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Sample records for amorphous polymer solution

  1. Aragonite nanorods in calcium carbonate/polymer hybrids formed through self-organization processes from amorphous calcium carbonate solution.

    PubMed

    Kajiyama, Satoshi; Nishimura, Tatsuya; Sakamoto, Takeshi; Kato, Takashi

    2014-04-24

    Nanostructured inorganic/polymer hybrid thin films comprising aragonite nanorods derived from aqueous suspensions of amorphous calcium carbonate (ACC) are prepared. For the formation of calcium carbonate (CaCO₃)/polymer hybrids, spincoated and annealed films of poly(vinyl alcohol) (PVA) that function as polymer matrices are soaked in aqueous colloidal solutions dispersing ACC stabilized by poly(acrylic acid) (PAA). In the initial stage, calcite thin films form on the surface. Subsequently, aragonite crystals start to form inside the PVA matrix that contains PVA crystallites which induce aragonite nucleation. Nanostructured hybrids composed of calcite thin films consisting of nanoparticles and assembled aragonite nanorods are formed in the matrices of PVA.

  2. Polymer solutions

    DOEpatents

    Krawczyk, Gerhard Erich; Miller, Kevin Michael

    2011-07-26

    There is provided a method of making a polymer solution comprising polymerizing one or more monomer in a solvent, wherein said monomer comprises one or more ethylenically unsaturated monomer that is a multi-functional Michael donor, and wherein said solvent comprises 40% or more by weight, based on the weight of said solvent, one or more multi-functional Michael donor.

  3. Design Requirements for Amorphous Piezoelectric Polymers

    NASA Technical Reports Server (NTRS)

    Ounaies, Z.; Young, J. A.; Harrison, J. S.

    1999-01-01

    An overview of the piezoelectric activity in amorphous piezoelectric polymers is presented. The criteria required to render a polymer piezoelectric are discussed. Although piezoelectricity is a coupling between mechanical and electrical properties, most research has concentrated on the electrical properties of potentially piezoelectric polymers. In this work, we present comparative mechanical data as a function of temperature and offer a summary of polarization and electromechanical properties for each of the polymers considered.

  4. Magnetoimpedance of cobalt-based amorphous ribbons/polymer composites

    NASA Astrophysics Data System (ADS)

    Semirov, A. V.; Derevyanko, M. S.; Bukreev, D. A.; Moiseev, A. A.; Kudryavtsev, V. O.; Safronov, A. P.

    2016-10-01

    The combined influence of the temperature, the elastic tensile stress and the external magnetic field on the total impedance and impedance components were studied for rapidly quenched amorphous Co75Fe5Si4B16 ribbons. Both as-cast amorphous ribbons and Co75Fe5Si4B16/polymer amorphous ribbon based composites were considered. Following polymer coverings were studied: modified rubber solution in o-xylene, solution of butyl methacrylate and methacrylic acid copolymer in isopropanol and solution of polymethylphenylsiloxane resin in toluene. All selected composites showed very good adhesion of the coverings and allowed to provide temperature measurements from 163 K up to 383 K under the applied deforming tensile force up to 30 N. The dependence of the modulus of the impedance and its components on the external magnetic field was influenced by the elastic tensile stresses and was affected by the temperature of the samples. It was shown that maximal sensitivity of the impedance and its components to the external magnetic field was observed at minimal temperature and maximal deforming force depended on the frequency of an alternating current.

  5. Polymer incorporation method affects the physical stability of amorphous indomethacin in aqueous suspension.

    PubMed

    Surwase, S A; Itkonen, L; Aaltonen, J; Saville, D; Rades, T; Peltonen, L; Strachan, C J

    2015-10-01

    This study reports the potential of different polymers and polymer incorporation methods to inhibit crystallisation and maintain supersaturation of amorphous indomethacin (IND) in aqueous suspensions during storage. Three different polymers (poly(vinyl pyrrolidone) (PVP), hydroxypropyl methylcellulose (HPMC) and Soluplus® (SP)) were used and included in the suspensions either as a solid dispersion (SD) with IND or dissolved in the suspension medium prior to the addition of amorphous IND. The total concentrations of both IND and the polymer in the suspensions were kept the same for both methods of polymer incorporation. All the polymers (with both incorporation methods) inhibited crystallisation of the amorphous IND. The SDs were better than the predissolved polymer solutions at inhibiting crystallisation. The SDs were also better at maintaining drug supersaturation. SP showed a higher IND crystallisation inhibition and supersaturation potential than the other polymers. However, this depended on the method of addition. IND in SD with SP did not crystallise, nor did the SD generate any drug supersaturation, whereas IND in the corresponding predissolved SP solution crystallised (into the recently characterised η polymorphic form of the drug) but also led to a more than 20-fold higher IND solution concentration than that observed for crystalline IND. The ranking of the polymers with respect to crystallisation inhibition potential in SDs was SP≫PVP>HPMC. Overall, this study showed that both polymer type and polymer incorporation method strongly impact amorphous form stability and drug supersaturation in aqueous suspensions. PMID:26092472

  6. Cyclic behaviors of amorphous shape memory polymers.

    PubMed

    Yu, Kai; Li, Hao; McClung, Amber J W; Tandon, Gyaneshwar P; Baur, Jeffery W; Qi, H Jerry

    2016-04-01

    Cyclic loading conditions are commonly encountered in the applications of shape memory polymers (SMPs), where the cyclic characteristics of the materials determine their performance during the service life, such as deformation resistance, shape recovery speed and shape recovery ratio. Recent studies indicate that in addition to the physical damage or some other irreversible softening effects, the viscoelastic nature could also be another possible reason for the degraded cyclic behavior of SMPs. In this paper, we explore in detail the influence of the viscoelastic properties on the cyclic tension and shape memory (SM) behavior of an epoxy based amorphous thermosetting polymer. Cyclic experiments were conducted first, which show that although the epoxy material does not have any visible damage or irreversible softening effect during deformation, it still exhibits obvious degradation in the cyclic tension and SM behaviors. A linear multi-branched model is utilized to assist in the prediction and understanding of the mechanical responses of amorphous SMPs. Parametric studies based on the applied model suggest that the shape memory performance can be improved by adjusting programming and recovery conditions, such as lowering the loading rate, increasing the programming temperature, and reducing the holding time. PMID:26924339

  7. Cyclic behaviors of amorphous shape memory polymers.

    PubMed

    Yu, Kai; Li, Hao; McClung, Amber J W; Tandon, Gyaneshwar P; Baur, Jeffery W; Qi, H Jerry

    2016-04-01

    Cyclic loading conditions are commonly encountered in the applications of shape memory polymers (SMPs), where the cyclic characteristics of the materials determine their performance during the service life, such as deformation resistance, shape recovery speed and shape recovery ratio. Recent studies indicate that in addition to the physical damage or some other irreversible softening effects, the viscoelastic nature could also be another possible reason for the degraded cyclic behavior of SMPs. In this paper, we explore in detail the influence of the viscoelastic properties on the cyclic tension and shape memory (SM) behavior of an epoxy based amorphous thermosetting polymer. Cyclic experiments were conducted first, which show that although the epoxy material does not have any visible damage or irreversible softening effect during deformation, it still exhibits obvious degradation in the cyclic tension and SM behaviors. A linear multi-branched model is utilized to assist in the prediction and understanding of the mechanical responses of amorphous SMPs. Parametric studies based on the applied model suggest that the shape memory performance can be improved by adjusting programming and recovery conditions, such as lowering the loading rate, increasing the programming temperature, and reducing the holding time.

  8. Lyophilization monophase solution technique for preparation of amorphous flutamide dispersions.

    PubMed

    Elgindy, Nazik; Elkhodairy, Kadria; Molokhia, Abdallah; Elzoghby, Ahmed

    2011-07-01

    Flutamide (FLT) is a poorly soluble anticancer drug. Therefore, lyophilized dispersions (LDs) of FLT with polyvinylpyrrolidone (PVP) K30, polyethylene glycol (PEG) 6000, and pluronic F127 were prepared via lyophilization monophase solution technique with the aim of increasing its dissolution rate. FLT showed an A(L)-type phase solubility diagrams with PVP and PEG, whereas A(N)-type diagram was obtained with pluronic. The amount of residual tertiary butyl alcohol, determined by gas chromatography, was 0.015-0.021% w/w. Differential scanning calorimetry and X-ray diffractometry revealed that FLT-polymer 1:1 LDs were partially amorphous, whereas the 1:3 and 1:5 LDs were completely amorphous. After 6 months storage, polymers under study inhibited FLT recrystallization maintaining its amorphous form. The particle size of FLT-polymer LDs was between 0.81 and 2.13 μm, with a high surface area (268.43-510.82 m²/g) and porosity (354.01-676.23 e⁻³ mL/g). Also, the poor flow properties of FLT could be improved but to a limited extent. FLT dissolution was significantly enhanced with the fastest dissolution that was achieved using pluronic. After 30 min, about 66.52%, 78.23%, and 81.64% of FLT was dissolved from 1:5 FLT-PVP, PEG, and pluronic LDs, respectively, compared with only 13.45% of FLT. These data suggest that these polymers might be useful adjuncts in preparation and stabilization of amorphous immediate-release FLT LDs.

