a parabolic profile with a diffuse tail. In addition, the NSE results show that the dynamics of the swollen bound chains in the polymer solutions can be explained by the collective dynamics, the so-called ``breathing mode''. Intriguingly, it was also indicative that the collective dynamics is independent of the polymer concentrations and is much faster than that predicted from the solution viscosity. We will discuss the mechanism at the bound polymer-free polymer interface at the nanometer scale. T.K. acknowledges the financial support from NSF Grant (CMMI-1332499).

High-Efficiency Nonfullerene Polymer Solar Cell Enabling by Integration of Film-Morphology Optimization, Donor Selection, and Interfacial Engineering.

PubMed

Zhang, Xin; Li, Weiping; Yao, Jiannian; Zhan, Chuanlang

2016-06-22

Carrier mobility is a vital factor determining the electrical performance of organic solar cells. In this paper we report that a high-efficiency nonfullerene organic solar cell (NF-OSC) with a power conversion efficiency of 6.94 ± 0.27% was obtained by optimizing the hole and electron transportations via following judicious selection of polymer donor and engineering of film-morphology and cathode interlayers: (1) a combination of solvent annealing and solvent vapor annealing optimizes the film morphology and hence both hole and electron mobilities, leading to a trade-off of fill factor and short-circuit current density (Jsc); (2) the judicious selection of polymer donor affords a higher hole and electron mobility, giving a higher Jsc; and (3) engineering the cathode interlayer affords a higher electron mobility, which leads to a significant increase in electrical current generation and ultimately the power conversion efficiency (PCE).

One-step synthesis of titania nanoparticles from PS-P4VP diblock copolymer solution

NASA Astrophysics Data System (ADS)

Song, Lixin; Lam, Yeng Ming; Boothroyd, Chris; Teo, Puat Wen

2007-04-01

Polymeric films containing titania nanoparticles have potential as dielectric films for flexible electronic applications. For this purpose, the nanoparticles must be homogeneously distributed. Self-assembly is emerging as a neat, elegant method for fabricating such nanostructured hybrid materials with well-distributed nanoparticles. In this work, we report a micellar solution approach for the assembly of copolymer-titanium precursor nanostructures in which titania nanoparticles were synthesized. The ratio of the amount of titanium precursor, titanium isopropoxide, to the blocks forming the micellar core, poly(4-vinylpyridine), was found to play a key role in controlling film morphology. A sphere-to-ribbon transition was observed when the amount of titanium isopropoxide was increased. The thin film morphology can be tuned using the precursor-copolymer interaction rather than just the polymer-polymer interaction or the polymer-solution interaction. This method provides yet another way to control the morphology of nanostructures.

Microcellular foaming of arabinoxylan and PEGylated arabinoxylan with supercritical CO2.

PubMed

Härdelin, Linda; Ström, Anna; Di Maio, Ernesto; Iannace, Salvatore; Larsson, Anette

2018-02-01

In this study, arabinoxylan extracted from barley husks was reacted with polyethylene glycol (PEG) of various molecular weights to introduce an internal plasticizer into the polymer matrix. A successful PEGylation reaction was identified using FTIR and elemental analysis. Thermal and mechanical properties were studied using dynamic mechanical analysis, which revealed that the attachment of PEG chains reduced the glass transition temperature by up to 25°C. Foaming experiments were conducted under different test conditions in a batch foaming process with supercritical CO 2 in a thermoregulated and pressurized cylinder. The foams were evaluated using SEM by studying the morphology of the samples foamed at different temperatures. The unmodified arabinoxylan sample was found to produce the best foam morphology, though the PEGylated samples could be produced at lower temperatures than could the unmodified arabinoxylan. This was interpreted as due to the decrease in the glass transition temperature. Copyright © 2017. Published by Elsevier Ltd.

Structure and Dynamics of Solvated Polymers near a Silica Surface: On the Different Roles Played by Solvent.

PubMed

Perrin, Elsa; Schoen, Martin; Coudert, François-Xavier; Boutin, Anne

2018-04-26

Whereas it is experimentally known that the inclusion of nanoparticles in hydrogels can lead to a mechanical reinforcement, a detailed molecular understanding of the adhesion mechanism is still lacking. Here we use coarse-grained molecular dynamics simulations to investigate the nature of the interface between silica surfaces and solvated polymers. We show how differences in the nature of the polymer and the polymer-solvent interactions can lead to drastically different behavior of the polymer-surface adhesion. Comparing explicit and implicit solvent models, we conclude that this effect cannot be fully described in an implicit solvent. We highlight the crucial role of polymer solvation for the adsorption of the polymer chain on the silica surface, the significant dynamics of polymer chains on the surface, and details of the modifications in the structure solvated polymer close to the interface.

Effects of humidity and solution viscosity on electrospun fiber morphology.

PubMed

Nezarati, Roya M; Eifert, Michelle B; Cosgriff-Hernandez, Elizabeth

2013-10-01

Electrospinning is a popular technique to fabricate tissue engineering scaffolds due to the exceptional tunability of fiber morphology that can be used to control scaffold mechanical properties, degradation rate, and cell behavior. Although the effects of modulating processing or solution parameters on fiber morphology have been extensively studied, there remains limited understanding of the impact of environmental parameters such as humidity. To address this gap, three polymers (poly(ethylene glycol) [PEG], polycaprolactone [PCL], and poly(carbonate urethane) [PCU]) were electrospun at a range of relative humidities (RH = 5%-75%) and the resulting fiber architecture characterized with scanning electron microscopy. Low relative humidity (< 50%) resulted in fiber breakage for all three polymers due to decreased electrostatic discharge from the jet. At high relative humidity (> 50%), three distinct effects were observed based on individual polymer properties. An increase in fiber breakage and loss of fiber morphology occurred in the PEG system as a result of increased water absorption at high relative humidity. In contrast, surface pores on PCL fibers were observed and hypothesized to have formed via vapor-induced phase separation. Finally, decreased PCU fiber collection occurred at high humidity likely due to increased electrostatic discharge. These findings highlight that the effects of relative humidity on electrospun fiber morphology are dependent on polymer hydrophobicity, solvent miscibility with water, and solvent volatility. An additional study was conducted to highlight that small changes in molecular weight can strongly influence solution viscosity and resulting fiber morphology. We propose that solution viscosity rather than concentration is a more useful parameter to report in electrospinning methodology to enable reproduction of findings. In summary, this study further elucidates key mechanisms in electrospun fiber formation that can be utilized to fabricate tissue engineering scaffolds with tunable and reproducible properties.

Effects of Humidity and Solution Viscosity on Electrospun Fiber Morphology

PubMed Central

Nezarati, Roya M.; Eifert, Michelle B.

2013-01-01

Electrospinning is a popular technique to fabricate tissue engineering scaffolds due to the exceptional tunability of fiber morphology that can be used to control scaffold mechanical properties, degradation rate, and cell behavior. Although the effects of modulating processing or solution parameters on fiber morphology have been extensively studied, there remains limited understanding of the impact of environmental parameters such as humidity. To address this gap, three polymers (poly(ethylene glycol) [PEG], polycaprolactone [PCL], and poly(carbonate urethane) [PCU]) were electrospun at a range of relative humidities (RH=5%–75%) and the resulting fiber architecture characterized with scanning electron microscopy. Low relative humidity (<50%) resulted in fiber breakage for all three polymers due to decreased electrostatic discharge from the jet. At high relative humidity (>50%), three distinct effects were observed based on individual polymer properties. An increase in fiber breakage and loss of fiber morphology occurred in the PEG system as a result of increased water absorption at high relative humidity. In contrast, surface pores on PCL fibers were observed and hypothesized to have formed via vapor-induced phase separation. Finally, decreased PCU fiber collection occurred at high humidity likely due to increased electrostatic discharge. These findings highlight that the effects of relative humidity on electrospun fiber morphology are dependent on polymer hydrophobicity, solvent miscibility with water, and solvent volatility. An additional study was conducted to highlight that small changes in molecular weight can strongly influence solution viscosity and resulting fiber morphology. We propose that solution viscosity rather than concentration is a more useful parameter to report in electrospinning methodology to enable reproduction of findings. In summary, this study further elucidates key mechanisms in electrospun fiber formation that can be utilized to fabricate tissue engineering scaffolds with tunable and reproducible properties. PMID:23469941

Free energy landscape of siRNA-polycation complexation: Elucidating the effect of molecular geometry, polymer flexibility, and charge neutralization.

PubMed

Grasso, Gianvito; Deriu, Marco Agostino; Patrulea, Viorica; Borchard, Gerrit; Möller, Michael; Danani, Andrea

2017-01-01

The success of medical threatments with DNA and silencing interference RNA is strongly related to the design of efficient delivery technologies. Cationic polymers represent an attractive strategy to serve as nucleic-acid carriers with the envisioned advantages of efficient complexation, low cost, ease of production, well-defined size, and low polydispersity index. However, the balance between efficacy and toxicity (safety) of these polymers is a challenge and in need of improvement. With the aim of designing more effective polycationic-based gene carriers, many parameters such as carrier morphology, size, molecular weight, surface chemistry, and flexibility/rigidity ratio need to be taken into consideration. In the present work, the binding mechanism of three cationic polymers (polyarginine, polylysine and polyethyleneimine) to a model siRNA target is computationally investigated at the atomistic level. In order to better understand the polycationic carrier-siRNA interactions, replica exchange molecular dynamic simulations were carried out to provide an exhaustive exploration of all the possible binding sites, taking fully into account the siRNA flexibility together with the presence of explicit solvent and ions. Moreover, well-tempered metadynamics simulations were employed to elucidate how molecular geometry, polycation flexibility, and charge neutralization affect the siRNA-polycations free energy landscape in term of low-energy binding modes and unbinding free energy barriers. Significant differences among polymer binding modes have been detected, revealing the advantageous binding properties of polyarginine and polylysine compared to polyethyleneimine.

Free energy landscape of siRNA-polycation complexation: Elucidating the effect of molecular geometry, polymer flexibility, and charge neutralization

PubMed Central

Patrulea, Viorica; Borchard, Gerrit; Möller, Michael; Danani, Andrea

2017-01-01

The success of medical threatments with DNA and silencing interference RNA is strongly related to the design of efficient delivery technologies. Cationic polymers represent an attractive strategy to serve as nucleic-acid carriers with the envisioned advantages of efficient complexation, low cost, ease of production, well-defined size, and low polydispersity index. However, the balance between efficacy and toxicity (safety) of these polymers is a challenge and in need of improvement. With the aim of designing more effective polycationic-based gene carriers, many parameters such as carrier morphology, size, molecular weight, surface chemistry, and flexibility/rigidity ratio need to be taken into consideration. In the present work, the binding mechanism of three cationic polymers (polyarginine, polylysine and polyethyleneimine) to a model siRNA target is computationally investigated at the atomistic level. In order to better understand the polycationic carrier-siRNA interactions, replica exchange molecular dynamic simulations were carried out to provide an exhaustive exploration of all the possible binding sites, taking fully into account the siRNA flexibility together with the presence of explicit solvent and ions. Moreover, well-tempered metadynamics simulations were employed to elucidate how molecular geometry, polycation flexibility, and charge neutralization affect the siRNA-polycations free energy landscape in term of low-energy binding modes and unbinding free energy barriers. Significant differences among polymer binding modes have been detected, revealing the advantageous binding properties of polyarginine and polylysine compared to polyethyleneimine. PMID:29088239

Computational fluid dynamics (CFD) simulations of molten steel flow patterns and particle-wall adhesion in continuous casting of steels

NASA Astrophysics Data System (ADS)

Mohammadi-Ghaleni, Mahdi

The Sun has long been the most important energy source for planet Earth. Sunlight offers the potential to function as a source of clean, renewable energy; photovoltaic (PV) cells have been designed to tap into this abundant solar energy to generate electricity. Organic photovoltaic (OPV) devices show promise as technologies capable of lightweight, low cost and flexible alternatives to traditional silicon PV but the nature of conjugated organic and polymeric semiconductors have limited performance and, therefore, application. However, recent advances have shown that the addition of pristine graphene (PG) to the active layer of OPV devices can yield three-fold performance improvements in blends of P3HT (poly(3-hexylthiophene-2,5-diyl) & PCBM (phenyl C 61 butyric acid methyl ester) and, later, in all-polymer blends of P3HT & F8BT (poly(9,9-dioctylfluorene-alt-benzothiadiazole). In both OPV systems, increased performance is believed to be due to high charge carrier mobility imparted by the PG additive to the composite active layer blend. In this work, the effect of addition of PG to the active layer blend of P3HT & PCPDTBT (poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta [2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]) systems was investigated. PV devices were designed, fabricated and tested using standard processing methods and testing procedures. Although PG increased OPV device performance relative to samples without PG, power conversion efficiency (eta) on an absolute scale was lower than expected despite the otherwise complementary properties of these materials. Based on the literature, the low performance of these devices was hypothesized to result from non-ideal active layer morphology, lacking charge carried percolation pathways to the electrodes. Small angle neutron scattering (SANS) was employed to probe the active layer morphology in polymer blend films similar to the active layers of the cells. Deuterated P3HT (d-P3HT) was used to exploit the large scattering length density (SLD) contrast between hydrogen and deuterium. Rigorous analysis of the SANS data allowed the nanostructure to be determined and a model of disk-like d-P3HT crystallites dispersed in a matrix of the amorphous polymers was constructed. This structure shows limited interfacial area for exciton dissociation and exhibits a lack of charge percolation pathways to the electrodes. Morphological insight offered by SANS analysis along with literature review allowed higher performance all-polymer photovoltaic cells to be designed and tested using the same semiconducting polymers. By introducing a co-solvent and modifying the thermal annealing procedure, significant performance gains were realized for subsequent devices. The increased performance observed following the change in procedure is believed to be due to enhanced active layer morphology and formation of a bulk heterojunction (BHJ) structure, to be studied in future work. Although there is room for further performance gains in P3HT-PCPDTBT devices as well as application to other OPV systems in future work, the methods, results and discussion presented here highlight the importance of structure-property relationships in all-polymer photovoltaic cells.

Fast Printing and In-Situ Morphology Observation of Organic Photovoltaics using Slot-Die Coating

NASA Astrophysics Data System (ADS)

Liu, Feng; Ferdous, Sunzida; Wang, Cheng; Hexamer, Alexander; Russell, Thomas; Cheng Wang Collaboration; Thomas Russell Team

2014-03-01

The solvent-processibility of polymer semiconductors is a key advantage for the fabrication of large area, organic bulk-heterojunction (BHJ) photovoltaic devices. Most reported power conversion efficiencies (PCE) are based on small active areas, fabricated by spin-coating technique. In general, this does not reflect device fabrication in an industrial setting. To realize commercial viability, devices need to be fabricated in a roll-to-roll fashion. The evolution of the morphology associated with different processing parameters, like solvent choice, concentration and temperature, needs to be understood and controlled. We developed a mini slot-die coater, to fabricate BHJ devices using various low band gap polymers mixed with phenyl-C71-butyric acid methyl ester (PCBM). Solvent choice, processing additives, coating rate and coating temperatures were used to control the final morphology. Efficiencies comparable to lab-setting spin-coated devices are obtained. The evolution of the morphology was monitored by in situ scattering measurements, detecting the onset of the polymer chain packing in solution that led to the formation of a fibrillar network in the film.

Confinement effects on thin polymer films

NASA Astrophysics Data System (ADS)

Dalnoki-Veress, Karoly J. T.

We present the results of four projects investigating the effects of confinement on polymeric systems. The first study dealt with polymer blends that are quenched using a spincoating technique rather than a temperature quench. The mass fraction of two blends was varied to determine the effect of the substrate-blend interface on the thin film phase separation morphology. Quantitative measurements of the morphology on three different substrates revealed significant differences in the phase separation morphology as a result of the different wetting properties of the polymer blend on the substrates. The second project dealt with the effect of mechanical confinement on the phase separation of polymer blend thin films. We measured the phase separation morphology of polystyrene/poly (methyl methacrylate) (PS/PMMA) blend films of thickness h on a silicon oxide (SiOx) substrate with a SiOx capping layer. A novel phase separation morphology was observed for small capping layer thicknesses L as well as a transition from lateral to lamellar morphology as L is increased. A simple model is presented which explains the observed lateral morphology, and the morphology transition, in terms of a balance between the free energy increase associated with forming the interfaces between PS-rich and PMMA-rich domains, and the free energy increase associated with the elastic bending of the SiOx capping layer. Direct control of the amplitude and period of the deformation is achieved by varying h and L. Reasonable agreement is obtained between the predicted amplitude of the rippling of the film surface and that measured directly using atomic force microscopy. For temperatures greater than the glass transition temperature Tg, thin freely-standing polymer films are unstable to the formation of holes. In the third project, we have studied the formation and growth of two types of holes: those which form spontaneously when the films are heated above Tg, and those purposely nucleated using a heated scanning tunneling microscope tip. For both types of holes, we observe exponential growth of the hole radius, corresponding to the viscous regime of hole formation, and a decrease in the film viscosity with decreasing film thickness h for h < 250 nm. In the last project the thermal stability of freely-standing films was enhanced by symmetrically confining the films between thin layers of silicon oxide to form SiOx/PS/SiOx trilayer films. Aggressive annealing of the films produced a novel morphology consisting of long, parallel domains with a well-defined periodicity. A simple model is presented which describes the scaling behavior of the morphology. We discuss the direct control of the morphology through manipulation of the individual film thicknesses and the long-range Van der Waals or dispersion interactions.

Interplay of Transport and Morphology in Nanostructured Ion-Containing Polymers

NASA Astrophysics Data System (ADS)

Park, Moon Jeong

The global energy crisis and an increase in environmental pollution in the recent years have drawn the attention of the scientific community to develop innovative ways to improve energy storage and find more efficient methods of transporting the energy. Polymers containing charged species that show high ionic conductivity and good mechanical integrity are the essential components of these energy storage and transport systems. In this talk, first, I will present a fundamental understanding of the thermodynamics and transport in ion-containing block copolymers with a focus on the structure-property relationships. Tailoring the intermolecular interactions between the polymer matrix and the embedded charges appeared to be vital for controlling the transport properties. Particularly, the achievement of well-defined self-assembled morphologies with three-dimensional symmetries has proven to facilitate fast ion transport by constructing less tortuous ion-conducting pathways. Examples of attained morphologies include disorder, lamellae, gyroid, Fddd, hexagonal cylinder, body-centered cubic, face-centered cubic, and A15 phases. Second, various strategies for accessing high cation transference number as well as improved ionic conductivity from ionic-containing polymers are enclosed; (1) the inclusion of terminal ionic units as a new means to control the nanoscale morphologies and the transport efficiency of block copolymer electrolytes and (2) the addition of zwitterions that offered a polar medium close to water, and accordingly increased the charge density and ionic conductivity. The obtained knowledge on polymer electrolytes could be used in a wide range of emerging nanotechnologies such as fuel cells, lithium batteries, and electro-active actuators.

Material properties of novel polymeric films

NASA Astrophysics Data System (ADS)

Kim, Gene

This dissertation will study the material properties of two types of novel polymer films (polyelectrolyte multilayer films and photolithographic polymer films). The formation of polylelectrolyte multilayer films onto functionalized aluminum oxide surfaces and functionalized poly(ethylene terephthaltate) (PET) were studied. Functionalization of the aluminum oxide surfaces was achieved via silane coupling. Functionalization of PET surfaces was achieved via hydrolysis and amidation. Surface characterization techniques such as X-ray photoelectron spectroscopy (XPS) and dynamic contact angle measurements were used to monitor the polyelectrolyte multilayer formation. Mechanical properties of the aluminum oxide supported polyelectrolyte multilayer films were tested using a simplified peel test. XPS was used to analyze the surfaces before and after peel. Single lap shear joint specimens were constructed to test the adhesive shear strength of the PET-supported polyelectrolyte multilayer film samples with the aid of a cyanoacrylate adhesive. The adhesive shear strength and its relation with the type of functionalization, number of polyelectrolyte layers, and the effect of polyelectrolyte conformation using added salt were explored. Also, characterization on the single lap joints after adhesive failure was carried out to determine the locus of failure within the multilayers by using XPS and SEM. Two types of photolithographic polymers were formulated and tested. These two polymers (photocrosslinkable polyacrylate (PUA), and a photocrosslinkable polyimide (HRP)) were used to investigate factors that would affect the structural integrity of these particular polymers under environmental variables such as processing (time, UV cure, pressure, and temperature) and ink exposure. Thermomechanical characterization was carried out to see the behavior of these two polymers under these environmental variables. Microscopic techniques were employed to study the morphological behavior of the two polymer systems. Also, unique in-house characterization methods such as the vibrational holographic interferometry to measure residual stress in these polymer coatings upon processing, and the environmental tensile tester (ETT) to measure ink diffusion and swelling stresses were used to further characterize these two polymers.

Measuring the change in hydration of a polypeptide-based block polymer vesicle as a function of pH

NASA Astrophysics Data System (ADS)

Smith, Ian; Charlier, Alban; Shishlov, Alexander; Savin, Daniel

Amphiphilic AB2 star polymers undergo directed self-assembly into vesicles in aqueous solution. The overall structure of the assembly is responsive to a change in solution pH by incorporating an ionizable polypeptide as the A-block and two lipid-like tails for the B-blocks. Herein, we present some recent results in the solution characterization of polyglutamate-octadecanethiol2 (PE-DDT2) star polymers using static and dynamic light scattering, as well as transmission electron microscopy. An increase in pH will induce a transition in secondary structure of the PE block from an α-helix to an extended coil, thereby perturbing the morphological structure and resulting in an expansion of the vesicle. The magnitude of this response is much larger than what is expected based on the conformational transition of the peptide. The mechanism of this process can be probed by measuring the change in hydration at the surface of the hydrophobic bilayer. Towards this end, we utilize 2,4,6-trichloro-1,3,5-triazine (TCT) as a modular linker to install spin labels into the assembly as a mechanism to directly interrogate local hydrophobicity using electron paramagnetic resonance (EPR). NSF 1539347.

Improving proton conduction pathways in di- and triblock copolymer membranes: Branched versus linear side chains

NASA Astrophysics Data System (ADS)

Dorenbos, G.

2017-06-01

Phase separation within a series of polymer membranes in the presence of water is studied by dissipative particle dynamics. Each polymer contains hydrophobic A beads and hydrophilic C beads. Three parent architectures are constructed from a backbone composed of connected hydrophobic A beads to which short ([C]), long ([A3C]), or symmetrically branched A5[AC][AC] side chains spring off. Three di-block copolymer derivatives are constructed by covalently bonding an A30 block to each parent architecture. Also three tri-blocks with A15 blocks attached to both ends of each parent architecture are modeled. Monte Carlo tracer diffusion calculations through the water containing pores for 1226 morphologies reveal that water diffusion for parent architectures is slowest and diffusion through the di-blocks is fastest. Furthermore, diffusion increases with side chain length and is highest for branched side chains. This is explained by the increase of water pore size with , which is the average number of bonds that A beads are separated from a nearest C bead. Optimization of within the amphiphilic parent architecture is expected to be essential in improving proton conduction in polymer electrolyte membranes.

Dynamics of polymers in elongational flow studied by the neutron spin-echo technique

NASA Astrophysics Data System (ADS)

Rheinstädter, Maikel C.; Sattler, Rainer; Häußler, Wolfgang; Wagner, Christian

2010-09-01

The nanoscale fluctuation dynamics of semidilute high molecular weight polymer solutions of polyethylenoxide (PEO) in D 2O under non-equilibrium flow conditions were studied by the neutron spin-echo technique. The sample cell was in contraction flow geometry and provided a pressure driven flow with a high elongational component that stretched the polymers most efficiently. Neutron scattering experiments in dilute polymer solutions are challenging because of the low polymer concentration and corresponding small quasi-elastic signals. A relaxation process with relaxation times of about 10 ps was observed, which shows anisotropic dynamics with applied flow.

Critical Role of Surface Energy in Guiding Crystallization of Solution-Coated Conjugated Polymer Thin Films

DOE PAGES

Zhang, Fengjiao; Mohammadi, Erfan; Luo, Xuyi; ...

2017-10-02

It is well-known that substrate surface properties have a profound impact on morphology of thin films solution coated atop and the resulting solid-state properties. However, design rules for guiding the substrate selection have not yet been established. Such design rules are particularly important for solution coated semiconducting polymers, as the substratedirected thin film morphology can impact charge transport properties by orders of magnitude. We hypothesize that substrate surface energies dictate the thin film morphology by modulating the free energy barrier to heterogeneous nucleation. To test this hypothesis, we systematically vary the substrate surface energy via surface functionalization techniques. We performmore » in-depth morphology and device characterizations to establish the relationship between substrate surface energy, thin film morphology and charge transport properties, employing a donor-accepter (D-A) conjugated polymer. Here, we find that decreasing the substrate surface energy progressively increases thin film crystallinity, degree of molecular ordering and extent of domain alignment. Notably, the enhanced morphology on the lowest surface energy substrate lead to a 10-fold increase in the charge carrier mobility. We further develop a free energy model relating the substrate surface energy to the penalty of heterogeneous nucleation from solution in the thin film geometry. The model correctly predicts the experimental trend, thereby validating our hypothesis. This work is a significant step towards establishing design rules and understanding the critical role of substrates in determining morphology of solution coated thin films.« less

Critical Role of Surface Energy in Guiding Crystallization of Solution-Coated Conjugated Polymer Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fengjiao; Mohammadi, Erfan; Luo, Xuyi

It is well-known that substrate surface properties have a profound impact on morphology of thin films solution coated atop and the resulting solid-state properties. However, design rules for guiding the substrate selection have not yet been established. Such design rules are particularly important for solution coated semiconducting polymers, as the substratedirected thin film morphology can impact charge transport properties by orders of magnitude. We hypothesize that substrate surface energies dictate the thin film morphology by modulating the free energy barrier to heterogeneous nucleation. To test this hypothesis, we systematically vary the substrate surface energy via surface functionalization techniques. We performmore » in-depth morphology and device characterizations to establish the relationship between substrate surface energy, thin film morphology and charge transport properties, employing a donor-accepter (D-A) conjugated polymer. Here, we find that decreasing the substrate surface energy progressively increases thin film crystallinity, degree of molecular ordering and extent of domain alignment. Notably, the enhanced morphology on the lowest surface energy substrate lead to a 10-fold increase in the charge carrier mobility. We further develop a free energy model relating the substrate surface energy to the penalty of heterogeneous nucleation from solution in the thin film geometry. The model correctly predicts the experimental trend, thereby validating our hypothesis. This work is a significant step towards establishing design rules and understanding the critical role of substrates in determining morphology of solution coated thin films.« less

Swollen poly(dimethylsiloxane) (PDMS) as a template for inorganic morphologies.

PubMed

Brennan, Daniel P; Dobley, Arthur; Sideris, Paul J; Oliver, Scott R J

2005-12-06

We report a series of silica, titania, and zirconia microstructures synthesized within swollen poly(dimethylsiloxane) (PDMS). Voids created by solvent-swelling the polymer are used to template the product. The inorganic morphologies range from spheres to networks, depending upon the nature of the polymer, its degree of swelling, and the synthetic conditions. Organic solvents as well as pure metal alkoxide liquids have been used to swell the polymer. Once the alkoxide precursor is inside the swollen polymer, water is introduced to bring about hydrolysis and condensation polymerization. The product is a textured metal oxide within a PDMS matrix. Scanning electron microscopy (SEM), optical microscopy, nuclear magnetic resonance (NMR), and powder X-ray diffraction (PXRD) were used to characterize the products. Microstructures formed in this manner have potential use as an inexpensive route to catalysts, fillers, capsules, or membranes for separations.

Morphological control of conductive polymers utilized electrolysis polymerization technique: trial of fabricating biocircuit.

PubMed

Onoda, Mitsuyoshi

2014-10-01

Conductive polymers are a strong contender for making electronic circuits. The growth pattern in conductive polymer synthesis by the electrolysis polymerization method was examined. The growth pattern is deeply related to the coupling reaction of the radical cation and the deprotonation reaction following it and changes suddenly depending on the kind and concentration of the supporting electrolyte and the solvent used. That is, when the electrophilic substitution coupling reaction becomes predominant, the three-dimensional growth form is observed, and when the radical coupling reaction becomes predominant, the two-dimensional growth morphology is observed. In addition, the growth pattern can be comparatively easily controlled by changing the value of the polymerization constant current, and it is considered that the indicator and development for biocircuit research with neuron-type devices made of conjugated polymers was obtained.

Ultrathin Au film on polymer surface for surface plasmon polariton waveguide application

NASA Astrophysics Data System (ADS)

Liu, Tong; Ji, Lanting; He, Guobing; Sun, Xiaoqiang; Wang, Fei; Zhang, Daming

2017-11-01

Formation of laterally continuous ultrathin gold films on polymer substrates is a technological challenge. In this work, the vacuum thermal evaporation method is adopted to form continuous Au films in the thickness range of 7-17 nm on polymers of Poly(methyl-methacrylate-glycidly-methacrylate) and SU-8 film surface without using the adhesion or metallic seeding layers. Absorption spectrum, scanning electron microscope and atomic force microscope images are used to characterize the Au film thickness, roughness and optical loss. The result shows that molecular-scale structure, surface energy and electronegativity have impacts on the Au film morphology on polymers. Wet chemical etching is used to fabricate 7-nm thick Au stripes embedded in polymer claddings. These long-range surface plasmon polariton waveguides demonstrate the favorable morphological configurations and cross-sectional states. Through the end-fire excitation method, propagation losses of 6-μm wide Au stripes are compared to theoretical values and analyzed from practical film status. The smooth, patternable gold films on polymer provide potential applications to plasmonic waveguides, biosensing, metamaterials and optical antennas.

Exploring Alkyl Chains in Benzobisthiazole-Naphthobisthiadiazole Polymers: Impact on Solar-Cell Performance, Crystalline Structures, and Optoelectronics.

PubMed

Al-Naamani, Eman; Gopal, Anesh; Ide, Marina; Osaka, Itaru; Saeki, Akinori

2017-11-01

The shapes and lengths of the alkyl chains of conjugated polymers greatly affect the efficiencies of organic photovoltaic devices. This often results in a trade-off between solubility and self-organizing behavior; however, each material has specific optimal chains. Here we report on the effect of alkyl side chains on the film morphologies, crystallinities, and optoelectronic properties of new benzobisthiazole-naphthobisthiadiazole (PBBT-NTz) polymers. The power conversion efficiencies (PCEs) of linear-branched and all-branched polymers range from 2.5% to 6.6%; the variations in these PCEs are investigated by atomic force microscopy, two-dimensional X-ray diffraction (2D-GIXRD), and transient photoconductivity techniques. The best-performing linear-branched polymer, bearing dodecyl and decyltetradecyl chains (C12-DT), exhibits nanometer-scale fibers along with the highest crystallinity, comprising predominant edge-on and partial face-on orientations. This morphology leads to the highest photoconductivity and the longest carrier lifetime. These results highlight the importance of long alkyl chains for inducing intermolecular stacking, which is in contrast to observations made for analogous previously reported polymers.

Dynamics of microemulsions bridged with hydrophobically end-capped star polymers studied by neutron spin-echo

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffmann, I., E-mail: ingo.hoffmann@tu-berlin.de; Institut Max von Laue-Paul Langevin; Malo de Molina, Paula

2014-01-21

The mesoscopic dynamical properties of oil-in-water microemulsions (MEs) bridged with telechelic polymers of different number of arms and with different lengths of hydrophobic stickers were studied with neutron spin-echo (NSE) probing the dynamics in the size range of individual ME droplets. These results then were compared to those of dynamicic light scattering (DLS) which allow to investigate the dynamics on a much larger length scale. Studies were performed as a function of the polymer concentration, number of polymer arms, and length of the hydrophobic end-group. In general it is observed that the polymer bridging has a rather small influence onmore » the local dynamics, despite the fact that the polymer addition leads to an increase of viscosity by several orders of magnitude. In contrast to results from rheology and DLS, where the dynamics on much larger length and time scales are observed, NSE shows that the linear polymer is more efficient in arresting the motion of individual ME droplets. This finding can be explained by a simple simulation, merely by the fact that the interconnection of droplets becomes more efficient with a decreasing number of arms. This means that the dynamics observed on the short and on the longer length scale depend in an opposite way on the number of arms and hydrophobic stickers.« less

Bulk heterojunction morphology of polymer:fullerene blends revealed by ultrafast spectroscopy

PubMed Central

Serbenta, Almis; Kozlov, Oleg V.; Portale, Giuseppe; van Loosdrecht, Paul H. M.; Pshenichnikov, Maxim S.

2016-01-01

Morphology of organic photovoltaic bulk heterojunctions (BHJs) – a nanoscale texture of the donor and acceptor phases – is one of the key factors influencing efficiency of organic solar cells. Detailed knowledge of the morphology is hampered by the fact that it is notoriously difficult to investigate by microscopic methods. Here we all-optically track the exciton harvesting dynamics in the fullerene acceptor phase from which subdivision of the fullerene domain sizes into the mixed phase (2–15 nm) and large (>50 nm) domains is readily obtained via the Monte-Carlo simulations. These results were independently confirmed by a combination of X-ray scattering, electron and atomic-force microscopies, and time-resolved photoluminescence spectroscopy. In the large domains, the excitons are lost due to the high energy disorder while in the ordered materials the excitons are harvested with high efficiency even from the domains as large as 100 nm due to the absence of low-energy traps. Therefore, optimizing of blend nanomorphology together with increasing the material order are deemed as winning strategies in the exciton harvesting optimization. PMID:27824085

Polymer brushes infiltrated by nanoparticles and applications to the nuclear pore complex

NASA Astrophysics Data System (ADS)

Opferman, Michael G.

Systems of grafted polymers in the presence of additives are useful in a variety of contexts including industrial applications, solar cells, organic electronics, drug delivery, and nucleocytoplasmic transport. In this thesis, we will consider the morphologies that polymer brushes attain when exposed to a solution of additives (which we generically term "nanoparticles"), particularly when those nanparticles interact attractively with the polymers. We find that nanoparticles of this type can have a dramatic effect on the height of the polymer chains above the grafting surface, and they can induce highly non-uniform morphologies, including ones in which a dense layer of nanoparticles and monomers forms near the grafting surface. We consider especially the relevance of the system to several experiments performed on biopolymers in the nuclear pore complex when they interact attractively with transport factors that regulate nucleocytoplasmic transport. We find that, although these experiments appear to give inconsistent results, the inconsistencies can be reconciled through two simple models: the Alexander-de Gennes polymer brush, and the Milner-Witten-Cates polymer brush. Our findings should contribute to the understanding of the nuclear pore complex in that experiments can be better understood in the context of their relevant control parameters.

Ordered polymer nanofibers enhance output brightness in bilayer light-emitting field-effect transistors.

PubMed

Hsu, Ben B Y; Seifter, Jason; Takacs, Christopher J; Zhong, Chengmei; Tseng, Hsin-Rong; Samuel, Ifor D W; Namdas, Ebinazar B; Bazan, Guillermo C; Huang, Fei; Cao, Yong; Heeger, Alan J

2013-03-26

Polymer light emitting field effect transistors are a class of light emitting devices that reveal interesting device physics. Device performance can be directly correlated to the most fundamental polymer science. Control over surface properties of the transistor dielectric can dramatically change the polymer morphology, introducing ordered phase. Electronic properties such as carrier mobility and injection efficiency on the interface can be promoted by ordered nanofibers in the polymer. Moreover, by controlling space charge in the polymer interface, the recombination zone can be spatially extended and thereby enhance the optical output.

Mechanisms Underlying Ionic Mobilities in Nanocomposite Polymer Electrolytes

NASA Astrophysics Data System (ADS)

Ganesan, Venkat; Hanson, Benjamin; Pryamitsyn, Victor

2014-03-01

Recently, a number of experiments have demonstrated that addition of ceramics with nanoscale dimensions can lead to substantial improvements in the low temperature conductivity of the polymeric materials. However, the origin of such behaviors, and more generally, the manner by which nanoscale fillers impact the ion mobilities remain unresolved. In this communication, we report the results of atomistic molecular dynamics simulations which used multibody polarizable force-fields to study lithium ion diffusivities in an amorphous poly(ethylene-oxide) (PEO) melt containing well-dispersed TiO2 nanoparticles. We observed that the lithium ion diffusivities decrease with increased particle loading. Our analysis suggests that the ion mobilities are correlated to the nanoparticle-induced changes in the polymer segmental dynamics. Interestingly, the changes in polymer segmental dynamics were seen to be related to the nanoparticle's influence on the polymer conformational features. Overall, our results indicate that addition of nanoparticle fillers modify polymer conformations and the polymer segmental dynamics, and thereby influence the ion mobilities of polymer electrolytes.

Thin Films Formed from Conjugated Polymers with Ionic, Water-Soluble Backbones.

PubMed

Voortman, Thomas P; Chiechi, Ryan C

2015-12-30

This paper compares the morphologies of films of conjugated polymers in which the backbone (main chain) and pendant groups are varied between ionic/hydrophilic and aliphatic/hydrophobic. We observe that conjugated polymers in which the pendant groups and backbone are matched, either ionic-ionic or hydrophobic-hydrophobic, form smooth, structured, homogeneous films from water (ionic) or tetrahydrofuran (hydrophobic). Mismatched conjugated polymers, by contrast, form inhomogeneous films with rough topologies. The polymers with ionic backbone chains are conjugated polyions (conjugated polymers with closed-shell charges in the backbone), which are semiconducting materials with tunable bad-gaps, not unlike uncharged conjugated polymers.

Effect of Sterilization Methods on Electrospun Poly(lactic acid) (PLA) Fiber Alignment for Biomedical Applications.

PubMed

Valente, T A M; Silva, D M; Gomes, P S; Fernandes, M H; Santos, J D; Sencadas, V

2016-02-10

Medically approved sterility methods should be a major concern when developing a polymeric scaffold, mainly when commercialization is envisaged. In the present work, poly(lactic acid) (PLA) fiber membranes were processed by electrospinning with random and aligned fiber alignment and sterilized under UV, ethylene oxide (EO), and γ-radiation, the most common ones for clinical applications. It was observed that UV light and γ-radiation do not influence fiber morphology or alignment, while electrospun samples treated with EO lead to fiber orientation loss and morphology changing from cylindrical fibers to ribbon-like structures, accompanied to an increase of polymer crystallinity up to 28%. UV light and γ-radiation sterilization methods showed to be less harmful to polymer morphology, without significant changes in polymer thermal and mechanical properties, but a slight increase of polymer wettability was detected, especially for the samples treated with UV radiation. In vitro results indicate that both UV and γ-radiation treatments of PLA membranes allow the adhesion and proliferation of MG 63 osteoblastic cells in a close interaction with the fiber meshes and with a growth pattern highly sensitive to the underlying random or aligned fiber orientation. These results are suggestive of the potential of both γ-radiation sterilized PLA membranes for clinical applications in regenerative medicine, especially those where customized membrane morphology and fiber alignment is an important issue.

Morphology Development During Deposition in OPV Low Band Gap Polymer:Bis-Fullerene Heterojunctions: Effect of a Second Solvent

NASA Astrophysics Data System (ADS)

Chen, Huipeng; Hsiao, Yu-Che; Hu, Bin; Dadmun, Mark

2014-03-01

Polymer based bulk-heterojunction solar cells, based on blends of conjugated polymers and fullerenes are one potential option for low cost renewable power generation. One way to improve power conversion efficiency (PCE) of this cell is to increase the open-circuit voltage (Voc) . It has been reported that replacing PCBM with bis-adduct fullerenes (i.e. ICBA) significantly improves Voc and PCE in P3HT device. However, for the most promising low band-gap polymer (LBP) system, replacing PCBM with ICBA gives very poor short-circuit current (Jsc) and PCE although Voc is significantly improved. As Jsc and PCE strongly depend on the morphology, we therefore tried to optimize the morphology of as-cast LBP/ICBA mixture by adding a second solvent with varying solubility to LBP and ICBA to the deposition solution. The results show that there is no change of LBP ordering by adding the second solvent regardless of its solubility. The morphology of all the as-cast samples is then determined by neutron scattering. A homogenous dispersion of ICBA in LBP is found in the sample where the second solvent is selective to LBP, giving poor PCE. Aggregates of ICBA are formed in those samples where the second solvent is selective to ICBA. The resultant morphology improves PCE by up to 246%. A quantitative analysis of neutron data shows that the interfacial area between ICBA aggregates and LBP/ICBA mixed phase is improved in these samples, which appears to facilitate charge transport and reduce the recombination of free charge carriers.

Shuttle Atlantis to deploy Galileo probe toward Jupiter

NASA Technical Reports Server (NTRS)

1989-01-01

The objectives of Space Shuttle Mission STS-34 are described along with major flight activities, prelaunch and launch operations, trajectory sequence of events, and landing and post-landing operations. The primary objective of STS-34 is to deploy the Galileo planetary exploration spacecraft into low earth orbit. Following deployment, Galileo will be propelled on a trajectory, known as Venus-Earth-Earth Gravity Assist (VEEGA), by an inertial upper stage (IUS). The objectives of the Galileo mission are to study the chemical composition, state, and dynamics of the Jovian atmosphere and satellites, and investigate the structure and physical dynamics of the Jovian magnetosphere. Secondary STS-34 payloads include the Shuttle Solar Backscatter Ultraviolet (SSBUV) instrument; the Mesoscale Lightning Experiment (MLE); and various other payloads involving polymer morphology, the effects of microgravity on plant growth hormone, and the growth of ice crystals.

Dynamic Mechanical Properties of Bio-Polymer Graphite Thin Films

NASA Astrophysics Data System (ADS)

Saddam Kamarudin, M.; Rus, Anika Zafiah M.; Munirah Abdullah, Nur; Abdullah, M. F. L.

2017-08-01

Waste cooking oil is used as the main substances in producing graphite biopolymer thin films. Biopolymer is produce from the reaction of bio-monomer and cross linker with the ratio of 2:1 and addition of graphite with an increment of 2% through a slip casting method. The morphological surface properties of the samples are observed by using Scanning Electron Microscope (SEM). It is shown that the graphite particle is well mixed and homogenously dispersed in biopolymer matrix. Meanwhile, the mechanical response of materials by monitoring the change in the material properties in terms of frequency and temperature of the samples were determined using Dynamic Mechanical Analysis (DMA). The calculated cross-linked density of biopolymer composites revealed the increment of graphite particle loading at 8% gives highest results with 260.012 x 103 M/m3.

Surface modification of cellulose using silane coupling agent.

PubMed

Thakur, Manju Kumari; Gupta, Raju Kumar; Thakur, Vijay Kumar

2014-10-13

Recently there has been a growing interest in substituting traditional synthetic polymers with natural polymers for different applications. However, natural polymers such as cellulose suffer from few drawbacks. To become viable potential alternatives of synthetic polymers, cellulosic polymers must have comparable physico-chemical properties to that of synthetic polymers. So in the present work, cellulose polymer has been modified by a series of mercerization and silane functionalization to optimize the reaction conditions. Structural, thermal and morphological characterization of the cellulose has been done using FTIR, TGA and SEM, techniques. Surface modified cellulose polymers were further subjected to evaluation of their properties like swelling and chemical resistance behavior. Published by Elsevier Ltd.

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

NASA Astrophysics Data System (ADS)

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.

Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

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

2016-09-06

A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

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

2014-05-13

A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Confined dynamics of grafted polymer chains in solutions of linear polymer

DOE PAGES

Poling-Skutvik, Ryan D.; Olafson, Katy N.; Narayanan, Suresh; ...

2017-09-11

Here, we measure the dynamics of high molecular weight polystyrene grafted to silica nanoparticles dispersed in semidilute solutions of linear polymer. Structurally, the linear free chains do not penetrate the grafted corona but increase the osmotic pressure of the solution, collapsing the grafted polymer and leading to eventual aggregation of the grafted particles at high matrix concentrations. Dynamically, the relaxations of the grafted polymer are controlled by the solvent viscosity according to the Zimm model on short time scales. On longer time scales, the grafted chains are confined by neighboring grafted chains, preventing full relaxation over the experimental time scale.more » Adding free linear polymer to the solution does not affect the initial Zimm relaxations of the grafted polymer but does increase the confinement of the grafted chains. Finally, our results elucidate the physics underlying the slow relaxations of grafted polymer.« less

Confined dynamics of grafted polymer chains in solutions of linear polymer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poling-Skutvik, Ryan D.; Olafson, Katy N.; Narayanan, Suresh

Here, we measure the dynamics of high molecular weight polystyrene grafted to silica nanoparticles dispersed in semidilute solutions of linear polymer. Structurally, the linear free chains do not penetrate the grafted corona but increase the osmotic pressure of the solution, collapsing the grafted polymer and leading to eventual aggregation of the grafted particles at high matrix concentrations. Dynamically, the relaxations of the grafted polymer are controlled by the solvent viscosity according to the Zimm model on short time scales. On longer time scales, the grafted chains are confined by neighboring grafted chains, preventing full relaxation over the experimental time scale.more » Adding free linear polymer to the solution does not affect the initial Zimm relaxations of the grafted polymer but does increase the confinement of the grafted chains. Finally, our results elucidate the physics underlying the slow relaxations of grafted polymer.« less

Dynamics of Hyperbranched Polymers under Confinement

NASA Astrophysics Data System (ADS)

Androulaki, Krystallenia; Chrissopoulou, Kiriaki; Anastasiadis, Spiros H.; Prevosto, Daniele; Labardi, Massimiliano

2015-03-01

The effect of severe confinement on the dynamics of three different generations of hyperbranched polyesters (Boltorns) is investigated by Dielectric Spectroscopy. The polymers are intercalated within the galleries of natural Na+-MMT, thus, forming 1nm polymer films confined between solid walls. The Tg's of the polymers determined by DSC show a clear dependence on the generation whereas the transition is completely suppressed when all the polymer chains are intercalated. The dynamic investigation of the bulk polymers reveals two sub-Tg processes, with similar behavior for the three polymers with the segmental relaxation observed above the Tg of each. For the nanocomposites, where all polymers are severely confined, the dynamics show significant differences compared to that of the bulk polymers. The sub-Tg processes are similar for the three generations but significantly faster and with weaker temperature dependence than those in the bulk. The segmental process appears at temperatures below the bulk polymer Tg, it exhibits an Arrhenius temperature dependence and shows differences for the three generations. A slow process that appears at higher temperatures is due to interfacial polarization. Co-financed by the EU and Greek funds through the Operational Program ``Education and Lifelong Learning'' of the NSRF-Research Funding Program: THALES-Investing in knowledge society through the Eur. Social Fund (MIS 377278) and COST Action MP0902-COINAPO.

Effect of PMMA polymer on the dynamic viscoelasticity and plasticizer leachability of PEMA-based tissue conditioners.

PubMed

Hong, Guang; Maeda, Takeshi; Li, YingAi; Sadamori, Shinsuke; Hamada, Taizo; Murata, Hiroshi

2010-08-01

The purpose of this study was to determine the effect of PMMA polymer on dynamic viscoelasticity and plasticizer leachability of PEMA-based tissue conditioners. One PEMA polymer and one PMMA polymer were used in powder form with four formulations. The combination of 80 wt% ATBC, 15 wt% BPBG and 5 wt% ethyl alcohol was used as the liquid phase. The dynamic viscoelasticity and plasticizer leaching of each specimen were measured after 0, 1, 3, 7, and 14 days of immersion (37 degrees C distilled water) using DMA and HPLC. A significant difference was found among the materials in the dynamic viscoelasticity and leaching of plasticizer. The materials containing 10 wt% PMMA showed the most stable dynamic viscoelasticity, and showed the lowest leaching of plasticizer. The results suggest that the addition of the PMMA polymer to the powder of a tissue conditioner can improve the durability of the PEMA-based tissue conditioner.

Sialic acid-triggered macroscopic properties switching on a smart polymer surface

NASA Astrophysics Data System (ADS)

Xiong, Yuting; Li, Minmin; Wang, Hongxi; Qing, Guangyan; Sun, Taolei

2018-01-01

Constructing smart surfaces with responsive polymers capable of dynamically and reversibly changing their chemical and physical properties by responding to the recognition of biomolecules remains a challenging task. And, the key to achieving this purpose relies on the design of polymers to precisely interact with the target molecule and successfully transform the interaction signal into tunable macroscopic properties, further achieve special bio-functions. Herein, inspired by carbohydrate-carbohydrate interaction (CCI) in life system, we developed a three-component copolymer poly(NIPAAm-co-PT-co-Glc) bearing a binding unit glucose (Glc) capable of recognizing sialic acid, a type of important molecular targets for cancer diagnosis and therapy, and reported the sialic acid triggered macroscopic properties switching on this smart polymer surface. Detailed mechanism studies indicated that multiple hydrogen bonding interactions between Glc unit and Neu5Ac destroyed the initial hydrogen bond network of the copolymer, leading to a reversible "contraction-to-swelling" conformational transition of the copolymer chains, accompanied with distinct macroscopic property switching (i.e., surface wettability, morphology, stiffness) of the copolymer film. And these features enabled this copolymer to selectively capture sialic acid-containing glycopeptides from complex protein samples. This work provides an inspiration for the design of novel smart polymeric materials with sensitive responsiveness to sialic acid, which would promote the development of sialic acid-specific bio-devices and drug delivery systems.

Intercalated Nanocomposites Based on High-Temperature Superconducting Ceramics and Their Properties

PubMed Central

Tonoyan, Anahit; Schiсk, Christoph; Davtyan, Sevan

2009-01-01

High temperature superconducting (SC) nanocomposites based on SC ceramics and various polymeric binders were prepared. Regardless of the size of the ceramics’ grains, the increase of their amount leads to an increase of resistance to rupture and modulus and a decrease in limiting deformation, whereas an increase in the average ceramic grain size worsens resistance properties. The SC, thermo-chemical, mechanical and dynamic-mechanical properties of the samples were investigated. Superconducting properties of the polymer ceramic nanocomposites are explained by intercalation of macromolecule fragments into the interstitial layer of the ceramics’ grains. This phenomenon leads to a change in the morphological structure of the superconducting nanocomposites.

Preparation And Evaluation Techniques of Porous Materials and Mixed Matrix Membranes for Targeted CO2 Separation Applications

NASA Astrophysics Data System (ADS)

Tessema, Tsemre Dingel Mesfin

The use of porous sorbents for physisorptive capture of CO2 from gas mixtures has been deemed attractive due to the low energy penalty associated with recycling of such materials. Porous organic polymers (POPs) have emerged as promising candidates with potential in the treatment of pre- and post- fuel combustion processes to separate CO2 from gas mixtures. Concurrently, significant advances have been made in establishing calculation methods that evaluate the practicality of porous sorbents for targeted gas separation applications. However, these methods rely on single gas adsorption isotherms without accounting for the dynamic gas mixtures encountered in real-life applications. To this end, the design and application of a dynamic gas mixture breakthrough apparatus to assess the CO2 separation performance of a new class of heteroatom (N and O) doped porous carbons derived from a Pyrazole precursor from flue gas mixtures is presented. Here in, two new benzimidazole linked polymers (BILPs) have been designed and synthesized. These polymers display high surface while their imidazole functionality and microporous nature resulted in high CO2 uptakes and isosteric heat of adsorption (Qst). BILP-30 displayed very good selectivity for CO2 in flue gas while BILP-31 was superior in CO2 separation from landfill gas mixtures at 298 K and 1 bar. Additionally, a new POP incorporating a highly conjugated pyrene core into a polymer framework linked by azo-bonds is presented. Azo-Py displays a nanofibrous morphology induced by the pi-pi stacking of the electron rich pyrene core. Due to its high surface area and microporous nature, Azo-Py displays impressive CO2 uptakes at 298 K and 1 bar. Evaluation of the S value for CO2 separation of Azo-Py revealed competitive values for flue gas and landfill gas at 298 K and 1 bar. Finally, a highly cross-linked benzimidazole linked polymer, BILP-4, was successfully incorporated into MatrimidRTM polymer to form a series of new mixed matrix membranes. The surface functionality of BILP-4 was exploited to enhance the interaction with MatrimidRTM polymer matrix to produce robust MMMs which displayed significantly improved CO2 gas permeabilities and ideal selectivities for CO 2/N2.

Processing and characterization of solid and microcellular biobased and biodegradable PHBV-based polymer blends and composites

NASA Astrophysics Data System (ADS)

Javadi, Alireza

Petroleum-based polymers have made a significant contribution to human society due to their extraordinary adaptability and processability. However, due to the wide-spread application of plastics over the past few decades, there are growing concerns over depleting fossil resources and the undesirable environmental impact of plastics. Most of the petroleum-based plastics are non-biodegradable and thus will be disposed in landfills. Inappropriate disposal of plastics may also become a potential threat to the environment. Many approaches, such as efficient plastics waste management and replacing petroleum-based plastics with biodegradable materials obtained from renewable resources, have been put forth to overcome these problems. Plastics waste management is at its beginning stages of development which is also more expensive than expected. Thus, there is a growing interest in developing sustainable biobased and biodegradable materials produced from renewable resources such as plants and crops, which can offer comparable performance with additional advantages, such as biodegradability, biocompatibility, and reducing the carbon footprint. Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is one of the most promising biobased and biodegradable polymers, In fact many petroleum based polymers such as poly(propylene) (PP) can be potentially replaced by PHBV because of the similarity in their properties. Despite PHBV's attractive properties, there are many drawbacks such as high cost, brittleness, and thermal instability, which hamper the widespread usage of this specific polymer. The goals of this study are to investigate various strategies to address these drawbacks, including blending with other biodegradable polymers such as poly (butylene adipate-coterephthalate) (PBAT) or fillers (e.g., coir fiber, recycled wood fiber, and nanofillers) and use of novel processing technologies such as microcellular injection molding technique. Microcellular injection molding technique will not only reduce cost but also improve processability due to the use of supercritical fluid. Various material properties of the solid (without the foaming agent) and microcellular components (with foaming agent) made of PHBV-based polymer blends or composites were investigated including static mechanical properties (tensile testing), dynamic mechanical properties (dynamic mechanical analysis), thermal properties (differential scanning calorimetry and thermo gravimetric analysis), crystallinity(wide angle X-ray scattering analysis), and morphology (scanning electron microscopy and transmission electron microscopy). The composition-processing-structure-property relationship of these solid and microcellular components were established.

Modelling morphology evolution during solidification of IPP in processing conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pantani, R., E-mail: rpantani@unisa.it, E-mail: fedesantis@unisa.it, E-mail: vsperanza@unisa.it, E-mail: gtitomanlio@unisa.it; De Santis, F., E-mail: rpantani@unisa.it, E-mail: fedesantis@unisa.it, E-mail: vsperanza@unisa.it, E-mail: gtitomanlio@unisa.it; Speranza, V., E-mail: rpantani@unisa.it, E-mail: fedesantis@unisa.it, E-mail: vsperanza@unisa.it, E-mail: gtitomanlio@unisa.it

During polymer processing, crystallization takes place during or soon after flow. In most of cases, the flow field dramatically influences both the crystallization kinetics and the crystal morphology. On their turn, crystallinity and morphology affect product properties. Consequently, in the last decade, researchers tried to identify the main parameters determining crystallinity and morphology evolution during solidification In processing conditions. In this work, we present an approach to model flow-induced crystallization with the aim of predicting the morphology after processing. The approach is based on: interpretation of the FIC as the effect of molecular stretch on the thermodynamic crystallization temperature; modelingmore » the molecular stretch evolution by means of a model simple and easy to be implemented in polymer processing simulation codes; identification of the effect of flow on nucleation density and spherulites growth rate by means of simple experiments; determination of the condition under which fibers form instead of spherulites. Model predictions reproduce most of the features of final morphology observed in the samples after solidification.« less

Interfaces in polymer nanocomposites – An NMR study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Böhme, Ute; Scheler, Ulrich, E-mail: scheler@ipfdd.de

Nuclear Magnetic Resonance (NMR) is applied for the investigation of polymer nanocomposites. Solid-state NMR is applied to study the modification steps to compatibilize layered double hydroxides with non-polar polymers. {sup 1}H relaxation NMR gives insight on the polymer dynamics over a wide range of correlation times. For the polymer chain dynamics the transverse relaxation time T{sub 2} is most suited. In this presentation we report on two applications of T{sub 2} measurements under external mechanical stress. In a low-field system relaxation NMR studies are performed in-situ under uniaxial stress. High-temperature experiments in a Couette cell permit the investigation of themore » polymer dynamics in the melt under shear flow.« less

Dynamics of Lithium Polymer Electrolytes using X-ray Photon Correlation Spectroscopy and Rheology

NASA Astrophysics Data System (ADS)

Oparaji, Onyekachi; Narayanan, Suresh; Sandy, Alec; Hallinan, Daniel, Jr.

Polymer electrolytes are promising materials for high energy density rechargeable batteries. Battery fade can be caused by structural evolution in the battery electrode and loss of electrode/electrolyte adhesion during cycling. Both of these effects are dependent on polymer mechanical properties. In addition, cycling rate is dictated by the ion mobility of the polymer electrolyte. Lithium ion mobility is expected to be strongly coupled to polymer dynamics. Therefore, we investigate polymer dynamics as a function of salt concentration using X-ray Photon Correlation Spectroscopy (XPCS) and rheology. We report the influence of lithium salt concentration on the structural relaxation time (XPCS) and stress relaxation time (rheology) of high molecular weight poly(styrene - ethylene oxide) block copolymer membranes.

Dynamics in Complex Coacervates

NASA Astrophysics Data System (ADS)

Perry, Sarah

Understanding the dynamics of a material provides detailed information about the self-assembly, structure, and intermolecular interactions present in a material. While rheological methods have long been used for the characterization of complex coacervate-based materials, it remains a challenge to predict the dynamics for a new system of materials. Furthermore, most work reports only qualitative trends exist as to how parameters such as charge stoichiometry, ionic strength, and polymer chain length impact self-assembly and material dynamics, and there is little information on the effects of polymer architecture or the organization of charges within a polymer. We seek to link thermodynamic studies of coacervation phase behavior with material dynamics through a carefully-controlled, systematic study of coacervate linear viscoelasticity for different polymer chemistries. We couple various methods of characterizing the dynamics of polymer-based complex coacervates, including the time-salt superposition methods developed first by Spruijt and coworkers to establish a more mechanistic strategy for comparing the material dynamics and linear viscoelasticity of different systems. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support of this research.

Neutron Reflectivity Measurement for Polymer Dynamics near Graphene Oxide Monolayers

NASA Astrophysics Data System (ADS)

Koo, Jaseung

We investigated the diffusion dynamics of polymer chains confined between graphene oxide layers using neutron reflectivity (NR). The bilayers of polymethylmetacrylate (PMMA)/ deuterated PMMA (d-PMMA) films and polystyrene (PS)/d-PS films with various film thickness sandwiched between Langmuir-Blodgett (LB) monolayers of graphene oxide (GO) were prepared. From the NR results, we found that PMMA diffusion dynamics was reduced near the GO surface while the PS diffusion was not significantly changed. This is due to the different strength of GO-polymer interaction. In this talk, these diffusion results will be compared with dewetting dynamics of polymer thin films on the GO monolayers. This has given us the basis for development of graphene-based nanoelectronics with high efficiency, such as heterojunction devices for polymer photovoltaic (OPV) applications.

Synthesis and Physical Properties of Poly(Perfluoroalkylether)Urethanes

DTIC Science & Technology

1989-05-30

Differential scanning calorimetry and dynamic mechanical analysis showed that the incorporation of PFEG into the soft segment phase slightly enhanced...for all the polymers, using electron spectroscopy for chemical analysis (ESCA). The dynamic contact angle results indicate that the polymer surfaces...these polymers were evaluated by a variety of techniques. Differential scanning calorimetry and dynamic mechanical analysis showed that the

Interplay between local dynamics and mechanical reinforcement in glassy polymer nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holt, Adam P.; Bocharova, Vera; Cheng, Shiwang

The modification of polymer dynamics in the presence of strongly interacting nanoparticles has been shown to significantly change themacroscopic properties above the glass transition temperature of polymer nanocomposites (PNCs). However, much less attention has been paid to changes in the dynamics of glassy PNCs. Analysis of neutron and light scattering data presented herein reveals a surprising enhancement of local dynamics, e.g., fast picosecond and secondary relaxations, in glassy PNCs accompanied with a strengthening of mechanical modulus. Here we ascribe this counter-intuitive behavior to the complex interplay between chain packing and stretching within the interfacial layer formed at the polymer-nanoparticle interface.

Interplay between local dynamics and mechanical reinforcement in glassy polymer nanocomposites

DOE PAGES

Holt, Adam P.; Bocharova, Vera; Cheng, Shiwang; ...

2017-11-17

The modification of polymer dynamics in the presence of strongly interacting nanoparticles has been shown to significantly change themacroscopic properties above the glass transition temperature of polymer nanocomposites (PNCs). However, much less attention has been paid to changes in the dynamics of glassy PNCs. Analysis of neutron and light scattering data presented herein reveals a surprising enhancement of local dynamics, e.g., fast picosecond and secondary relaxations, in glassy PNCs accompanied with a strengthening of mechanical modulus. Here we ascribe this counter-intuitive behavior to the complex interplay between chain packing and stretching within the interfacial layer formed at the polymer-nanoparticle interface.

Dynamics of Model Hydraulic Fracturing Liquid Studied by Two-Dimensional Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Daley, Kim; Kubarych, Kevin J.

2014-06-01

The technique of two-dimensional infrared (2DIR) spectroscopy is used to expose the chemical dynamics of various concentrations of polymers and their monomers in heterogeneous mixtures. An environmentally relevant heterogeneous mixture, which inspires this study, is hydraulic fracturing liquid (HFL). Hydraulic fracking is a technique used to extract natural gas from shale deposits. HFL consists of mostly water, proppant (sand), an emulsifier (guar), and other chemicals specific to the drilling site. Utilizing a metal carbonyl as a probe, we observe the spectral dynamics of the polymer, guar, and its monomer, mannose, and compare the results to see how hydration dynamics change with varying concentration. Another polymer, Ficoll, and its monomer, sucrose, are also compared to see how polymer size affects hydration dynamics. The two results are as follows: (1) Guar experiences collective hydration at high concentrations, where as mannose experiences independent hydration; (2) no collective hydration is observed for Ficoll in the same concentration range as guar, possibly due to polymer shape and size. HFL experiences extremely high pressure during natural gas removal, so future studies will focus on how increased pressure affects the hydration dynamics of polymers and monomers.

Dynamics of comb-of-comb-network polymers in random layered flows

NASA Astrophysics Data System (ADS)

Katyal, Divya; Kant, Rama

2016-12-01

We analyze the dynamics of comb-of-comb-network polymers in the presence of external random flows. The dynamics of such structures is evaluated through relevant physical quantities, viz., average square displacement (ASD) and the velocity autocorrelation function (VACF). We focus on comparing the dynamics of the comb-of-comb network with the linear polymer. The present work displays an anomalous diffusive behavior of this flexible network in the random layered flows. The effect of the polymer topology on the dynamics is analyzed by varying the number of generations and branch lengths in these networks. In addition, we investigate the influence of external flow on the dynamics by varying flow parameters, like the flow exponent α and flow strength Wα. Our analysis highlights two anomalous power-law regimes, viz., subdiffusive (intermediate-time polymer stretching and flow-induced diffusion) and superdiffusive (long-time flow-induced diffusion). The anomalous long-time dynamics is governed by the temporal exponent ν of ASD, viz., ν =2 -α /2 . Compared to a linear polymer, the comb-of-comb network shows a shorter crossover time (from the subdiffusive to superdiffusive regime) but a reduced magnitude of ASD. Our theory displays an anomalous VACF in the random layered flows that scales as t-α /2. We show that the network with greater total mass moves faster.

An Electrochemical NO2 Sensor Based on Ionic Liquid: Influence of the Morphology of the Polymer Electrolyte on Sensor Sensitivity

PubMed Central

Kuberský, Petr; Altšmíd, Jakub; Hamáček, Aleš; Nešpůrek, Stanislav; Zmeškal, Oldřich

2015-01-01

A systematic study was carried out to investigate the effect of ionic liquid in solid polymer electrolyte (SPE) and its layer morphology on the characteristics of an electrochemical amperometric nitrogen dioxide sensor. Five different ionic liquids were immobilized into a solid polymer electrolyte and key sensor parameters (sensitivity, response/recovery times, hysteresis and limit of detection) were characterized. The study revealed that the sensor based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)2]) showed the best sensitivity, fast response/recovery times, and low sensor response hysteresis. The working electrode, deposited from water-based carbon nanotube ink, was prepared by aerosol-jet printing technology. It was observed that the thermal treatment and crystallinity of poly(vinylidene fluoride) (PVDF) in the solid polymer electrolyte influenced the sensitivity. Picture analysis of the morphology of the SPE layer based on [EMIM][N(Tf)2] ionic liquid treated under different conditions suggests that the sensor sensitivity strongly depends on the fractal dimension of PVDF spherical objects in SPE. Their deformation, e.g., due to crowding, leads to a decrease in sensor sensitivity. PMID:26569248

Effect of Processing Parameters on the Morphology of PVDF Electrospun Nanofiber

NASA Astrophysics Data System (ADS)

Zulfikar, M. A.; Afrianingsih, I.; Nasir, M.; Alni, A.

2018-03-01

Electrospinning is a process that produces continuous polymer fibers with diameters in the submicron range through the action of an external electric field imposed on a polymer solution or melt. Because of the tiny diameter in several hundreds of nanometers and the high porosity, electrospun membranes show potential applications in extensive areas such as filtration systems, biomedical tissue templates, drug delivery membranes, and so on. In the electrospinning process, some parameters such as polymer concentration, feeding rate of the polymer solution, additives, humidity, viscosity, surface tension, applied voltage, and nozzle-to ground collector distance will affect the fiber diameter and morphology. In this work, we have evaluated the effects of two processing parameters including the flow rate of the polymer solution and nozzle-to ground collector distance, on the morphology of the fibers formed. The solutions used in the electrospinning experiments were prepared using Poly(vinylidene fluoride) (PVDF). This material was dissolved in N,N-dimethylformamide (DMF) to make solutions with concentrations of 20 wt%. These solutions was electrospun using a 5 mL plastic syringe with an 8 gauge stainless needle at an applied voltage of 20.0 kV, a flow rate of 0.02-0.04 mL/min and nozzle-to ground collector distance of 12 and 15 cm. Electrospinning of PVDF polymer solution was performed in horizontal alignment having a grounded aluminum foil which serves as a collector. The nanofibers obtained were characterized by polarizing optical microscope. We find that the low flow rate of the polymer solution and nozzle-to ground collector distance are strongly correlated with the formation of bead defects in the fibers.

Dielectric Properties of Generation 3 Pamam Dendrimer Nanocomposites

NASA Astrophysics Data System (ADS)

Ristić, Sanja; Mijović, Jovan

2008-08-01

Broadband dielectric relaxation spectroscopy (DRS) was employed to study molecular dynamics of blends composed of generation 3 poly(amidoamine) (PAMAM) dendrimers with ethylenediamine core and amino surface groups and four linear polymers: poly(propylene oxide)—PPO, two block copolymers, poly(propylene oxide)/poly(ethylene oxide)—PPO/PEO with different mol ratios (29/6 and 10/31) and poly(ethylene oxide)—PEO. The results were generated over a broad range of frequency. Dielectric spectra of dendrimers in PPO matrix reveal slight shift of normal and segmental processes to higher frequency with increasing concentration of dendrimers. In the 29PPO/6PEO matrix, no effect of concentration on the average relaxation time for normal and segmental processes was observed. In the 10PPO/31PEO matrix the relaxation time of the segmental process increases with increasing dendrimer concentration, while in the PEO matrix, local processes in dendrimers slow down. A detailed analysis of the effect of concentration of dendrimers and morphology of polymer matrix on the dielectric properties of dendrimer nanocomposites will be presented.

Dynamics of polydots: Soft luminescent polymeric nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maskey, Sabina; Osti, Naresh C.; Grest, Gary S.