  9. Enhanced Physical Stability of Amorphous Drug Formulations via Dry Polymer Coating.

    PubMed

    Capece, Maxx; Davé, Rajesh

    2015-06-01

    Although amorphous solid drug formulations may be advantageous for enhancing the bioavailability of poorly soluble active pharmaceutical ingredients, they exhibit poor physical stability and undergo recrystallization. To address this limitation, this study investigates stability issues associated with amorphous solids through analysis of the crystallization behavior for acetaminophen (APAP), known as a fast crystallizer, using a modified form of the Avrami equation that kinetically models both surface and bulk crystallization. It is found that surface-enhanced crystallization, occurring faster at the free surface than in the bulk, is the major impediment to the stability of amorphous APAP. It is hypothesized that a novel use of a dry-polymer-coating process referred to as mechanical-dry-polymer-coating may be used to inhibit surface crystallization and enhance stability. The proposed process, which is examined, simultaneously mills and coats amorphous solids with polymer, while avoiding solvents or solutions, which may otherwise cause stability or crystallization issues during coating. It is shown that solid dispersions of APAP (64% loading) with a small particle size (28 μm) could be prepared and coated with the polymer, carnauba wax, in a vibratory ball mill. The resulting amorphous solid was found to have excellent stability as a result of inhibition of surface crystallization. PMID:25902736

  10. Enhanced Physical Stability of Amorphous Drug Formulations via Dry Polymer Coating.

    PubMed

    Capece, Maxx; Davé, Rajesh

    2015-06-01

    Although amorphous solid drug formulations may be advantageous for enhancing the bioavailability of poorly soluble active pharmaceutical ingredients, they exhibit poor physical stability and undergo recrystallization. To address this limitation, this study investigates stability issues associated with amorphous solids through analysis of the crystallization behavior for acetaminophen (APAP), known as a fast crystallizer, using a modified form of the Avrami equation that kinetically models both surface and bulk crystallization. It is found that surface-enhanced crystallization, occurring faster at the free surface than in the bulk, is the major impediment to the stability of amorphous APAP. It is hypothesized that a novel use of a dry-polymer-coating process referred to as mechanical-dry-polymer-coating may be used to inhibit surface crystallization and enhance stability. The proposed process, which is examined, simultaneously mills and coats amorphous solids with polymer, while avoiding solvents or solutions, which may otherwise cause stability or crystallization issues during coating. It is shown that solid dispersions of APAP (64% loading) with a small particle size (28 μm) could be prepared and coated with the polymer, carnauba wax, in a vibratory ball mill. The resulting amorphous solid was found to have excellent stability as a result of inhibition of surface crystallization.

  11. Induced birefringence and dichroism in azo polymers. Comparison between amorphous and liquid crystalline polymers

    SciTech Connect

    Natansohn, A.; Brown, D.; Rochon, P.

    1993-12-31

    Macroscopic order can be induced in amorphous high-Tg azo polymers (usually containing electron-donor - electron-acceptor substituted azobenzene moieties) by exposure to polarized light. The phenomenon is based on a series of trans-cis-trans isomerization cycles and the induced birefringence is typically of 2x10{sup {minus}2}. The ordered domains can be returned to randomness ({open_quotes}erased{close_quotes}) using circularly polarized light. This paper will present a comparison between amorphous and liquid crystalline azo polymers. The most significant difference between these two types of polymers is that any other type of concert with the azo moiety. Consequently the dichroism and birefringence induced in the liquid crystalline polymers can be one order of magnitude higher than in the amorphous polymers. At the same time, however, the time required to achieve saturation also increases by at least one order of magnitude.

  12. Tandem solar cells made from amorphous silicon and polymer bulk heterojunction sub-cells.

    PubMed

    Park, Sung Heum; Shin, Insoo; Kim, Kwang Ho; Street, Robert; Roy, Anshuman; Heeger, Alan J

    2015-01-14

    A tandem solar cell based on a combination of an amorphous silicon (a-Si) and polymer solar cell (PSC) is demonstrated. As these tandem devices can be readily fabricated by low-cost methods, they require only a minor increase in the total manufacturing cost. Therefore, a combination of a-Si and PSC provides a compelling solution to reduce the cost of electricity produced by photovoltaics.

  13. Tandem solar cells made from amorphous silicon and polymer bulk heterojunction sub-cells.

    PubMed

    Park, Sung Heum; Shin, Insoo; Kim, Kwang Ho; Street, Robert; Roy, Anshuman; Heeger, Alan J

    2015-01-14

    A tandem solar cell based on a combination of an amorphous silicon (a-Si) and polymer solar cell (PSC) is demonstrated. As these tandem devices can be readily fabricated by low-cost methods, they require only a minor increase in the total manufacturing cost. Therefore, a combination of a-Si and PSC provides a compelling solution to reduce the cost of electricity produced by photovoltaics. PMID:25410395

  14. Amorphous stabilization and dissolution enhancement of amorphous ternary solid dispersions: combination of polymers showing drug-polymer interaction for synergistic effects.

    PubMed

    Prasad, Dev; Chauhan, Harsh; Atef, Eman

    2014-11-01

    The purpose of this study was to understand the combined effect of two polymers showing drug-polymer interactions on amorphous stabilization and dissolution enhancement of indomethacin (IND) in amorphous ternary solid dispersions. The mechanism responsible for the enhanced stability and dissolution of IND in amorphous ternary systems was studied by exploring the miscibility and intermolecular interactions between IND and polymers through thermal and spectroscopic analysis. Eudragit E100 and PVP K90 at low concentrations (2.5%-40%, w/w) were used to prepare amorphous binary and ternary solid dispersions by solvent evaporation. Stability results showed that amorphous ternary solid dispersions have better stability compared with amorphous binary solid dispersions. The dissolution of IND from the ternary dispersion was substantially higher than the binary dispersions as well as amorphous drug. Melting point depression of physical mixtures reveals that the drug was miscible in both the polymers; however, greater miscibility was observed in ternary physical mixtures. The IR analysis confirmed intermolecular interactions between IND and individual polymers. These interactions were found to be intact in ternary systems. These results suggest that the combination of two polymers showing drug-polymer interaction offers synergistic enhancement in amorphous stability and dissolution in ternary solid dispersions.

  15. Superior electric storage on an amorphous perfluorinated polymer surface.

    PubMed

    Fukuhara, Mikio; Kuroda, Tomoyuki; Hasegawa, Fumihiko; Sueyoshi, Takashi

    2016-01-01

    Amorphous perfluoroalkenyl vinyl ether polymer devices can store a remarkably powerful electric charge because their surface contains nanometre-sized cavities that are sensitive to the so-called quantum-size effect. With a work function of approximately 10 eV, the devices show a near-vertical line in the Nyquist diagram and a horizontal line near the -90° phase angle in the Bode diagram. Moreover, they have an integrated effect on the surface area for constant current discharging. This effect can be explained by the distributed constant electric circuit with a parallel assembly of nanometre-sized capacitors on a highly insulating polymer. The device can illuminate a red LED light for 3 ms after charging it with 1 mA at 10 V. Further gains might be attained by integrating polymer sheets with a micro-electro mechanical system. PMID:26902953

  16. Superior electric storage on an amorphous perfluorinated polymer surface

    NASA Astrophysics Data System (ADS)

    Fukuhara, Mikio; Kuroda, Tomoyuki; Hasegawa, Fumihiko; Sueyoshi, Takashi

    2016-02-01

    Amorphous perfluoroalkenyl vinyl ether polymer devices can store a remarkably powerful electric charge because their surface contains nanometre-sized cavities that are sensitive to the so-called quantum-size effect. With a work function of approximately 10 eV, the devices show a near-vertical line in the Nyquist diagram and a horizontal line near the -90° phase angle in the Bode diagram. Moreover, they have an integrated effect on the surface area for constant current discharging. This effect can be explained by the distributed constant electric circuit with a parallel assembly of nanometre-sized capacitors on a highly insulating polymer. The device can illuminate a red LED light for 3 ms after charging it with 1 mA at 10 V. Further gains might be attained by integrating polymer sheets with a micro-electro mechanical system.

  17. Superior electric storage on an amorphous perfluorinated polymer surface

    NASA Astrophysics Data System (ADS)

    Fukuhara, Mikio; Kuroda, Tomoyuki; Hasegawa, Fumihiko; Sueyoshi, Takashi

    2016-02-01

    Amorphous perfluoroalkenyl vinyl ether polymer devices can store a remarkably powerful electric charge because their surface contains nanometre-sized cavities that are sensitive to the so-called quantum-size effect. With a work function of approximately 10 eV, the devices show a near-vertical line in the Nyquist diagram and a horizontal line near the ‑90° phase angle in the Bode diagram. Moreover, they have an integrated effect on the surface area for constant current discharging. This effect can be explained by the distributed constant electric circuit with a parallel assembly of nanometre-sized capacitors on a highly insulating polymer. The device can illuminate a red LED light for 3 ms after charging it with 1 mA at 10 V. Further gains might be attained by integrating polymer sheets with a micro-electro mechanical system.

  18. Superior electric storage on an amorphous perfluorinated polymer surface.

    PubMed

    Fukuhara, Mikio; Kuroda, Tomoyuki; Hasegawa, Fumihiko; Sueyoshi, Takashi

    2016-02-23

    Amorphous perfluoroalkenyl vinyl ether polymer devices can store a remarkably powerful electric charge because their surface contains nanometre-sized cavities that are sensitive to the so-called quantum-size effect. With a work function of approximately 10 eV, the devices show a near-vertical line in the Nyquist diagram and a horizontal line near the -90° phase angle in the Bode diagram. Moreover, they have an integrated effect on the surface area for constant current discharging. This effect can be explained by the distributed constant electric circuit with a parallel assembly of nanometre-sized capacitors on a highly insulating polymer. The device can illuminate a red LED light for 3 ms after charging it with 1 mA at 10 V. Further gains might be attained by integrating polymer sheets with a micro-electro mechanical system.

  19. Superior electric storage on an amorphous perfluorinated polymer surface

    PubMed Central

    Fukuhara, Mikio; Kuroda, Tomoyuki; Hasegawa, Fumihiko; Sueyoshi, Takashi

    2016-01-01

    Amorphous perfluoroalkenyl vinyl ether polymer devices can store a remarkably powerful electric charge because their surface contains nanometre-sized cavities that are sensitive to the so-called quantum-size effect. With a work function of approximately 10 eV, the devices show a near-vertical line in the Nyquist diagram and a horizontal line near the −90° phase angle in the Bode diagram. Moreover, they have an integrated effect on the surface area for constant current discharging. This effect can be explained by the distributed constant electric circuit with a parallel assembly of nanometre-sized capacitors on a highly insulating polymer. The device can illuminate a red LED light for 3 ms after charging it with 1 mA at 10 V. Further gains might be attained by integrating polymer sheets with a micro-electro mechanical system. PMID:26902953

  20. Soft confinement for polymer solutions

    NASA Astrophysics Data System (ADS)

    Oya, Yutaka; Kawakatsu, Toshihiro

    2014-07-01

    As a model of soft confinement for polymers, we investigated equilibrium shapes of a flexible vesicle that contains a phase-separating polymer solution. To simulate such a system, we combined the phase field theory (PFT) for the vesicle and the self-consistent field theory (SCFT) for the polymer solution. We observed a transition from a symmetric prolate shape of the vesicle to an asymmetric pear shape induced by the domain structure of the enclosed polymer solution. Moreover, when a non-zero spontaneous curvature of the vesicle is introduced, a re-entrant transition between the prolate and the dumbbell shapes of the vesicle is observed. This re-entrant transition is explained by considering the competition between the loss of conformational entropy and that of translational entropy of polymer chains due to the confinement by the deformable vesicle. This finding is in accordance with the recent experimental result reported by Terasawa et al. (Proc. Natl. Acad. Sci. U.S.A., 108 (2011) 5249).

  1. Free volume and microscopic dynamics in amorphous polymers

    NASA Astrophysics Data System (ADS)

    Bartoš, J.; Krištiak, J.; Kanaya, T.

    1997-02-01

    The free-volume microstructure in three amorphous polymers cis-1, 4-polybutadiene (PBD), polyisobutylene (PIB) and atactic polypropylene (a-PP) has been studied by positron annihilation spectroscopy via the annihilation characteristics of ortho-positronium, lifetime > 3 and relative intensity I3. Simultaneously, the local chain dynamics has been studied by neutron scattering. The temperature coefficients of hole size below and above Tg are comparable with those of mean-square displacements indicating that the free-volume hole expansion is governed by the microscopic chain mobility. In addition, the relative intensity anomalies in simple polymers (PBD, PIB) are related to the onset of the fast process. This is a structural indicator for the course of fast process.

  2. Impact of polymers on the crystallization and phase transition kinetics of amorphous nifedipine during dissolution in aqueous media.

    PubMed

    Raina, Shweta A; Alonzo, David E; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

    2014-10-01

    The commercial and clinical success of amorphous solid dispersions (ASD) in overcoming the low bioavailability of poorly soluble molecules has generated momentum among pharmaceutical scientists to advance the fundamental understanding of these complex systems. A major limitation of these formulations stems from the propensity of amorphous solids to crystallize upon exposure to aqueous media. This study was specifically focused on developing analytical techniques to evaluate the impact of polymers on the crystallization behavior during dissolution, which is critical in designing effective amorphous formulations. In the study, the crystallization and polymorphic conversions of a model compound, nifedipine, were explored in the absence and presence of polyvinylpyrrolidone (PVP), hydroxypropylmethyl cellulose (HPMC), and HPMC-acetate succinate (HPMC-AS). A combination of analytical approaches including Raman spectroscopy, polarized light microscopy, and chemometric techniques such as multivariate curve resolution (MCR) were used to evaluate the kinetics of crystallization and polymorphic transitions as well as to identify the primary route of crystallization, i.e., whether crystallization took place in the dissolving solid matrix or from the supersaturated solutions generated during dissolution. Pure amorphous nifedipine, when exposed to aqueous media, was found to crystallize rapidly from the amorphous matrix, even when polymers were present in the dissolution medium. Matrix crystallization was avoided when amorphous solid dispersions were prepared, however, crystallization from the solution phase was rapid. MCR was found to be an excellent data processing technique to deconvolute the complex phase transition behavior of nifedipine.

  3. Monolithic amorphous silicon modules on continuous polymer substrate

    SciTech Connect

    Grimmer, D.P. )

    1992-03-01

    This report examines manufacturing monolithic amorphous silicon modules on a continuous polymer substrate. Module production costs can be reduced by increasing module performance, expanding production, and improving and modifying production processes. Material costs can be reduced by developing processes that use a 1-mil polyimide substrate and multilayers of low-cost material for the front encapsulant. Research to speed up a-Si and ZnO deposition rates is needed to improve throughputs. To keep throughput rates compatible with depositions, multibeam fiber optic delivery systems for laser scribing can be used. However, mechanical scribing systems promise even higher throughputs. Tandem cells and production experience can increase device efficiency and stability. Two alternative manufacturing processes are described: (1) wet etching and sheet handling and (2) wet etching and roll-to-roll fabrication.

  4. Free energy of binding of a small molecule to an amorphous polymer in a solvent.

    PubMed

    Chunsrivirot, Surasak; Trout, Bernhardt L

    2011-06-01

    Crystallization is a commonly used purification process in industrial practice. It usually begins with heterogeneous nucleation on a foreign surface. The complicated mechanism of heterogeneous nucleation is not well understood, but we hypothesize that a possible correlation between binding affinity to a surface and nucleation enhancement might exist. Amorphous polymers have been used in controlling crystallization. However, to our knowledge, no attempt has been made to calculate the free energy of binding of a small molecule to an amorphous polymer in a solvent, and to characterize the binding sites/conformations of this system at a molecular level. We developed a two-step approach, first using Adsorption Locator to identify probable binding sites and molecular dynamics to screen for the best binding sites and then using the Blue-Moon Ensemble method to compute the free energy of binding. A system of ethylene glycol, polyvinyl alcohol (PVA), and heavy water (D(2)O) was used for validation, since experimental data exists on a related system. Looking at four independently constructed surfaces, we found that ethylene glycol binds to an indentation on the surface or in a hole beneath the surface. We focused on the indentation binding sites because they are easily accessible and do not have large free energy barriers. The closest system for which experimental data on binding energetics exists is ethylene glycol on PVA in aqueous solutions/gels, and the magnitudes of the free energy of binding to the three best indentation binding sites are close to the experimental value, 0.4-3.7 kcal/mol higher. Our approach offers a way to compute the free energy of binding and characterize the binding sites/conformations, and is general enough to apply to other small molecule/amorphous polymer/solvent systems.

  5. Design of polymer nanocomposites in solution by polymer functionalization

    NASA Astrophysics Data System (ADS)

    Anderson, J. A.; Sknepnek, R.; Travesset, A.

    2010-08-01

    Polymer nanocomposites, materials combining polymers and inorganic components such as nanosized crystallites or nanoparticles have attracted significant attention in recent years. A successful strategy for designing polymer nanocomposites is polymer functionalization via attaching functional groups with specific affinity for the inorganic component. In this paper, a systematic investigation by molecular dynamics of polymer functionalization for design of composites combining nanosize crystallites with multiblock polymers in solution is presented. It is shown that functionalization is an example of active self-assembly, where the resulting polymer nanocomposite exhibits a different type of order than the original pure polymer system (without inorganic components). Optimal polymer architectures and concentrations are identified appropriate for different applications, alongside an in-depth analysis on the origin and stability of the resulting phases as well as its experimental implications.

  6. Temperature memory effect in amorphous shape memory polymers.

    PubMed

    Yu, Kai; Qi, H Jerry

    2014-12-21

    Temperature memory effect (TME) refers to the ability of shape memory polymers (SMPs) to memorize the temperature at which pre-deformation was conducted. In the past few years, this TME was experimentally demonstrated by comparing the applied programming temperature (Td) with a characteristic recovery temperature (Tc), which corresponds to either the maximum recovery stress or free recovery speed. In these well-designed experiments, Tc was observed to be close to Td, which is consistent with the intuitive understanding of 'memorization'. However, since the polymer recovery behavior has been proved to be strongly dependent on various programming and recovery conditions, a new question that whether Tc is always equal to Td in any thermo-temporal conditions remains to be addressed. In this paper, we answered this question by examining the free recovery profile of an acrylate based amorphous SMP. The recovery Tc, which is the temperature with the maximum recovery speed, versus the recovery temperature is shown to be strongly dependent on both programming and recovery conditions. Their detailed influence could be explained by using the reduced time. During a thermomechanical working cycle of SMPs, in addition to the Td, any other thermo-temporal conditions, such as the holding time (th), cooling rate, recovery heating rate (q), etc., can affect the observed Tc by changing the reduced programming or recovery time. In this manner, the relationship between Tc and Td is not uniquely determined. Besides, the TME in SMPs can only be achieved within a given temperature range. Both onset and offset of this temperature range are shown to be influenced by the programming history, but are independent of the recovery conditions.

  7. Ultraflexible polymer solar cells using amorphous zinc-indium-tin oxide transparent electrodes.

    PubMed

    Zhou, Nanjia; Buchholz, Donald B; Zhu, Guang; Yu, Xinge; Lin, Hui; Facchetti, Antonio; Marks, Tobin J; Chang, Robert P H

    2014-02-01

    Polymer solar cells are fabricated on highly conductive, transparent amorphous zinc indium tin oxide (a-ZITO) electrodes. For two representative active layer donor polymers, P3HT and PTB7, the power conversion efficiencies (PCEs) are comparable to reference devices using polycrystalline indium tin oxide (ITO) electrodes. Benefitting from the amorphous character of a-ZITO, the new devices are highly flexible and can be repeatedly bent to a radius of 5 mm without significant PCE reduction. PMID:24123578

  8. Dynamic measurement of stress optical behavior of three amorphous polymers

    NASA Astrophysics Data System (ADS)

    Min, Inki; Yoon, Kyunghwan

    2012-03-01

    In the present study, rheo-optical and mechanical properties of three amorphous polymers, i.e., PS (polystyrene), PC(polycarbonate) and COC(cyclo olefin copolymer), widely used for optical products have been investigated. Accurate measurement of stress optical coefficients and elastic modulus data across the glass transition region are essential for predicting optical anisotropy in many injection molded optical products like pickup lenses and waveguide in LCD module since the final products have both flow and thermal history from the melt to glass. To obtain stress optical behavior in wide range of frequency and temperature including rubbery, glassy and glass transition regime, frequency sweep tests with extensional bar and shear sandwich tools were undertaken. As a result, glassy and melt extreme values of stress optical coefficient of PS and PC were evaluated as well as master plots in wide frequency region. The sign change of stress optical coefficient was shown clearly for PS as the frequency increased. On the other hand, the sign of stress optical coefficient over the whole frequency region is always positive for PC. For COC's of different composition, even though the glass transition temperature can vary, the stress optical coefficient of COC's with different composition stays almost constant at two extremes.