The conformation and dynamics of luminescent polymers collapsed into nanoparticles or polydots were studied using fully atomistic molecular dynamics (MD) simulations, providing a first insight into their internal dynamics. Controlling the conformation and dynamics of confined polymers is essential for realization of the full potential of polydots in nanomedicine and biotechnology. Specifically, the shape and internal dynamics of polydots that consist of highly rigid dialkyl p-phenylene ethynylene (PPE) are probed as a function of temperature. At room temperature, the polydots are spherical without any correlations between the aromatic rings on the PPE backbone. With increasing temperature, they expand and becomemore » slightly aspherical; however, the polymers remain confined. The coherent dynamic structure factor reveals that the internal motion of the polymer backbone is arrested, and the side chains dominate the internal dynamics of the polydots. Lastly, these new soft nanoparticles retain their overall shape and dynamics over an extended temperature range, and their conformation is tunable via their degree of expansion.« less

Dynamics of polydots: Soft luminescent polymeric nanoparticles

DOE PAGES

Maskey, Sabina; Osti, Naresh C.; Grest, Gary S.; ...

2016-03-04

The conformation and dynamics of luminescent polymers collapsed into nanoparticles or polydots were studied using fully atomistic molecular dynamics (MD) simulations, providing a first insight into their internal dynamics. Controlling the conformation and dynamics of confined polymers is essential for realization of the full potential of polydots in nanomedicine and biotechnology. Specifically, the shape and internal dynamics of polydots that consist of highly rigid dialkyl p-phenylene ethynylene (PPE) are probed as a function of temperature. At room temperature, the polydots are spherical without any correlations between the aromatic rings on the PPE backbone. With increasing temperature, they expand and becomemore » slightly aspherical; however, the polymers remain confined. The coherent dynamic structure factor reveals that the internal motion of the polymer backbone is arrested, and the side chains dominate the internal dynamics of the polydots. Lastly, these new soft nanoparticles retain their overall shape and dynamics over an extended temperature range, and their conformation is tunable via their degree of expansion.« less

Minimum free-energy paths for the self-organization of polymer brushes.

PubMed

Gleria, Ignacio; Mocskos, Esteban; Tagliazucchi, Mario

2017-03-22

A methodology to calculate minimum free-energy paths based on the combination of a molecular theory and the improved string method is introduced and applied to study the self-organization of polymer brushes under poor solvent conditions. Polymer brushes in a poor solvent cannot undergo macroscopic phase separation due to the physical constraint imposed by the grafting points; therefore, they microphase separate forming aggregates. Under some conditions, the theory predicts that the homogeneous brush and the aggregates can exist as two different minima of the free energy. The theoretical methodology introduced in this work allows us to predict the minimum free-energy path connecting these two minima as well as the morphology of the system along the path. It is shown that the transition between the homogeneous brush and the aggregates may involve a free-energy barrier or be barrierless depending on the relative stability of the two morphologies and the chain length and grafting density of the polymer. In the case where a free-energy barrier exists, one of the morphologies is a metastable structure and, therefore, the properties of the brush as the quality of the solvent is cycled are expected to display hysteresis. The theory is also applied to study the adhesion/deadhesion transition between two opposing surfaces modified by identical polymer brushes and it is shown that this process may also require surpassing a free-energy barrier.

Molecular packing and electronic processes in amorphous-like polymer bulk heterojunction solar cells with fullerene intercalation.

PubMed

Xiao, Ting; Xu, Haihua; Grancini, Giulia; Mai, Jiangquan; Petrozza, Annamaria; Jeng, U-Ser; Wang, Yan; Xin, Xin; Lu, Yong; Choon, Ng Siu; Xiao, Hu; Ong, Beng S; Lu, Xinhui; Zhao, Ni

2014-06-09

The interpenetrating morphology formed by the electron donor and acceptor materials is critical for the performance of polymer:fullerene bulk heterojunction (BHJ) photovoltaic (PV) cells. In this work we carried out a systematic investigation on a high PV efficiency (>6%) BHJ system consisting of a newly developed 5,6-difluorobenzo[c] thiadiazole-based copolymer, PFBT-T20TT, and a fullerene derivative. Grazing incidence X-ray scattering measurements reveal the lower-ordered nature of the BHJ system as well as an intermixing morphology with intercalation of fullerene molecules between the PFBT-T20TT lamella. Steady-state and transient photo-induced absorption spectroscopy reveal ultrafast charge transfer (CT) at the PFBT-T20TT/fullerene interface, indicating that the CT process is no longer limited by exciton diffusion. Furthermore, we extracted the hole mobility based on the space limited current (SCLC) model and found that more efficient hole transport is achieved in the PFBT-T20TT:fullerene BHJ as compared to pure PFBT-T20TT, showing a different trend as compared to the previously reported highly crystalline polymer:fullerene blend with a similar intercalation manner. Our study correlates the fullerene intercalated polymer lamella morphology with device performance and provides a coherent model to interpret the high photovoltaic performance of some of the recently developed weakly-ordered BHJ systems based on conjugated polymers with branched side-chain.

Measuring Exciton Diffusion in Conjugated Polymer Films with Super-resolution Microscopy

NASA Astrophysics Data System (ADS)

Penwell, Samuel; Ginsberg, Lucas; Noriega Manez, Rodrigo; Ginsberg, Naomi

2015-03-01

Conjugated polymers are highly tunable organic semiconductors, which can be solution processed to form thin films, making them prime candidates for organic photovoltaic devices. One of the most important parameters in a conjugated polymer solar cell is the exciton diffusion length, which depends on intermolecular couplings, and is typically on the order of 10 nm. This mean exciton migration can vary dramatically between films and within a single film due to heterogeneities in morphology on length scales of 10's to 100's nm. To study the variability of exciton diffusion and morphology within individual conjugated polymer films, we are adapting stimulated emission depletion microscopy. STED is typically used in biology with well-engineered fluorescent labels or on NV-centers in diamond. I will, however, describe how we have demonstrated STED in conjugated polymer films of MEH-PPV and CN-PPV by taking care to first understand the film's photophysical properties. This new approach provides a way to study exciton diffusion by utilizing subdiffraction optical excitation volumes. In this way, we will obtain a spatiotemporal map of exciton distributions that will help to correlate the energetic landscape to film morphology at the nanoscale. This research is supported in part by the Department of Energy Office of Science Graduate Fellowship Program (DOE SCGF), made possible in part by the American Recovery and Reinvestment Act of 2009, administered by ORISE-ORAU under Contract No. DE-AC05-06.

Equilibrium Field Theoretic and Dynamic Mean Field Simulations of Inhomogeneous Polymeric Materials

NASA Astrophysics Data System (ADS)

Chao, Huikuan

Inhomogeneous polymeric materials is a large family of promising materials including but limited to block copolymers (BCPs), polymer nanocomposites (PNCs) and microscopically confined polymer films. The promising application of the materials originates from the materials' unique microstructures, which offer enhanced mechanical, thermal, optical and electrical properties to the materials. Due to the complex interactions and the large parameter space, behaviors of the microstructures formed by grafted nanoparticles and nanorods in PNCs are difficult to understand. Separately, because of relatively weak interactions, the microstructures are typically achieved through rapid processing that are kinetically controlled and beyond equilibrium. However, efficient simulation framework to study nonequilbrium dynamics of the materials is currently not available. To attack the first difficulty, I extended an efficient simulation framework, polymer nanocomposite field theory (PNC-FT), to incorporate grafted nanoparticles and nanorods. This extended framework is demonstrated against existing experimental studies and implemented to study how the nanoparticle design affects the nanoparticle distribution in binary homopolymer blends. The grafted nanoparticle model is also used as a platform to adopt an advanced optimization method to inversely design nanoparticles which are able to self-assemble into targeted two dimensional lattices. The nanorod model under PNC-FT framework is used to investigate the design of nanorod and block copolymer thin films to control the nanorod distribution. To attack the second difficulty, I established an efficient framework (SCMF-LD) based on a recently proposed dynamic mean field theory and used SCMF-LD to study how to kinetically control the nanoparticle distribution at the end of solvent annealing block copolymer thin films. The framework is then extended to incorporate hydrodynamics (SCMF-DPD) and the extended framework is implemented to study morphology development in phase inversion processing polymer thin films, where hydrodynamic effects play an important role. By exploring both equilibrium and nonequilibrium properties in a spectrum of inhomogeneous polymeric material systems, I successfully extended PNC-FT and established SCMF-LD and SCMF-DPD frameworks, which are expected to be efficient and powerful tools in studies of inhomogeneous polymeric material design and processing.

Mechanical properties of micro-injected HDPE composites

NASA Astrophysics Data System (ADS)

Bongiorno, A.; Pagano, C.; Agnelli, S.; Baldi, F.; Fassi, I.

2016-03-01

Micro-injection moulding is one of the key manufacturing technologies for the mass production of high value polymeric miniaturized-components. However, this process is not just a straightforward down scaling of the conventional injection moulding technique. Indeed, during the micro-injection the polymer melt is forced to flow at high strain rates through very small channels in non-isothermal conditions, and this can lead to complex microstructures and to parts with unexpected performances. In this work, the relationships among the processing conditions, the mechanical properties and the microstructural characteristics of miniaturized specimens obtained by injection moulding were investigated. Two model systems were considered with the same filler content of 15% wt. (HDPE-talc and HDPE-glass beads), representative of two different types of micro-composites: containing lamellar and spherical micro-particles, respectively. The attention was focused on the influence of the filler type and the process conditions on the mechanical behaviour, examined by uniaxial tensile tests and dynamic-mechanical analyses, and on the morphological characteristics of the specimens, examined by microscopy analyses. The results highlight that mechanical response of the miniaturized specimens is significantly affected by both the filler and the process conditions that can have an influence on the polymer microstructure. Lamellar composites showed the best performance due to the orientation of the talc particles during the micro-injection process, while, different morphologies of the skin/core transition region in dependence on the process temperatures were observable.

COMMUNICATION: Resonant activation in polymer translocation: new insights into the escape dynamics of molecules driven by an oscillating field

NASA Astrophysics Data System (ADS)

Pizzolato, N.; Fiasconaro, A.; Persano Adorno, D.; Spagnolo, B.

2010-09-01

The translocation of molecules across cellular membranes or through synthetic nanopores is strongly affected by thermal fluctuations. In this work we study how the dynamics of a polymer in a noisy environment changes when the translocation process is driven by an oscillating electric field. An improved version of the Rouse model for a flexible polymer has been adopted to mimic the molecular dynamics, by taking into account the harmonic interactions between adjacent monomers and the excluded-volume effect by introducing a Lennard-Jones potential between all beads. A bending recoil torque has also been included in our model. The polymer dynamics is simulated in a two-dimensional domain by numerically solving the Langevin equations of motion. Thermal fluctuations are taken into account by introducing a Gaussian uncorrelated noise. The mean first translocation time of the polymer centre of inertia shows a minimum as a function of the frequency of the oscillating forcing field. This finding represents the first evidence of the resonant activation behaviour in the dynamics of polymer translocation.

Single polymer dynamics under large amplitude oscillatory extension

NASA Astrophysics Data System (ADS)

Zhou, Yuecheng; Schroeder, Charles M.

2016-09-01

Understanding the conformational dynamics of polymers in time-dependent flows is of key importance for controlling materials properties during processing. Despite this importance, however, it has been challenging to study polymer dynamics in controlled time-dependent or oscillatory extensional flows. In this work, we study the dynamics of single polymers in large-amplitude oscillatory extension (LAOE) using a combination of experiments and Brownian dynamics (BD) simulations. Two-dimensional LAOE flow is generated using a feedback-controlled stagnation point device known as the Stokes trap, thereby generating an oscillatory planar extensional flow with alternating principal axes of extension and compression. Our results show that polymers experience periodic cycles of compression, reorientation, and extension in LAOE, and dynamics are generally governed by a dimensionless flow strength (Weissenberg number Wi) and dimensionless frequency (Deborah number De). Single molecule experiments are compared to BD simulations with and without intramolecular hydrodynamic interactions (HI) and excluded volume (EV) interactions, and good agreement is obtained across a range of parameters. Moreover, transient bulk stress in LAOE is determined from simulations using the Kramers relation, which reveals interesting and unique rheological signatures for this time-dependent flow. We further construct a series of single polymer stretch-flow rate curves (defined as single molecule Lissajous curves) as a function of Wi and De, and we observe qualitatively different dynamic signatures (butterfly, bow tie, arch, and line shapes) across the two-dimensional Pipkin space defined by Wi and De. Finally, polymer dynamics spanning from the linear to nonlinear response regimes are interpreted in the context of accumulated fluid strain in LAOE.

Nanoscale structure, dynamics and power conversion efficiency correlations in small molecule and oligomer-based photovoltaic devices

PubMed Central

Szarko, Jodi M.; Guo, Jianchang; Rolczynski, Brian S.; Chen, Lin X.

2011-01-01

Photovoltaic functions in organic materials are intimately connected to interfacial morphologies of molecular packing in films on the nanometer scale and molecular levels. This review will focus on current studies on correlations of nanoscale morphologies in organic photovoltaic (OPV) materials with fundamental processes relevant to photovoltaic functions, such as light harvesting, exciton splitting, exciton diffusion, and charge separation (CS) and diffusion. Small molecule photovoltaic materials will be discussed here. The donor and acceptor materials in small molecule OPV devices can be fabricated in vacuum-deposited, multilayer, crystalline thin films, or spin-coated together to form blended bulk heterojunction (BHJ) films. These two methods result in very different morphologies of the solar cell active layers. There is still a formidable debate regarding which morphology is favored for OPV optimization. The morphology of the conducting films has been systematically altered; using variations of the techniques above, the whole spectrum of film qualities can be fabricated. It is possible to form a highly crystalline material, one which is completely amorphous, or an intermediate morphology. In this review, we will summarize the past key findings that have driven organic solar cell research and the current state-of-the-art of small molecule and conducting oligomer materials. We will also discuss the merits and drawbacks of these devices. Finally, we will highlight some works that directly compare the spectra and morphology of systematically elongated oligothiophene derivatives and compare these oligomers to their polymer counterparts. We hope this review will shed some new light on the morphology differences of these two systems. PMID:22110870

Metal-polymer composites comprising nanostructures and applications thereof

DOEpatents

Wang, Hsing-Lin [Los Alamos, NM; Jeon, Sea Ho [Dracut, MA; Mack, Nathan H [Los Alamos, NM

2011-08-02

Metal-polymer composites, and methods of making and use thereof, said composites comprising a thermally-cured dense polyaniline substrate; an acid dopant; and, metal nanostructure deposits wherein the deposits have a morphology dependent upon the acid dopant.

Metal-polymer composites comprising nanostructures and applications thereof

DOEpatents

Wang, Hsing-Lin [Los Alamos, NM; Jeon, Sea Ho [Dracut, MA; Mack, Nathan H [Los Alamos, NM

2012-04-03

Metal-polymer composites, and methods of making and use thereof, said composites comprising a thermally-cured dense polyaniline substrate; an acid dopant; and, metal nanostructure deposits wherein the deposits have a morphology dependent upon the acid dopant.

Slowing down of ring polymer diffusion caused by inter-ring threading.

PubMed

Lee, Eunsang; Kim, Soree; Jung, YounJoon

2015-06-01

Diffusion of long ring polymers in a melt is much slower than the reorganization of their internal structures. While direct evidence for entanglements has not been observed in the long ring polymers unlike linear polymer melts, threading between the rings is suspected to be the main reason for slowing down of ring polymer diffusion. It is, however, difficult to define the threading configuration between two rings because the rings have no chain end. In this work, evidence for threading dynamics of ring polymers is presented by using molecular dynamics simulation and applying a novel analysis method. The simulation results are analyzed in terms of the statistics of persistence and exchange times that have proved useful in studying heterogeneous dynamics of glassy systems. It is found that the threading time of ring polymer melts increases more rapidly with the degree of polymerization than that of linear polymer melts. This indicates that threaded ring polymers cannot diffuse until an unthreading event occurs, which results in the slowing down of ring polymer diffusion. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoparticle Motion in Entangled Melts of Linear and Nonconcatenated Ring Polymers

PubMed Central

2017-01-01

The motion of nanoparticles (NPs) in entangled melts of linear polymers and nonconcatenated ring polymers are compared by large-scale molecular dynamics simulations. The comparison provides a paradigm for the effects of polymer architecture on the dynamical coupling between NPs and polymers in nanocomposites. Strongly suppressed motion of NPs with diameter d larger than the entanglement spacing a is observed in a melt of linear polymers before the onset of Fickian NP diffusion. This strong suppression of NP motion occurs progressively as d exceeds a and is related to the hopping diffusion of NPs in the entanglement network. In contrast to the NP motion in linear polymers, the motion of NPs with d > a in ring polymers is not as strongly suppressed prior to Fickian diffusion. The diffusion coefficient D decreases with increasing d much slower in entangled rings than in entangled linear chains. NP motion in entangled nonconcatenated ring polymers is understood through a scaling analysis of the coupling between NP motion and the self-similar entangled dynamics of ring polymers. PMID:28392603

High-Efficiency Polymer Solar Cells by Using Co-solvents 1-Chloronaphthalene and 1,8-Octanedithiol as Processing Additives

NASA Astrophysics Data System (ADS)

Gao, Bowen; Meng, Jing

2018-07-01

The copolymer poly-BDT-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (PC20BDTDPP) with the bulkier alkoxy on BDT and alkyl on DPP is widely used in organic photovoltaic cells as a potential donor material. Power conversion efficiency (PCE) of polymer solar cells fabricated withPC20BDTDPP as the electron donor blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as the electron acceptor was improved from 4.90% to 9.10% by adding 1-5% of the co-solvents (1-chloronaphthalene and 1,8-octanedithiol) as processing additives. The enhanced PCE was attributed to optimized surface morphology and packed polymer chains leading to better phase separation morphology by the solvent additive. Furthermore, owing to its very narrow band gap, the synthesized polymer demonstrates a great potential for tandem or parallel-like solar cells.

Polymer Morphological Change Induced by Terahertz Irradiation

NASA Astrophysics Data System (ADS)

Hoshina, Hiromichi; Suzuki, Hal; Otani, Chiko; Nagai, Masaya; Kawase, Keigo; Irizawa, Akinori; Isoyama, Goro

2016-06-01

As terahertz (THz) frequencies correspond to those of the intermolecular vibrational modes in a polymer, intense THz wave irradiation affects the macromolecular polymorph, which determines the polymer properties and functions. THz photon energy is quite low compared to the covalent bond energy; therefore, conformational changes can be induced “softly,” without damaging the chemical structures. Here, we irradiate a poly(3-hydroxybutylate) (PHB) / chloroform solution during solvent casting crystallization using a THz wave generated by a free electron laser (FEL). Morphological observation shows the formation of micrometer-sized crystals in response to the THz wave irradiation. Further, a 10-20% increase in crystallinity is observed through analysis of the infrared (IR) absorption spectra. The peak power density of the irradiating THz wave is 40 MW/cm2, which is significantly lower than the typical laser intensities used for material manipulation. We demonstrate for the first time that the THz wave effectively induces the intermolecular rearrangement of polymer macromolecules.

Flow-enhanced solution printing of all-polymer solar cells

DOE PAGES

Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; ...

2015-08-12

Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a similar to 90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhancedmore » all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. However, we expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility.« less

High-Efficiency Polymer Solar Cells by Using Co-solvents 1-Chloronaphthalene and 1,8-Octanedithiol as Processing Additives

NASA Astrophysics Data System (ADS)

Gao, Bowen; Meng, Jing

2018-04-01

The copolymer poly-BDT-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (PC20BDTDPP) with the bulkier alkoxy on BDT and alkyl on DPP is widely used in organic photovoltaic cells as a potential donor material. Power conversion efficiency (PCE) of polymer solar cells fabricated withPC20BDTDPP as the electron donor blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as the electron acceptor was improved from 4.90% to 9.10% by adding 1-5% of the co-solvents (1-chloronaphthalene and 1,8-octanedithiol) as processing additives. The enhanced PCE was attributed to optimized surface morphology and packed polymer chains leading to better phase separation morphology by the solvent additive. Furthermore, owing to its very narrow band gap, the synthesized polymer demonstrates a great potential for tandem or parallel-like solar cells.

One-Pot Synthesis of Co-Based Coordination Polymer Nanowire for Li-Ion Batteries with Great Capacity and Stable Cycling Stability

NASA Astrophysics Data System (ADS)

Wang, Peng; Lou, Xiaobing; Li, Chao; Hu, Xiaoshi; Yang, Qi; Hu, Bingwen

2018-06-01

Nanowire coordination polymer cobalt-terephthalonitrile (Co-BDCN) was successfully synthesized using a simple solvothermal method and applied as anode material for lithium-ion batteries (LIBs). A reversible capacity of 1132 mAh g-1 was retained after 100 cycles at a rate of 100 mA g-1, which should be one of the best LIBs performances among metal organic frameworks and coordination polymers-based anode materials at such a rate. On the basis of the comprehensive structural and morphology characterizations including fourier transform infrared spectroscopy, 1H NMR, 13C NMR, and scanning electron microscopy, we demonstrated that the great electrochemical performance of the as-synthesized Co-BDCN coordination polymer can be attributed to the synergistic effect of metal centers and organic ligands, as well as the stability of the nanowire morphology during cycling.[Figure not available: see fulltext.

Flow-enhanced solution printing of all-polymer solar cells

PubMed Central

Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; Shaw, Leo; Wang, Cheng; Park, Steve; Guo, Yikun; Reinspach, Julia A.; Gu, Kevin; Gu, Xiaodan; Tee, Benjamin C. K.; Pang, Changhyun; Yan, Hongping; Zhao, Dahui; Toney, Michael F.; Mannsfeld, Stefan C. B.; Bao, Zhenan

2015-01-01

Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a ∼90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhanced all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. We expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility. PMID:26264528

CRISTAPRESS: an optical cell for structure development in high-pressure crystallization.

PubMed

Boyer, S A E; Fournier, F E J; Gandin, Ch-A; Haudin, J-M

2014-01-01

An original optical high-pressure cell, named CRISTAPRESS, has been especially designed to investigate phase transitions of complex liquids, i.e., polymers, polymer blends, nano-composites, etc. The design of the cell is based on the optical properties of morphological entities through in situ light depolarizing microscopic observations. Pressure up to 200 MPa with a fine temperature control up to 300 °C can be applied. A striking advantage of this cell is the possibility to select the pressure transmitting medium that can be water, silicone oil, a fluid in the supercritical state, etc. The potential of the novel technique was demonstrated by carrying out time-resolved measurements during polymer crystallization induced by water pressure. These preliminary experimental investigations permit to discriminate the role of the barometric and thermal histories on the kinetics of polymer growth, as well as on the subsequent morphologies. It should lead to new reliable crystallization kinetics models.

PLLA-PHB fiber membranes obtained by solvent-free electrospinning for short-time drug delivery.

PubMed

Cao, K; Liu, Y; Olkhov, A A; Siracusa, V; Iordanskii, A L

2018-02-01

Fibers of poly(L-lactic acid) (PLLA)/polyhydroxybutyrate (PHB) with different concentrations of the drug dipyridamole (DPD) were prepared using solvent-free melt electrospinning to obtain a polymeric drug delivery system. The electrospun fibers were morphologically, structurally, thermally, and dynamically characterized. Crazes that resemble lotus root crevices were interestingly observed in the 7:3 PLLA/PHB fibers with 1% DPD. The crystallinity of PLLA slightly decreased as PHB was incorporated, and the addition of DPD significantly reduced the melting temperature of the composite. The interactions between PLLA and PHB mainly occurred at a proportion of 7:3, and drug encapsulation in the fibers was verified. The kinetic profiles of drug release demonstrated the predominant multiple patterns involving a diffusional stage in the short-term mode of release and kinetic process related to the hydrolysis of the biopolymers. Furthermore, the dynamic behavior of the polymer molecules was evaluated based on the segmental mobility using probe electron spin resonance spectroscopy. The segmental mobility in the amorphous fraction of PLLA decreased with increasing PLLA content. The 9:1 PLLA/PHB system was more resistant to polymer hydrolysis than to the 7:3 system and the rate of diffusion transport was approximately two times higher for the 7:3 PLLA/PHB fibers than for the 9:1 PLLA/PHB fibers.

A modified dynamical model of drying process of polymer blend solution coated on a flat substrate

NASA Astrophysics Data System (ADS)

Kagami, Hiroyuki

2008-05-01

We have proposed and modified a model of drying process of polymer solution coated on a flat substrate for flat polymer film fabrication. And for example numerical simulation of the model reproduces a typical thickness profile of the polymer film formed after drying. Then we have clarified dependence of distribution of polymer molecules on a flat substrate on a various parameters based on analysis of numerical simulations. Then we drove nonlinear equations of drying process from the dynamical model and the fruits were reported. The subject of above studies was limited to solution having one kind of solute though the model could essentially deal with solution having some kinds of solutes. But nowadays discussion of drying process of a solution having some kinds of solutes is needed because drying process of solution having some kinds of solutes appears in many industrial scenes. Polymer blend solution is one instance. And typical resist consists of a few kinds of polymers. Then we introduced a dynamical model of drying process of polymer blend solution coated on a flat substrate and results of numerical simulations of the dynamical model. But above model was the simplest one. In this study, we modify above dynamical model of drying process of polymer blend solution adding effects that some parameters change with time as functions of some variables to it. Then we consider essence of drying process of polymer blend solution through comparison between results of numerical simulations of the modified model and those of the former model.

Biodistribution of newly synthesized PHEA-based polymer-coated SPION in Sprague Dawley rats as magnetic resonance contrast agent

PubMed Central

Park, Junsung; Cho, Wonkyung; Park, Hee Jun; Cha, Kwang-Ho; Ha, Dae-Chul; Choi, Youn-Woong; Lee, Ha-Young; Cho, Sun-Hang; Hwang, Sung-Joo

2013-01-01

Objectives The purpose of this study was to observe the pharmacokinetic behavior of newly synthesized biocompatible polymers based on polyhydroxyethylaspartamide (PHEA) to be used to coat an iron oxide core to make superparamagnetic iron oxide nanoparticles (SPION). Materials and methods The isotopes [14C] and [59Fe] were used to label the polymer backbone (CLS) and iron oxide core (FLS), respectively. In addition, unradiolabeled cold superparamagnetic iron oxide nanoparticles (SPION/ULS) were synthesized to characterize particle size by dynamic light scattering, morphology by transmission electron microscopy, and in vivo magnetic resonance imaging (MRI). CLS and FLS were used separately to investigate the behavior of both the synthesized polymer and [Fe] in Sprague Dawley (SD) rats, respectively. Because radioactivity of the isotopes was different by β for CLS and γ for FLS, synthesis of the samples had to be separately prepared. Results The mean particle size of the ULS was 66.1 nm, and the biodistribution of CLS concentrations in various organs, in rank order of magnitude, was liver > kidney > small intestine > other. The biodistribution of FLS concentrations was liver > spleen > lung > other. These rank orders show that synthesized SPION mainly accumulates in the liver. The differences in the distribution were caused by the SPION metabolism. Radiolabeled polymer was metabolized by the kidney and excreted mainly in the urine; [59Fe] was recycled for erythrocyte production in the spleen and excreted mainly in the feces. The MR image of the liver after intravenous injection demonstrated that [Fe] effectively accumulated in the liver and exhibited high-contrast enhancement on T2-weighted images. Conclusion This newly synthesized, polymer-coated SPION appears to be a promising candidate for use as a liver-targeted, biocompatible iron oxide MR imaging agent. PMID:24204138

Poly(N-vinylpyrrolidone)-block-poly(vinyl acetate) as a drug delivery vehicle for hydrophobic drugs.

PubMed

Bailly, Nathalie; Thomas, Mark; Klumperman, Bert

2012-12-10

Poly((N-vinylpyrrolidone)-block-poly(vinyl acetate)) (PVP-b-PVAc) block copolymers of varying molecular weight and hydrophobic block lengths were synthesized via controlled radical polymerization and investigated as carriers for the solubilization of highly hydrophobic riminophenazine compounds. These compounds have recently been shown to exhibit a strong activity against a variety of cancer types. PVP-b-PVAc self-assembles into polymer vesicles in aqueous media, and the dialysis method was used to load the water-insoluble drug (clofazimine) into these polymer vesicles. The polymer vesicles were characterized by 1H NMR spectroscopy to confirm vesicle formation and the incorporation of the anticancer drugs into the polymer vesicles. Dynamic light scattering was used to determine the particle size and particle size distribution of the drug-loaded vesicles as well as the stability of the vesicles under physiological conditions. The size of the polymer vesicles did not increase upon loading with clofazimine, and the particle size of 180-200 nm and the narrow particle size distribution were maintained. The morphology of the vesicles was examined by transmission electron microscopy. The polymer vesicles had a relatively high drug loading capacity of 20 wt %. In vitro cytotoxicity studies of PVP-b-PVAc and drug-loaded PVP-b-PVAc were performed against MDA-MB-231 multidrug-resistant breast epithelial cancer cells and MCF12A nontumorigenic breast epithelial cells. In vitro experiments demonstrated that the PVP-b-PVAc drug carrier showed no cytotoxicity, which confirms the biocompatibility of the PVP-b-PVAc drug carrier. The results indicate that the present PVP-b-PVAc block copolymer could be a potential candidate as a drug carrier for hydrophobic drugs.

Investigations into the mechanical and physical behavior of thermoplastic elastomers

NASA Astrophysics Data System (ADS)

Wright, Kathryn Janelle

This thesis describes investigations into the physical and mechanical characteristics of two commercial thermoplastic elastomer (TPE) systems. Both systems studied exhibit elastomeric behavior similar to more traditional crosslinked elastomers; however, in these TPEs non-conventional polymer architectures and morphologies are used to produce their elastomeric behavior. The two TPEs of interest are ethylene-propylene random copolymers and dynamically vulcanized blends of ethylene-propylene-diene monomer (EPDM) and isotactic polypropylene (iPP). Very few studies have examined the mechanical behavior of these materials in terms of their composition and morphology. As such, the primary goal of this research is to both qualitatively and quantitatively understand the influence of composition and morphology on mechanical behavior. In additional very little information is available that compares their performance with that of crosslinked elastomers. As a result, the secondary goal is to qualitatively compare the mechanical responses of these TPEs with that of their more traditional counterparts. The ethylene-propylene copolymers studied have very high comonomer contents and exhibit slow crystallization kinetics. Their morphology consists of nanoscale crystallites embedded in an amorphous rubbery matrix. These crystallites act as physical crosslinks that allow for elasticity. Slow crystallization causes subsequent changes in mechanical behavior that take place over days and even weeks. Physical responses (e.g., density, crystallization kinetics, and crystal structure) of five copolymer compositions are investigated. Mechanical responses (e.g., stiffness, ductility, yielding, and reversibility) are also examined. Finally, the influence of morphology on deformation is studied using in situ analytical techniques. The EPDM/iPP blends are dynamically vulcanized which produces a complex morphology consisting of chemically crosslinked EPDM domains embedded within a semicrystalline iPP matrix. Six compositions are investigated as a function of three parameters: major volume fraction, iPP molecular weight, and EPDM cure state. The influence of these parameters on morphology and resulting mechanical behavior is examined. This work culminates in the development of a morphological model to describe the steady-state reversibility of these EPDM/iPP blends. The model is then evaluated in terms of composition and cure state.

Structure of a tethered polymer under flow using molecular dynamics and hybrid molecular-continuum simulations

NASA Astrophysics Data System (ADS)

Delgado-Buscalioni, Rafael; Coveney, Peter V.

2006-03-01

We analyse the structure of a single polymer tethered to a solid surface undergoing a Couette flow. We study the problem using molecular dynamics (MD) and hybrid MD-continuum simulations, wherein the polymer and the surrounding solvent are treated via standard MD, and the solvent flow farther away from the polymer is solved by continuum fluid dynamics (CFD). The polymer represents a freely jointed chain (FJC) and is modelled by Lennard-Jones (LJ) beads interacting through the FENE potential. The solvent (modelled as a LJ fluid) and a weakly attractive wall are treated at the molecular level. At large shear rates the polymer becomes more elongated than predicted by existing theoretical scaling laws. Also, along the normal-to-wall direction the structure observed for the FJC is, surprisingly, very similar to that predicted for a semiflexible chain. Comparison with previous Brownian dynamics simulations (which exclude both solvent and wall potential) indicates that these effects are due to the polymer-solvent and polymer-wall interactions. The hybrid simulations are in perfect agreement with the MD simulations, showing no trace of finite size effects. Importantly, the extra cost required to couple the MD and CFD domains is negligible.

Focus: Structure and dynamics of the interfacial layer in polymer nanocomposites with attractive interactions

DOE PAGES

Cheng, Shiwang; Carroll, Bobby; Bocharova, Vera; ...

2017-03-30

In recent years it has become clear that the interfacial layer formed around nanoparticles in polymer nanocomposites (PNCs) is critical for controlling their macroscopic properties. The interfacial layer occupies a significant volume fraction of the polymer matrix in PNCs and creates strong intrinsic heterogeneity in their structure and dynamics. In this paper, we focus on analysis of the structure and dynamics of the interfacial region in model PNCs with well-dispersed, spherical nanoparticles with attractive interactions. First, we discuss several experimental techniques that provide structural and dynamic information on the interfacial region in PNCs. Then, we discuss the role of variousmore » microscopic parameters in controlling structure and dynamics of the interfacial layer. The analysis presented emphasizes the importance of the polymer-nanoparticle interactions for the slowing down dynamics in the interfacial region, while the thickness of the interfacial layer appears to be dependent on chain rigidity, and has been shown to increase with cooling upon approaching the glass transition. Aside from chain rigidity and polymer-nanoparticle interactions, the interfacial layer properties are also affected by the molecular weight of the polymer and the size of the nanoparticles. Finally, in the last part of this focus article, we emphasize the important challenges in the field of polymer nanocomposites and a potential analogy with the behavior observed in thin films.« less

Why we need to look beyond the glass transition temperature to characterize the dynamics of thin supported polymer films.