  9. Functionalized polymers for binding to solutes in aqueous solutions

    DOEpatents

    Smith, Barbara F.; Robison, Thomas W.

    2006-11-21

    A functionalized polymer for binding a dissolved molecule in an aqueous solution is presented. The polymer has a backbone polymer to which one or more functional groups are covalently linked. The backbone polymer can be such polymers as polyethylenimine, polyvinylamine, polyallylamine, and polypropylamine. These polymers are generally water-soluble, but can be insoluble when cross-linked. The functional group can be for example diol derivatives, polyol derivatives, thiol and dithiol derivatives, guest-host groups, affinity groups, beta-diphosphonic acids, and beta-diamides

  10. Microcellular foams prepared from demixed polymer solutions

    SciTech Connect

    Aubert, J.H.

    1990-01-01

    Low-density, microcellular polymer foams have numerous applications as structural supports in high-energy physics experiments, in catalysis, ion exchange, and filtration, and for a variety of biomedical uses. A versatile method to prepare such foams is by thermally-induced phase separation (TIPS) of polymer solutions. Demixed solutions can be transformed into a foam by freezing the demixed solution and removing the solvent by freeze-drying. The morphology of these foams is determined by the the thermodynamics and kinetics of phase separation. A model of both the early and late stage structure development for demixed polymer solutions will be presented. For semi-crystalline polymers, gels can be prepared by crystallizing the polymer from solution, either a homogeneous solution or a demixed solution. Foams can be prepared from these gels by the supercritical extraction of the solvent. By understanding and utilizing the phase separation behavior of polymer solutions, engineered microcellular foams can be prepared. To design the foams for any application one must be able to characterize their morphology. Results will be presented on the morphological characterization of these foams and the relationship of the morphology to their processing history. 14 refs., 12 figs.

  11. Drug-polymer-water interaction and its implication for the dissolution performance of amorphous solid dispersions.

    PubMed

    Chen, Yuejie; Liu, Chengyu; Chen, Zhen; Su, Ching; Hageman, Michael; Hussain, Munir; Haskell, Roy; Stefanski, Kevin; Qian, Feng

    2015-02-01

    The in vitro dissolution mechanism of an amorphous solid dispersion (ASD) remains elusive and highly individualized, yet rational design of ASDs with optimal performance and prediction of their in vitro/in vivo performance are very much desirable in the pharmaceutical industry. To this end, we carried out comprehensive investigation of various ASD systems of griseofulvin, felodipine, and ketoconazole, in PVP-VA or HPMC-AS at different drug loading. Physiochemical properties and processes related to drug-polymer-water interaction, including the drug crystallization tendency in aqueous medium, drug-polymer interaction before and after moisture exposure, supersaturation of drug in the presence of polymer, polymer dissolution kinetics, etc., were characterized and correlated with the dissolution performance of ASDs at different dose and different drug/polymer ratio. It was observed that ketoconazole/HPMC-AS ASD outperformed all other ASDs in various dissolution conditions, which was attributed to the drug's low crystallization tendency, the strong ketoconazole/HPMC-AS interaction and the robustness of this interaction against water disruption, the dissolution rate and the availability of HPMC-AS in solution, and the ability of HPMC-AS in maintaining ketoconazole supersaturation. It was demonstrated that all these properties have implications for the dissolution performance of various ASD systems, and further quantification of them could be used as potential predictors for in vitro dissolution of ASDs. For all ASDs investigated, HPMC-AS systems performed better than, or at least comparably with, their PVP-VA counterparts, regardless of the drug loading or dose. This observation cannot be solely attributed to the ability of HPMC-AS in maintaining drug supersaturation. We also conclude that, for fast crystallizers without strong drug-polymer interaction, the only feasible option to improve dissolution might be to lower the dose and the drug loading in the ASD. In this

  12. Effect of Packing on Formation of Deep Carrier Traps in Amorphous Conjugated Polymers.

    PubMed

    Kilina, Svetlana; Dandu, Naveen; Batista, Enrique R; Saxena, Avadh; Martin, Richard L; Smith, Darryl L; Tretiak, Sergei

    2013-05-01

    We theoretically investigate the role of conformational disorder and intermolecular interactions on the localization properties of electronic states, leading to the formation of carrier traps in amorphous aggregates of conjugated polymers. Samples of amorphous conformations of poly(p-phenylene vinylene) (PPV), poly2-methoxy-5-(2-ethyl-hexyloxy)PPV (MEH-PPV), and [poly-(9,9'-dioctyluorene)] (PFO) oligomers are simulated by classical molecular dynamics, while their electronic structure is calculated using first-principles density functional theory. Localization and delocalization properties of molecular orbitals are studied based on the participation ratio analysis, an approach commonly used in inorganic semiconductors. Our simulations confirm that the alkyl side chains insignificantly affect the conformational disorder in amorphous polymers while having a dramatic effect on the intermolecular disorder and packing. The nature of the disorder and its impact on charge-carrier localization in amorphous polymers with alkyl side chains differ drastically from those of disordered polymers without side chains, such as PPVs. Thus, long-range intermolecular interactions and sparse packing are responsible for the formation of multiple, deep, highly localized trap states in amorphous MEH-PPVs and PFOs, while close packing in combination with conformational disorder leads to the trap states distributed mostly near the bandgap edges in PPV aggregates. PMID:26282298

  13. Influence of different polymers on the crystallization tendency of molecularly dispersed amorphous felodipine.

    PubMed

    Konno, Hajime; Taylor, Lynne S

    2006-12-01

    The ability of various polymers to inhibit the crystallization of amorphous felodipine was studied in amorphous molecular dispersions. Spin-coated films of felodipine with poly(vinylpyrrolidone) (PVP), hydroxypropylmethylcellulose acetate succinate (HPMCAS), and hydroxypropylmethylcellulose (HPMC) were prepared and used for measurement of the nucleation rate and to probe drug-polymer intermolecular interactions. Bulk solid dispersions were prepared by a solvent evaporation method and characterized using thermal analysis. It was found that each polymer was able to significantly decrease the nucleation rate of amorphous felodipine even at low concentrations (3-25% w/w). Each polymer was found to affect the nucleation rate to a similar extent at an equivalent weight fraction. For HPMC and HPMCAS, thermal analysis indicated that the glass transition temperature (T(g)) of the solid dispersions were not significantly different from that of felodipine alone, whereas an increase in T(g) was observed for the PVP containing solid dispersions. Infrared spectroscopic studies indicated that hydrogen bonding interactions were formed between felodipine and each of the polymers. These interactions were stronger between felodipine and PVP than for the other polymers. It was speculated that, at the concentrations employed, the polymers reduce the nucleation rate through increasing the kinetic barrier to nucleation.

  14. Photo-oxidation of polymer-like amorphous hydrogenated carbon under visible light illumination

    SciTech Connect

    Baxamusa, Salmaan; Laurence, Ted; Worthington, Matthew; Ehrmann, Paul

    2015-11-10

    Amorphous hydrogenated carbon (a-C:H), a polymer-like network typically synthesized by plasma chemical vapor deposition, has long been understood to exhibit optical absorption of visible light (λ > 400 nm). In this report we explain that this absorption is accompanied by rapid photo-oxidation (within minutes) that behaves in most respects like classic polymer photo-oxidation with the exception that it occurs under visible light illumination rather than ultraviolet illumination.

  15. Swimming of bacteria in polymer solutions

    NASA Astrophysics Data System (ADS)

    Morozov, Alexander; Martinez, Vincent; Schwarz-Linek, Jana; Reufer, Mathias; Wilson, Laurence; Poon, Wilson

    2014-11-01

    The ``standard model'' of bacteria swimming in polymer solutions consists of experimental observations that the swimming speed first increases and then decreases as the function of the polymer concentration. This non-monotonic behaviour is usually explained by either swimming in pores in the polymer solutions or by its viscoelasticity. Using new, high-throughput methods for characterising motility, we have measured the swimming speed and the angular frequency of cell-body rotation of motile Escherichia coli as a function of polymer concentration in polyvinylpyrrolidone (PVP) and Ficoll solutions of different molecular weights. We find that non-monotonic speed-concentration curves are typically due to low-molecular weight impurities and, when cleaned, most molecular weight solutions exhibit Newtonian behaviour. For the highest molecular weight of PVP we observe non-newtonian effects. We present a simple theory that consists of the fast-rotating flagella ``seeing'' a lower viscosity than the cell body but otherwise Newtonian in nature. We show that our theory successfully describes the experimental observations and suggest that flagella can be seen as nano-rheometers for probing the non-newtonian behaviour of high polymer solutions on a molecular scale.

  16. Inhibition of surface crystallisation of amorphous indomethacin particles in physical drug-polymer mixtures.

    PubMed

    Priemel, Petra A; Laitinen, Riikka; Barthold, Sarah; Grohganz, Holger; Lehto, Vesa-Pekka; Rades, Thomas; Strachan, Clare J

    2013-11-18

    Surface coverage may affect the crystallisation behaviour of amorphous materials. This study investigates crystallisation inhibition in powder mixtures of amorphous drug and pharmaceutical excipients. Pure amorphous indomethacin (IMC) powder and physical mixtures thereof with Eudragit(®) E or Soluplus(®) in 3:1, 1:1 and 1:3 (w/w) ratios were stored at 30 °C and 23 or 42% RH. Samples were analysed during storage by X-ray powder diffraction, thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy (SEM). IMC Eudragit(®) mixtures showed higher physical stability than pure IMC whereas IMC Soluplus(®) mixtures did not. Water uptake was higher for mixtures containing Soluplus(®) than for amorphous IMC or IMC Eudragit(®) mixtures. However, the Tg of amorphous IMC was unaffected by the presence (and nature) of polymer. SEM revealed that Eudragit(®) particles aggregated on the surface of IMC particles, whereas Soluplus(®) particles did not. The drug particles developed multiple crystallites at their surface with subsequent crystal growth. The intimate contact between the surface agglomerated Eudragit(®) particles and drug is believed to inhibit crystallisation through reduced IMC surface molecular mobility. Polymer particles may also mechanically hinder crystal growth outwards from the surface. This work highlights the importance of microparticulate surface coverage of amorphous drug particles on their stability.

  17. Power laws in polymer solution dynamics.

    PubMed

    Uematsu, T; Svanberg, C; Nydén, M; Jacobsson, P

    2003-11-01

    The dynamical screening length xi(h) in semidilute to highly concentrated polymer solutions of poly(methyl methacrylate) in propylene carbonate has been examined using photon correlation spectroscopy and pulsed field gradient nuclear magnetic resonance. A crossover between different concentration dependent regimes, xi(h) approximately phi(-alpha), where alpha is found to be approximately 0.5, approximately 1, and approximately 2, is observed when the local viscosity is taken into account. Here phi is the volume fraction of polymer in the solution. Well-defined crossovers between alpha=0.5 and alpha=1 corresponding to a transition from a marginal solvent to a theta solvent behavior have been predicted to occur due to the reduction of excluded-volume effects between the spatially correlated polymer segments with increasing polymer volume fraction. However, a clear experimental validation of the crossover has never been presented before. The third regime (alpha approximately 2) is observed in the highly concentrated region where the static screening length is comparable to the persistence length of the polymer. The observation indicates that the rigid rod model previously used to describe concentrated solutions is an oversimplification valid only in the very high concentration limit. The obtained results at high concentrations are discussed in the frame of a simple physical model where segments at the persistence length scale are treated as flexible rodlike segments. PMID:14682813

  18. Effect of polymers and media type on extending the dissolution of amorphous pioglitazone and inhibiting the recrystallization from a supersaturated state.

    PubMed

    Shi, Nian-Qiu; Yao, Jing; Wang, Xing-Lin

    2014-08-01

    Amorphous forms of crystalline drug are widely utilized for bioavailability enhancement of low solubility drugs in the pharmaceutical industry. Polymers have been found to be effective crystallization inhibitors for amorphous forms in solid states during storage or in liquid states during dissolution process. The dissolution and crystallization behaviors of these amorphous forms in the presence or absence of polymers are still far from adequately understood especially in different dissolution environments. The objective of this study was to investigate the effects of polymers and media type on extending the dissolution of amorphous pioglitazone and inhibiting the recrystallization from a supersaturated state. Polyvinylpyrrolidone K30 (PVPK30), polyvinylpyrrolidone K90 (PVPK90), polyethylene glycol 6000 (PEG6000), polyethylene-polypropylene glycol 188 (F-68), hydroxypropylmethylcellulose (HPMC) and beta-cyclodextrin (β-CD) were employed to understand these behaviors changes because these polymers were used widely. Three solutions including neutral water and phosphate buffer solutions (PBS, pH6.8 and pH7.4) were adopted as dissolution media to determine the behaviors changes comprehensively. In the presence of polymers, dissolution and solubility were extended to different degrees in three media. Polymers can delay the crystallization routes dependently of the medium type. Buffer salts in media reduced the dissolution and accelerated the crystallization process. Crystallization inhibition of these polymers was strongly dependent on the type and pH of media. HPMC displayed the strongest crystallization inhibition effects, resulting in the greatest degree of maintaining a supersaturated state that can sustain most effectively for biologically relevant timeframes.

  19. Effect of polymers and media type on extending the dissolution of amorphous pioglitazone and inhibiting the recrystallization from a supersaturated state.

    PubMed

    Shi, Nian-Qiu; Yao, Jing; Wang, Xing-Lin

    2014-08-01

    Amorphous forms of crystalline drug are widely utilized for bioavailability enhancement of low solubility drugs in the pharmaceutical industry. Polymers have been found to be effective crystallization inhibitors for amorphous forms in solid states during storage or in liquid states during dissolution process. The dissolution and crystallization behaviors of these amorphous forms in the presence or absence of polymers are still far from adequately understood especially in different dissolution environments. The objective of this study was to investigate the effects of polymers and media type on extending the dissolution of amorphous pioglitazone and inhibiting the recrystallization from a supersaturated state. Polyvinylpyrrolidone K30 (PVPK30), polyvinylpyrrolidone K90 (PVPK90), polyethylene glycol 6000 (PEG6000), polyethylene-polypropylene glycol 188 (F-68), hydroxypropylmethylcellulose (HPMC) and beta-cyclodextrin (β-CD) were employed to understand these behaviors changes because these polymers were used widely. Three solutions including neutral water and phosphate buffer solutions (PBS, pH6.8 and pH7.4) were adopted as dissolution media to determine the behaviors changes comprehensively. In the presence of polymers, dissolution and solubility were extended to different degrees in three media. Polymers can delay the crystallization routes dependently of the medium type. Buffer salts in media reduced the dissolution and accelerated the crystallization process. Crystallization inhibition of these polymers was strongly dependent on the type and pH of media. HPMC displayed the strongest crystallization inhibition effects, resulting in the greatest degree of maintaining a supersaturated state that can sustain most effectively for biologically relevant timeframes. PMID:23808528

  20. Photodeposition of amorphous polydiacetylene films from monomer solutions onto transparent substrates

    NASA Technical Reports Server (NTRS)

    Paley, M. S.; Frazier, D. O.; Abdeldeyem, H.; Armstrong, S.; McManus, S. P.

    1995-01-01

    Polydiacetylenes are a very promising class of polymers for both photonic and electronic applications because of their highly conjugated structures. For these applications, high-quality thin polydiacetylene films are required. We have discovered a novel technique for obtaining such films of a polydiacetylene derivative of 2-methyl-4-nitroaniline using photodeposition from monomer solutions onto UV transparent substrates. This heretofore unreported process yields amorphous polydiacetylene films with thicknesses on the order of I micron that have optical quality superior to that of films grown by standard crystal growth techniques. Furthermore, these films exhibit good third-order nonlinear optical susceptibilities; degenerate four-wave mixing experiments give x(3) values on the order of 10(exp -8) - 10(exp -7) esu. We have conducted masking experiments which demonstrate that photodeposition occurs only where the substrate is directly irradiated, clearly indicating that the reaction occurs at the surface. Additionally, we have also been able to carry out photodeposition using lasers to form thin polymer circuits. In this work, we discuss the photodeposition of polydiacetylene thin films from solution, perform chemical characterization of these films, investigate the role of the substrate, speculate on the mechanism of the reaction, and make a preliminary determination of the third-order optical nonlinearity of the films. This simple, straightforward technique may ultimately make feasible the production of polydiacetylene thin films for technological applications.

  1. Adjustable flow rate controller for polymer solutions

    DOEpatents

    Jackson, Kenneth M.

    1981-01-01

    An adjustable device for controlling the flow rate of polymer solutions which results in only little shearing of the polymer molecules, said device comprising an inlet manifold, an outlet manifold, a plurality of tubes capable of providing communication between said inlet and outlet manifolds, said tubes each having an internal diameter that is smaller than that of the inlet manifold and large enough to insure that viscosity of the polymer solution passing through each said tube will not be reduced more than about 25 percent, and a valve associated with each tube, said valve being capable of opening or closing communication in that tube between the inlet and outlet manifolds, each said valve when fully open having a diameter that is substantially at least as great as that of the tube with which it is associated.

  2. A Polymer "Pollution Solution" Classroom Activity.

    ERIC Educational Resources Information Center

    Helser, Terry L.

    1996-01-01

    Explains an approach to presenting polymer chemistry to nonmajors that employs polystyrene foam, foam peanuts made from water soluble starch, and water soluble plastic bags. Students are presented with a pollution scenario and are guided to the discovery of solutions. (DDR)

  3. Role of amorphous and aggregate phases on field-induced exciton dissociation in a conjugated polymer

    NASA Astrophysics Data System (ADS)

    Mróz, Marta M.; Lüer, Larry; Houarner-Rassin, Coralie; Anderson, Harry L.; Cabanillas-Gonzalez, Juan

    2013-01-01

    We have applied electric field assisted pump-probe spectroscopy in order to unravel the interplay of amorphous and aggregate phases on the polaron-pair photogeneration process in a conjugated porphyrin polymer. We find that excitons photogenerated in both phases are precursors for polaron pairs with different yields. Kinetic modeling indicates a substantially larger barrier for exciton dissociation in aggregates compared to amorphous areas. The majority of polaron pairs are however formed in aggregate phases due to efficient energy transfer from the amorphous phase. Based on the change in the Stark shift associated with the photogenerated polaron density, we provide a picture of the motion of polaron pairs under the external electric field.

  4. Highly Efficient Hybrid Polymer and Amorphous Silicon Multijunction Solar Cells with Effective Optical Management.

    PubMed

    Tan, Hairen; Furlan, Alice; Li, Weiwei; Arapov, Kirill; Santbergen, Rudi; Wienk, Martijn M; Zeman, Miro; Smets, Arno H M; Janssen, René A J

    2016-03-16

    Highly efficient hybrid multijunction solar cells are constructed with a wide-bandgap amorphous silicon for the front subcell and a low-bandgap polymer for the back subcell. Power conversion efficiencies of 11.6% and 13.2% are achieved in tandem and triple-junction configurations, respectively. The high efficiencies are enabled by deploying effective optical management and by using photoactive materials with complementary absorption. PMID:26780260

  5. Reduced Crystallization Temperature Methodology for Polymer Selection in Amorphous Solid Dispersions: Stability Perspective.