PubMed

Zhang, Wengang; Douglas, Jack F; Starr, Francis W

2018-05-29

There is significant variation in the reported magnitude and even the sign of [Formula: see text] shifts in thin polymer films with nominally the same chemistry, film thickness, and supporting substrate. The implicit assumption is that methods used to estimate [Formula: see text] in bulk materials are relevant for inferring dynamic changes in thin films. To test the validity of this assumption, we perform molecular simulations of a coarse-grained polymer melt supported on an attractive substrate. As observed in many experiments, we find that [Formula: see text] based on thermodynamic criteria (temperature dependence of film height or enthalpy) decreases with decreasing film thickness, regardless of the polymer-substrate interaction strength ε. In contrast, we find that [Formula: see text] based on a dynamic criterion (relaxation of the dynamic structure factor) also decreases with decreasing thickness when ε is relatively weak, but [Formula: see text] increases when ε exceeds the polymer-polymer interaction strength. We show that these qualitatively different trends in [Formula: see text] reflect differing sensitivities to the mobility gradient across the film. Apparently, the slowly relaxing polymer segments in the substrate region make the largest contribution to the shift of [Formula: see text] in the dynamic measurement, but this part of the film contributes less to the thermodynamic estimate of [Formula: see text] Our results emphasize the limitations of using [Formula: see text] to infer changes in the dynamics of polymer thin films. However, we show that the thermodynamic and dynamic estimates of [Formula: see text] can be combined to predict local changes in [Formula: see text] near the substrate, providing a simple method to infer information about the mobility gradient.

Enhanced adherence of mouse fibroblast and vascular cells to plasma modified polyethylene.

PubMed

Reznickova, Alena; Novotna, Zdenka; Kolska, Zdenka; Kasalkova, Nikola Slepickova; Rimpelova, Silvie; Svorcik, Vaclav

2015-01-01

Since the last decade, tissue engineering has shown a sensational promise in providing more viable alternatives to surgical procedures for harvested tissues, implants and prostheses. Biomedical polymers, such as low-density polyethylene (LDPE), high-density polyethylene (HDPE) and ultra-high molecular weight polyethylene (UHMWPE), were activated by Ar plasma discharge. Degradation of polymer chains was examined by determination of the thickness of ablated layer. The amount of an ablated polymer layer was measured by gravimetry. Contact angle, measured by goniometry, was studied as a function of plasma exposure and post-exposure aging times. Chemical structure of modified polymers was characterized by angle resolved X-ray photoelectron spectroscopy. Surface chemistry and polarity of the samples were investigated by electrokinetic analysis. Changes in surface morphology were followed using atomic force microscopy. Cytocompatibility of plasma activated polyethylene foils was studied using two distinct model cell lines; VSMCs (vascular smooth muscle cells) as a model for vascular graft testing and connective tissue cells L929 (mouse fibroblasts) approved for standardized material cytotoxicity testing. Specifically, the cell number, morphology, and metabolic activity of the adhered and proliferated cells on the polyethylene matrices were studied in vitro. It was found that the plasma treatment caused ablation of the polymers, resulting in dramatic changes in their surface morphology and roughness. ARXPS and electrokinetic measurements revealed oxidation of the polymer surface. It was found that plasma activation has a positive effect on the adhesion and proliferation of VSMCs and L929 cells. Copyright © 2015 Elsevier B.V. All rights reserved.

Determination of active layer morphology in all-polymer photovoltaic cells

DOE PAGES

Mulderig, Andrew J.; Jin, Yan; Yu, Fei; ...

2017-08-18

This paper investigates the structure of films spin-coated from blends of the semiconducting polymers poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly{2,6-[4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene]-alt-4,7(2,1,3-benzo­thiadiazole)} (PCPDTBT). Such blends are of potential use in all-polymer solar cells in which both the acceptor and the donor material generate excitons to contribute to the photocurrent. Prompted by threefold performance gains seen in polymer/fullerene and polymer blend solar cells upon addition of pristine graphene, devices are prepared from P3HT/PCPDTBT blends both with and without graphene. This report focuses on the morphology of the active layer since this is of critical importance in determining performance. Small-angle neutron scattering (SANS) is utilized tomore » study this polymer blend with deuterated P3HT to provide contrast and permit the investigation of buried structure in neat and graphene-doped films. SANS reveals the presence of P3HT crystallites dispersed in an amorphous blend matrix of P3HT and PCPDTBT. The crystallites are approximately disc shaped and do not show any evidence of higher-order structure or aggregation. While the structure of the films does not change with the addition of graphene, there is a perceptible effect on the electronic properties and energy conversion efficiency in solar cells made from such films. Finally, determination of the active layer morphology yields crucial insight into structure–property relationships in organic photovoltaic devices.« less

Determination of active layer morphology in all-polymer photovoltaic cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mulderig, Andrew J.; Jin, Yan; Yu, Fei

This paper investigates the structure of films spin-coated from blends of the semiconducting polymers poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly{2,6-[4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene]-alt-4,7(2,1,3-benzo­thiadiazole)} (PCPDTBT). Such blends are of potential use in all-polymer solar cells in which both the acceptor and the donor material generate excitons to contribute to the photocurrent. Prompted by threefold performance gains seen in polymer/fullerene and polymer blend solar cells upon addition of pristine graphene, devices are prepared from P3HT/PCPDTBT blends both with and without graphene. This report focuses on the morphology of the active layer since this is of critical importance in determining performance. Small-angle neutron scattering (SANS) is utilized tomore » study this polymer blend with deuterated P3HT to provide contrast and permit the investigation of buried structure in neat and graphene-doped films. SANS reveals the presence of P3HT crystallites dispersed in an amorphous blend matrix of P3HT and PCPDTBT. The crystallites are approximately disc shaped and do not show any evidence of higher-order structure or aggregation. While the structure of the films does not change with the addition of graphene, there is a perceptible effect on the electronic properties and energy conversion efficiency in solar cells made from such films. Finally, determination of the active layer morphology yields crucial insight into structure–property relationships in organic photovoltaic devices.« less

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

NASA Astrophysics Data System (ADS)

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.

Studies on surface morphology and electrical conductivity of PEDOT:PSS thin films in presence of gold nanoparticles

NASA Astrophysics Data System (ADS)

Bhowal, Ashim Chandra; Kundu, Sarathi

2018-04-01

PEDOT:PSS is a water soluble conducting polymer consists of positively charged PEDOT and negatively charged PSS. However, this polymer suffers low conductivity problem which restrict its use. In this paper, electrical conductivity of PEDOT:PSS thin films is improved by using charged gold nanoparticles. The nanoparticles used are synthesized using lysozyme protein. The nanoparticles coated with lysozyme protein possess positive zeta potential. In the presence of gold nanoparticles due to electrostatic interaction between positively charged nanoparticles and negatively charged PSS chains, modification takes place in the surface morphology and electrical behaviors of PEDOT:PSS thin films. The changes in the polymer matrix conformations in the presence of nanoparticles are studied by Fourier transformed Infra-red (FTIR) spectroscopy, whereas the surface morphology of prepared thin films before and after interaction with nanoparticles is investigated through atomic force microscopy (AFM). Four probe method is used to measure the variation of electrical conductivity from I-V characteristics curves.

Polymer dynamics in turbulent flow

NASA Astrophysics Data System (ADS)

Muthukumar, Murugappan

2014-03-01

Presence of dilute amounts of high-molecular weight polymers in liquids undergoing turbulent wall-bounded shear flows leads to significant drag reduction. There are two major proposed mechanisms of drag reduction in the literature. One is based on enhanced viscosity due to chain extension; the other is based on the assumption that elastic energy stored in polymer conformations is comparable to the kinetic energy in some eddies. Using the Navier-Stokes equation for the fluid and the Kirkwood-Riseman-Zimm equation for polymer chains, we have addressed the coupling between the near-wall turbulence dynamics and polymer dynamics. Our theoretical results show that the torque associated with polymer conformations contributes more significantly than the chain stretching and that the characteristic dimensions of polymer coils are much smaller than eddy sizes required for possible exchange of energy. We thus emphasize an additional mechanism to the existing two schools of thought in the search of an understanding of drag reduction.

Biopolymer dynamics driven by helical flagella

NASA Astrophysics Data System (ADS)

Balin, Andrew K.; Zöttl, Andreas; Yeomans, Julia M.; Shendruk, Tyler N.

2017-11-01

Microbial flagellates typically inhabit complex suspensions of polymeric material which can impact the swimming speed of motile microbes, filter feeding of sessile cells, and the generation of biofilms. There is currently a need to better understand how the fundamental dynamics of polymers near active cells or flagella impacts these various phenomena, in particular, the hydrodynamic and steric influence of a rotating helical filament on suspended polymers. Our Stokesian dynamics simulations show that as a stationary rotating helix pumps fluid along its long axis, polymers migrate radially inward while being elongated. We observe that the actuation of the helix tends to increase the probability of finding polymeric material within its pervaded volume. This accumulation of polymers within the vicinity of the helix is stronger for longer polymers. We further analyze the stochastic work performed by the helix on the polymers and show that this quantity is positive on average and increases with polymer contour length.

Poly(2-aminothiazole)-silica nanocomposite particles: Synthesis and morphology control

NASA Astrophysics Data System (ADS)

Zou, Hua; Wu, Di; Sun, Hao; Chen, Suwu; Wang, Xia

2018-04-01

Synthesis of conducting polymer-silica colloidal nanocomposites has been recognized as an effective method to overcome the poor processability of heterocyclic conducting polymers prepared by chemical oxidative method. However, the morphology control of such conducting polymer-silica nanocomposites was seldomly reported in the literature. Novel poly(2-aminothiazole)(PAT)-silica nanocomposite particles can be conveniently prepared by chemical oxidative polymerization of 2-aminothiazole using CuCl2 oxidant in the presence of ∼20 nm silica nanoparticles. The effects of varying the oxidant/monomer ratio and silica sol concentration on the morphology and size of the resulting PAT-silica nanocmposites have been studied. Optimization of the oxidant/monomer molar ratio and initial silica sol concentration allows relatively round spherical particles of 150-350 nm in diameter to be achieved. The nanocomposite particles have a well-defined raspberry-like morphology with a silica-rich surface, but a significant fraction of PAT component still exists on the surface and, which is beneficial for its applications. Furthermore, the surface compositions of the colloidal nanocomposites could be regulated to some extent. Based on the above results, a possible formation mechanism of the spherical nanocomposite particles is proposed.

Nanoparticle Motion in Entangled Melts of Linear and Nonconcatenated Ring Polymers [Nanoparticle Motion in Entangled Melts of Non-Concatenated Ring Polymers].

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ge, Ting; Kalathi, Jagannathan T.; Halverson, Jonathan D.

The motion of nanoparticles (NPs) in entangled melts of linear polymers and non-concatenated ring polymers are compared by large-scale molecular dynamics simulations. The comparison provides a paradigm for the effects of polymer architecture on the dynamical coupling between NPs and polymers in nanocomposites. Strongly suppressed motion of NPs with diameter d larger than the entanglement spacing a is observed in a melt of linear polymers before the onset of Fickian NP diffusion. This strong suppression of NP motion occurs progressively as d exceeds a, and is related to the hopping diffusion of NPs in the entanglement network. In contrast tomore » the NP motion in linear polymers, the motion of NPs with d > a in ring polymers is not as strongly suppressed prior to Fickian diffusion. The diffusion coefficient D decreases with increasing d much slower in entangled rings than in entangled linear chains. NP motion in entangled non-concatenated ring polymers is understood through a scaling analysis of the coupling between NP motion and the self-similar entangled dynamics of ring polymers.« less

Nanoparticle Motion in Entangled Melts of Linear and Nonconcatenated Ring Polymers [Nanoparticle Motion in Entangled Melts of Non-Concatenated Ring Polymers].

DOE PAGES

Ge, Ting; Kalathi, Jagannathan T.; Halverson, Jonathan D.; ...

2017-02-13

The motion of nanoparticles (NPs) in entangled melts of linear polymers and non-concatenated ring polymers are compared by large-scale molecular dynamics simulations. The comparison provides a paradigm for the effects of polymer architecture on the dynamical coupling between NPs and polymers in nanocomposites. Strongly suppressed motion of NPs with diameter d larger than the entanglement spacing a is observed in a melt of linear polymers before the onset of Fickian NP diffusion. This strong suppression of NP motion occurs progressively as d exceeds a, and is related to the hopping diffusion of NPs in the entanglement network. In contrast tomore » the NP motion in linear polymers, the motion of NPs with d > a in ring polymers is not as strongly suppressed prior to Fickian diffusion. The diffusion coefficient D decreases with increasing d much slower in entangled rings than in entangled linear chains. NP motion in entangled non-concatenated ring polymers is understood through a scaling analysis of the coupling between NP motion and the self-similar entangled dynamics of ring polymers.« less

Single-polymer dynamics under constraints: scaling theory and computer experiment.

PubMed

Milchev, Andrey

2011-03-16

The relaxation, diffusion and translocation dynamics of single linear polymer chains in confinement is briefly reviewed with emphasis on the comparison between theoretical scaling predictions and observations from experiment or, most frequently, from computer simulations. Besides cylindrical, spherical and slit-like constraints, related problems such as the chain dynamics in a random medium and the translocation dynamics through a nanopore are also considered. Another particular kind of confinement is imposed by polymer adsorption on attractive surfaces or selective interfaces--a short overview of single-chain dynamics is also contained in this survey. While both theory and numerical experiments consider predominantly coarse-grained models of self-avoiding linear chain molecules with typically Rouse dynamics, we also note some recent studies which examine the impact of hydrodynamic interactions on polymer dynamics in confinement. In all of the aforementioned cases we focus mainly on the consequences of imposed geometric restrictions on single-chain dynamics and try to check our degree of understanding by assessing the agreement between theoretical predictions and observations.

Impact of polymer modification on mechanical and viscoelastic properties.

DOT National Transportation Integrated Search

2015-10-01

This study was initiated with the aim of evaluating the relative impact of different cross-linking agents : on the rheological and morphological properties of polymer modified asphalt binders (PMAs). To : complete this objective, two cross-linking ag...

Synthesis, electronic structure, molecular packing/morphology evolution, and carrier mobilities of pure oligo-/poly(alkylthiophenes).

PubMed

Zhang, Lei; Colella, Nicholas S; Liu, Feng; Trahan, Stephan; Baral, Jayanta K; Winter, H Henning; Mannsfeld, Stefan C B; Briseno, Alejandro L

2013-01-16

Monodispersed conjugated oligothiophenes are receiving attention in fundamental and applied science due to their interesting optical, optoelectronic, and charge transport properties. These "low molecular weight" polymers serve as model structures for the corresponding polymer analogues, which are inherently polydispersed. Here we report the synthesis, electronic structure, molecular packing/morphology, and charge transport properties of monodispersed oligothiophenes with up to six didodecylquaterthiophene (DDQT) building block repeat units (i.e., 24 thiophene units). At the point where the effective conjugation length is reached, the electronic structure showed convergence behavior to the corresponding polymer, poly(3,3"-didodecyl-quaterthiophene) (PQT-12). X-ray crystal structure analysis of the dimer (DDQT-2) showed that terminal thiophenes exhibit syn-conformations, similar to the terminal syn-conformations observed in the trimer (DDQT-3). The dimer also exhibits a rare bending of the terminal alkyl side chains in order to prevent steric hindrance with neighboring hydrogens attached to core thiophenes. Grazing incidence X-ray scattering measurements revealed a morphology evolution from small molecule-like packing to polymer-like packing in thin films, with a morphology transition occurring near the effective conjugation length. Charge transport measurements showed a mobility increase with decreasing chain length. We correlated the molecular packing and morphology to charge transport and determined that carrier mobilities are most sensitive to crystallinity and crystal grain misorientation. This indicates that molecular weight is not a decisive factor for improved carrier mobility in the low molecular weight region, but rather the degree in crystallinity and in-plane crystal orientation. These results represent a fundamental advancement in understanding the relationship between conjugation length and carrier mobilities in oligothiophene semiconductors.

Nonlinear dynamics that appears in the dynamical model of drying process of a polymer solution coated on a flat substrate

NASA Astrophysics Data System (ADS)

Kagami, Hiroyuki

2007-01-01

We have proposed and modified the dynamical model of drying process of polymer solution coated on a flat substrate for flat polymer film fabrication and have presented the fruits through some meetings and so on. Though basic equations of the dynamical model have characteristic nonlinearity, character of the nonlinearity has not been studied enough yet. In this paper, at first, we derive nonlinear equations from the dynamical model of drying process of polymer solution. Then we introduce results of numerical simulations of the nonlinear equations and consider roles of various parameters. Some of them are indirectly concerned in strength of non-equilibriumity. Through this study, we approach essential qualities of nonlinearity in non-equilibrium process of drying process.

Active Polymers — Emergent Conformational and Dynamical Properties: A Brief Review

NASA Astrophysics Data System (ADS)

Winkler, Roland G.; Elgeti, Jens; Gompper, Gerhard

2017-10-01

Active matter exhibits a wealth of emerging nonequilibrium behaviours. A paradigmatic example is the interior of cells, where active components, such as the cytoskeleton, are responsible for its structural organization and the dynamics of the various components. Of particular interest are the properties of polymers and filaments. The intimate coupling of thermal and active noise, hydrodynamic interactions, and polymer conformations implies the emergence of novel structural and dynamical features. In this article, we review recent theoretical and simulation developments and results for the structural and dynamical properties of polymers exposed to activity. Two- and three-dimensional filaments are considered propelled by different mechanisms such as active Brownian particles or hydrodynamically-coupled force dipoles.

Comparative Study of Structure-Property Relationships in Polymer Networks Based on Bis-GMA, TEGDMA and Various Urethane-Dimethacrylates

PubMed Central

Barszczewska-Rybarek, Izabela; Jurczyk, Sebastian

2015-01-01

The effect of various dimethacrylates on the structure and properties of homo- and copolymer networks was studied. The 2,2-bis-[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]-propane) (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA) and 1,6-bis-(methacryloyloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane (HEMA/TMDI), all popular in dentistry, as well as five urethane-dimethacrylate (UDMA) alternatives of HEMA/TMDI were used as monomers. UDMAs were obtained from mono-, di- and tri(ethylene glycol) monomethacrylates and various commercial diisocyanates. The chemical structure, degree of conversion (DC) and scanning electron microscopy (SEM) fracture morphology were related to the mechanical properties of the polymers: flexural strength and modulus, hardness, as well as impact strength. Impact resistance was widely discussed, being lower than expected in the case of poly(UDMA)s. It was caused by the heterogeneous morphology of these polymers and only moderate strength of hydrogen bonds between urethane groups, which was not high enough to withstand high impact energy. Bis-GMA, despite having the highest polymer morphological heterogeneity, ensured fair impact resistance, due to having the strongest hydrogen bonds between hydroxyl groups. The TEGDMA homopolymer, despite being heterogeneous, produced the smoothest morphology, which resulted in the lowest brittleness. The UDMA monomer, having diethylene glycol monomethacrylate wings and the isophorone core, could be the most suitable HEMA/TMDI alternative. Its copolymer with Bis-GMA and TEGDMA had improved DC as well as all the mechanical properties. PMID:28787999

New Secondary Batteries Using Electronically Conductive Polymer Cathodes

NASA Technical Reports Server (NTRS)

Martin, Charles R.; White, Ralph E.

1991-01-01

A Li/Polypyrrole secondary battery was designed and built, and the effect of controlling the morphology of the polymer on enhancement of counterion diffusion in the polymer phase was explored. The experimental work was done at Colorado State University, while the mathematical modeling of the battery was done at Texas A and M University. Manuscripts and publications resulting from the project are listed.

Colossal Room-Temperature Electrocaloric Effect in Ferroelectric Polymer Nanocomposites Using Nanostructured Barium Strontium Titanates.

PubMed

Zhang, Guangzu; Zhang, Xiaoshan; Yang, Tiannan; Li, Qi; Chen, Long-Qing; Jiang, Shenglin; Wang, Qing

2015-07-28

The electrocaloric effect (ECE) refers to conversion of thermal to electrical energy of polarizable materials and could form the basis for the next-generation refrigeration and power technologies that are highly efficient and environmentally friendly. Ferroelectric materials such as ceramic and polymer films exhibit large ECEs, but each of these monolithic materials has its own limitations for practical cooling applications. In this work, nanosized barium strontium titanates with systematically varied morphologies have been prepared to form polymer nanocomposites with the ferroelectric polymer matrix. The solution-processed polymer nanocomposites exhibit an extraordinary room-temperature ECE via the synergistic combination of the high breakdown strength of a ferroelectric polymer matrix and the large change of polarization with temperature of ceramic nanofillers. It is found that a sizable ECE can be generated under both modest and high electric fields, and further enhanced greatly by tailoring the morphology of the ferroelectric nanofillers such as increasing the aspect ratio of the nanoinclusions. The effect of the geometry of the nanofillers on the dielectric permittivity, polarization, breakdown strength, ECE and crystallinity of the ferroelectric polymer has been systematically investigated. Simulations based on the phase-field model have been carried out to substantiate the experimental results. With the remarkable cooling energy density and refrigerant capacity, the polymer nanocomposites are promising for solid-state cooling applications.

Rheology and microstructure of filled polymer melts

NASA Astrophysics Data System (ADS)

Anderson, Benjamin John

The states of particle dispersion in polymer nanocomposite melts are studied through rheological characterization of nanocomposite melt mechanical properties and small angle X-ray scattering measurement of the particle microstructure. The particle microstructure probed with scattering is related to bulk flow mechanics to determine the origin of slow dynamics in these complex dispersions: whether a gel or glass transition or a slowing down of dispersing phase dynamics. These studies were conducted to understand polymer mediated particle-particle interactions and potential particle-polymer phase separation. The phase behavior of the dispersion will be governed by enthalpic and entropic contributions. A variety of phases are expected: homogeneous fluid, phase separated, or non-equilibrium gel. The effects of dispersion control parameters, namely particle volume fraction, polymer molecular weight, and polymer-particle surface affinity, on the phase behavior of 44 nm silica dispersions are studied in low molecular weight polyethylene oxide (PEO), polyethylene oxide dimethylether (PEODME), and polytetrahydrofuran (PTHF). Scattering measurements of the particle second virial coefficient in PEO melts indicates repulsive particles by a value slightly greater than unity. In PEO nanocomposites, dispersion dynamics slow down witnessed by a plateau in the elastic modulus as the particle separation approaches the length scale of the polymer radius of gyration. As the polymer molecular weight is increased, the transition shifts to lower particle volume fractions. Below polymer entanglement, the slow dynamics mimics that of a colloidal glass by the appearance of two relaxation times in the viscous modulus that display power law scaling with volume fraction. Above entanglement, the slow dynamics is qualitatively different resembling the behavior of a gelled suspension yet lacking any sign of scattering from particle agglomerates. As polymer molecular weight is increased at a fixed volume fraction, two strain yielding events emerge. Further particle loading leads to the formation of a particle-polymer network and the onset of brittle mechanical behavior. The performance of PEO nanocomposites is contrasted by PEODME and PTHF nanocomposites where a change in the polymer segment-surface activity changes the slow dynamics of the nanocomposite and the microstructure of particles in the melt. Slow dynamics and the particle microstructure indicate a gelled suspension as volume fraction is raised with particles in or near contact and support the turning on of particle attractions in the melt.

Critical role of morphology on the dielectric constant of semicrystalline polyolefins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Misra, Mayank; Kumar, Sanat K., E-mail: sk2794@columbia.edu; Mannodi-Kanakkithodi, Arun

2016-06-21

A particularly attractive method to predict the dielectric properties of materials is density functional theory (DFT). While this method is very popular, its large computational requirements allow practical treatments of unit cells with just a small number of atoms in an ordered array, i.e., in a crystalline morphology. By comparing DFT and Molecular Dynamics (MD) simulations on the same ordered arrays of functional polyolefins, we confirm that both methodologies yield identical estimates for the dipole moments and hence the ionic component of the dielectric storage modulus. Additionally, MD simulations of more realistic semi-crystalline morphologies yield estimates for this polar contributionmore » that are in good agreement with the limited experiments in this field. However, these predictions are up to 10 times larger than those for pure crystalline simulations. Here, we show that the constraints provided by the surrounding chains significantly impede dipolar relaxations in the crystalline regions, whereas amorphous chains must sample all configurations to attain their fully isotropic spatial distributions. These results, which suggest that the amorphous phase is the dominant player in the context, argue strongly that the proper polymer morphology needs to be modeled to ensure accurate estimates of the ionic component of the dielectric constant.« less

Solvent-annealing-induced nanowetting in templates: towards tailored polymer nanostructures.

PubMed

Chen, Jiun-Tai; Lee, Chih-Wei; Chi, Mu-Huan; Yao, I-Chun

2013-02-25

We study the solvent-annealing-induced nanowetting in templates using porous anodic aluminum oxide membranes. The morphology of polystyrene and poly(methyl methacrylate) nanostructures can be controlled, depending on whether the swollen polymers are in the partial or complete wetting regimes, which are characterized by the spreading coefficient. When the swollen polymers are in the partial wetting regime, polymers wet the nanopores by capillary action, resulting in the formation of polymer nanorods. When the swollen polymers are in the complete wetting regime, polymers form wetting layers in the nanopores, resulting in the formation of polymer nanotubes. The solubility parameters of polymers and solvents are also used to predict the wetting behavior of swollen polymers in cylindrical geometry. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved performance by morphology control via fullerenes in PBDT-TBT-alkoBT based organic solar cells

DOE PAGES

Khatiwada, Devendra; Venkatesan, Swaminathan; Chen, QIliang; ...

2015-07-03

In this work, we report improved performance by controlling morphology using different fullerene derivatives in poly{2-octyldodecyloxy-benzo[1,2-b;3,4-b]dithiophene-alt-5,6-bis(dodecyloxy)-4,7- di(thieno[3,2-b]thiophen-2-yl)-benzo[c][1,2,5]thiadiazole} (PBDT-TBT-alkoBT) based organic solar cells. PC60BM and PC70BM fullerenes were used to investigate the characteristic change in morphology and device performance. Fullerene affects device efficiency by changing active layer morphology. PC70BM with broader absorption than PC 60BM resulted in reduced device performance which was elucidated by the intermixed granular morphology separating each larger grain in the PC70BM/polymer composite layer which created higher density of traps. However after adding additive 1,8-diiodooctane (DIO), the fibrous morphology was observed due to reduced solubility of polymer andmore » increased solubility of PC 70BM in chloroform. The fibrous morphology improved charge transport leading to increase in overall device performance. Atomic force microscopies (AFM), photo induced charge extraction by linearly increasing voltage (photo-CELIV), and Kelvin prove force microscope (KPFM) were used to investigate nanoscale morphology of active layer with different fullerene derivatives. For PC 60BM based active layer, AFM images revealed dense fibrous morphology and more distinct fibrous morphology was observed by adding DIO. The PC 70BM based active layer only exhibited intermixed granular morphology instead of fibrous morphology observed in PC60BM based active layer. However, addition of DIO in PC 70BM based active layer led to fibrous morphology. When additive DIO was not used, a wider distribution of surface potential was observed for PC 70BM than PC 60BM based active layer by KPFM measurements, indicating 2 polymer and fullerene domains are separated. When DIO was used, narrower distribution of surface potential for both PC 70BM and PC 60BM based active layers was observed. Photo-CELIV experiment showed larger extracted charge carrier density and mobility in PC 70BM/DIO film.« less

Improved performance by morphology control via fullerenes in PBDT-TBT-alkoBT based organic solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khatiwada, Devendra; Venkatesan, Swaminathan; Chen, QIliang

In this work, we report improved performance by controlling morphology using different fullerene derivatives in poly{2-octyldodecyloxy-benzo[1,2-b;3,4-b]dithiophene-alt-5,6-bis(dodecyloxy)-4,7- di(thieno[3,2-b]thiophen-2-yl)-benzo[c][1,2,5]thiadiazole} (PBDT-TBT-alkoBT) based organic solar cells. PC60BM and PC70BM fullerenes were used to investigate the characteristic change in morphology and device performance. Fullerene affects device efficiency by changing active layer morphology. PC70BM with broader absorption than PC 60BM resulted in reduced device performance which was elucidated by the intermixed granular morphology separating each larger grain in the PC70BM/polymer composite layer which created higher density of traps. However after adding additive 1,8-diiodooctane (DIO), the fibrous morphology was observed due to reduced solubility of polymer andmore » increased solubility of PC 70BM in chloroform. The fibrous morphology improved charge transport leading to increase in overall device performance. Atomic force microscopies (AFM), photo induced charge extraction by linearly increasing voltage (photo-CELIV), and Kelvin prove force microscope (KPFM) were used to investigate nanoscale morphology of active layer with different fullerene derivatives. For PC 60BM based active layer, AFM images revealed dense fibrous morphology and more distinct fibrous morphology was observed by adding DIO. The PC 70BM based active layer only exhibited intermixed granular morphology instead of fibrous morphology observed in PC60BM based active layer. However, addition of DIO in PC 70BM based active layer led to fibrous morphology. When additive DIO was not used, a wider distribution of surface potential was observed for PC 70BM than PC 60BM based active layer by KPFM measurements, indicating 2 polymer and fullerene domains are separated. When DIO was used, narrower distribution of surface potential for both PC 70BM and PC 60BM based active layers was observed. Photo-CELIV experiment showed larger extracted charge carrier density and mobility in PC 70BM/DIO film.« less

Comparison of nanoparticle diffusion using fluorescence correlation spectroscopy and differential dynamic microscopy within concentrated polymer solutions

NASA Astrophysics Data System (ADS)

Shokeen, Namita; Issa, Christopher; Mukhopadhyay, Ashis

2017-12-01

We studied the diffusion of nanoparticles (NPs) within aqueous entangled solutions of polyethylene oxide (PEO) by using two different optical techniques. Fluorescence correlation spectroscopy, a method widely used to investigate nanoparticle dynamics in polymer solution, was used to measure the long-time diffusion coefficient (D) of 25 nm radius particles within high molecular weight, Mw = 600 kg/mol PEO in water solutions. Differential dynamic microscopy (DDM) was used to determine the wave-vector dependent dynamics of NPs within the same polymer solutions. Our results showed good agreement between the two methods, including demonstration of normal diffusion and almost identical diffusion coefficients obtained by both techniques. The research extends the scope of DDM to study the dynamics and rheological properties of soft matter at a nanoscale. The measured diffusion coefficients followed a scaling theory, which can be explained by the coupling between polymer dynamics and NP motion.

Bubble Dynamics in Polymer Solutions Undergoing Shear.

DTIC Science & Technology

1985-04-01

cavitation bubble in water has been established as the fundamental theoretical approach to understanding this phenomenon. LA_ Laser -induced...cavitation inception. 1-2 Polymer effects on cavity appearance. 2-1 Spherical laser -induced bubble dynamics. 2-2 Vapor cavity jet formation. 2-3 Bubble...distilled water. 2-6B Nonspherical bubble dynamics in dilute polymer. 3-1 Closed-loop hydraulic cavitation tunnel. 3-2 Laser system optical components. 3-3

Investigating the Modification of Spontaneous Emission using Layer-by-Layer Self-Assembly

NASA Astrophysics Data System (ADS)

Ashry, Islam Ahmed Ibrahim Youssef

The process of spontaneous emission can be dramatically modified by optical micro- and nanostructures. We studied the modification of fluorescence dynamics using a polymer spacer layer fabricated through layer-by-layer (LbL) self-assembly. The advantages of this method are numerous: The self-assembled spacers can possess exceptional smooth surface morphology; The thickness of the spacer can be controlled with nanometer accuracy; And depending on fabrication conditions, the spacer layer is stimuli responsive and its thickness can be dynamically tuned. This thesis contains three interlinked components. First, we vary LbL spacer layer thickness and explore the change in fluorescence lifetime induced by the modified photonic density of states (PDOS), i.e., Purcell effects. Our experimental results agree well with theoretical predictions based on a classical dipole model, which also yields consistent values for the fluorophores' intrinsic fluorescence lifetime and quantum yield near a dielectric as well as a plasmonic interface. Based on this observation, we further demonstrate that self-assembled fluorophores can be used to probe the modified PDOS near optical micro- and nano-structures. These results naturally lead to the second component of our research. In particularly, based on the PDOS-induced changes in fluorescent lifetime, we develop a non-contact method that can measure morphological changes with nanoscale resolution. Our method relies on quantitatively linking fluorophore position with PDOS, and is validated through direct comparison with ellipsometry and atomic force microscopy (AFM) measurements. To demonstrate the potential application of this method, we investigated the swelling/deswelling of LbL films induced by pH changes. Our results indicate significant difference between a LbL film composed of a single polymer monolayer and a LbL film with 3 monolayers. Such stimuli-responsive polymers can be used to construct active and tunable plasmonic nano-devices. As a proof-of-principle demonstration, we experimentally confirm that it is possible to utilize the swelling/deswelling behavior of stimuli-responsive films to dynamically control the separation between Au nanoparticles and Texas Red (TR) dyes. This result is based on the strong correlation of TR fluorescence lifetime and nanoparticles-TR separation. Finally, we investigate the impact of different lithography processes on the fluorescence properties of self-assembled fluorophores. We consider three methods: direct fluorophore patterning through ultraviolet (UV) ablation, focused ion beam (FIB) milling of self-assembled fluorophores, and self-assembly of fluorescent materials over plasmonic nano-patterns.

Effects on Photovoltaic Performance of Dialkyloxy-benzothiadiazole Copolymers by Varying the Thienoacene Donor.

PubMed

Kini, Gururaj P; Oh, Sora; Abbas, Zaheer; Rasool, Shafket; Jahandar, Muhammad; Song, Chang Eun; Lee, Sang Kyu; Shin, Won Suk; So, Won-Wook; Lee, Jong-Cheol

2017-04-12

A series of four donor-acceptor alternating copolymers based on dialkyloxy-benzothiadiazole (ROBT) as an acceptor and thienoacenes as donor units were synthesized and tested for polymer solar cells (PSCs). These new polymers had different donor units with varied electron-donating ability (thieno[3,2-b]thiophene (TT), dithieno[3,2-b:2',3'-d]thiophene (DTT), benzo[1,2-b:4,5-b']dithiophene (BDT), and naphtha[1,2-b:5,6-b']dithiophene (NDT)) in the polymer backbone. To understand the effect of these thienoacenes on the optoelectronic and photovoltaic properties of the copolymers, we systematically analyzed and compared the energy levels, crystallinity, morphology, charge recombination, and charge carrier mobility in the resulting polymers. In this series, optimized photovoltaic cells yielded power conversion efficiency (PCE) values of 6.25% (TT), 9.02% (DTT), 6.34% (BDT), and 2.29% (NDT) with different thienoacene donors. The introduction of DTT into the thienoacene-ROBT polymer enabled the generation of well-ordered molecular packings with a π-π stacking distance of 3.72 Å, high charge mobilities, and an interconnected nanofibrillar morphology in blend films. As a result, the PSC employing the polymer with DTT exhibited the highest PCE of 9.02%. Thus, our structure-property relationship studies of thienoacene-ROBT-based polymers emphasize that the molecular design of the polymers must be carefully optimized to develop high efficient PSCs. These findings will help us to understand the impact of the donor thienoacene on the optoelectronic and photovoltaic performance of polymers.