    PubMed

    Bhugra, Chandan; Telang, Chitra; Schwabe, Robert; Zhong, Li

    2016-09-01

    API-polymer interactions, used to select the right polymeric matrix with an aim to stabilize an amorphous dispersion, are routinely studied using spectroscopic and/or calorimetric techniques (i.e., melting point depression). An alternate selection tool has been explored to rank order polymers for formation of stable amorphous dispersions as a pragmatic method for polymer selection. Reduced crystallization temperature of API, a parameter introduced by Zhou et al.,1 was utilized in this study for rank ordering interactions in API-polymeric systems. The trends in reduced crystallization temperature monitored over polymer concentration range of up to 20% polymer loading were utilized to calculate "crystallization parameter" or CP for two model systems (nifedipine and BI ABC). The rank order of CP, i.e., a measure of API-polymer interaction, for nifedipine followed the order PVP > PVP-VA > Soluplus > HPMCAS > PV Ac > PAA. This rank ordering was correlated to published results of molecular interactions and physical stability for nifedipine. A different rank ordering was observed for BI ABC: PAA > PVP > HPMCAS > Soluplus > PVPV-VA > PVAc. Interactions for BI ABC were not as differentiated when compared to nifedipine based on CP trends. BI ABC dispersions at drug loadings between 40 and 60% were physically stable for prolonged periods under ICH conditions as well as accelerated stress. We propose that large CP differences among polymers could be predictive of stability outcomes. Acceptable stability at pharmaceutically relevant drug loadings would suggest that the relative influence of downstream processes, such as polymer solubility in various solvents, process suitability and selection, and more importantly supersaturation potential, should be higher compared to stability considerations while developing compounds like BI ABC. PMID:27414755

  6. Light-emitting nanocomposites and novel amorphous polymers for optical applications

    NASA Astrophysics Data System (ADS)

    Gipson, Kyle Garrod

    Polymeric optical materials generally are comprised of amorphous polymers that are transparent in at visible wavelengths but exhibit strong absorption bands in the near-infrared making them less useful for many optical applications. Attenuation, which is the absorption per unit length, largely results from the high vibrational energy associated with carbon-hydrogen bonds contained in the polymer backbone. Attenuation can be mitigated by optical amplification utilizing light emitting additives. Investigated in this dissertation are synthesis techniques for the fabrication of light-emitting polymer nanocomposites and their resultant thermal and rheological characteristics for potential use as polymer optical fibers or films. Inorganic nanocrystals doped with optically active rare-earth ions (Tb 3+:LaF3) treated with organic ligands were synthesized in water and methanol in order to produce polymethyl methacrylate (PMMA) light-emitting nanocomposites. Two different aromatic ligands (acetylsalicylic acid, ASA and 2-picolinic acid, PA) were employed to functionalize the surface of Tb 3+:LaF3 nanocrystals. We have used infrared spectroscopy, thermal analysis, elemental analysis, dynamic light scattering, rheological measurements and optical spectroscopy to investigate the nanoparticle structure and composition response of ligand-capped nanocrystals under various synthesis parameters. A theoretical interpretation of particle-to-particle interactions also was conducted which supported our study of the potential of agglomeration within the nanoparticle suspensions. Novel amorphous polymers (e.g. perfluorocyclobutyl aryl ethers, PFCB), which do not exhibit strong C-H vibrations, have been reported to possess excellent optical properties. Little is known of the intrinsic properties of PFCBs (e.g. biphenylvinyl ether, BPVE and hexafluoroisopropylidene vinyl ether, 6F) as well as the behavior of the polymer melt during extrusion. We preformed empirical and experimental thermal

  7. Symposium Report. Battery materials : amorphous carbons and polymer electrolytes.

    SciTech Connect

    Gerald, R. E., II; Chemical Engineering

    2000-01-01

    The motivation for research in battery materials lies in the expanding consumer demand for compact, high-energy density power sources for portable electronic devices, and environmental issues such as global warming and air pollution that have provided the impetus for mass transportation by electric vehicles. The Battery Materials Symposium, chaired by Jacqueline Johnson (ANL), focused on three topics: the structure and electrochemical properties of new and existing electrolytes, devices for fabricating and investigating thin films, and large-scale computer simulations. The symposium opened with a presentation by the author on a recently invented device for in situ investigations of batteries using nuclear magnetic resonance. Joop Schoonman (Delft University) described several methods for preparing and analyzing thin films made of solid electrolytes. These methods included chemical vapor deposition, electrostatic spray deposition and the Solufill process. Aiichiro Nakano discussed large-scale (10 million to 2 billion atoms) computer simulations of polymer and ceramic systems. An overview was given of a DOE Cooperative Research 2000 program, in the initial stages, that was set up to pursue these atomistic simulations. Doug MacFarlane (Monash University) described conductive plastic crystals based on pyrrolidinium imides. Joseph Pluth (U of Chicago) presented his recent crystallographic studies of Pb compounds found in the ubiquitous lead-acid battery. He showed the structures of tribasic lead sulfate and tetrabasic lead sulfate. Austen Angell (Arizona State Univ.) discussed the general problem of electrolyte polarization in Li-ion battery systems with cation transference numbers less than unity. Steven Greenbaum (Hunter College) provided an introduction of NMR interactions that are useful for investigations of lithium-ion battery materials. Analysis by NMR is nuclear specific, probes local environments and dynamics, and is non-destructive. He discussed {sup 7}Li NMR

  8. Configuration diffusion in glassy, amorphous polymers: Effects of polymer structure and dynamics on permeation via molecular simulation

    NASA Astrophysics Data System (ADS)

    Boshoff, Jan H. D.

    The goals of this dissertation are to provide a basis for understanding the fundamental mechanisms of, and the effects of nano-confinement on, diffusion in glassy, amorphous polymers. These polymers are extensively used as membranes in numerous separation applications such as drug delivery devices, air separation and water desalination. Molecular simulation is used to elucidate the effects of the structure and dynamics of glassy polymers on small molecule permeation. Particularly, the effects of thermal fluctuations on the diffusion mechanism and anomalous diffusion regime is shown for small gas diffusion in atactic polypropylene. Furthermore, polymer backbone conformational statistics of three different polypropylene models show that the united atom approximation favors gauche conformations in the polymer backbone, leading to artificially high values for Cinfinity for stereo-regular polypropylene. Diffusion results of He and CH4 in the refined model is presented using a force-decomposed/replicated data parallel molecular dynamics algorithm on a pseudo-explicit atom model proposed in literature. Excellent agreement with experimental values of the diffusivity is obtained. These results constitute the most accurate a priori prediction of small molecule diffusion in atactic polypropylene to date. Finally, the effects of nano-confinement on the polymer structure and dynamics, and consequently the permeation and selectivity was probed by He and CH4 permeation in aPP "adsorbed" in idealized pores of size smaller than the radius of gyration of the polymer. The extent of polymer structural changes is found to be closely correlated with the local correlation length xi of the polymer. Within xi from the pore surface, the polymer has a lower density, aligns with the pore direction and is found to pack in layers, while the polymer structure is identical to the bulk further than xi from the pore surface. These changes in polymer structure lead to substantial increases (up to

  9. Embrittlement of Metal by Solute Segregation-Induced Amorphization

    SciTech Connect

    Chen, H.-P.; Kalia, Rajiv K.; Nakano, Aiichiro; Nomura, Ken-ichi; Vashishta, Priya; Yuan, Zaoshi; Kaxiras, Efthimios; Lu, Gang; Duin, Adri C. T. van

    2010-04-16

    Impurities segregated to grain boundaries of a material essentially alter its fracture behavior. A prime example is sulfur segregation-induced embrittlement of nickel, where an observed relation between sulfur-induced amorphization of grain boundaries and embrittlement remains unexplained. Here, 48x10{sup 6}-atom reactive-force-field molecular dynamics simulations provide the missing link. Namely, an order-of-magnitude reduction of grain-boundary shear strength due to amorphization, combined with tensile-strength reduction, allows the crack tip to always find an easy propagation path.

  10. Evaluation of the amorphous content of lactose by solution calorimetry and Raman spectroscopy.

    PubMed

    Katainen, Erja; Niemelä, Pentti; Harjunen, Päivi; Suhonen, Janne; Järvinen, Kristiina

    2005-11-15

    Solution calorimetry can be used to determine the amorphous content of a compound when the solubility and dissolution rate of the compound in the chosen solvent are reasonably high. Sometimes, it can be difficult find a solvent in which a sample is freely soluble. The present study evaluated the use of solution calorimetry for the assessment of the amorphous content of a sample that is poorly soluble in a solvent. Physical mixtures of lactose and spray-dried lactose samples (the amorphous content varied from 0 to 100%) were analyzed by a solution calorimeter and the results were compared with Raman spectroscopy determinations. The heat of solvation of the samples was determined by solution calorimetry in organic solvents MeOH, EtOH, ACN, THF, acetone (400mg sample/100ml solvent). Lactose is virtually insoluble in ACN, THF and acetone and very slightly soluble in EtOH and MeOH. The amorphous content of the samples could not be determined by solution calorimetry in EtOH, ACN, THF or acetone. However, an excellent correlation was observed between the heat of solvation and the amorphous content of the samples in MeOH. Furthermore, the heat of solvation values of the samples in MeOH showed a linear correlation with the Raman quantifications. Therefore, our results demonstrate that solution calorimetry may represent a rapid and simple method for determining the amorphous content also in samples that are not freely soluble in the solvent. PMID:18970276

  11. Role of Chain Morphology and Stiffness in Thermal Conductivity of Amorphous Polymers.

    PubMed

    Zhang, Teng; Luo, Tengfei

    2016-02-01

    Designing thermally conductive polymer is of scientific interest and practical importance for applications like thermal interface materials, electronics packing, and plastic heat exchangers. In this work, we study the fundamental relationship between the molecular morphology and thermal conductivity in bulk amorphous polymers. We use polyethylene as a model system and performed systematic parametric study in molecular dynamics simulations. We find that the thermal conductivity is a strong function of the radius of gyration of the molecular chains, which is further correlated to persistence length, an intrinsic property of the molecule that characterizes molecular stiffness. Larger persistence length can lead to more extended chain morphology and thus higher thermal conductivity. Further thermal conductivity decomposition analysis shows that thermal transport through covalent bonds dominates the effective thermal conductivity over other contributions from nonbonded interactions (van der Waals) and translation of molecules disregarding the morphology. As a result, the more extended chains due to larger persistence length provide longer spatial paths for heat to transfer efficiently and thus lead to higher thermal conductivity. In addition, rigid rod-like polymers with very large persistence length tend to spontaneously crystallize and form orientated chains, leading to a thermal conductivity increase by more than 1 order of magnitude. Our results will provide important insights into the design of thermally conductive amorphous polymers. PMID:26751002