Fluorescent nanoscale zinc(II)-carboxylate coordination polymers for explosive sensing.

PubMed

Zhang, Chengyi; Che, Yanke; Zhang, Zengxing; Yang, Xiaomei; Zang, Ling

2011-02-28

Fluorescent nanoscale coordination polymers with cubic morphology and long range ordered structure were fabricated and exhibited efficient sensing for both nitroaromatic explosive and nitromethane due to large surface area to volume ratio and strong binding affinity to explosive molecules.

Dynamic mechanical properties of hydroxyapatite/polyethylene oxide nanocomposites: characterizing isotropic and post-processing microstructures

NASA Astrophysics Data System (ADS)

Shofner, Meisha; Lee, Ji Hoon

2012-02-01

Compatible component interfaces in polymer nanocomposites can be used to facilitate a dispersed morphology and improved physical properties as has been shown extensively in experimental results concerning amorphous matrix nanocomposites. In this research, a block copolymer compatibilized interface is employed in a semi-crystalline matrix to prevent large scale nanoparticle clustering and enable microstructure construction with post-processing drawing. The specific materials used are hydroxyapatite nanoparticles coated with a polyethylene oxide-b-polymethacrylic acid block copolymer and a polyethylene oxide matrix. Two particle shapes are used: spherical and needle-shaped. Characterization of the dynamic mechanical properties indicated that the two nanoparticle systems provided similar levels of reinforcement to the matrix. For the needle-shaped nanoparticles, the post-processing step increased matrix crystallinity and changed the thermomechanical reinforcement trends. These results will be used to further refine the post-processing parameters to achieve a nanocomposite microstructure with triangulated arrays of nanoparticles.

Nanoscale Morphology of PTB7 Based Organic Photovoltaics as a Function of Fullerene Size

DOE PAGES

Roehling, John D.; Baran, Derya; Sit, Joseph; ...

2016-08-08

High efficiency polymer:fullerene photovoltaic device layers self-assemble with hierarchical features from ångströms to 100’s of nanometers. The feature size, shape, composition, orientation, and order all contribute to device efficiency and are simultaneously difficult to study due to poor contrast between carbon based materials. This study seeks to increase device efficiency and simplify morphology measurements by replacing the typical fullerene acceptor with endohedral fullerene Lu 3N@PC 80BEH. The metal atoms give excellent scattering contrast for electron beam and x-ray experiments. Additionally, Lu 3N@PC 80BEH has a lower electron affinity than standard fullerenes, which can raise the open circuit voltage of photovoltaicmore » devices. Electron microscopy techniques are used to produce a detailed account of morphology evolution in mixtures of Lu 3N@PC 80BEH with the record breaking donor polymer, PTB7 and coated using solvent mixtures. We demonstrate that common solvent additives like 1,8-diiodooctane or chloronapthalene do not improve the morphology of endohedral fullerene devices as expected. The poor device performance is attributed to the lack of mutual miscibility between this particular polymer:fullerene combination and to co-crystallization of Lu 3N@PC 80BEH with 1,8-diiodooctane. This negative result explains why solvent additives mixtures are not necessarily a morphology cure-all.« less

Nanoscale Morphology of PTB7 Based Organic Photovoltaics as a Function of Fullerene Size

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roehling, John D.; Baran, Derya; Sit, Joseph

High efficiency polymer:fullerene photovoltaic device layers self-assemble with hierarchical features from ångströms to 100’s of nanometers. The feature size, shape, composition, orientation, and order all contribute to device efficiency and are simultaneously difficult to study due to poor contrast between carbon based materials. This study seeks to increase device efficiency and simplify morphology measurements by replacing the typical fullerene acceptor with endohedral fullerene Lu 3N@PC 80BEH. The metal atoms give excellent scattering contrast for electron beam and x-ray experiments. Additionally, Lu 3N@PC 80BEH has a lower electron affinity than standard fullerenes, which can raise the open circuit voltage of photovoltaicmore » devices. Electron microscopy techniques are used to produce a detailed account of morphology evolution in mixtures of Lu 3N@PC 80BEH with the record breaking donor polymer, PTB7 and coated using solvent mixtures. We demonstrate that common solvent additives like 1,8-diiodooctane or chloronapthalene do not improve the morphology of endohedral fullerene devices as expected. The poor device performance is attributed to the lack of mutual miscibility between this particular polymer:fullerene combination and to co-crystallization of Lu 3N@PC 80BEH with 1,8-diiodooctane. This negative result explains why solvent additives mixtures are not necessarily a morphology cure-all.« less

Dynamics of ultra-thin polystyrene with and without a (artificial) dead layer studied by resonance enhanced dynamic light scattering

NASA Astrophysics Data System (ADS)

Vianna, S. D. B.; Lin, F. Y.; Plum, M. A.; Duran, H.; Steffen, W.

2017-05-01

Using non-invasive, marker-free resonance enhanced dynamic light scattering, the dynamics of capillary waves on ultrathin polystyrene films' coupling to the viscoelastic and mechanical properties have been studied. The dynamics of ultrathin polymer films is still debated. In particular the question of what influence either the solid substrate and/or the fluid-gas interface has on the dynamics and the mechanical properties of films of glass forming liquids as polymers is in the focus of the present research. As a consequence, e.g., viscosity close to interfaces and thus the average viscosity of very thin films are prone to change. This study is focused on atactic, non-entangled polystyrene thin films on the gold surface. A slow dynamic mode was observed with Vogel-Fulcher-Tammann temperature dependence, slowing down with decreasing film thickness. We tentatively attribute this relaxation mode to overdamped capillary waves because of its temperature dependence and the dispersion with a wave vector which was found. No signs of a more mobile layer at the air/polymer interface or of a "dead layer" at the solid/polymer interface were found. Therefore we investigated the influence of an artificially created dead layer on the capillary wave dynamics by introducing covalently bound polystyrene polymer brushes as anchors. The dynamics was slowed down to a degree more than expected from theoretical work on the increase of density close to the solid liquid interface—instead of a "dead layer" of 2 nm, the interaction seems to extend more than 10 nm into the polymer.

Polyaniline-CuO hybrid nanocomposite with enhanced electrical conductivity

NASA Astrophysics Data System (ADS)

de Souza, Vânia S.; da Frota, Hidembergue O.; Sanches, Edgar A.

2018-02-01

A hybrid nanocomposite based on a polymer matrix constituted of Polyaniline Emeraldine-salt form (PANI-ES) reinforced by copper oxide II (CuO) particles was obtained by in situ polymerization. Structural, morphological and electrical properties of the pure materials and nanocomposite form were investigated. The presence of CuO particles in the nanocomposite material affected the natural alignment of the polymer chains. XRD technique allowed the visualization of the polymer amorphization in the nanocomposite form, suggesting an interaction between both phases. The FTIR spectra confirmed this molecular interaction due to the blue shift of the characteristic absorption peaks of PANI-ES in the nanocomposite form. SEM images revealed that the polymer nanofiber morphology was no longer observed in the nanocomposite. The CuO spherical particles are randomly dispersed in the polymer matrix. The density functional theory plus the Coulomb interaction method revealed a charge transfer from PANI to CuO slab. Moreover, the density of states (DOS) has revealed that the nanocomposite behaves as a metal. In agreement, the electrical conductivity showed an increase of 60% in the nanocomposite material.

Fabrication of Polyvinylpyrrolidone Fibers by Means of Rotary Forcespinning Method

NASA Astrophysics Data System (ADS)

Andjani, D.; Sriyanti, I.; Fauzi, A.; Edikresnha, D.; Munir, M. M.; Khairurrijal

2018-05-01

Fibers made from polymer materials have been widely developed as a carrier medium of active ingredients in drug delivery systems. In this research, PVP polymer was chosen because of its wide and safe use in the medical field. The purpose of this study was to produce PVP fibers that can later be applied as a carrier of active ingredients in drug delivery systems. The rotary forcespinning (RFS) method was chosen to shorten the time of production and to overcome the limitations of electrospinning method such as the use of high voltage and dielectric solutions. The PVP solution was varied in several concentrations (8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, and 18 wt%) to achieve the best fibers morphology. The morphology and the diameter of fibers were analyzed using a digital microscope. From the microscope images, it can be shown that beaded fibers were formed when the concentration of polymer in the precursor solution was low. The number of beads decreased as the concentration of polymer increased. Beads-free fibers were fully formed at above certain polymer concentration.

Drug-releasing shape-memory polymers - the role of morphology, processing effects, and matrix degradation.

PubMed

Wischke, Christian; Behl, Marc; Lendlein, Andreas

2013-09-01

Shape-memory polymers (SMPs) have gained interest for temporary drug-release systems that should be anchored in the body by self-sufficient active movements of the polymeric matrix. Based on the so far published scientific literature, this review highlights three aspects that require particular attention when combining SMPs with drug molecules: i) the defined polymer morphology as required for the shape-memory function, ii) the strong effects that processing conditions such as drug-loading methodologies can have on the drug-release pattern from SMPs, and iii) the independent control of drug release and degradation by their timely separation. The combination of SMPs with a drug-release functionality leads to multifunctional carriers that are an interesting technology for pharmaceutical sciences and can be further expanded by new materials such as thermoplastic SMPs or temperature-memory polymers. Experimental studies should include relevant molecules as (model) drugs and provide a thermomechanical characterization also in an aqueous environment, report on the potential effect of drug type and loading levels on the shape-memory functionality, and explore the potential correlation of polymer degradation and drug release.

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer.

PubMed

Baker, Matthew B; Albertazzi, Lorenzo; Voets, Ilja K; Leenders, Christianus M A; Palmans, Anja R A; Pavan, Giovanni M; Meijer, E W

2015-02-20

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer

NASA Astrophysics Data System (ADS)

Baker, Matthew B.; Albertazzi, Lorenzo; Voets, Ilja K.; Leenders, Christianus M. A.; Palmans, Anja R. A.; Pavan, Giovanni M.; Meijer, E. W.

2015-02-01

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Luminescent tunable polydots: Charge effects in confined geometry

DOE PAGES

Wijesinghe, Sidath; Maskey, Sabina; Perahia, Dvora; ...

2017-06-28

Long-lived soft nanoparticles, formed by conjugated polymers, constitute a new class of far-from-equilibrium responsive structures for nano-medicine. Tethering ionizable groups to the polymers enables functionality. However concurrently, the ionic groups perturb the delicate balance of interactions that governs these particles. Using fully atomistic molecular dynamics simulations, this study probed the effects of charged groups tethered to poly para phenylene ethynylene substituted by alkyl groups on the polymer conformation and dynamics in confined geometry. As a result, we find that the ionizable groups affect the entire shape of the polydots and impact the conformation and dynamics of the polymer.

Network dynamics in nanofilled polymers

NASA Astrophysics Data System (ADS)

Baeza, Guilhem P.; Dessi, Claudia; Costanzo, Salvatore; Zhao, Dan; Gong, Shushan; Alegria, Angel; Colby, Ralph H.; Rubinstein, Michael; Vlassopoulos, Dimitris; Kumar, Sanat K.

2016-04-01

It is well accepted that adding nanoparticles (NPs) to polymer melts can result in significant property improvements. Here we focus on the causes of mechanical reinforcement and present rheological measurements on favourably interacting mixtures of spherical silica NPs and poly(2-vinylpyridine), complemented by several dynamic and structural probes. While the system dynamics are polymer-like with increased friction for low silica loadings, they turn network-like when the mean face-to-face separation between NPs becomes smaller than the entanglement tube diameter. Gel-like dynamics with a Williams-Landel-Ferry temperature dependence then result. This dependence turns particle dominated, that is, Arrhenius-like, when the silica loading increases to ~31 vol%, namely, when the average nearest distance between NP faces becomes comparable to the polymer's Kuhn length. Our results demonstrate that the flow properties of nanocomposites are complex and can be tuned via changes in filler loading, that is, the character of polymer bridges which `tie' NPs together into a network.

Structure and Entanglement Factors on Dynamics of Polymer-Grafted Nanoparticles

DOE PAGES

Liu, Siqi; Senses, Erkan; Jiao, Yang; ...

2016-04-15

Nanoparticles functionalized with long polymer chains at low graft density are interesting systems to study structure–dynamic relationships in polymer nanocomposites since they are shown to aggregate into strings in both solution and melts and also into spheres and branched aggregates in the presence of free polymer chains. Our work investigates structure and entanglement effects in composites of polystyrene-grafted iron oxide nanoparticles by measuring particle relaxations using X-ray photon correlation spectroscopy. And for particles within highly ordered strings and aggregated systems, they experience a dynamically heterogeneous environment displaying hyperdiffusive relaxation commonly observed in jammed soft glassy systems. Furthermore, particle dynamics ismore » diffusive for branched aggregated structures which could be caused by less penetration of long matrix chains into brushes. These results suggest that particle motion is dictated by the strong interactions of chains grafted at low density with the host matrix polymer.« less

Simulating the flow of entangled polymers.

PubMed

Masubuchi, Yuichi

2014-01-01

To optimize automation for polymer processing, attempts have been made to simulate the flow of entangled polymers. In industry, fluid dynamics simulations with phenomenological constitutive equations have been practically established. However, to account for molecular characteristics, a method to obtain the constitutive relationship from the molecular structure is required. Molecular dynamics simulations with atomic description are not practical for this purpose; accordingly, coarse-grained models with reduced degrees of freedom have been developed. Although the modeling of entanglement is still a challenge, mesoscopic models with a priori settings to reproduce entangled polymer dynamics, such as tube models, have achieved remarkable success. To use the mesoscopic models as staging posts between atomistic and fluid dynamics simulations, studies have been undertaken to establish links from the coarse-grained model to the atomistic and macroscopic simulations. Consequently, integrated simulations from materials chemistry to predict the macroscopic flow in polymer processing are forthcoming.

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

PubMed

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.

Dynamics in Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Clarke, Nigel

2015-03-01

Since nanoparticles are increasingly being added to polymers to impart mechanical and functional properties, we are exploring how nanoparticles impact polymer dynamics with a focus on the diffusion coefficients. In high molecular weight polymer melts, chain diffusion is well described by the reptation model. Motion proceeds as a snake-like diffusion of the chain as a whole, along the contour of a tube that mimics the role of physical entanglements, or topological constraints, with other chains. In polymer nanocomposites there are additional constraints due to the dispersed nanoparticles in the polymer matrix. Chain motion can be altered by nanoparticle size, shape , aspect ratio, surface area, loading and the nature of the interactions between the nanoparticles and the polymer matrix. We have observed a minimum in the diffusion coefficient as a function of nanoparticle concentration when the nanoparticles are rod-like and a collapse of the diffusion coefficient onto a master curve when the nanoparticles are spherical. We are simulating the dynamics using molecular and dissipative particle simulations in order to provide physical insight into the local structure and dynamics, and have also carried out highly coarse grained Monte Carlo simulations of entangled polymers to explore how reptation is affected by the presence of larger scale obstacles. We acknowledge support from the NSF/EPSRC Materials World Network Program.

Diketopyrrolopyrrole-based polymer:fullerene nanoparticle films with thermally stable morphology for organic photovoltaic applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holmes, Natalie P.; Vaughan, Ben; Williams, Evan L.

Polymer:fullerene nanoparticles (NPs) offer two key advantages over bulk heterojunction (BHJ) films for organic photovoltaics (OPVs), water-processability and potentially superior morphological control. Once an optimal active layer morphology is reached, maintaining this morphology at OPV operating temperatures is key to the lifetime of a device. Here in this paper we study the morphology of the PDPP-TNT (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene}):PC 71BM ([6,6]-phenyl C 71 butyric acid methyl ester) NP system and then compare the thermal stability of NP and BHJ films to the common poly(3-hexylthiophene) (P3HT): phenyl C 61 butyric acid methyl ester (PC 61BM) system. We find that material T g playsmore » a key role in the superior thermal stability of the PDPP-TNT:PC 71BM system; whereas for the P3HT:PC 61BM system, domain structure is critical.« less

Single polymer dynamics in semi-dilute unentangled and entangled solutions: from molecular conformation to normal stress

NASA Astrophysics Data System (ADS)

Schroeder, Charles

Semi-dilute polymer solutions are encountered in a wide array of applications such as advanced 3D printing technologies. Semi-dilute solutions are characterized by large fluctuations in concentration, such that hydrodynamic interactions, excluded volume interactions, and transient chain entanglements may be important, which greatly complicates analytical modeling and theoretical treatment. Despite recent progress, we still lack a complete molecular-level understanding of polymer dynamics in these systems. In this talk, I will discuss three recent projects in my group to study semi-dilute solutions that focus on single molecule studies of linear and ring polymers and a new method to measure normal stresses in microfluidic devices based on the Stokes trap. In the first effort, we use single polymer techniques to investigate the dynamics of semi-dilute unentangled and semi-dilute entangled DNA solutions in extensional flow, including polymer relaxation from high stretch, transient stretching dynamics in step-strain experiments, and steady-state stretching in flow. In the semi-dilute unentangled regime, our results show a power-law scaling of the longest polymer relaxation time that is consistent with scaling arguments based on the double cross-over regime. Upon increasing concentration, we observe a transition region in dynamics to the entangled regime. We also studied the transient and steady-state stretching dynamics in extensional flow using the Stokes trap, and our results show a decrease in transient polymer stretch and a milder coil-to-stretch transition for semi-dilute polymer solutions compared to dilute solutions, which is interpreted in the context of a critical Weissenberg number Wi at the coil-to-stretch transition. Interestingly, we observe a unique set of polymer conformations in semi-dilute unentangled solutions that are highly suggestive of transient topological entanglements in solutions that are nominally unentangled at equilibrium. Taken together, these results suggest that the transient stretching pathways in semi-dilute solution extensional flows are qualitatively different than for both dilute solutions and for semi-dilute solutions in shear flow. In a second effort, we studied the dynamics of ring polymers in background solutions of semi-dilute linear polymers. Interestingly, we observe strikingly large fluctuations in steady-state polymer extension for ring polymers in flow, which occurs due to the interplay between polymer topology and concentration leading to chain `threading' in flow. In a third effort, we developed a new microfluidic method to measure normal stress and extensional viscosity that can be loosely described as passive yet non-linear microrheology. In particular, we incorporated 3-D particle imaging velocimetry (PIV) with the Stokes trap to study extensional flow-induced particle migration in semi-dilute polymer solutions. Experimental results are analyzed using the framework of a second-order-fluid model, which allows for measurement of normal stress and extensional viscosity in semi-dilute polymer solutions, all of which is a first-of-its-kind demonstration. Microfluidic measurements of extensional viscosity are directly compared to the dripping-onto-substrate or DOS method, and good agreement is generally observed. Overall, our work aims to provide a molecular-level understanding of the role of polymer topology and concentration on bulk rheological properties by using single polymer techniques.

Electron beam irradiated polymer electrolyte film: Morphology, dielectric and AC conductivity studies

NASA Astrophysics Data System (ADS)

Yesappa, L.; Niranjana, M.; Ashokkumar, S. P.; Vijeth, H.; Ganesh, S.; Devendrappa, H.

2018-05-01

The polymer (PVdF-co-HFP: LiClO4=90:10, PHL10) electrolyte films prepared by solution casting method and studied morphology, dielectric properties and ac conductivity before and after electron beam (EB) irradiation. The polarized optical micrographs reveals size of spherulite reduced with increasing EB dose represents increase in amorphousity. The dielectric measurements were studied at different temperatures and observed increase with frequency at different temperatures upon EB irradiation. The ac conductivity increases with frequency due to effect of EB dose.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Youm, Sang Gil; Hwang, Euiyong; Chavez, Carlos A.

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe themore » development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.« less

Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies

DOE PAGES

Youm, Sang Gil; Hwang, Euiyong; Chavez, Carlos A.; ...

2016-06-15

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe themore » development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.« less

Comparison of solution-mixed and sequentially processed P3HT: F4TCNQ films: effect of doping-induced aggregation on film morphology

DOE PAGES

Jacobs, Ian E.; Aasen, Erik W.; Oliveira, Julia L.; ...

2016-03-23

Doping polymeric semiconductors often drastically reduces the solubility of the polymer, leading to difficulties in processing doped films. Here, we compare optical, electrical, and morphological properties of P3HT films doped with F4TCNQ, both from mixed solutions and using sequential solution processing with orthogonal solvents. We demonstrate that sequential doping occurs rapidly (<1 s), and that the film doping level can be precisely controlled by varying the concentration of the doping solution. Furthermore, the choice of sequential doping solvent controls whether dopant anions are included or excluded from polymer crystallites. Atomic force microscopy (AFM) reveals that sequential doping produces significantly moremore » uniform films on the nanoscale than the mixed-solution method. In addition, we show that mixed-solution doping induces the formation of aggregates even at low doping levels, resulting in drastic changes to film morphology. Sequentially coated films show 3–15 times higher conductivities at a given doping level than solution-doped films, with sequentially doped films processed to exclude dopant anions from polymer crystallites showing the highest conductivities. In conclusion, we propose a mechanism for doping induced aggregation in which the shift of the polymer HOMO level upon aggregation couples ionization and solvation energies. To show that the methodology is widely applicable, we demonstrate that several different polymer:dopant systems can be prepared by sequential doping.« less

Comparison of solution-mixed and sequentially processed P3HT: F4TCNQ films: effect of doping-induced aggregation on film morphology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobs, Ian E.; Aasen, Erik W.; Oliveira, Julia L.

Doping polymeric semiconductors often drastically reduces the solubility of the polymer, leading to difficulties in processing doped films. Here, we compare optical, electrical, and morphological properties of P3HT films doped with F4TCNQ, both from mixed solutions and using sequential solution processing with orthogonal solvents. We demonstrate that sequential doping occurs rapidly (<1 s), and that the film doping level can be precisely controlled by varying the concentration of the doping solution. Furthermore, the choice of sequential doping solvent controls whether dopant anions are included or excluded from polymer crystallites. Atomic force microscopy (AFM) reveals that sequential doping produces significantly moremore » uniform films on the nanoscale than the mixed-solution method. In addition, we show that mixed-solution doping induces the formation of aggregates even at low doping levels, resulting in drastic changes to film morphology. Sequentially coated films show 3–15 times higher conductivities at a given doping level than solution-doped films, with sequentially doped films processed to exclude dopant anions from polymer crystallites showing the highest conductivities. In conclusion, we propose a mechanism for doping induced aggregation in which the shift of the polymer HOMO level upon aggregation couples ionization and solvation energies. To show that the methodology is widely applicable, we demonstrate that several different polymer:dopant systems can be prepared by sequential doping.« less

Fiber lubrication: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Liu, Hongyi

Molecular and mesoscopic level description of friction and lubrication remains a challenge because of difficulties in the phenomenological understanding of to the behaviors of solid-liquid interfaces during sliding. Fortunately, there is the computational simulation approach opens an opportunity to predict and analyze interfacial phenomena, which were studied with molecular dynamics (MD) and mesoscopic dynamics (MesoDyn) simulations. Polypropylene (PP) and cellulose are two of most common polymers in textile fibers. Confined amorphous surface layers of PP and cellulose were built successfully with xenon crystals which were used to compact the polymers. The physical and surface properties of the PP and cellulose surface layers were investigated by MD simulations, including the density, cohesive energy, volumetric thermal expansion, and contact angle with water. The topology method was employed to predict the properties of poly(alkylene glycol) (PAG) diblock copolymers and Pluronic triblock copolymers used as lubricants on surfaces. Density, zero shear viscosity, shear module, cohesive energy and solubility parameter were predicted with each block copolymer. Molecular dynamics simulations were used to study the interaction energy per unit contact area of block copolymer melts with PP and cellulose surfaces. The interaction energy is defined as the ratio of interfacial interaction energy to the contact area. Both poly(proplene oxide) (PPO) and poly(ethylene oxide) (PEO) segments provided a lipophilic character to both PP and cellulose surfaces. The PPO/PEO ratio and the molecular weight were found to impact the interaction energy on both PP and cellulose surfaces. In aqueous solutions, the interaction energy is complicated due to the presence of water and the cross interactions between the multiple molecular components. The polymer-water-surface (PWS) calculation method was proposed to calculate such complex systems. In a contrast with a vacuum condition, the presence of water increases the attractive interaction energy of the diblock copolymer on the cellulose surface, compared with that on the PP surface. Water decreases the interaction energy of the triblock copolymer on the cellulose surface, compared with that on the PP surface. MesoDyn was adopted to investigate the self-assembled morphology of the triblock copolymer, in aqueous solution, confined and sheared at solid-liquid interfaces. In a bulk aqueous solution, when the polymer concentration reached 10% v/v, micelles were observed with PPO blocks in the core and PEO blocks in the shell of the micelles. At the concentrations of 25% and 50%, worm-like micelles and irregular cylinders were observed in solutions, respectively. The micelles were formed faster in aqueous solutions confined by cellulose surfaces than that in the bulk. The formed micelles were broken under shearing, which led to a depletion of polymers at the interfaces. During the shearing on the PP surfaces, the polymers were adsorbed on the surfaces protecting the PP surfaces. This simulation study in the fiber lubrication was in good agreement with the experimental results and so provided an approach to visualize the polymer configuration at the liquid-solid interface, predict the lubricant-surface systems, and theoretically guide the experiments of designing new/efficient lubricants for fibers.

Biocompatibility of modified ultra-high-molecular-weight polyethylene

NASA Astrophysics Data System (ADS)

Novotná, Z.; Lacmanová, V.; Rimpelová, S.; Juřik, P.; Polívková, M.; Å vorčik, V.

2016-09-01

Ultra-high-molecular-weight polyethylene (UHMWPE, PE) is a synthetic polymer used for biomedical applications because of its high impact resistance, ductility and stability in contact with physiological fluids. Therefore this material is being used in human orthopedic implants such as total joint replacements. Surface modification of this material relates to changes of its surface hydrophilicity, energy, microstructure, roughness, and morphology, all influencing its biological response. In our recent work, PE was treated by an Ar+ plasma discharge and then grafted with biologically active polyethylene glycol in order to enhance adhesion and proliferation of mouse fibroblast (L929). The surface properties of pristine PE and its grafted counterparts were studied by goniometry (surface wettability). Furthermore, Atomic Force Microscopy was used to determine the surface morphology and roughness. The biological response of the L929 cell lines seeded on untreated and plasma treated PE matrices was quantified in terms of the cell adhesion, density, and metabolic activity. Plasma treatment leads to the ablation of the polymer surface layers. Plasma treatment and subsequent poly(ethylene glycol) grafting lead to dramatic changes in the polymer surface morphology and roughness. Biological tests, performed in vitro, show increased adhesion and proliferation of cells on modified polymers. Grafting with poly(ethylene glycol) increases cell proliferation compared to plasma treatment.

Human monocyte adhesion and activation on crystalline polymers with different morphology and wettability in vitro.

PubMed

Young, T H; Lin, D T; Chen, L Y

2000-06-15

This study evaluated the effects of crystalline polyamide (Nylon-66), poly(ethylene-co-vinyl alcohol) (PEVA), and poly(vinylidene fluoride) (PVDF) polymers with nonporous and porous morphologies on the ability of monocytes to adhere and subsequently activate to produce IL-1beta, IL-6, and tumor necrosis factor alpha. The results indicated monocyte adhesion and activation on a material might differ to a great extent, depending on the surface morphology and wettability. As the polymer wettability increases, the ability of monocytes to adhere increases but the ability to produce cytokines decreases. Similarly, these polymers, when prepared with porous surfaces, enhance monocyte adhesion but suppress monocyte release of cytokines. Therefore, the hydrophobic PVDF with a nonporous surface stimulates the most activity in adherent monocytes but shows the greatest inhibition of monocyte adhesion when compared with all of the other membranes. In contrast, the hydrophilic Nylon-66, which has a porous surface, is a relatively better substrate for this work. Therefore, monocyte behavior on a biomaterial may be influenced by a specific surface property. Based on this result, we propose that monocyte adhesion is regulated by a different mechanism than monocyte activation. Consequently, the generation of cytokines by monocytes is not proportional to the number of cells adherent to the surface. Copyright 2000 John Wiley & Sons, Inc.

Comparison study of morphology and crystallization behavior of polyethylene and poly(ethylene oxide) on single-walled carbon nanotubes.

PubMed

Zheng, Xiaoli; Xu, Qun

2010-07-29

In this work, we provided a comparison study of morphology and crystallization behavior of polyethylene (PE) and poly(ethylene oxide) (PEO) on single-walled carbon nanotubes (SWNTs) with assistance of supercritical CO(2). The resulting polymer/SWNT nanohybrids were characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectra, wide-angle X-ray diffraction, and differential scanning calorimetry. SWNT small bundles were decorated by PE lamellar crystals, forming nanohybrid "shish-kebab" (NHSK) structure, whereas SWNTs were only wrapped by a thin amorphous polymer coating in the case of PEO. The varying morphologies of the nanohybrids were found to depend on the molecular conformation and the interactions between polymer chains and SWNTs. Nonisothermal experiments showed that SWNTs provided heterogeneous nucleation sites for PE crystallization, while the NHSK structure hindered polymer chain diffusion and crystal growth. Also, SWNTs played antinucleation effect on PEO. In addition, the formation mechanism analysis indicated that PE chains preferred to form a homogeneous coating along the tube axis before proceeding to kebab crystal growth. The purpose of this work is to enlarge the area of theoretical understanding of introducing precisely hierarchical structures on carbon nanotubes, which are important for functional design in nanodevice applications.

Polymer dynamics driven by a helical filament

NASA Astrophysics Data System (ADS)

Balin, Andrew; Shendruk, Tyler; Zoettl, Andreas; Yeomans, Julia

Microbial flagellates typically inhabit complex suspensions of extracellular polymeric material which can impact the swimming speed of motile microbes, filter-feeding of sessile cells, and the generation of biofilms. There is currently a need to better understand how the fundamental dynamics of polymers near active cells or flagella impacts these various phenomena. We study the hydrodynamic and steric influence of a rotating helical filament on suspended polymers using Stokesian Dynamics simulations. Our results show that as a stationary rotating helix pumps fluid along its long axis, nearby polymers migrate radially inwards and are elongated in the process. We observe that the actuation of the helix tends to increase the probability of finding polymeric material within its pervaded volume. At larger Weissenberg numbers, this accumulation of polymers within the vicinity of the helix is greater. Further, we have analysed the stochastic work performed by the helix on the polymers and we show that this quantity is positive on average and increases with polymer contour length. Our results provide a basis for understanding the microscopic interactions that govern cell dynamics in complex media. This work was supported through funding from the ERC Advanced Grant 291234 MiCE and we acknowledge EMBO funding to TNS (ALTF181-2013).

The interplay of morphology and carrier recombination in dendrimer-based organic photovoltaics.

NASA Astrophysics Data System (ADS)

Shaheen, Sean; Kopidakis, Nikos; Mitchell, William; Rance, William; van de Lagemaat, Jao; Rumbles, Garry

2007-03-01

Pi-conjugated dendrimers provide an alternative to polymers in organic photovoltaic devices that allow for systematic study of how the molecular structure affects the morphology of the donor and acceptor components and subsequently how the device operates. The degree of mixing and specific geometry of the donor-acceptor blend play a determining role in the rate of exciton dissociation as well as the efficacy of charge transport out of the active layer. We find that pi-conjugated dendrimers are more miscible with the fullerene-derivative acceptor than their polymeric counterparts, which leads to smaller domains than are commonly found in polymer-fullerene blends. Here we discuss how these differing morphologies affect exciton dissociation, carrier transport, and carrier recombination in the devices.

Morphological Characterization of Silicone Hydrogels

NASA Astrophysics Data System (ADS)

Gido, Samuel

2007-03-01

Silicone hydrogel materials are used in the latest generation of extended wear soft contact lenses. To ensure comfort and eye health, these materials must simultaneously exhibit high oxygen permeability and high water permeability / hydrophilicity. The materials achieve these opposing requirements based on bicontinuous composite of nanoscale domains of oxygen permeable (silicones) and hydrophilic (water soluble polymer) materials. The microphase separated morphology of silicone hydrogel contact lens materials was imaged using field emission gun scanning transmission electron microscopy (FEGSTEM), and atomic force microscopy (AFM). Additional morphological information was provided by small angle X-ray scattering (SAXS). These results all indicate a nanophase separated structure of silicone rich (oxygen permeable) and carbon rich (water soluble polymer) domains separated on a length scale of about 10 nm.

Microcellular poly(hydroxybutyrate-co-hydroxyvalerate)-hyperbranched polymer-nanoclay nanocomposites

Treesearch

Alireza Javadi; Yottha Srithep; Srikanth Pilla; Craig C. Clemons; Shaoqin Gong; Lih-Sheng Turng

2012-01-01

The effects of incorporating hyperbranched polymers (HBPs) and different nanoclays [Cloisite® 30B and halloysite nanotubes (HNT)] on the mechanical, morphological, and thermal properties of solid and microcellular poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) were investigated. According to the X-ray diffraction (...

Structural Evolution and Mechanical Properties of PMR-15/Layered Silicate Nanocomposites

NASA Technical Reports Server (NTRS)

Campbell, Sandi (Technical Monitor); Dean, Derrick; Abdalla, Mohamed; Green, Keith; Small, Sharee

2003-01-01

In the first year of this research, we successfully synthesized and characterized Polymer/ Layered Silicate nanocomposite using the polyimide PMR-15 as the polymer and several layered silicate nanoparticles. We have scaled up the process to allow fabrication of monoliths using these nanocomposites. The morphology of these systems was found to evolve during processing to an exfoliated structure for one system and intercalated for the rest. Correlation with Transmission Electron Microscopy studies is underway. Dynamic mechanical analysis (DMA) results showed a significant increase in the thermomechanical properties (E' and E'') of 2.5 wt.% clay loaded nanocomposites in comparison to the neat polyimide. Increasing the clay loading to 5 wt.% decreased these properties. Higher glass transition temperatures were observed for 2.5 wt.% nanocomposites compared to the neat polyimide. A lower coefficient of thermal expansion was observed only for the PGV/PMR-15 nanocomposite. An improvement in the flexural properties (modulus, strength and elongation) was observed for the 2.5 wt.% nanocomposite but not for the 5 wt.% nanocomposites. The improved barrier properties polymer/ silicate nanocomposites suggest that moisture uptake should be decreased for PMR-15 nanocomposites. The results of some recent experiments to examine delineate the ability of the silicate nanoparticles in improving the hydrolytic degradation of PMR-15 will be discussed.

Star Polymers Reduce Islet Amyloid Polypeptide Toxicity via Accelerated Amyloid Aggregation.

PubMed

Pilkington, Emily H; Lai, May; Ge, Xinwei; Stanley, William J; Wang, Bo; Wang, Miaoyi; Kakinen, Aleksandr; Sani, Marc-Antonie; Whittaker, Michael R; Gurzov, Esteban N; Ding, Feng; Quinn, John F; Davis, Thomas P; Ke, Pu Chun

2017-12-11

Protein aggregation into amyloid fibrils is a ubiquitous phenomenon across the spectrum of neurodegenerative disorders and type 2 diabetes. A common strategy against amyloidogenesis is to minimize the populations of toxic oligomers and protofibrils by inhibiting protein aggregation with small molecules or nanoparticles. However, melanin synthesis in nature is realized by accelerated protein fibrillation to circumvent accumulation of toxic intermediates. Accordingly, we designed and demonstrated the use of star-shaped poly(2-hydroxyethyl acrylate) (PHEA) nanostructures for promoting aggregation while ameliorating the toxicity of human islet amyloid polypeptide (IAPP), the peptide involved in glycemic control and the pathology of type 2 diabetes. The binding of PHEA elevated the β-sheet content in IAPP aggregates while rendering a new morphology of "stelliform" amyloids originating from the polymers. Atomistic molecular dynamics simulations revealed that the PHEA arms served as rodlike scaffolds for IAPP binding and subsequently accelerated IAPP aggregation by increased local peptide concentration. The tertiary structure of the star nanoparticles was found to be essential for driving the specific interactions required to impel the accelerated IAPP aggregation. This study sheds new light on the structure-toxicity relationship of IAPP and points to the potential of exploiting star polymers as a new class of therapeutic agents against amyloidogenesis.

Characterization of Hydrophobic Interactions of Polymers with Water and Phospholipid Membranes Using Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Drenscko, Mihaela

Polymers and lipid membranes are both essential soft materials. The structure and hydrophobicity/hydrophilicity of polymers, as well as the solvent they are embedded in, ultimately determines their size and shape. Understating the variation of shape of the polymer as well as its interactions with model biological membranes can assist in understanding the biocompatibility of the polymer itself. Computer simulations, in particular molecular dynamics, can aid in characterization of the interaction of polymers with solvent, as well as polymers with model membranes. In this thesis, molecular dynamics serve to describe polymer interactions with a solvent (water) and with a lipid membrane. To begin with, we characterize the hydrophobic collapse of single polystyrene chains in water using molecular dynamics simulations. Specifically, we calculate the potential of mean force for the collapse of a single polystyrene chain in water using metadynamics, comparing the results between all atomistic with coarse-grained molecular simulation. We next explore the scaling behavior of the collapsed globular shape at the minimum energy configuration, characterized by the radius of gyration, as a function of chain length. The exponent is close to one third, consistent with that predicted for a polymer chain in bad solvent. We also explore the scaling behavior of the Solvent Accessible Surface Area (SASA) as a function of chain length, finding a similar exponent for both all-atomistic and coarse-grained simulations. Furthermore, calculation of the local water density as a function of chain length near the minimum energy configuration suggests that intermediate chain lengths are more likely to form dewetted states, as compared to shorter or longer chain lengths. Next, in order to investigate the molecular interactions between single hydrophobic polymer chains and lipids in biological membranes and at lipid membrane/solvent interface, we perform a series of molecular dynamics simulations of small membranes using all atomistic and coarse-grained methods. The molecular interaction between common polymer chains used in biomedical applications and the cell membrane is unknown. This interaction may affect the biocompatibility of the polymer chains. Molecular dynamics simulations offer an emerging tool to characterize the interaction between common degradable polymer chains used in biomedical applications, such as polycaprolactone, and model cell membranes. We systematically characterize with long-time all-atomistic molecular dynamics simulations the interaction between single polycaprolactone chains of varying chain lengths with a model phospholipid membrane. We find that the length of polymer chain greatly affects the nature of interaction with the membrane, as well as the membrane properties. Furthermore, we next utilize advanced sampling techniques in molecular dynamics to characterize the two-dimensional free energy surface for the interaction of varying polymer chain lengths (short, intermediate, and long) with model cell membranes. We find that the free energy minimum shifts from the membrane-water interface to the hydrophobic core of the phospholipid membrane as a function of chain length. These results can be used to design polymer chain lengths and chemistries to optimize their interaction with cell membranes at the molecular level.

Micelle Morphology and Mechanical Response of Triblock Gels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seitz, Michelle E.; Burghardt, Wesley R.; Shull, Kenneth R.

2010-01-12

The effect of polymer concentration on mechanical response and micelle morphology of ABA and AB copolymers in B-selective solvents has been systematically studied. Micelle morphology was determined using a combination of small-angle X-ray scattering, shear, and birefringence while mechanical response at low and high strains was determined using indentation techniques. Self-consistent field theory calculations were used to determine micelle volume fraction profiles and to construct an equilibrium phase map. The transition from spherical to cylindrical micelles increases the triblock gel modulus and energy dissipation. Combining knowledge of gel relaxation time, which determines the rate at which the gel can equilibratemore » its micelle structure, with the equilibrium phase map allows estimation of the experimental temperatures and time scales over which kinetic trapping will arrest micelle structure evolution. Kinetic trapping enables cylindrical morphologies to be obtained at significantly lower polymer fractions than is possible in equilibrated systems.« less

An iterative method for hydrodynamic interactions in Brownian dynamics simulations of polymer dynamics

NASA Astrophysics Data System (ADS)

Miao, Linling; Young, Charles D.; Sing, Charles E.

2017-07-01

Brownian Dynamics (BD) simulations are a standard tool for understanding the dynamics of polymers in and out of equilibrium. Quantitative comparison can be made to rheological measurements of dilute polymer solutions, as well as direct visual observations of fluorescently labeled DNA. The primary computational challenge with BD is the expensive calculation of hydrodynamic interactions (HI), which are necessary to capture physically realistic dynamics. The full HI calculation, performed via a Cholesky decomposition every time step, scales with the length of the polymer as O(N3). This limits the calculation to a few hundred simulated particles. A number of approximations in the literature can lower this scaling to O(N2 - N2.25), and explicit solvent methods scale as O(N); however both incur a significant constant per-time step computational cost. Despite this progress, there remains a need for new or alternative methods of calculating hydrodynamic interactions; large polymer chains or semidilute polymer solutions remain computationally expensive. In this paper, we introduce an alternative method for calculating approximate hydrodynamic interactions. Our method relies on an iterative scheme to establish self-consistency between a hydrodynamic matrix that is averaged over simulation and the hydrodynamic matrix used to run the simulation. Comparison to standard BD simulation and polymer theory results demonstrates that this method quantitatively captures both equilibrium and steady-state dynamics after only a few iterations. The use of an averaged hydrodynamic matrix allows the computationally expensive Brownian noise calculation to be performed infrequently, so that it is no longer the bottleneck of the simulation calculations. We also investigate limitations of this conformational averaging approach in ring polymers.

Synthesis and characterization of monodispersed polymer/polydiacetylene nanocrystal composite particles.

PubMed

Wei, Zhong; Ujiiye-Ishii, Kento; Masuhara, Akito; Kasai, Hitoshi; Okada, Shuji; Matsune, Hideki; Asahi, Tsuyoshi; Masuhara, Hiroshi; Nakanishi, Hachiro

2005-06-01

Monodispersed polymer/polydiacetylenecomposite particles were synthesized by soap-free seeded emulsion polymerization of styrene andmethyl methacrylate; the products were characterized by XRD, SEM, TEM, UV-visible spectroscopy, and single particle scattering spectroscopy. In the synthesis process, polydiacetylene nanocrystals were found to act as inhibitor, and consequently a relatively low concentration was necessary. Different monomers lead to the differences in reaction condition and particle morphology; the PMMA composite particles were simpler in preparation than polystyrene particles, but the latter havebetter spherical morphology. The composite particles were composed of polymer shells and polydiacetylene cores, which kept their crystal structure and optical properties. A high percentage of cored particles could be achieved with optimized reaction conditions where the amount of seed was sufficient and the oily oligomer by-product was suppressed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Causa, Andrea; Acierno, Domenico; Filippone, Giovanni

We prepare and characterize multiphase systems in which small amounts of recycled polymer, namely polyethylene terephtalate (PET) ground from waste bottles, are dispersed in a co-continuous blend of high-density polyethylene (HDPE) and polypropylene (PP). Some of such ternary systems are also filled with plate-like clay nanoparticles with different polarities, in order to assess their influence on the morphology and mechanical behaviour of the blends. On the basis of preliminary wettability considerations and inspections by means of scanning electron microscopy (SEM), the PET is found to preferentially locate within the PP phase. Such a positioning is desirable in order to minimizemore » the presence of multiple interfaces, which is one of the major issues in the recycling process of co-mingles plastics. By means of SEM, dynamic-mechanical analysis and tensile tests we show that the addition of a filler with low polarity, which locates at the PET-matrix interface, has relevant implications on the structure and properties of the ternary systems, refining their morphology at the micro-scale and enhancing their high-temperature mechanical behaviour.« less

Towards the Development of a Low-Cost Device for the Detection of Explosives Vapors by Fluorescence Quenching of Conjugated Polymers in Solid Matrices.

PubMed

Martelo, Liliana M; das Neves, Tiago F Pimentel; Figueiredo, João; Marques, Lino; Fedorov, Alexander; Charas, Ana; Berberan-Santos, Mário N; Burrows, Hugh D

2017-11-03

Conjugated polymers (CPs) have proved to be promising chemosensory materials for detecting nitroaromatic explosives vapors, as they quickly convert a chemical interaction into an easily-measured high-sensitivity optical output. The nitroaromatic analytes are strongly electron-deficient, whereas the conjugated polymer sensing materials are electron-rich. As a result, the photoexcitation of the CP is followed by electron transfer to the nitroaromatic analyte, resulting in a quenching of the light-emission from the conjugated polymer. The best CP in our studies was found to be poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-bithiophene] (F8T2). It is photostable, has a good absorption between 400 and 450 nm, and a strong and structured fluorescence around 550 nm. Our studies indicate up to 96% quenching of light-emission, accompanied by a marked decrease in the fluorescence lifetime, upon exposure of the films of F8T2 in ethyl cellulose to nitrobenzene (NB) and 1,3-dinitrobenzene (DNB) vapors at room temperature. The effects of the polymeric matrix, plasticizer, and temperature have been studied, and the morphology of films determined by scanning electron microscopy (SEM) and confocal fluorescence microscopy. We have used ink jet printing to produce sensor films containing both sensor element and a fluorescence reference. In addition, a high dynamic range, intensity-based fluorometer, using a laser diode and a filtered photodiode was developed for use with this system.

Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics

PubMed Central

Grindy, Scott C.; Learsch, Robert; Mozhdehi, Davoud; Cheng, Jing; Barrett, Devin G.; Guan, Zhibin; Messersmith, Phillip B.; Holten-Andersen, Niels

2015-01-01

In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or copolymer-block design1. Here, by means of a model system of 4-arm poly(ethylene glycol) hydrogels crosslinked with multiple, kinetically distinct dynamic metal-ligand coordinate complexes, we show that polymer materials with decoupled spatial structure and mechanical performance can be designed. By tuning the relative concentration of two types of metal-ligand crosslinks, we demonstrate control over the material’s mechanical hierarchy of energy-dissipating modes under dynamic mechanical loading, and therefore the ability to engineer a priori the viscoelastic properties of these materials by controlling the types of crosslinks rather than by modifying the polymer itself. This strategy to decouple material mechanics from structure may inform the design of soft materials for use in complex mechanical environments. PMID:26322715

Inkjet-Printed Organic Transistors Based on Organic Semiconductor/Insulating Polymer Blends.

PubMed

Kwon, Yoon-Jung; Park, Yeong Don; Lee, Wi Hyoung

2016-08-02

Recent advances in inkjet-printed organic field-effect transistors (OFETs) based on organic semiconductor/insulating polymer blends are reviewed in this article. Organic semiconductor/insulating polymer blends are attractive ink candidates for enhancing the jetting properties, inducing uniform film morphologies, and/or controlling crystallization behaviors of organic semiconductors. Representative studies using soluble acene/insulating polymer blends as an inkjet-printed active layer in OFETs are introduced with special attention paid to the phase separation characteristics of such blended films. In addition, inkjet-printed semiconducting/insulating polymer blends for fabricating high performance printed OFETs are reviewed.

Inkjet-Printed Organic Transistors Based on Organic Semiconductor/Insulating Polymer Blends

PubMed Central

Kwon, Yoon-Jung; Park, Yeong Don; Lee, Wi Hyoung

2016-01-01

Recent advances in inkjet-printed organic field-effect transistors (OFETs) based on organic semiconductor/insulating polymer blends are reviewed in this article. Organic semiconductor/insulating polymer blends are attractive ink candidates for enhancing the jetting properties, inducing uniform film morphologies, and/or controlling crystallization behaviors of organic semiconductors. Representative studies using soluble acene/insulating polymer blends as an inkjet-printed active layer in OFETs are introduced with special attention paid to the phase separation characteristics of such blended films. In addition, inkjet-printed semiconducting/insulating polymer blends for fabricating high performance printed OFETs are reviewed. PMID:28773772

Medium Bandgap Conjugated Polymer for High Performance Polymer Solar Cells Exceeding 9% Power Conversion Efficiency.

PubMed

Jung, Jae Woong; Liu, Feng; Russell, Thomas P; Jo, Won Ho

2015-12-02

Two medium-bandgap polymers composed of benzo[1,2-b:4,5-b']dithiohpene and 2,1,3-benzothiadiazole with 6-octyl-thieno[3,2-b]thiophene as a π-bridge unit are synthesized and their photovoltaic properties are analyzed. The two polymers have deep highest occupied molecular orbital energy levels, high crystallinity, optimal bulk-heterojunction morphology, and efficient charge transport, resulting in a power conversion efficiency of as high as 9.44% for a single-junction polymer solar-cell device. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer physics experiments with single DNA molecules

NASA Astrophysics Data System (ADS)

Smith, Douglas E.

1999-11-01

Bacteriophage DNA molecules were taken as a model flexible polymer chain for the experimental study of polymer dynamics at the single molecule level. Video fluorescence microscopy was used to directly observe the conformational dynamics of fluorescently labeled molecules, optical tweezers were used to manipulate individual molecules, and micro-fabricated flow cells were used to apply controlled hydrodynamic strain to molecules. These techniques constitute a powerful new experimental approach in the study of basic polymer physics questions. I have used these techniques to study the diffusion and relaxation of isolated and entangled polymer molecules and the hydrodynamic deformation of polymers in elongational and shear flows. These studies revealed a rich, and previously unobserved, ``molecular individualism'' in the dynamical behavior of single molecules. Individual measurements on ensembles of identical molecules allowed the average conformation to be determined as well as the underlying probability distributions for molecular conformation. Scaling laws, that predict the dependence of properties on chain length and concentration, were also tested. The basic assumptions of the reptation model were directly confirmed by visualizing the dynamics of entangled chains.

Water transport, free volume, and polymer dynamics in crosslinked polymer networks

NASA Astrophysics Data System (ADS)

Frieberg, Bradley; Soles, Christopher

Many technologies rely on amorphous polymer membranes that selectively transport small molecules or ions, which has led to a significant scientific interest in elucidating the mechanisms of transport. A recurring theme among several different materials systems is that free volume and polymer chain dynamics facilitate transport. In order to understand the interplay between free volume, transport and polymer dynamics we quantify these properties for a model epoxy network. The epoxy chemistry allows for systematically varying both the structural rigidity of the network as well as the cross-link density. We performed positron annihilation lifetime spectroscopy measurements to characterize the unoccupied volume and correlated the unoccupied volume to the equilibrium moisture uptake and effective diffusion coefficient. We have recently extended this work to include polymer dynamics measured by quasi-elastic neutron scattering on the NIST High Flux Backscatter Spectrometer. These measurements reveal a strong correlation between the MSD and the transport kinetics, which was even stronger than the correlation previously observed between free volume and water diffusion. These observations challenge previous theories that suggest free volume governs transport.

Effects of Morphology Constraint on Electrophysiological Properties of Cortical Neurons

NASA Astrophysics Data System (ADS)

Zhu, Geng; Du, Liping; Jin, Lei; Offenhäusser, Andreas

2016-04-01

There is growing interest in engineering nerve cells in vitro to control architecture and connectivity of cultured neuronal networks or to build neuronal networks with predictable computational function. Pattern technologies, such as micro-contact printing, have been developed to design ordered neuronal networks. However, electrophysiological characteristics of the single patterned neuron haven’t been reported. Here, micro-contact printing, using polyolefine polymer (POP) stamps with high resolution, was employed to grow cortical neurons in a designed structure. The results demonstrated that the morphology of patterned neurons was well constrained, and the number of dendrites was decreased to be about 2. Our electrophysiological results showed that alterations of dendritic morphology affected firing patterns of neurons and neural excitability. When stimulated by current, though both patterned and un-patterned neurons presented regular spiking, the dynamics and strength of the response were different. The un-patterned neurons exhibited a monotonically increasing firing frequency in response to injected current, while the patterned neurons first exhibited frequency increase and then a slow decrease. Our findings indicate that the decrease in dendritic complexity of cortical neurons will influence their electrophysiological characteristics and alter their information processing activity, which could be considered when designing neuronal circuitries.

Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight

DOE PAGES

Aryal, Dipak; Agrawal, Anupriya; Perahia, Dvora; ...

2017-08-23

Controlling the structure and dynamics of thin films of ionizable polymers at water interfaces is critical to their many applications. As the chemical diversity within one polymer is increased, controlling the structure and dynamics of the polymer, which is a key to their use, becomes a challenge. Here molecular dynamics simulations (MD) are used to obtain molecular insight into the structure and dynamics of thin films of one such macromolecule at the interface with water. The polymer consists of an ABCBA topology with randomly sulfonated polystyrene (C), tethered symmetrically to flexible poly(ethylene- r-propylene) blocks (B), and end-capped by a poly(more » t-butylstyrene) block (A). The compositions of the interfacial and bulk regions of thin films of the ABCBA polymers are followed as a function of exposure time to water. We find that interfacial rearrangements take place where buried ionic segments migrate toward the water interface. The hydrophobic blocks collapse and rearrange to minimize their exposure to water. In conclusion, the water that initially drives interfacial reengagements breaks the ionic clusters within the film, forming a dynamic hydrophilic internal network within the hydrophobic segments.« less

Coarse-Grained Molecular Dynamics Simulation of Ionic Polymer Networks

DTIC Science & Technology

2008-07-01

AFRL-RX-WP-TP-2009-4198 COARSE-GRAINED MOLECULAR DYNAMICS SIMULATION OF IONIC POLYMER NETWORKS (Postprint) T.E. Dirama, V. Varshney, K.L...GRAINED MOLECULAR DYNAMICS SIMULATION OF IONIC POLYMER NETWORKS (Postprint) 5a. CONTRACT NUMBER FA8650-05-D-5807-0052 5b. GRANT NUMBER 5c...We studied two types of networks which differ only by one containing ionic pairs that amount to 7% of the total number of bonds present. The stress

Atomistic simulation of graphene-based polymer nanocomposites

NASA Astrophysics Data System (ADS)

Rissanou, Anastassia N.; Bačová, Petra; Harmandaris, Vagelis

2016-05-01

Polymer/graphene nanostructured systems are hybrid materials which have attracted great attention the last years both for scientific and technological reasons. In the present work atomistic Molecular Dynamics simulations are performed for the study of graphene-based polymer nanocomposites composed of pristine, hydrogenated and carboxylated graphene sheets dispersed in polar (PEO) and nonpolar (PE) short polymer matrices (i.e., matrices containing chains of low molecular weight). Our focus is twofold; the one is the study of the structural and dynamical properties of short polymer chains and the way that they are affected by functionalized graphene sheets while the other is the effect of the polymer matrices on the behavior of graphene sheets.

Polymer relaxation and stretching dynamics in semi-dilute DNA solutions: a single molecule study

NASA Astrophysics Data System (ADS)

Hsiao, Kai-Wen; Brockman, Christopher; Schroeder, Charles

2015-03-01

In this work, we study polymer relaxation and stretching dynamics in semi-dilute DNA solutions using single molecule techniques. Using this approach, we uncover a unique scaling relation for longest polymer relaxation time that falls in the crossover regime described by semi-flexible polymer solutions, which is distinct from truly flexible polymer chains. In addition, we performed a series of step-strain experiments on single polymers in semi-dilute solutions in planar extensional flow using an automated microfluidic trap. In this way, we are able to precisely control the flow strength and the amount of strain applied to single polymer chains, thereby enabling direct observation of the full stretching and relaxation process in semi-dilute solutions during transient start-up and flow cessation. Interestingly, we observe polymer individualism in the conformation of single chains in semi-dilute solutions, which to our knowledge has not yet been observed. In addition, we observe the relaxation data can be explained by a multi-exponential decay process after flow cessation in semi-dilute solutions. Overall, our work reports key advance in non-dilute polymer systems from a molecular perspective via direct observation of dynamics in strong flows. DOW fellowship.

Control of Geminate Recombination by the Material Composition and Processing Conditions in Novel Polymer: Nonfullerene Acceptor Photovoltaic Devices.

PubMed

Zhang, Jiangbin; Gu, Qinying; Do, Thu Trang; Rundel, Kira; Sonar, Prashant; Friend, Richard H; McNeill, Christopher R; Bakulin, Artem A

2018-02-08

Herein, we report on the charge dynamics of photovoltaic devices based on two novel small-molecule nonfullerene acceptors featuring a central ketone unit. Using ultrafast near-infrared spectroscopy with optical and photocurrent detection methods, we identify one of the key loss channels in the devices as geminate recombination (GR) of interfacial charge transfer states (CTSs). We find that the magnitude of GR is highly sensitive to the choice of solvent and annealing conditions. Interestingly, regardless of these processing conditions, the same lifetime for GR (∼130 ps) is obtained by both detection methods upon decomposing the complex broadband transient optical spectra, suggesting this time scale is inherent and independent of morphology. These observations suggest that the CTSs in the studied material blends are mostly strongly bound, and that charge generation from these states is highly inefficient. We further rationalize our results by considering the impact of the processing on the morphology of the mixed donor and acceptor domains and discuss the potential consequences of the early charge dynamics on the performance of emerging nonfullerene photovoltaic devices. Our results demonstrate that careful choice of processing conditions enables enhanced exciton harvesting and suppression of GR by more than 3 orders of magnitude.

Correlating Polymer Crystals via Self-Induced Nucleation

NASA Astrophysics Data System (ADS)

Reiter, Günter

Crystallizable polymers often form multiple stacks of uniquely oriented lamellae, which have good registry despite being separated by amorphous fold surfaces. These correlations require multiple synchronized, yet unidentified, nucleation events. Here, we demonstrate that in thin films of isotactic polystyrene, the probability of generating correlated lamellae is controlled by the branched morphology of a single primary lamella. The nucleation density ns of secondary lamellae is found to be dependent on the width of the branches of the primary lamella. This relation is independent of molecular weight, crystallization temperature, and film thickness. We propose a nucleation mechanism based on the insertion of polymers into a branched primary lamellar crystal. Even in single crystals, characterized by faceted structures with a well-defined envelope reflecting the underlying crystal unit cell, polymers are folded and thus in a meta-stable state. Annealing such meta-stable single crystals allowed to unveil the initial morphological framework of a dendritic single crystal, i.e. the initial stages of growth.

Stimuli Responsive Morphological Changes of Pnipa Polymer Brushes Synthesized on Silicon Substrate

NASA Astrophysics Data System (ADS)

Huda, Muhammad Nurul; Kabir, A. N. M. Hamidul

2013-08-01

High-density polymer brushes were grown from the silicon surface by atom transfer radical polymerization of Poly(N-isopropylacrylamide) (PNIPA) at different polymerization conditions. PNIPA brushes were prepared using Copper (I) Chloride/tris(2-(dimetylamino)ethyl)amine (Me6TREN) as a catalytic system in DMSO at 20°C. Free polymer formed during the brush formation was characterized by gel permeation chromatography. The grafting densities up to 0.52 chains/nm2 were obtained. The layer thickness of polymer brush increases with the increase of conversion of the monomer conversion as well as polymerization time. Atomic force microscopy and air bubble contact angle under pH solution were employed to study the surface morphology, reversible conformational changes of and stimulus-response behavior. PNIPA brushes exhibited a different nanomorphology after treatment with different pH solution. It also revealed a unique reversible wetting behavior with pH. The reversible properties of the PNIPA brushes can be used to regulate the adsorption of the sulfonated PS nanoparticles.

Polymer Morphological Change Induced by Terahertz Irradiation

PubMed Central

Hoshina, Hiromichi; Suzuki, Hal; Otani, Chiko; Nagai, Masaya; Kawase, Keigo; Irizawa, Akinori; Isoyama, Goro

2016-01-01

As terahertz (THz) frequencies correspond to those of the intermolecular vibrational modes in a polymer, intense THz wave irradiation affects the macromolecular polymorph, which determines the polymer properties and functions. THz photon energy is quite low compared to the covalent bond energy; therefore, conformational changes can be induced “softly,” without damaging the chemical structures. Here, we irradiate a poly(3-hydroxybutylate) (PHB) / chloroform solution during solvent casting crystallization using a THz wave generated by a free electron laser (FEL). Morphological observation shows the formation of micrometer-sized crystals in response to the THz wave irradiation. Further, a 10−20% increase in crystallinity is observed through analysis of the infrared (IR) absorption spectra. The peak power density of the irradiating THz wave is 40 MW/cm2, which is significantly lower than the typical laser intensities used for material manipulation. We demonstrate for the first time that the THz wave effectively induces the intermolecular rearrangement of polymer macromolecules. PMID:27272984

An extended micromechanics method for probing interphase properties in polymer nanocomposites [An extended micromechanics method for overlapping geometries with application to polymer nanocomposites

DOE PAGES

Liu, Zeliang; Moore, John A.; Liu, Wing Kam

2016-05-03

Inclusions comprised on filler particles and interphase regions commonly form complex morphologies in polymer nanocomposites. Addressing these morphologies as systems of overlapping simple shapes allows for the study of dilute particles, clustered particles, and interacting interphases all in one general modeling framework. To account for the material properties in these overlapping geometries, weighted-mean and additive overlapping conditions are introduced and the corresponding inclusion-wise integral equations are formulated. An extended micromechanics method based on these overlapping conditions for linear elastic and viscoelastic heterogeneous material is then developed. An important feature of the proposed approach is that the effect of both themore » geometric overlapping (clustered particles) and physical overlapping (interacting interphases) on the effective properties can be distinguished. Lastly, we apply the extended micromechanics method to a viscoelastic polymer nanocomposite with interphase regions, and estimate the properties and thickness of the interphase region based on experimental data for carbon-black filled styrene butadiene rubbers.« less

An extended micromechanics method for probing interphase properties in polymer nanocomposites [An extended micromechanics method for overlapping geometries with application to polymer nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zeliang; Moore, John A.; Liu, Wing Kam

Inclusions comprised on filler particles and interphase regions commonly form complex morphologies in polymer nanocomposites. Addressing these morphologies as systems of overlapping simple shapes allows for the study of dilute particles, clustered particles, and interacting interphases all in one general modeling framework. To account for the material properties in these overlapping geometries, weighted-mean and additive overlapping conditions are introduced and the corresponding inclusion-wise integral equations are formulated. An extended micromechanics method based on these overlapping conditions for linear elastic and viscoelastic heterogeneous material is then developed. An important feature of the proposed approach is that the effect of both themore » geometric overlapping (clustered particles) and physical overlapping (interacting interphases) on the effective properties can be distinguished. Lastly, we apply the extended micromechanics method to a viscoelastic polymer nanocomposite with interphase regions, and estimate the properties and thickness of the interphase region based on experimental data for carbon-black filled styrene butadiene rubbers.« less

Molecular organization in MAPLE-deposited conjugated polymer thin films and the implications for carrier transport characteristics

DOE PAGES

Dong, Ban Xuan; Li, Anton; Strzalka, Joseph; ...

2016-09-18

The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. We found that the MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, π-π stacking, and conjugated backbone directions. Furthermore, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. In spite of the seemingly unfavorable molecular orientations andmore » the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 meV versus 54 meV) to those reported in the literature for high mobility polymers.« less

Molecular organization in MAPLE-deposited conjugated polymer thin films and the implications for carrier transport characteristics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Ban Xuan; Li, Anton; Strzalka, Joseph

The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. We found that the MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, π-π stacking, and conjugated backbone directions. Furthermore, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. In spite of the seemingly unfavorable molecular orientations andmore » the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 meV versus 54 meV) to those reported in the literature for high mobility polymers.« less

How the Dynamics of a Supramolecular Polymer Determines Its Dynamic Adaptivity and Stimuli-Responsiveness: Structure-Dynamics-Property Relationships From Coarse-Grained Simulations.

PubMed

Torchi, Andrea; Bochicchio, Davide; Pavan, Giovanni M

2018-04-12

The rational design of supramolecular polymers that can adapt or respond in time to specific stimuli in a controlled way is interesting for many applications, but this requires understanding the molecular factors that make the material faster or slower in responding to the stimulus. To this end, it is necessary to study the dynamic adaptive properties at submolecular resolution, which is difficult at an experimental level. Here we show coarse-grained molecular dynamics simulations (<5 Å resolution) demonstrating how the dynamic adaptivity and stimuli responsiveness of a supramolecular polymer is controlled by the intrinsic dynamics of the assembly, which is in turn determined by the structure of the monomers. As a representative case, we focus on a water-soluble 1,3,5-benzenetricarboxamide (BTA) supramolecular polymer incorporating (charged) receptor monomers, experimentally seen to undergo dynamic clustering following the superselective binding to a multivalent recruiter. Our simulations show that the dynamic reorganization of the supramolecular structure proceeds via monomer diffusion on the dynamic fiber surface (exchange within the fiber). Rationally changing the structure of the monomers to make the fiber surface more or less dynamic allows tuning the rate of response to the stimulus and of supramolecular reconfiguration. Simple in silico experiments draw a structure-dynamics-property relationship revealing the key factors underpinning the dynamic adaptivity and stimuli-responsiveness of these supramolecular polymers. We come out with clear evidence that to master the bioinspired properties of these fibers, it is necessary to control their intrinsic dynamics, while the high-resolution of our molecular models permits us to show how.

Dynamical behavior of a single polymer chain under nanometric confinement

NASA Astrophysics Data System (ADS)

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.

Statistical Mechanical Theory of Coupled Slow Dynamics in Glassy Polymer-Molecule Mixtures

NASA Astrophysics Data System (ADS)

Zhang, Rui; Schweizer, Kenneth

The microscopic Elastically Collective Nonlinear Langevin Equation theory of activated relaxation in one-component supercooled liquids and glasses is generalized to polymer-molecule mixtures. The key idea is to account for dynamic coupling between molecule and polymer segment motion. For describing the molecule hopping event, a temporal casuality condition is formulated to self-consistently determine a dimensionless degree of matrix distortion relative to the molecule jump distance based on the concept of coupled dynamic free energies. Implementation for real materials employs an established Kuhn sphere model of the polymer liquid and a quantitative mapping to a hard particle reference system guided by the experimental equation-of-state. The theory makes predictions for the mixture dynamic shear modulus, activated relaxation time and diffusivity of both species, and mixture glass transition temperature as a function of molecule-Kuhn segment size ratio and attraction strength, composition and temperature. Model calculations illustrate the dynamical behavior in three distinct mixture regimes (fully miscible, bridging, clustering) controlled by the molecule-polymer interaction or chi-parameter. Applications to specific experimental systems will be discussed.

Local Dynamics of Acid- and Ion-containing Copolymer Melts

NASA Astrophysics Data System (ADS)

Winey, Karen; Middleton, Robert; Tarver, Jacob; Tyagi, Madhusudan; Soles, Christopher; Frischknecht, Amalie

Interest in acid- and ion-containing polymers arises in part from applications as single-ion conductors for selectively transporting a counter ion for battery applications. Structurally, the low dielectric constant of organic polymers and strong ionic interactions leads to ionic aggregation. Here the polymer backbone motion was investigated through quasi-elastic neutron scattering measurements (QENS) and compared with fully atomistic molecular dynamic simulations of precise poly(ethylene-acrylic acid) copolymers and their ionomers (pxAA-y%Li). The effect of carbon spacer length (x =9, 15, 21) between the acid groups and the degree of neutralization (y) with Li on PE backbone dynamics were considered. Systematic slowing in chain dynamics were observed with increasing neutralization where polymer dynamics appear constrained due to anchoring effects. Simulations provide complementary viewpoints indicating a gradient in chain dynamics as a distance away from acid groups. These results indicate that the addition of pendant acid groups inhibit typical PE backbone motion and the neutralized forms strongly suppress the fraction of mobile PE chain.

Resolving Dynamic Properties of Polymers through Coarse-Grained Computational Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salerno, K. Michael; Agrawal, Anupriya; Perahia, Dvora

2016-02-05

Coupled length and time scales determine the dynamic behavior of polymers and underlie their unique viscoelastic properties. To resolve the long-time dynamics it is imperative to determine which time and length scales must be correctly modeled. In this paper, we probe the degree of coarse graining required to simultaneously retain significant atomistic details and access large length and time scales. The degree of coarse graining in turn sets the minimum length scale instrumental in defining polymer properties and dynamics. Using linear polyethylene as a model system, we probe how the coarse-graining scale affects the measured dynamics. Iterative Boltzmann inversion ismore » used to derive coarse-grained potentials with 2–6 methylene groups per coarse-grained bead from a fully atomistic melt simulation. We show that atomistic detail is critical to capturing large-scale dynamics. Finally, using these models we simulate polyethylene melts for times over 500 μs to study the viscoelastic properties of well-entangled polymer melts.« less

Morphology design of porous coordination polymer crystals by coordination modulation.