  12. Role of Chain Morphology and Stiffness in Thermal Conductivity of Amorphous Polymers.

    PubMed

    Zhang, Teng; Luo, Tengfei

    2016-02-01

    Designing thermally conductive polymer is of scientific interest and practical importance for applications like thermal interface materials, electronics packing, and plastic heat exchangers. In this work, we study the fundamental relationship between the molecular morphology and thermal conductivity in bulk amorphous polymers. We use polyethylene as a model system and performed systematic parametric study in molecular dynamics simulations. We find that the thermal conductivity is a strong function of the radius of gyration of the molecular chains, which is further correlated to persistence length, an intrinsic property of the molecule that characterizes molecular stiffness. Larger persistence length can lead to more extended chain morphology and thus higher thermal conductivity. Further thermal conductivity decomposition analysis shows that thermal transport through covalent bonds dominates the effective thermal conductivity over other contributions from nonbonded interactions (van der Waals) and translation of molecules disregarding the morphology. As a result, the more extended chains due to larger persistence length provide longer spatial paths for heat to transfer efficiently and thus lead to higher thermal conductivity. In addition, rigid rod-like polymers with very large persistence length tend to spontaneously crystallize and form orientated chains, leading to a thermal conductivity increase by more than 1 order of magnitude. Our results will provide important insights into the design of thermally conductive amorphous polymers.

  13. Polymer solution phase separation: Microgravity simulation

    NASA Technical Reports Server (NTRS)

    Cerny, Lawrence C.; Sutter, James K.

    1989-01-01

    In many multicomponent systems, a transition from a single phase of uniform composition to a multiphase state with separated regions of different composition can be induced by changes in temperature and shear. The density difference between the phase and thermal and/or shear gradients within the system results in buoyancy driven convection. These differences affect kinetics of the phase separation if the system has a sufficiently low viscosity. This investigation presents more preliminary developments of a theoretical model in order to describe effects of the buoyancy driven convection in phase separation kinetics. Polymer solutions were employed as model systems because of the ease with which density differences can be systematically varied and because of the importance of phase separation in the processing and properties of polymeric materials. The results indicate that the kinetics of the phase separation can be performed viscometrically using laser light scattering as a principle means of following the process quantitatively. Isopycnic polymer solutions were used to determine the viscosity and density difference limits for polymer phase separation.

  14. Irreversible adsorption from concentrated polymer solutions

    NASA Astrophysics Data System (ADS)

    Auvray, Loïc; Cruz, Margerida; Auroy, Philippe

    1992-05-01

    We study the adsorption of concentrated Poly(dimethylsiloxane) (PDMS) solutions in Dichloromethane on porous silica. We vary the plymerization index N and the chain volume fraction Φ from the overlap concentration to the melt. The adsorption of PDMS on silica by hydrogen bonding is very strong and a large amount of polymer remains bound to the surface after the washing of the silica with a good solvent of the chains. We measure this quantity Γ by small angle neutron scattering. If there is no chain desorption, Γ represents the weight of polymer attached to the solid in the initial solution, which varies as the product N^{1/2} Φ^{7/8} according to a recent prediction. This relation of proportionality indeed interprets our experimental results. When the size of the chains is comparable to the pore diameter (either 500, 1 200, or 3 000 Å depending on the samples) we observe confinement effects which lower the adsorbed amount. Nous étudions d'adsorption de solutions concentrées de Poly(dimethylsiloxane) (PDMS) dans le chlorure de méthylène sur de la silice poreuse. Nous varions le degré de polymérisation N et la fraction volumique Φ des chaînes depuis la concentration de recouvrement jusqu'au fondu. L'adsorption de PDMS sur la silice par liaison hydrogène est très forte et une grande quantité de polymère reste liée à la surface après lavage de la silice par du bon solvant. Nous mesurons cette quantité Γ par diffusion centrale des neutrons. S'il n'y a pas eu désorption des chaînes, Γ représente le poids de polymère attaché au solide dans la solution initiale qui varie selon une prédiction récente comme le produit N^{1/2} Φ^{7/8}. Cette relation de proportionnalité rend effectivement compte de nos résultats. Quand la taille des chaînes est du même ordre de grandeur que le diamètre des pores (qui prend les valeurs 500, 1 200 et 3 000 Å selon les échantillons), nous observons des effets de confinement abaissant la quantité adsorbée.

  15. Structuring of polymer solutions upon solvent evaporation

    NASA Astrophysics Data System (ADS)

    Schaefer, C.; van der Schoot, P.; Michels, J. J.

    2015-02-01

    The morphology of solution-cast, phase-separated polymers becomes finer with increasing solvent evaporation rate. We address this observation theoretically for a model polymer where demixing is induced by steady solvent evaporation. In contrast to what is the case for a classical, thermal quench involving immiscible blends, the spinodal instability initially develops slowly and the associated length scale is not time invariant but decreases with time as t-1 /2. After a time lag, phase separation accelerates. Time lag and characteristic length exhibit power-law behavior as a function of the evaporation rate with exponents of -2 /3 and -1 /6 . Interestingly, at later stages the spinodal structure disappears completely while a second length scale develops. The associated structure coarsens but does not follow the usual Lifshitz-Slyozov-Wagner kinetics.

  16. Molecular Dynamics and Physical Stability of Amorphous Nimesulide Drug and Its Binary Drug-Polymer Systems.

    PubMed

    Knapik, J; Wojnarowska, Z; Grzybowska, K; Tajber, L; Mesallati, H; Paluch, K J; Paluch, M

    2016-06-01

    In this article we study the effectiveness of three well-known polymers: inulin, Soluplus, and PVP in stabilizing the amorphous form of nimesulide (NMS) drug. The recrystallization tendency of pure drug as well as measured drug-polymer systems were examined at isothermal conditions by broadband dielectric spectroscopy (BDS) and at nonisothermal conditions by differential scanning calorimetry (DSC). Our investigation has shown that the crystallization half-life time of pure NMS at 328 K is equal to 33 min. We found that this time can be prolonged to 40 years after adding 20% w/w PVP to NMS. This polymer proved to be the best NMS stabilizer, while the worst stabilization effect was exhibited by inulin. Additionally, our DSC, BDS, and FTIR studies indicate that for suppression of NMS recrystallization in the NMS-PVP system, the two mechanisms are responsible: the polymeric steric hindrances and the antiplastization effect exerted by the excipient. PMID:27149568

  17. Formation, Structure and Properties of Amorphous Carbon Char from Polymer Materials in Extreme Atmospheric Reentry Environments

    NASA Technical Reports Server (NTRS)

    Lawson, John W.

    2010-01-01

    Amorphous carbonaceous char produced from the pyrolysis of polymer solids has many desirable properties for ablative heat shields for space vehicles. Molecular dynamics simulations are presented to study the transformation of the local atomic structure from virgin polymer to a dense, disordered char [1]. Release of polymer hydrogen is found to be critical to allow the system to collapse into a highly coordinated char structure. Mechanisms of the char formation process and the morphology of the resulting structures are elucidated. Thermal conductivity and mechanical response of the resulting char are evaluated [2]. During reenty, the optical response and oxidative reactivity of char are also important properties. Results of ab initio computations of char optical functions [3] and char reactivity [4] are also presented.

  18. Solution-processed amorphous silicon surface passivation layers

    SciTech Connect

    Mews, Mathias Sontheimer, Tobias; Korte, Lars; Rech, Bernd; Mader, Christoph; Traut, Stephan; Wunnicke, Odo

    2014-09-22

    Amorphous silicon thin films, fabricated by thermal conversion of neopentasilane, were used to passivate crystalline silicon surfaces. The conversion is investigated using X-ray and constant-final-state-yield photoelectron spectroscopy, and minority charge carrier lifetime spectroscopy. Liquid processed amorphous silicon exhibits high Urbach energies from 90 to 120 meV and 200 meV lower optical band gaps than material prepared by plasma enhanced chemical vapor deposition. Applying a hydrogen plasma treatment, a minority charge carrier lifetime of 1.37 ms at an injection level of 10{sup 15}/cm{sup 3} enabling an implied open circuit voltage of 724 mV was achieved, demonstrating excellent silicon surface passivation.

  19. Pressure-induced amorphization of a dense coordination polymer and its impact on proton conductivity

    SciTech Connect

    Umeyama, Daiki; Hagi, Keisuke; Ogiwara, Naoki; Horike, Satoshi E-mail: kitagawa@icems.kyoto-u.ac.jp; Tassel, Cedric; Kageyama, Hiroshi; Higo, Yuji; Kitagawa, Susumu E-mail: kitagawa@icems.kyoto-u.ac.jp

    2014-12-01

    The proton conductivity of a dense coordination polymer (CP) was investigated under high-pressure conditions. Impedance measurements under high pressures revealed that the proton conductivity of the CP decreased more than 1000-fold at pressures of 3–7 GPa and that the activation energy for proton conduction almost doubled compared with that at ambient pressure. A synchrotron X-ray study under high pressure identified the amorphization process of the CP during compression, which rationally explains the decrease in conductivity and increase in activation energy. This phenomenon is categorized as reversible pressure-induced amorphization of a dense CP and is regarded as a demonstration of the coupling of the mechanical and electrical properties of a CP.