PubMed

Umemura, Ayako; Diring, Stéphane; Furukawa, Shuhei; Uehara, Hiromitsu; Tsuruoka, Takaaki; Kitagawa, Susumu

2011-10-05

The design of crystal morphology, or exposed crystal facets, has enabled the development (e.g., catalytic activities, material attributes, and oriented film formation) of porous coordination polymers (PCPs) without changing material compositions. However, because crystal growth mechanisms are not fully understood, control of crystal morphology still remains challenging. Herein, we report the morphology design of [Cu(3)(btc)(2)](n) (btc = benzene-1,3,5-tricarboxylate) by the coordination modulation method (modulator = n-dodecanoic acid or lauric acid). A morphological transition (octahedron-cuboctahedron-cube) in the [Cu(3)(btc)(2)](n) crystal was observed with an increase in concentration of the modulator. By suitably defining a coarse-grained standard unit of [Cu(3)(btc)(2)](n) as its cuboctahedron main pore and determining its attachment energy on crystal surfaces, Monte Carlo coarse-grain modeling revealed the population and orientation of carboxylates and elucidated an important role of the modulator in determining the <100>- and <111>-growth throughout the crystal growth process. This comprehension, in fact, successfully led to designed crystal morphologies with oriented growth on bare substrates. Because selective crystal orientations on the bare substrates were governed by crystal morphology, this contribution also casts a new light on the unexplored issue of the significance of morphology design of PCPs.

Electric Field-Mediated Processing of Polymers. Appendix 1

NASA Technical Reports Server (NTRS)

Wnek, G. E.; Bowlin, G. L.; Haas, T. W.

2000-01-01

Significant opportunities exist for the processing of polymers (homopolymers and blends) using electric fields. We suggest that a broad range of properties can be achieved using a relatively small number of polymers, with electric fields providing the ability to tailor properties via the control of shape, morphology, and orientation. Specific attention is given to electrospinning, but we note that electroaerosol formation and field-modulated film casting represent additional processing options.

Synthesis of Au@polymer nanohybrids with transited core-shell morphology from concentric to eccentric Emoji-N or Janus nanoparticles.

PubMed

Guarrotxena, Nekane; García, Olga; Quijada-Garrido, Isabel

2018-04-10

The combination of multifunctionality and synergestic effect displayed by hybrid nanoparticles (NPs) has been revealed as an effective stratagem in the development of advanced nanostructures with unique biotechnology and optoelectronic applications. Although important work has been devoted, the demand of facile, versatile and efficient synthetic approach remains still challenging. Herein, we report a feasible and innovative way for polymer-shell assembling onto gold nanoparticles in competitive conditions of hydrophobic/hydrophilic feature and interfacial energy of components to generate core-shell nanohybrids with singular morphologies. The fine control of reaction parameters allows a modulated transformation from concentric to eccentric nanostructure-geometries. In this regard, a rational selection of the components and solvent ratio guarantee the reproducibility and efficiency on hybrid-nanoassembly. Furthermore, the simplicity of the synthetic approach offers the possibility to obtain asymmetric Janus NPs and new morphologies (quizzical-aspheric polymer-shell, named Emoji-N-hybrids) with adjustable surface-coating, leading to new properties and applications that are unavailable to their symmetrical or single components.

Responsive polymer-based colloids for drug delivery and bioconversion

NASA Astrophysics Data System (ADS)

Kudina, Olena

Responsive polymer-based colloids (RPBC) are the colloidal structures containing responsive polymeric component which is able to adapt its physico-chemical properties to the environment by undergoing chemical and/or conformational changes. The goal of the dissertation is to develop and characterize several groups of RPBC with different morphological complexity and explore their potential in drug delivery and bioconversion. The role of RPBC morphology for these specific applications is discussed in details. Three groups of RPBC were fabricated: i. polymeric micelles; ii. mixed polymeric micelles; iii. hybrid polymer-inorganic particles. All fabricated RPBCs contain polymeric component in their structure. The dissertation investigates how the changes of the responsive polymeric component properties are reflected in morphologies of RPBC. The first group of RPBC, polymeric micelles, was formed by the self-assembly of amphiphilic invertible polymers (AIPs) synthesized in our group. AIPs self-assemble into invertible micellar assemblies (IMAs) in solvents of different polarity. In this work, IMAs ability to invert the structure as a response to the change in solvent polarity was demonstrated using 1H NMR spectroscopy and SANS. It was shown that the IMAs incorporate hydrophobic cargo either in the core or in the shell, depending on the chemical structure of cargo molecules. Following in vitro study demonstrates that loaded with drug (curcumin) IMAs are cytotoxic to osteosarcoma cells. Mixed polymeric micelles represent another, more complex, RPBC morphologies studied in the dissertation. Mixed micelles were fabricated from AIPs and amphiphilic oligomers synthesized from pyromellitic dianhydride, polyethylene glycol methyl ethers, and alkanols/cholesterol. The combination of selected AIP and oligomers based on cholesterol results in mixed micelles with an increased drug-loading capacity (from 10% w/w loaded curcumin in single component IMAs to 26%w/w in mixed micelles). Even more complex colloids are hybrid polymer-inorganic particles, the third RPBC group studied in dissertation. Material was designed as core--shell particles with superparamagnetic core engulfed by grafted polymer brushes. These particles were loaded with enzymes (cellulases), thus, are turned into enzymogels for cellulose bioconversion. The study demonstrates that such RPBCs can be used multiple times during hydrolysis and provide an about four-fold increase in glucose production in comparison to free enzymes.

All-Polymer Solar Cell Performance Optimized via Systematic Molecular Weight Tuning of Both Donor and Acceptor Polymers.

PubMed

Zhou, Nanjia; Dudnik, Alexander S; Li, Ting I N G; Manley, Eric F; Aldrich, Thomas J; Guo, Peijun; Liao, Hsueh-Chung; Chen, Zhihua; Chen, Lin X; Chang, Robert P H; Facchetti, Antonio; Olvera de la Cruz, Monica; Marks, Tobin J

2016-02-03

The influence of the number-average molecular weight (Mn) on the blend film morphology and photovoltaic performance of all-polymer solar cells (APSCs) fabricated with the donor polymer poly[5-(2-hexyldodecyl)-1,3-thieno[3,4-c]pyrrole-4,6-dione-alt-5,5-(2,5-bis(3-dodecylthiophen-2-yl)thiophene)] (PTPD3T) and acceptor polymer poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2); N2200) is systematically investigated. The Mn effect analysis of both PTPD3T and N2200 is enabled by implementing a polymerization strategy which produces conjugated polymers with tunable Mns. Experimental and coarse-grain modeling results reveal that systematic Mn variation greatly influences both intrachain and interchain interactions and ultimately the degree of phase separation and morphology evolution. Specifically, increasing Mn for both polymers shrinks blend film domain sizes and enhances donor-acceptor polymer-polymer interfacial areas, affording increased short-circuit current densities (Jsc). However, the greater disorder and intermixed feature proliferation accompanying increasing Mn promotes charge carrier recombination, reducing cell fill factors (FF). The optimized photoactive layers exhibit well-balanced exciton dissociation and charge transport characteristics, ultimately providing solar cells with a 2-fold PCE enhancement versus devices with nonoptimal Mns. Overall, it is shown that proper and precise tuning of both donor and acceptor polymer Mns is critical for optimizing APSC performance. In contrast to reports where maximum power conversion efficiencies (PCEs) are achieved for the highest Mns, the present two-dimensional Mn optimization matrix strategy locates a PCE "sweet spot" at intermediate Mns of both donor and acceptor polymers. This study provides synthetic methodologies to predictably access conjugated polymers with desired Mn and highlights the importance of optimizing Mn for both polymer components to realize the full potential of APSC performance.

Thermoreversible gelation of poly(vinylidene fluoride) in phthalates: the influence of aliphatic chain length of solvents.

PubMed

Yadav, P Jaya Prakash; Ghosh, Goutam; Maiti, Biswajit; Aswal, Vinod K; Goyal, P S; Maiti, Pralay

2008-04-17

Thermoreversible gelation of poly(vinylidene fluoride) (PVDF) has been studied in a new series of solvents (phthalates), for example, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), and dihexyl phthalate (DHP) as a function of temperature and polymer concentration, both by test tube tilting and dynamic light scattering (DLS) method. The effect of aliphatic chain length (n) of diesters on the gelation kinetics, structure/microstructure and morphology of PVDF gels has been examined. Gelation rate was found to increase with increasing aliphatic chain length of diester. DLS results indicate that the sol-gel transformation proceeds via two-steps: first, microgel domains were formed, and then the infinite three-dimensional (3D) network is established by connecting microgels through polymer chains. The crystallites are responsible for 3D network for gelation in phthalates, and alpha-polymorph is formed during gelation producing higher amount of crystallinity with increasing aliphatic chain length of diester. Morphology of the networks of dried gels in different phthalates showed that fibril thickness and lateral dimensions decrease with higher homologues of phthalates. The scattering intensity is fitted with Debye-Bueche model in small-angle neutron scattering and suggested that both the correlation length and interlamellar spacing increases with n. A model has been proposed, based on electronic structure calculations, to explain the conformation of PVDF chain in presence of various phthalates and their complexes, which offer the cause of higher gelation rate for longer aliphatic chain length.

Silver-cotton nanocomposites: nano-design of microfibrillar structure causes morphological changes and increased tenacity

USDA-ARS?s Scientific Manuscript database

The interactions of nanoparticles with polymer hosts have important implications for directing the macroscopic properties of composite fibers, yet little is known about such interactions with hierarchically ordered natural polymers due to the difficulty of achieving uniform dispersion of nanoparticl...

Host polymer influence on dilute polystyrene segmental dynamics

NASA Astrophysics Data System (ADS)

Lutz, T. R.

2005-03-01

We have utilized deuterium NMR to investigate the segmental dynamics of dilute (2%) d3-polystyrene (PS) chains in miscible polymer blends with polybutadiene, poly(vinyl ethylene), polyisoprene, poly(vinyl methylether) and poly(methyl methacrylate). In the dilute limit, we find qualitative differences depending upon whether the host polymer has dynamics that are faster or slower than that of pure PS. In blends where PS is the fast (low Tg) component, segmental dynamics are slowed upon blending and can be fit by the Lodge-McLeish model. When PS is the slow (high Tg) component, PS segmental dynamics speed up upon blending, but cannot be fit by the Lodge-McLeish model unless a temperature dependent self-concentration is employed. These results are qualitatively consistent with a recent suggestion by Kant, Kumar and Colby (Macromolecules, 2003, 10087), based upon data at higher concentrations. Furthermore, as the slow component, we find the segmental dynamics of PS has a temperature dependence similar to that of its host. This suggests viewing the high Tg component dynamics in a miscible blend as similar to a polymer in a low molecular weight solvent.

Morphology in electrochemically grown conducting polymer films

DOEpatents

Rubinstein, Israel; Gottesfeld, Shimshon; Sabatani, Eyal

1992-01-01

A conducting polymer film with an improved space filling is formed on a metal electrode surface. A self-assembling monolayer is formed directly on the metal surface where the monolayer has a first functional group that binds to the metal surface and a second chemical group that forms a chemical bonding site for molecules forming the conducting polymer. The conducting polymer is then conventioonally deposited by electrochemical deposition. In one example, a conducting film of polyaniline is formed on a gold electrode surface with an intermediate monolayer of p-aminothiophenol.

Morphology in electrochemically grown conducting polymer films

DOEpatents

Rubinstein, I.; Gottesfeld, S.; Sabatani, E.

1992-04-28

A conducting polymer film with an improved space filling is formed on a metal electrode surface. A self-assembling monolayer is formed directly on the metal surface where the monolayer has a first functional group that binds to the metal surface and a second chemical group that forms a chemical bonding site for molecules forming the conducting polymer. The conducting polymer is then conventionally deposited by electrochemical deposition. In one example, a conducting film of polyaniline is formed on a gold electrode surface with an intermediate monolayer of p-aminothiophenol. 2 figs.

Periodic surface instabilities in stressed polymer solids

NASA Astrophysics Data System (ADS)

Tsukruk, Vladimir V.; Reneker, Darrell H.

1995-03-01

The surface morphology of isothermally grown polymer single crystals of polypropylene is observed by atomic force microscopy. The distinguishing features of the polymer single crystals studied are periodic undulations and transverse fractures (cracks) across the single crystal laths. Up to 20 wrinkles are observed near the edges of the cracks. The periodicity of these surface perturbations is 400+/-100 nm and the amplitude is 6+/-3 nm. The formation of the periodic modulations and transverse fractures is attributed to surface stress relief caused by the uniaxial thermal contraction of polymer solids.

Characterization of Homopolymer and Polymer Blend Films by Phase Sensitive Acoustic Microscopy

NASA Astrophysics Data System (ADS)

Ngwa, Wilfred; Wannemacher, Reinhold; Grill, Wolfgang

2003-03-01

CHARACTERIZATION OF HOMOPOLYMER AND POLYMER BLEND FILMS BY PHASE SENSITIVE ACOUSTIC MICROSCOPY W Ngwa, R Wannemacher, W Grill Institute of Experimental Physics II, University of Leipzig, 04103 Leipzig, Germany Abstract We have used phase sensitive acoustic microscopy (PSAM) to study homopolymer thin films of polystyrene (PS) and poly (methyl methacrylate) (PMMA), as well as PS/PMMA blend films. We show from our results that PSAM can be used as a complementary and highly valuable technique for elucidating the three-dimensional (3D) morphology and micromechanical properties of thin films. Three-dimensional image acquisition with vector contrast provides the basis for: complex V(z) analysis (per image pixel), 3D image processing, height profiling, and subsurface image analysis of the polymer films. Results show good agreement with previous studies. In addition, important new information on the three dimensional structure and properties of polymer films is obtained. Homopolymer film structure analysis reveals (pseudo-) dewetting by retraction of droplets, resulting in a morphology that can serve as a starting point for the analysis of polymer blend thin films. The outcome of confocal laser scanning microscopy studies, performed on the same samples are correlated with the obtained results. Advantages and limitations of PSAM are discussed.

Molecular dynamics study of the adsorption of anionic surfactant in a nonionic polymer brush.

PubMed

Wang, Hua; Zhang, Heng; Yuan, Shiling; Liu, Chengbu; Xu, Zhen

2014-06-01

The adsorption of the anionic surfactant, sodium dodecylsulfate (SDS) in poly(ethylene oxide) (PEO) brush was studied by molecular dynamics simulations. Our simulations revealed that surfactant can adsorb in polymer brush as micellar aggregates and the polymer would reside at the hydrocarbon-water interface of SDS micelles. This association between surfactant and polymer was mainly driven by the hydrophobic interaction between the polymer and surfactant tails. In the simulation, with the increasing of surfactant concentration, a plateau value representing saturated adsorption was observed. The height of polymer brush was mainly affected by the adsorbed surfactant at low grafting density of polymer; however, it was primarily controlled by the grafting density at high grafting density. Our conclusions at the molecular level were in close agreement with experiment about the adsorption of surfactant in polymer brushes.

Phthalimide Copolymer Solar Cells

NASA Astrophysics Data System (ADS)

Xin, Hao; Guo, Xugang; Ren, Guoqiang; Kim, Felix; Watson, Mark; Jenekhe, Samson

2010-03-01

Photovoltaic properties of bulk heterojunction solar cells based on phthalimide donor-acceptor copolymers have been investigated. Due to the strong π-π stacking of the polymers, the state-of-the-art thermal annealing approach resulted in micro-scale phase separation and thus negligible photocurrent. To achieve ideal bicontinuous morphology, different strategies including quickly film drying and mixed solvent for film processing have been explored. In these films, nano-sale phase separation was achieved and a power conversion efficiency of 3.0% was obtained. Absorption and space-charge limited current mobility measurements reveal similar light harvesting and hole mobilities in all the films, indicating that the morphology is the dominant factor determining the photovoltaic performance. Our results demonstrate that for highly crystalline and/or low-solubility polymers, finding a way to prevent polymer aggregation and large scale phase separation is critical to realizing high performance solar cells.

Using molecular dynamics simulations and finite element method to study the mechanical properties of nanotube reinforced polyethylene and polyketone

NASA Astrophysics Data System (ADS)

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

2015-09-01

Molecular dynamics simulations are used to study the mechanical behavior of single-walled carbon nanotube reinforced composites. Polyethylene and polyketone are selected as the polymer matrices. The effects of nanotube atomic structure and diameter on the mechanical properties of polymer matrix nanocomposites are investigated. It is shown that although adding nanotube to the polymer matrix raises the longitudinal elastic modulus significantly, the transverse tensile and shear moduli do not experience important change. As the previous finite element models could not be used for polymer matrices with the atom types other than carbon, molecular dynamics simulations are used to propose a finite element model which can be used for any polymer matrices. It is shown that this model can predict Young’s modulus with an acceptable accuracy.

Dynamics of hairpin vortices and polymer-induced turbulent drag reduction.

PubMed

Kim, Kyoungyoun; Adrian, Ronald J; Balachandar, S; Sureshkumar, R

2008-04-04

It has been known for over six decades that the dissolution of minute amounts of high molecular weight polymers in wall-bounded turbulent flows results in a dramatic reduction in turbulent skin friction by up to 70%. First principles simulations of turbulent flow of model polymer solutions can predict the drag reduction (DR) phenomenon. However, the essential dynamical interactions between the coherent structures present in turbulent flows and polymer conformation field that lead to DR are poorly understood. We examine this connection via dynamical simulations that track the evolution of hairpin vortices, i.e., counter-rotating pairs of quasistreamwise vortices whose nonlinear autogeneration and growth, decay and breakup are centrally important to turbulence stress production. The results show that the autogeneration of new vortices is suppressed by the polymer stresses, thereby decreasing the turbulent drag.

Light-responsive polymer microcapsules as delivery systems for natural active agents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bizzarro, Valentina; Carfagna, Cosimo; Cerruti, Pierfrancesco

2016-05-18

In this work we report the preparation and the release behavior of UV-responsive polymeric microcapsules containing essential oils as a core. The oil acted also as a monomer solvent during polymerization. Accordingly, the potentially toxic organic solvent traditionally used was replaced with a natural active substance, resulting in a more sustainable functional system. Polymer shell was based on a lightly cross-linked polyamide containing UV-sensitive azobenzene moieties in the main chain. The micro-sized capsules were obtained via interfacial polycondensation in o/w emulsion, and their mean size was measured via Dynamic Light Scattering. Shape and morphology were analyzed through Scanning Electron andmore » Optical Microscopy. UV-responsive behavior was evaluated via spectrofluorimetry, by assessing the release kinetics of a fluorescent probe molecule upon UV light irradiation (λ{sub max}=360 nm). The irradiated samples showed an increase in fluorescence intensity, in accordance with the increase of the probe molecule concentration in the release medium. As for the un-irradiated sample, no changes could be detected demonstrating the effectiveness of the obtained releasing system.« less

Dually actuated triple shape memory polymers of cross-linked polycyclooctene-carbon nanotube/polyethylene nanocomposites.

PubMed

Wang, Zhenwen; Zhao, Jun; Chen, Min; Yang, Minhao; Tang, Luyang; Dang, Zhi-Min; Chen, Fenghua; Huang, Miaoming; Dong, Xia

2014-11-26

In this work, electrically and thermally actuated triple shape memory polymers (SMPs) of chemically cross-linked polycyclooctene (PCO)-multiwalled carbon nanotube (MWCNT)/polyethylene (PE) nanocomposites with co-continuous structure and selective distribution of fillers in PCO phase are prepared. We systematically studied not only the microstructure including morphology and fillers' selective distribution in one phase of the PCO/PE blends, but also the macroscopic properties including thermal, mechanical, and electrical properties. The co-continuous window of the immiscible PCO/PE blends is found to be the volume fraction of PCO (vPCO) of ca. 40-70 vol %. The selective distribution of fillers in one phase of co-continuous blends is obtained by a masterbatch technique. The prepared triple SMP materials show pronounced triple shape memory effects (SMEs) on the dynamic mechanical thermal analysis (DMTA) and the visual observation by both thermal and electric actuations. Such polyolefin samples with well-defined microstructure, electrical actuation, and triple SMEs might have potential applications as, for example, multiple autochoke elements for engines, self-adjusting orthodontic wires, and ophthalmic devices.

Computational Design of High-χ Block Oligomers for Accessing 1 nm Domains.

PubMed

Chen, Qile P; Barreda, Leonel; Oquendo, Luis E; Hillmyer, Marc A; Lodge, Timothy P; Siepmann, J Ilja

2018-05-22

Molecular dynamics simulations are used to design a series of high-χ block oligomers (HCBOs) that can self-assemble into a variety of mesophases with domain sizes as small as 1 nm. The exploration of these oligomers with various chain lengths, volume fractions, and chain architectures at multiple temperatures reveals the presence of ordered lamellae, perforated lamellae, and hexagonally packed cylinders. The achieved periods are as small as 3.0 and 2.1 nm for lamellae and cylinders, respectively, which correspond to polar domains of approximately 1 nm. Interestingly, the detailed phase behavior of these oligomers is distinct from that of either solvent-free surfactants or block polymers. The simulations reveal that the behavior of these HCBOs is a product of an interplay between both "surfactant factors" (headgroup interactions, chain flexibility, and interfacial curvature) and "block polymer factors" (χ, chain length N, and volume fraction f). This insight promotes the understanding of molecular features pivotal for mesophase formation at the sub-5 nm length scale, which facilitates the design of HCBOs tailored toward particular desired morphologies.

Polymer Electronics: Power from Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Venkataraman, D.; Russell, Thomas P.

We review polymer-based electronics and photovoltaics to provide the reader with a sense of how the field has developed, where we stand at present, and what possibilities are looming in the future. Expertise in areas ranging from synthesis to morphology to device design was sought to achieve this end. While these reviews cannot be exhaustive, they do provide a snapshot of the field at present and give some sense of where the key impediments are.

All-Polymer Solar Cell Performance Optimized via Systematic Molecular Weight Tuning of Both Donor and Acceptor Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Nanjia; Dudnik, Alexander S.; Li, Ting I. N. G.

2016-01-21

The influence of the number-average molecular weight (Mn) on the blend film morphology and photovoltaic performance of all-polymer solar cells (APSCs) fabricated with the donor polymer poly[5-(2-hexyldodecyl)-1,3-thieno[3,4-c]pyrrole-4,6-dione-alt-5,5-(2,5-bis(3-dodecylthiophen-2-yl)thiophene)] (PTPD3T) and acceptor polymer poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2); N2200) is systematically investigated. The Mn effect analysis of both PTPD3T and N2200 is enabled by implementing a polymerization strategy which produces conjugated polymers with tunable Mns. Experimental and coarse-grain modeling results reveal that systematic Mn variation greatly influences both intrachain and interchain interactions and ultimately the degree of phase separation and morphology evolution. Specifically, increasing Mn for both polymers shrinks blend film domain sizes and enhancesmore » donor–acceptor polymer–polymer interfacial areas, affording increased short-circuit current densities (Jsc). However, the greater disorder and intermixed feature proliferation accompanying increasing Mn promotes charge carrier recombination, reducing cell fill factors (FF). The optimized photoactive layers exhibit well-balanced exciton dissociation and charge transport characteristics, ultimately providing solar cells with a 2-fold PCE enhancement versus devices with nonoptimal Mns. Overall, it is shown that proper and precise tuning of both donor and acceptor polymer Mns is critical for optimizing APSC performance. In contrast to reports where maximum power conversion efficiencies (PCEs) are achieved for the highest Mns, the present two-dimensional Mn optimization matrix strategy locates a PCE “sweet spot” at intermediate Mns of both donor and acceptor polymers. This study provides synthetic methodologies to predictably access conjugated polymers with desired Mn and highlights the importance of optimizing Mn for both polymer components to realize the full potential of APSC performance.« less

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

PubMed

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.

Validating clustering of molecular dynamics simulations using polymer models.

PubMed

Phillips, Joshua L; Colvin, Michael E; Newsam, Shawn

2011-11-14

Molecular dynamics (MD) simulation is a powerful technique for sampling the meta-stable and transitional conformations of proteins and other biomolecules. Computational data clustering has emerged as a useful, automated technique for extracting conformational states from MD simulation data. Despite extensive application, relatively little work has been done to determine if the clustering algorithms are actually extracting useful information. A primary goal of this paper therefore is to provide such an understanding through a detailed analysis of data clustering applied to a series of increasingly complex biopolymer models. We develop a novel series of models using basic polymer theory that have intuitive, clearly-defined dynamics and exhibit the essential properties that we are seeking to identify in MD simulations of real biomolecules. We then apply spectral clustering, an algorithm particularly well-suited for clustering polymer structures, to our models and MD simulations of several intrinsically disordered proteins. Clustering results for the polymer models provide clear evidence that the meta-stable and transitional conformations are detected by the algorithm. The results for the polymer models also help guide the analysis of the disordered protein simulations by comparing and contrasting the statistical properties of the extracted clusters. We have developed a framework for validating the performance and utility of clustering algorithms for studying molecular biopolymer simulations that utilizes several analytic and dynamic polymer models which exhibit well-behaved dynamics including: meta-stable states, transition states, helical structures, and stochastic dynamics. We show that spectral clustering is robust to anomalies introduced by structural alignment and that different structural classes of intrinsically disordered proteins can be reliably discriminated from the clustering results. To our knowledge, our framework is the first to utilize model polymers to rigorously test the utility of clustering algorithms for studying biopolymers.

Validating clustering of molecular dynamics simulations using polymer models

PubMed Central

2011-01-01

Background Molecular dynamics (MD) simulation is a powerful technique for sampling the meta-stable and transitional conformations of proteins and other biomolecules. Computational data clustering has emerged as a useful, automated technique for extracting conformational states from MD simulation data. Despite extensive application, relatively little work has been done to determine if the clustering algorithms are actually extracting useful information. A primary goal of this paper therefore is to provide such an understanding through a detailed analysis of data clustering applied to a series of increasingly complex biopolymer models. Results We develop a novel series of models using basic polymer theory that have intuitive, clearly-defined dynamics and exhibit the essential properties that we are seeking to identify in MD simulations of real biomolecules. We then apply spectral clustering, an algorithm particularly well-suited for clustering polymer structures, to our models and MD simulations of several intrinsically disordered proteins. Clustering results for the polymer models provide clear evidence that the meta-stable and transitional conformations are detected by the algorithm. The results for the polymer models also help guide the analysis of the disordered protein simulations by comparing and contrasting the statistical properties of the extracted clusters. Conclusions We have developed a framework for validating the performance and utility of clustering algorithms for studying molecular biopolymer simulations that utilizes several analytic and dynamic polymer models which exhibit well-behaved dynamics including: meta-stable states, transition states, helical structures, and stochastic dynamics. We show that spectral clustering is robust to anomalies introduced by structural alignment and that different structural classes of intrinsically disordered proteins can be reliably discriminated from the clustering results. To our knowledge, our framework is the first to utilize model polymers to rigorously test the utility of clustering algorithms for studying biopolymers. PMID:22082218

Molecular mechanism of melting of a helical polymer crystal: Role of conformational order, packing and mobility of polymers

NASA Astrophysics Data System (ADS)

Cheerla, Ramesh; Krishnan, Marimuthu

2018-03-01

The molecular mechanism of melting of a superheated helical polymer crystal has been investigated using isothermal-isobaric molecular dynamics simulation that allows anisotropic deformation of the crystal lattice. A detailed microscopic analysis of the onset and progression of melting and accompanying changes in the polymer conformational order, translational, and orientation order of the solid along the melting pathway is presented. Upon gradual heating from room temperature to beyond the melting point at ambient pressure, the crystal exhibits signatures of premelting well below the solid-to-liquid melting transition at the melting point. The melting transition is manifested by abrupt changes in the crystal volume, lattice energy, polymer conformation, and dynamical properties. In the premelting stage, the crystal lattice structure and backbone orientation of the polymer chains are retained but with the onset of weakening of long-range helical order and interchain packing of polymers perpendicular to the fibre axis of the crystal. The premelting also marks the onset of conformational defects and anisotropic solid-state diffusion of polymers along the fibre axis. The present study underscores the importance of the interplay between intermolecular packing, interactions, and conformational dynamics at the atomic level in determining the macroscopic melting behavior of polymer crystals.

Solvent-vapor-assisted dewetting of prepatterned thin polymer films: control of morphology, order, and pattern miniaturization.

PubMed

Bhandaru, Nandini; Goohpattader, Partho Sarathi; Faruqui, Danish; Mukherjee, Rabibrata; Sharma, Ashutosh

2015-03-17

Ultrathin (<100 nm) unstable polymer films exposed to a solvent vapor dewet by the growth of surface instability, the wavelength (λ) of which depends on the film thickness (h(f)). While the dewetting of a flat polymer thin film results in random structures, we show that the dewetting of a prepatterned film results in myriad ordered mesoscale morphologies under specific conditions. Such a film undergoes rupture over the thinnest parts when the initial local thickness of these zones (h(rm)) is lower than a limiting thickness h(lim) ≈ 10 nm. Additionally, the width of the pattern grooves (l(s)) must be wider than λ(s) corresponding to a flat film having a thickness of h(rm) for pattern-directed dewetting to take place over surface-tension-induced flattening. We first present an experimentally obtained morphology phase diagram that captures the conditions where a transition from surface-tension-induced flattening to pattern-directed-rupture takes place. Subsequently, we show the versatility of this technique in achieving a variety of aligned mesopatterns starting from a prepatterned film with simple grating geometry. The morphology of the evolving patterns depends on several parameters such as the initial film thickness (h(f)), prepattern amplitude (h(st)), duration of solvent vapor exposure (SVE), and wettability of the stamp used for patterning. Periodic rupture of the film at regular intervals imposes directionality on the evolving patterns, resulting in isolated long threads/cylindrical ridges of polymers, which subsequently disintegrate into an aligned array of droplets due to Rayleigh-Plateau instability under specific conditions. Other patterns such as a double periodic array of droplets and an array of holes are also possible to obtain. The evolution can be interrupted at any intermediate stage by terminating the solvent vapor annealing, allowing the creation of pattern morphology on demand. The created patterns are significantly miniaturized in size as compared to features obtained from dewetting a flat film with the same hf.

The role of electrostatics and temperature on morphological transitions of hydrogel nanostructures self-assembled by peptide amphiphiles via molecular dynamics simulations.

PubMed

Fu, Iris W; Markegard, Cade B; Chu, Brian K; Nguyen, Hung D

2013-10-01

Smart biomaterials that are self-assembled from peptide amphiphiles (PA) are known to undergo morphological transitions in response to specific physiological stimuli. The design of such customizable hydrogels is of significant interest due to their potential applications in tissue engineering, biomedical imaging, and drug delivery. Using a novel coarse-grained peptide/polymer model, which has been validated by comparison of equilibrium conformations from atomistic simulations, large-scale molecular dynamics simulations are performed to examine the spontaneous self-assembly process. Starting from initial random configurations, these simulations result in the formation of nanostructures of various sizes and shapes as a function of the electrostatics and temperature. At optimal conditions, the self-assembly mechanism for the formation of cylindrical nanofibers is deciphered involving a series of steps: (1) PA molecules quickly undergo micellization whose driving force is the hydrophobic interactions between alkyl tails; (2) neighboring peptide residues within a micelle engage in a slow ordering process that leads to the formation of β-sheets exposing the hydrophobic core; (3) spherical micelles merge together through an end-to-end mechanism to form cylindrical nanofibers that exhibit high structural fidelity to the proposed structure based on experimental data. As the temperature and electrostatics vary, PA molecules undergo alternative kinetic mechanisms, resulting in the formation of a wide spectrum of nanostructures. A phase diagram in the electrostatics-temperature plane is constructed delineating regions of morphological transitions in response to external stimuli. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Packaging stiff polymers in small containers: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Rapaport, D. C.

2016-09-01

The question of how stiff polymers are able to pack into small containers is particularly relevant to the study of DNA packaging in viruses. A reduced version of the problem based on coarse-grained representations of the main components of the system—the DNA polymer and the spherical viral capsid—has been studied by molecular dynamics simulation. The results, involving longer polymers than in earlier work, show that as polymers become more rigid there is an increasing tendency to self-organize as spools that wrap from the inside out, rather than the inverse direction seen previously. In the final state, a substantial part of the polymer is packed into one or more coaxial spools, concentrically layered with different orientations, a form of packaging achievable without twisting the polymer.

Unique nucleation activity of inorganic fullerene-like WS2 nanoparticles in polyphenylene sulfide nanocomposites: isokinetic and isoconversional study of dynamic crystallization kinetics.

PubMed

Naffakh, Mohammed; Marco, Carlos; Gómez, Marián A; Jiménez, Ignacio

2009-05-21

The dynamic crystallization kinetics of polyphenylene sulfide (PPS) nanocomposites with inorganic fullerene WS2 nanopartices (IF-WS2) content varying from 0.05 to 8 wt % has been studied using differential scanning calorimetry (DSC). The analysis of the crystallization at different cooling rates demonstrates that the completely isokinetic description of the crystallization process is not possible. However, the isoconversional methods in combination with the JMAEK equation provide a better understanding of the kinetics of the dynamic crystallization process. The addition of IF-WS2 influences the crystallization kinetics of PPS but in ways unexpected for polymer nanocomposites. A drastic change from retardation to promotion of crystallization is observed with increasing nanoparticle content. In the same way, the results of the nucleation activity and the effective energy barrier confirmed the unique dependence of the crystallization behavior of PPS on composition. In addition, the morphological data obtained from the polarized optical microscopy (POM) and time-resolved synchrotron X-ray diffraction is consistent with results of the crystallization kinetics of PPS/IF-WS2 nanocomposites.

Distinct charge dynamics in battery electrodes revealed by in situ and operando soft X-ray spectroscopy

PubMed Central

Liu, Xiaosong; Wang, Dongdong; Liu, Gao; Srinivasan, Venkat; Liu, Zhi; Hussain, Zahid; Yang, Wanli

2013-01-01

Developing high-performance batteries relies on material breakthroughs. During the past few years, various in situ characterization tools have been developed and have become indispensible in studying and the eventual optimization of battery materials. However, soft X-ray spectroscopy, one of the most sensitive probes of electronic states, has been mainly limited to ex situ experiments for battery research. Here we achieve in situ and operando soft X-ray absorption spectroscopy of lithium-ion battery cathodes. Taking advantage of the elemental, chemical and surface sensitivities of soft X-rays, we discover distinct lithium-ion and electron dynamics in Li(Co1/3Ni1/3Mn1/3)O2 and LiFePO4 cathodes in polymer electrolytes. The contrast between the two systems and the relaxation effect in LiFePO4 is attributed to a phase transformation mechanism, and the mesoscale morphology and charge conductivity of the electrodes. These discoveries demonstrate feasibility and power of in situ soft X-ray spectroscopy for studying integrated and dynamic effects in batteries. PMID:24100759

Energetic fluctuations in amorphous semiconducting polymers: Impact on charge-carrier mobility

NASA Astrophysics Data System (ADS)

Gali, Sai Manoj; D'Avino, Gabriele; Aurel, Philippe; Han, Guangchao; Yi, Yuanping; Papadopoulos, Theodoros A.; Coropceanu, Veaceslav; Brédas, Jean-Luc; Hadziioannou, Georges; Zannoni, Claudio; Muccioli, Luca

2017-10-01

We present a computational approach to model hole transport in an amorphous semiconducting fluorene-triphenylamine copolymer (TFB), which is based on the combination of molecular dynamics to predict the morphology of the oligomeric system and Kinetic Monte Carlo (KMC), parameterized with quantum chemistry calculations, to simulate hole transport. Carrying out a systematic comparison with available experimental results, we discuss the role that different transport parameters play in the KMC simulation and in particular the dynamic nature of positional and energetic disorder on the temperature and electric field dependence of charge mobility. It emerges that a semi-quantitative agreement with experiments is found only when the dynamic nature of the disorder is taken into account. This study establishes a clear link between microscopic quantities and macroscopic hole mobility for TFB and provides substantial evidence of the importance of incorporating fluctuations, at the molecular level, to obtain results that are in good agreement with temperature and electric field-dependent experimental mobilities. Our work makes a step forward towards the application of nanoscale theoretical schemes as a tool for predictive material screening.

Size-Dependent Particle Dynamics in Entangled Polymer Nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mangal, Rahul; Srivastava, Samanvaya; Narayanan, Suresh

Polymer-grafted nanoparticles with diameter d homogeneously dispersed in entangled polymer melts with varying random coil radius R0, but fixed entanglement mesh size ae, are used to study particle motions in entangled polymers. We focus on materials in the transition region between the continuum regime (d > R0), where the classical Stokes-Einstein (S-E) equation is known to describe polymer drag on particles, and the non-continuum regime (d < ae), in which several recent studies report faster diffusion of particles than expected from continuum S-E analysis, based on the bulk polymer viscosity. Specifically, we consider dynamics of particles with sizes d ≥more » ae in entangled polymers with varying molecular weight Mw in order to investigate how the transition from non-continuum to continuum dynamics occur. We take advantage of favorable enthalpic interactions between SiO2 nanoparticles tethered with PEO molecules and entangled PMMA host polymers to create model nanoparticle-polymer composites, in which spherical nanoparticles are uniformly dispersed in entangled polymers. Investigation of the particle dynamics via X-ray photon correlation spectroscopy measurements reveal a transition from fast to slow particle motion as the PMMA molecular weight is increased beyond the entanglement threshold, with a much weaker Mw dependence for Mw>Me than expected from S-E analysis based on bulk viscosity of entangled PMMA melts. We rationalize these observations using a simple force balance analysis around particles and find that nanoparticle motion in entangled melts can be described using a variant of the S-E analysis in which motion of particles is assumed to only disturb sub-chain entangled host segments with sizes comparable to the particle diameter.« less

Size-Dependent Particle Dynamics in Entangled Polymer Nanocomposites.

PubMed

Mangal, Rahul; Srivastava, Samanvaya; Narayanan, Suresh; Archer, Lynden A

2016-01-19

Polymer-grafted nanoparticles with diameter d homogeneously dispersed in entangled polymer melts with varying random coil radius R0, but fixed entanglement mesh size a(e), are used to study particle motions in entangled polymers. We focus on materials in the transition region between the continuum regime (d > R0), where the classical Stokes-Einstein (S-E) equation is known to describe polymer drag on particles, and the noncontinuum regime (d < a(e)), in which several recent studies report faster diffusion of particles than expected from continuum S-E analysis, based on the bulk polymer viscosity. Specifically, we consider dynamics of particles with sizes d ≥ a(e) in entangled polymers with varying molecular weight M(w) in order to investigate how the transition from noncontinuum to continuum dynamics occur. We take advantage of favorable enthalpic interactions between SiO2 nanoparticles tethered with PEO molecules and entangled PMMA host polymers to create model nanoparticle-polymer composites, in which spherical nanoparticles are uniformly dispersed in entangled polymers. Investigation of the particle dynamics via X-ray photon correlation spectroscopy measurements reveals a transition from fast to slow particle motion as the PMMA molecular weight is increased beyond the entanglement threshold, with a much weaker M(w) dependence for M(w) > M(e) than expected from S-E analysis based on bulk viscosity of entangled PMMA melts. We rationalize these observations using a simple force balance analysis around particles and find that nanoparticle motion in entangled melts can be described using a variant of the S-E analysis in which motion of particles is assumed to only disturb subchain entangled host segments with sizes comparable to the particle diameter.

Hydrodynamically Coupled Brownian Dynamics: A coarse-grain particle-based Brownian dynamics technique with hydrodynamic interactions for modeling self-developing flow of polymer solutions

NASA Astrophysics Data System (ADS)

Ahuja, V. R.; van der Gucht, J.; Briels, W. J.

2018-01-01

We present a novel coarse-grain particle-based simulation technique for modeling self-developing flow of dilute and semi-dilute polymer solutions. The central idea in this paper is the two-way coupling between a mesoscopic polymer model and a phenomenological fluid model. As our polymer model, we choose Responsive Particle Dynamics (RaPiD), a Brownian dynamics method, which formulates the so-called "conservative" and "transient" pair-potentials through which the polymers interact besides experiencing random forces in accordance with the fluctuation dissipation theorem. In addition to these interactions, our polymer blobs are also influenced by the background solvent velocity field, which we calculate by solving the Navier-Stokes equation discretized on a moving grid of fluid blobs using the Smoothed Particle Hydrodynamics (SPH) technique. While the polymers experience this frictional force opposing their motion relative to the background flow field, our fluid blobs also in turn are influenced by the motion of the polymers through an interaction term. This makes our technique a two-way coupling algorithm. We have constructed this interaction term in such a way that momentum is conserved locally, thereby preserving long range hydrodynamics. Furthermore, we have derived pairwise fluctuation terms for the velocities of the fluid blobs using the Fokker-Planck equation, which have been alternatively derived using the General Equation for the Non-Equilibrium Reversible-Irreversible Coupling (GENERIC) approach in Smoothed Dissipative Particle Dynamics (SDPD) literature. These velocity fluctuations for the fluid may be incorporated into the velocity updates for our fluid blobs to obtain a thermodynamically consistent distribution of velocities. In cases where these fluctuations are insignificant, however, these additional terms may well be dropped out as they are in a standard SPH simulation. We have applied our technique to study the rheology of two different concentrations of our model linear polymer solutions. The results show that the polymers and the fluid are coupled very well with each other, showing no lag between their velocities. Furthermore, our results show non-Newtonian shear thinning and the characteristic flattening of the Poiseuille flow profile typically observed for polymer solutions.

Hydrodynamically Coupled Brownian Dynamics: A coarse-grain particle-based Brownian dynamics technique with hydrodynamic interactions for modeling self-developing flow of polymer solutions.

PubMed

Ahuja, V R; van der Gucht, J; Briels, W J

2018-01-21

We present a novel coarse-grain particle-based simulation technique for modeling self-developing flow of dilute and semi-dilute polymer solutions. The central idea in this paper is the two-way coupling between a mesoscopic polymer model and a phenomenological fluid model. As our polymer model, we choose Responsive Particle Dynamics (RaPiD), a Brownian dynamics method, which formulates the so-called "conservative" and "transient" pair-potentials through which the polymers interact besides experiencing random forces in accordance with the fluctuation dissipation theorem. In addition to these interactions, our polymer blobs are also influenced by the background solvent velocity field, which we calculate by solving the Navier-Stokes equation discretized on a moving grid of fluid blobs using the Smoothed Particle Hydrodynamics (SPH) technique. While the polymers experience this frictional force opposing their motion relative to the background flow field, our fluid blobs also in turn are influenced by the motion of the polymers through an interaction term. This makes our technique a two-way coupling algorithm. We have constructed this interaction term in such a way that momentum is conserved locally, thereby preserving long range hydrodynamics. Furthermore, we have derived pairwise fluctuation terms for the velocities of the fluid blobs using the Fokker-Planck equation, which have been alternatively derived using the General Equation for the Non-Equilibrium Reversible-Irreversible Coupling (GENERIC) approach in Smoothed Dissipative Particle Dynamics (SDPD) literature. These velocity fluctuations for the fluid may be incorporated into the velocity updates for our fluid blobs to obtain a thermodynamically consistent distribution of velocities. In cases where these fluctuations are insignificant, however, these additional terms may well be dropped out as they are in a standard SPH simulation. We have applied our technique to study the rheology of two different concentrations of our model linear polymer solutions. The results show that the polymers and the fluid are coupled very well with each other, showing no lag between their velocities. Furthermore, our results show non-Newtonian shear thinning and the characteristic flattening of the Poiseuille flow profile typically observed for polymer solutions.

Comparing selected morphological models of hydrated Nafion using large scale molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Knox, Craig K.

Experimental elucidation of the nanoscale structure of hydrated Nafion, the most popular polymer electrolyte or proton exchange membrane (PEM) to date, and its influence on macroscopic proton conductance is particularly challenging. While it is generally agreed that hydrated Nafion is organized into distinct hydrophilic domains or clusters within a hydrophobic matrix, the geometry and length scale of these domains continues to be debated. For example, at least half a dozen different domain shapes, ranging from spheres to cylinders, have been proposed based on experimental SAXS and SANS studies. Since the characteristic length scale of these domains is believed to be ˜2 to 5 nm, very large molecular dynamics (MD) simulations are needed to accurately probe the structure and morphology of these domains, especially their connectivity and percolation phenomena at varying water content. Using classical, all-atom MD with explicit hydronium ions, simulations have been performed to study the first-ever hydrated Nafion systems that are large enough (~2 million atoms in a ˜30 nm cell) to directly observe several hydrophilic domains at the molecular level. These systems consisted of six of the most significant and relevant morphological models of Nafion to-date: (1) the cluster-channel model of Gierke, (2) the parallel cylinder model of Schmidt-Rohr, (3) the local-order model of Dreyfus, (4) the lamellar model of Litt, (5) the rod network model of Kreuer, and (6) a 'random' model, commonly used in previous simulations, that does not directly assume any particular geometry, distribution, or morphology. These simulations revealed fast intercluster bridge formation and network percolation in all of the models. Sulfonates were found inside these bridges and played a significant role in percolation. Sulfonates also strongly aggregated around and inside clusters. Cluster surfaces were analyzed to study the hydrophilic-hydrophobic interface. Interfacial area and cluster volume significantly increased during the simulations, suggesting the need for morphological model refinement and improvement. Radial distribution functions and structure factors were calculated. All nonrandom models exhibited the characteristic experimental scattering peak, underscoring the insensitivity of this measurement to hydrophilic domain structure and highlighting the need for future work to clearly distinguish morphological models of Nafion.

Stochastic entangled chain dynamics of dense polymer solutions.

PubMed

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.

Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2005-05-01

Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

Communication: Polymer entanglement dynamics: Role of attractive interactions

DOE PAGES

Grest, Gary S.

2016-10-10

The coupled dynamics of entangled polymers, which span broad time and length scales, govern their unique viscoelastic properties. To follow chain mobility by numerical simulations from the intermediate Rouse and reptation regimes to the late time diffusive regime, highly coarse grained models with purely repulsive interactions between monomers are widely used since they are computationally the most efficient. In this paper, using large scale molecular dynamics simulations, the effect of including the attractive interaction between monomers on the dynamics of entangled polymer melts is explored for the first time over a wide temperature range. Attractive interactions have little effect onmore » the local packing for all temperatures T and on the chain mobility for T higher than about twice the glass transition T g. Finally, these results, across a broad range of molecular weight, show that to study the dynamics of entangled polymer melts, the interactions can be treated as pure repulsive, confirming a posteriori the validity of previous studies and opening the way to new large scale numerical simulations.« less

Active Curved Polymers Form Vortex Patterns on Membranes.

PubMed

Denk, Jonas; Huber, Lorenz; Reithmann, Emanuel; Frey, Erwin

2016-04-29

Recent in vitro experiments with FtsZ polymers show self-organization into different dynamic patterns, including structures reminiscent of the bacterial Z ring. We model FtsZ polymers as active particles moving along chiral, circular paths by Brownian dynamics simulations and a Boltzmann approach. Our two conceptually different methods point to a generic phase behavior. At intermediate particle densities, we find self-organization into vortex structures including closed rings. Moreover, we show that the dynamics at the onset of pattern formation is described by a generalized complex Ginzburg-Landau equation.

Directed Self-Organization of Polymer-Grafted Nanoparticles in Polymer Thin Films

NASA Astrophysics Data System (ADS)

Zhang, Ren

The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. Surface modification of NPs with grafted polymer ligands has emerged as a versatile means to control the interaction and organization of particle constituents in polymer-matrix composite materials. In this study, by incorporating polymer-grafted nanoparticles (PGNPs) into polymeric thin films, we aim to understand and control the spatial organization of PGNPs through the interactions between polymer brush layer and matrix chains. As model systems, we investigate thermodynamic behaviors of polystyrene-tethered gold nanoparticles (denoted as AuPS) dispersed in polymer thin film matrices with identical and different chemical compositions (PS and PMMA, respectively), and evaluate the influence of external perturbation fields on directed organization of nanofillers. With the presence of unfavorable enthalpic interactions between grafted and free polymer chains (i.e. AuPS/ PMMA blend thin films), phase-separated structures are generated upon thermal annealing, characterized with morphologies ranging from discrete droplets to spinodal structures, which is consistent with composition-dependent classic binary polymer blends phase separation. The phase separation kinetics of AuPS/ PMMA blends exhibit distinct features compared to the parent PS/ PMMA homopolymer blends. We further illustrate phase-separated AuPS-rich domains can be directed into unidirectionally aligned anisotropic structures through soft-shear dynamic zone annealing (DZA-SS) process with tunable domain aspect ratios. To exert exquisite control over the shape, size and location of phase-separated PGNP domains, topographically patterned elastomer confinement is introduced to PGNP/ polymer blend thin films during thermal annealing. When the phase-separated lengthscale coincides with confined pattern dimension, long-range ordered submicron-sized AuPS domains are generated in PMMA matrices with dense and well-dispersed nanoparticle distribution. Furthermore, preferential segregation of AuPS nanoparticles at patterned mesa regions can be induced in PS matrices where enthalpic interactions are absent. This selective segregation is achieved due to the local perturbation of grafted chains when confined in a restricted space. The efficiency of this particle segregation process within patterned mesa-trench films can be tuned by changing the relative entropic confinement effects on grafted and matrix chains. This physical pattern directed PGNP organization strategy is applicable to versatile pattern geometries and nanoparticle compositions.

Desolvation of polymers by ultrafast heating: Influence of hydrophilicity

NASA Astrophysics Data System (ADS)

Sun, Si Neng; Urbassek, Herbert M.

2010-10-01

Using molecular-dynamics simulation, we investigate the consequences of ultrafast laser-induced heating of a small water droplet containing a solvated polymer. Two polymers are studied: polyethylene as an example of a hydrophobic, and polyketone as an example of a hydrophilic polymer. In both cases, when the droplet is heated below the critical temperature of water, strong water evaporation is started, but the polymer remains in contact with a central water cluster. However, upon heating beyond the critical temperature, the hydrophilic polyethylene becomes completely desolvated, while polyketone still remains solvated. We analyze this behavior in terms of the intermolecular interactions and of the expansion dynamics of the heated droplet.

Functional Supramolecular Polymers*

PubMed Central

Aida, T.; Meijer, E.W.; Stupp, S.I.

2012-01-01

Supramolecular polymers can be random and entangled coils with the mechanical properties of plastics and elastomers, but with great capacity for processability, recycling, and self-healing due to their reversible monomer-to-polymer transitions. At the other extreme, supramolecular polymers can be formed by self-assembly among designed subunits to yield shape-persistent and highly ordered filaments. The use of strong and directional interactions among molecular subunits can achieve not only rich dynamic behavior but also high degrees of internal order that are not known in ordinary polymers. They can resemble, for example, the ordered and dynamic one-dimensional supramolecular assemblies of the cell cytoskeleton, and possess useful biological and electronic functions. PMID:22344437

Interfacial Interaction in Anodic Aluminum Oxide Templates Modifies Morphology, Surface Area, and Crystallization of Polyamide-6 Nanofibers.

PubMed

Xue, Junhui; Xu, Yizhuang; Jin, Zhaoxia

2016-03-08

Here, we demonstrated that, when the precipitation process of polyamide-6 (PA6) solution happens in cylindrical channels of an anodized aluminum oxide membrane (AAO), interface interactions between a solid surface, solvent, non-solvent, and PA6 will influence the obtained polymer nanostructures, resulting in complex morphologies, increased surface area, and crystallization changes. With the enhancing interaction of PA6 and the AAO surface, the morphology of PA6 nanostructures changes from solid nanofibers, mesoporous, to bamboo-like, while at the same time, metastable γ-phase domains increase in these PA6 nanostructures. Brunauer-Emmett-Teller (BET) surface areas of solid, bamboo-like, and mesoporous PA6 nanofibers rise from 16, 20.9, to 25 m(2)/g. This study shows that interfacial interaction in AAO template fabrication can be used in manipulating the morphology and crystallization of one-dimensional polymer nanostructures. It also provides us a simple and novel method to create porous PA6 nanofibers with a large surface area.

Resolving Properties of Polymers and Nanoparticle Assembly through Coarse-Grained Computational Studies.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grest, Gary S.

2017-09-01

Coupled length and time scales determine the dynamic behavior of polymers and polymer nanocomposites and underlie their unique properties. To resolve the properties over large time and length scales it is imperative to develop coarse grained models which retain the atomistic specificity. Here we probe the degree of coarse graining required to simultaneously retain significant atomistic details a nd access large length and time scales. The degree of coarse graining in turn sets the minimum length scale instrumental in defining polymer properties and dynamics. Using polyethylene as a model system, we probe how the coarse - graining scale affects themore » measured dynamics with different number methylene group s per coarse - grained beads. Using these models we simulate polyethylene melts for times over 500 ms to study the viscoelastic properties of well - entangled polymer melts and large nanoparticle assembly as the nanoparticles are driven close enough to form nanostructures.« less

Observation of dynamic equilibrium cluster phase in nanoparticle-polymer system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Sugam, E-mail: sugam@barc.gov.in; Mehan, S.; Aswal, V. K.

2016-05-23

Small-angle neutron scattering (SANS) and dynamic light scattering (DLS) have been used to investigate the existence of a cluster phase in a nanoparticle-polymer system. The nanoparticle-polymer system shows an interesting reentrant phase behavior where the charge stabilized silica nanoparticles undergo particle clustering and back to individual nanoparticles as a function of polymer concentration. This kind of phase behavior is believed to be directed by opposing attractive and repulsive interactions present in the system. The phase behavior shows two narrow regions of polymer concentration immediately before and after the two-phase formation indicating the possibility of the existence of some equilibrium clusters.more » DLS results show a much higher size of particles than individuals in these two regions which remains unchanged even after dilution. The SANS data show the evolution of attraction with increased volume fraction of the particles supporting the dynamic nature of these clusters.« less

Self-organization in suspensions of end-functionalized semiflexible polymers under shear flow

NASA Astrophysics Data System (ADS)

Myung, Jin Suk; Winkler, Roland G.; Gompper, Gerhard

2015-12-01

The nonequilibrium dynamical behavior and structure formation of end-functionalized semiflexible polymer suspensions under flow are investigated by mesoscale hydrodynamic simulations. The hybrid simulation approach combines the multiparticle collision dynamics method for the fluid, which accounts for hydrodynamic interactions, with molecular dynamics simulations for the semiflexible polymers. In equilibrium, various kinds of scaffold-like network structures are observed, depending on polymer flexibility and end-attraction strength. We investigate the flow behavior of the polymer networks under shear and analyze their nonequilibrium structural and rheological properties. The scaffold structure breaks up and densified aggregates are formed at low shear rates, while the structural integrity is completely lost at high shear rates. We provide a detailed analysis of the shear- rate-dependent flow-induced structures. The studies provide a deeper understanding of the formation and deformation of network structures in complex materials.

Local-feature analysis for automated coarse-graining of bulk-polymer molecular dynamics simulations.

PubMed

Xue, Y; Ludovice, P J; Grover, M A

2012-12-01

A method for automated coarse-graining of bulk polymers is presented, using the data-mining tool of local feature analysis. Most existing methods for polymer coarse-graining define superatoms based on their covalent bonding topology along the polymer backbone, but here superatoms are defined based only on their correlated motions, as observed in molecular dynamics simulations. Correlated atomic motions are identified in the simulation data using local feature analysis, between atoms in the same or in different polymer chains. Groups of highly correlated atoms constitute the superatoms in the coarse-graining scheme, and the positions of their seed coordinates are then projected forward in time. Based on only the seed positions, local feature analysis enables the full reconstruction of all atomic positions. This reconstruction suggests an iterative scheme to reduce the computation of the simulations to initialize another short molecular dynamic simulation, identify new superatoms, and again project forward in time.

Mechanical and thermal properties of polylactic acid composites reinforced with cellulose nanoparticles extracted from kenaf fibre

NASA Astrophysics Data System (ADS)

Ketabchi, Mohammad Reza; Khalid, Mohammad; Thevy Ratnam, Chantara; Walvekar, Rashmi

2016-12-01

Different approaches have been attempted to use biomass as filler for production of biodegradable polymer composites. In this study, cellulose nanoparticles (CNP) extracted from kenaf fibres were used to produce polylactic acid (PLA) based biodegradable nanocomposites. CNP concentration was varied from 1-5 wt. % and blended with PLA using Brabender twin-screw compounder. Effects of CNP loading on the mechanical, thermal and dynamic properties of PLA were investigated. Studies on the morphological properties and influence of CNP loading on the properties of CNP/PLA nanocomposite were also conducted. The results show an adequate compatibility between CNP and PLA matrix. Moreover, addition of 3 wt. % of CNP improved the PLA tensile strength by 25%.

Different interface orientations of pentacene and PTCDA induce different degrees of disorder

PubMed Central

2012-01-01

Organic polymers or crystals are commonly used in manufacturing of today‘s electronically functional devices (OLEDs, organic solar cells, etc). Understanding their morphology in general and at the interface in particular is of paramount importance. Proper knowledge of molecular orientation at interfaces is essential for predicting optoelectronic properties such as exciton diffusion length, charge carrier mobility, and molecular quadrupole moments. Two promising candidates are pentacene and 3,4:9,10-perylenetetracarboxylic dianhydride (PTCDA). Different orientations of pentacene on PTCDA have been investigated using an atomistic molecular dynamics approach. Here, we show that the degree of disorder at the interface depends largely on the crystal orientation and that more ordered interfaces generally suffer from large vacancy formation. PMID:22583772

Rapid Self-healing Nanocomposite Hydrogel with Tunable Dynamic Mechanics

NASA Astrophysics Data System (ADS)

Li, Qiaochu; Mishra, Sumeet; Chapman, Brian; Chen, Pangkuan; Tracy, Joseph; Holten-Andersen, Niels

The macroscopic healing rate and efficiency in self-repairing hydrogel materials are largely determined by the dissociation dynamics of their polymer network, which is hardly achieved in a controllable manner. Inspired by mussel's adhesion chemistry, we developed a novel approach to assemble inorganic nanoparticles and catechol-decorated PEG polymer into a hydrogel network. When utilized as reversible polymer-particle crosslinks, catechol-metal coordination bonds yield a unique gel network with dynamic mechanics controlled directly by interfacial crosslink structure. Taking advantage of this structure-property relationship at polymer-particle interfaces, we designed a hierarchically structured hybrid gel with two distinct relaxation timescales. By tuning the relative contribution of the two relaxation modes, we are able to finely control the gel's dynamic mechanical behavior from a viscoelastic fluid to a stiff solid, yet preserving its rapid self-healing property without the need for external stimuli.

Structure and Dynamics Ionic Block co-Polymer Melts: Computational Study

NASA Astrophysics Data System (ADS)

Aryal, Dipak; Perahia, Dvora; Grest, Gary S.

Tethering ionomer blocks into co-polymers enables engineering of polymeric systems designed to encompass transport while controlling structure. Here the structure and dynamics of symmetric pentablock copolymers melts are probed by fully atomistic molecular dynamics simulations. The center block consists of randomly sulfonated polystyrene with sulfonation fractions f = 0 to 0.55 tethered to a hydrogenated polyisoprene (PI), end caped with poly(t-butyl styrene). We find that melts with f = 0.15 and 0.30 consist of isolated ionic clusters whereas melts with f = 0.55 exhibit a long-range percolating ionic network. Similar to polystyrene sulfonate, a small number of ionic clusters slow the mobility of the center of mass of the co-polymer, however, formation of the ionic clusters is slower and they are often intertwined with PI segments. Surprisingly, the segmental dynamics of the other blocks are also affected. NSF DMR-1611136; NERSC; Palmetto Cluster Clemson University; Kraton Polymers US, LLC.

The properties of water in swollen cross-linked polystyrene sulfo acids

NASA Astrophysics Data System (ADS)

Gagarin, A. N.; Tokmachev, M. G.; Kovaleva, S. S.; Ferapontov, N. B.

2008-11-01

The properties of water in polystyrene sulfo acid gels with various cross-linking degrees were studied by optical volumetry and dynamic desorption porosimetry. The isotherms of water desorption obtained by dynamic desorption porosimetry coincided with isopiestic isotherms, which allowed this method to be recommended for the determination of the amount of water in polymer gels. Joint optical volumetry and dynamic desorption porosimetry studies showed that the interphase boundary in the cross-liked hydrophilic polymer-water system did not coincide with the visible gel boundary, because gels were two-phase systems, which contained water of two types, “free” and “bound.” The influence of the degree of polymer cross-linking on the amounts and properties of water of the two types was studied. It was shown that constants of water distribution in the polymer could be calculated from the dynamic desorption porosimetry data.

Insights into the interfacial strengthening mechanisms of calcium-silicate-hydrate/polymer nanocomposites.

PubMed

Zhou, Yang; Hou, Dongshuai; Geng, Guoqing; Feng, Pan; Yu, Jiao; Jiang, Jinyang

2018-03-28

The mechanical properties of organic/inorganic composites can be highly dependent on the interfacial interactions. In this work, with organic polymers intercalated into the interlayer of inorganic calcium silicate hydrate (C-S-H), the primary binding phase of Portland cement, great ductility improvement is obtained for the nanocomposites. Employing reactive molecular dynamics, the simulation results indicate that strong interfacial interactions between the polymers and the substrate contribute greatly to strengthening the materials, when C-S-H/poly ethylene glycol (PEG), C-S-H/poly acrylic acid (PAA), and C-S-H/poly vinyl alcohol (PVA) were subject to uniaxial tension along different lattice directions. In the x and z direction tensile processes, the Si-OCa bonds of the C-S-H gel, which were elongated and broken to form Si-OH and Ca-OH, play a critical role in loading resistance, while the incorporation of polymers bridged the neighboring silicate sheets, and activated more the hydrolytic reactions at the interfaces to avoid strain localization, thus increasing the tensile strength and postponing the fracture. On the other hand, Si-O-Si bonds of C-S-H mainly take the load when tension was applied along the y direction. During the post-yield stage, rearrangements of silicate tetrahedra occurred to prevent rapid damage. The polymer intercalation further elongates this post-yield period by forming interfacial Si-O-C bonds, which promote rearrangements and improve the connectivity of the defective silicate morphology, significantly improving the ductility. Among the polymers, PEG exhibits the strongest interaction with C-S-H, and thus C-S-H/PEG possesses the highest ductility. We expect that the molecular-scale mechanisms interpreted here will shed new light on the stress-activated chemical interactions at the organic/inorganic interfaces, and help eliminate the brittleness of cement-based materials on a genetic level.

Determination of Quantum Chemistry Based Force Fields for Molecular Dynamics Simulations of Aromatic Polymers

NASA Technical Reports Server (NTRS)

Jaffe, Richard; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

Ab initio quantum chemistry calculations for model molecules can be used to parameterize force fields for molecular dynamics simulations of polymers. Emphasis in our research group is on using quantum chemistry-based force fields for molecular dynamics simulations of organic polymers in the melt and glassy states, but the methodology is applicable to simulations of small molecules, multicomponent systems and solutions. Special attention is paid to deriving reliable descriptions of the non-bonded and electrostatic interactions. Several procedures have been developed for deriving and calibrating these parameters. Our force fields for aromatic polyimide simulations will be described. In this application, the intermolecular interactions are the critical factor in determining many properties of the polymer (including its color).

Biocompatible, Biodegradable Polymers for Use in Bone Repair,

DTIC Science & Technology

1987-01-01

as intact polymers and because their degradation products are carbon dioxide and water. 7 B. Microstructure, Morphology, Synthesis The microstructure...Hydrophilic flIe x iblIe 0 6. Carbonate R-O-C-O-R Hydrophilic r ig id Hollinger Ibav %lark page 15 D. Potential Biodegradable Polymers For producing high...diacids or hydroxvacids. Lactone rings with three to six carbons within the ring can be used as monomers. This limits the ratio ot sp4 to sp2 carbons

Roll-to-Roll printed large-area all-polymer solar cells with 5% efficiency based on a low crystallinity conjugated polymer blend

NASA Astrophysics Data System (ADS)

Gu, Xiaodan; Zhou, Yan; Gu, Kevin; Kurosawa, Tadanori; Yan, Hongping; Wang, Cheng; Toney, Micheal; Bao, Zhenan

The challenge of continuous printing in high efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution coated all-polymer bulk heterojunction (BHJ) solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, our results showed that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. We were able to continuously roll-to-roll slot die print large area all-polymer solar cells with power conversion efficiencies of 5%, with combined cell area up to 10 cm2. This is among the highest efficiencies realized with R2R coated active layer organic materials on flexible substrate. DOE BRIDGE sunshot program. Office of Naval Research.

Polymer Self-Assembled Nanostructures as Innovative Drug Nanocarrier Platforms.

PubMed

Pippa, Natassa; Pispas, Stergios; Demetzos, Costas

2016-01-01

Polymer self-assembled nanostructures are used in pharmaceutical sciences as bioactive molecules' delivery systems for therapeutic and diagnostic purposes. Micelles, polyelectrolyte complexes, polymersomes, polymeric nanoparticles, nanogels and polymer grafted liposomes represent delivery vehicles that are marketed and/or under clinical development, as drug formulations. In this mini-review, these, recently appeared in the literature, innovative polymer drug nanocarrier platforms are discussed, starting from their technological development in the laboratory to their potential clinical use, through studies of their biophysics, thermodynamics, physical behavior, morphology, bio-mimicry, therapeutic efficacy and safety. The properties of an ideal drug delivery system are the structural control over size and shape of drug or imaging agent cargo/domain, biocompatibility, nontoxic polymer/ pendant functionality and the precise, nanoscale container and/or scaffolding properties with high drug or imaging agent capacity features. Self-assembled polymer nanostructures exhibit all these properties and could be considered as ideal drug nanocarriers through control of their size, structure and morphology, with the aid of a large variety of parameters, in vitro and in vivo. These modern trends reside at the interface of soft matter self-assembly and pharmaceutical sciences and the technologies for health. Great advantages related to basic science and applications are expected by understanding the self-assembly behavior of these polymeric nanotechnological drug delivery systems, created through bio-inspiration and biomimicry and have potential utilization into clinical applications.

Hierarchical multifunctional composites by conformally coating aligned carbon nanotube arrays with conducting polymer.

PubMed

Vaddiraju, Sreeram; Cebeci, Hülya; Gleason, Karen K; Wardle, Brian L

2009-11-01

A novel method for the fabrication of carbon nanotube (CNT)-conducting polymer composites is demonstrated by conformally coating extremely high aspect ratio vertically aligned-CNT (A-CNT) arrays with conducting polymer via oxidative chemical vapor deposition (oCVD). A mechanical densification technique is employed that allows the spacing of the A-CNTs to be controlled, yielding a range of inter-CNT distances between 20 and 70 nm. Using this morphology control, oCVD is shown to conformally coat 8-nm-diameter CNTs having array heights up to 1 mm (an aspect ratio of 10(5)) at all inter-CNT spacings. Three phase CNT-conducting polymer nanocomposites are then fabricated by introducing an insulating epoxy via capillary-driven wetting. CNT morphology is maintained during processing, allowing quantification of direction-dependent (nonisotropic) composite properties. Electrical conductivity occurs primarily along the CNT axial direction, such that the conformal conducting polymer has little effect on the activation energy required for charge conduction. In contrast, the conducting polymer coating enhanced the conductivity in the radial direction by lowering the activation energy required for the creation of mobile charge carriers, in agreement with variable-range-hopping models. The fabrication strategy introduced here can be used to create many multifunctional materials and devices (e.g., direction-tailorable hydrophobic and highly conducting materials), including a new four-phase advanced fiber composite architecture.

Roll-to-Roll Printed Large-Area All-Polymer Solar Cells with 5% Efficiency Based on a Low Crystallinity Conjugated Polymer Blend

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, Xiaodan; Zhou, Yan; Gu, Kevin

The challenge of continuous printing in high-efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution-coated all-polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers.more » This particular methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small-scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. Large-area all-polymer solar cells are continuously roll-to-roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm 2. This is among the highest efficiencies realized with R2R-coated active layer organic materials on flexible substrate.« less