  20. Solution-state polymer assemblies influence BCS class II drug dissolution and supersaturation maintenance.

    PubMed

    Dalsin, Molly C; Tale, Swapnil; Reineke, Theresa M

    2014-02-10

    Spray dried dispersions (SDDs), solid dispersions of polymer excipients and active pharmaceuticals, are important to the field of oral drug delivery for improving active stability, bioavailability, and efficacy. Herein, we examine the influence of solution-state polymer assemblies on amorphous spray-dried dispersion (SDD) performance with two BCS II model drugs, phenytoin and probucol. These drugs were spray dried with 4 model polymer excipients consisting of poly(ethylene-alt-propylene) (PEP), N,N,-dimethylacrylamide (DMA), or 2-methacrylamido glucopyranose (MAG): amphiphilic diblock ter- and copolymers, PEP-P(DMA-grad-MAG) and PEP-PDMA, and their respective hydrophilic analogues, P(DMA-grad-MAG) and PDMA. Selective and nonselective solvents for the hydrophilic block of the diblock ter- and copolymers were used to induce or repress solution-state assemblies prior to spray drying. Prespray dried solution-state assemblies of these four polymers were probed with dynamic light scattering (DLS) and showed differences in solution assembly size and structure (free polymer versus aggregates versus micelles). Solid-state structures of spray dried dispersions (SDDs) showed a single glass transition event implying a homogeneous mixture of drug/polymer. Crystallization temperatures and enthalpies indicated that the drugs interact mostly with the DMA-containing portions of the polymers. Scanning electron microscopy was used to determine SDD particle size and morphology for the various polymer-drug pairings. In vitro dissolution tests showed excellent performance for one system, spray-dried PEP-PDMA micelles with probucol. Dissolution structures were investigated through DLS to determine drug-polymer aggregates that lead to enhanced SDD performance. Forced aggregation of the polymer into regular micelle structures was found to be a critical factor to increase the dissolution rate and supersaturation maintenance of SDDs, and may be an attractive platform to exploit in excipient

  1. Tungsten solution kinetics and amorphization of nickel in mechanically alloyed Ni-W alloys

    NASA Technical Reports Server (NTRS)

    Aning, A. O.; Wang, Z.; Courtney, T. H.

    1993-01-01

    The kinetics of solution of W, and the subsequent amorphization of Ni, in mechanically alloyed Ni-W alloys has been investigated. As W is a highly abrasive material in the energy intensive devices used for mechanical alloying, we studied the above reactions in different mills. One used hardened steel balls as the grinding media, and the other Al2O3. Abrasion is common to both mills, but Fe wear debris from the hardened steel enters into solution in the Ni rich phases whereas Al2O3 debris is present as small dispersoids. The kinetics of W solution and those of subsequent amorphization do not appear strongly affected by the Fe in solution or the Al2O3 dispersoid. Tungsten dissolves in crystalline Ni in amounts in excess of the equilibrium solubility during alloying. Amorphization of the Ni phase occurs if the W content in this phase exceeds ca. 28 at. pct.

  2. Charge transport in amorphous low bandgap conjugated polymer/fullerene films

    NASA Astrophysics Data System (ADS)

    Kim, Jung Yong; Cho, Hyunduck; Noh, Seunguk; Lee, Yoonkyoo; Nam, Young Min; Lee, Changhee; Jo, Won Ho

    2012-02-01

    The structural and charge transport properties of a low bandgap copolymer poly(3-hexylthiophene -alt-6,7-dimethyl-4,9-bis-(4-hexylthien-2yl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline) (P(3HT-MeTDQ)) and its blend with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) are investigated. Thermal analysis, X-ray scattering diffraction (XRD), atomic force microscopy and transmission electron microscopy (TEM) of P(3HT-MeTDQ) reveal that the polymer is amorphous in solid state. As the hole mobility of P(3HT-MeTDQ) was measured by the time-of-flight photoconductivity method, the mobility was 3.35 × 10-4 cm2/V s, which is very comparable to that of semicrystalline poly(3-hexyl thiophene). When the mobility of amorphous P(3HT-MeTDQ) was analyzed according to the Gaussian disorder model, the polymer has the energetic and positional disorders with the values of σ = 62 meV and Σ = 1.7, respectively, indicating that the polymer has a relatively narrow Gaussian distribution of transport states. Interestingly, when P(3HT-MeTDQ) is blended with PCBM, the amorphous P(3HT-MeTDQ) becomes partially ordered, as evidenced by observation of two discernible XRD peaks at 2θ = 5° (d = 17.7 Å) and 25.5° (d = 3.5 Å) corresponding to the interchain distance and π-stacking distance, respectively. The bicontinuous network morphology was identified at the blend with 60 wt. % PCBM by TEM, at which the charge carrier transport changes from hole-only to ambipolar.

  3. Entropic attractions in colloid-polymer solutions

    NASA Astrophysics Data System (ADS)

    Verma, Ritu

    We explore the depletion attractions that arise between hard colloidal spheres immersed in a non-adsorbing polymeric solution of DNA molecules. Using a scanning optical tweezer we were able to spatially confine colloidal particles along a line and quantitatively examine the interaction potential between two 1.25 m m silica spheres moving in various complex fluids. At fixed DNA concentration, we found that the range and depth of the inter-particle potentials did not change for background salt concentrations between 0.1 and 20 mM. Then we fixed the background salt concentration at 10 mM, and measured the inter-particle potentials as a function of DNA concentration. The potentials obtained display variations in depth and range that are consistent with scaling behavior expected for semi-flexible polymers near the theta point. In particular we clearly observe the crossover from a dilute solution of Gaussian coils to the weakly fluctuating semi-dilute regime dominated by two-point collisions. We also quantitatively test the Asakura-Oosawa Model for these systems and show how it can be used in both the dilute as well as the semi-dilute regime. We also explore the dynamics of colloidal particles in background DNA solutions. We find that the Stokes-Einstein picture breaks down in these complex fluids as the size ratio of the probe particle to the characteristic polymer length scale is decreased. We explain these deviations in terms of the changes in the microenvironment caused by the presence of the depletion cavity. The colloidal spheres were also used to probe the transition time scales from the viscoelastic regime to the purely viscous regime.

  4. Experimental and modelling studies of the shape memory properties of amorphous polymer network composites

    NASA Astrophysics Data System (ADS)

    Arrieta, J. S.; Diani, J.; Gilormini, P.

    2014-09-01

    Shape memory polymer composites (SMPCs) have become an important way to leverage improvements in the development of applications featuring shape memory polymers (SMPs). In this study, an amorphous SMP matrix has been filled with different types of reinforcements. An experimental set of results is presented and then compared to three-dimensional (3D) finite-element simulations. Thermomechanical shape memory cycles were performed in uniaxial tension. The fillers effect was studied in stress-free and constrained-strain recoveries. Experimental observations indicate complete shape recovery and put in evidence the increased sensitivity of constrained length stress recoveries to the heating ramp on the tested composites. The simulations reproduced a simplified periodic reinforced composite and used a model for the matrix material that has been previously tested on regular SMPs. The latter combines viscoelasticity at finite strain and time-temperature superposition. The simulations easily allow representation of the recovery properties of a reinforced SMP.

  5. Polarization holograms in a bifunctional amorphous polymer exhibiting equal values of photoinduced linear and circular birefringences.

    PubMed

    Provenzano, Clementina; Pagliusi, Pasquale; Cipparrone, Gabriella; Royes, Jorge; Piñol, Milagros; Oriol, Luis

    2014-10-01

    Light-controlled molecular alignment is a flexible and useful strategy introducing novelty in the fields of mechanics, self-organized structuring, mass transport, optics, and photonics and addressing the development of smart optical devices. Azobenzene-containing polymers are well-known photocontrollable materials with large and reversible photoinduced optical anisotropies. The vectorial holography applied to these materials enables peculiar optical devices whose properties strongly depend on the relative values of the photoinduced birefringences. Here is reported a polarization holographic recording based on the interference of two waves with orthogonal linear polarization on a bifunctional amorphous polymer that, exceptionally, exhibits equal values of linear and circular birefringence. The peculiar photoresponse of the material coupled with the holographic technique demonstrates an optical device capable of decomposing the light into a set of orthogonally polarized linear components. The holographic structures are theoretically described by the Jones matrices method and experimentally investigated. PMID:25187982

  6. A bifunctional amorphous polymer exhibiting equal linear and circular photoinduced birefringences.

    PubMed

    Royes, Jorge; Provenzano, Clementina; Pagliusi, Pasquale; Tejedor, Rosa M; Piñol, Milagros; Oriol, Luis

    2014-11-01

    The large and reversible photoinduced linear and circular birefringences in azo-compounds are at the basis of the interest in these materials, which are potentially useful for several applications. Since the onset of the linear and circular anisotropies relies on orientational processes, which typically occur on the molecular and supramolecular length scale, respectively, a circular birefringence at least one order of magnitude lower than the linear one is usually observed. Here, the synthesis and characterization of an amorphous polymer with a dimeric repeating unit containing a cyanoazobenzene and a cyanobiphenyl moiety are reported, in which identical optical linear and circular birefringences are induced for proper light dose and ellipticity. A pump-probe technique and an analytical method based on the Stokes-Mueller formalism are used to investigate the photoinduced effects and to evaluate the anisotropies. The peculiar photoresponse of the polymer makes it a good candidate for applications in smart functional devices. PMID:25257542

  7. Constitutive modeling of large inelastic deformation of amorphous polymers: Free volume and shear transformation zone dynamics

    NASA Astrophysics Data System (ADS)

    Voyiadjis, George Z.; Samadi-Dooki, Aref

    2016-06-01

    Due to the lack of the long-range order in their molecular structure, amorphous polymers possess a considerable free volume content in their inter-molecular space. During finite deformation, these free volume holes serve as the potential sites for localized permanent plastic deformation inclusions which are called shear transformation zones (STZs). While the free volume content has been experimentally shown to increase during the course of plastic straining in glassy polymers, thermal analysis of stored energy due to the deformation shows that the STZ nucleation energy decreases at large plastic strains. The evolution of the free volume, and the STZs number density and nucleation energy during the finite straining are formulated in this paper in order to investigate the uniaxial post-yield softening-hardening behavior of the glassy polymers. This study shows that the reduction of the STZ nucleation energy, which is correlated with the free volume increase, brings about the post-yield primary softening of the amorphous polymers up to the steady-state strain value; and the secondary hardening is a result of the increased number density of the STZs, which is required for large plastic strains, while their nucleation energy is stabilized beyond the steady-state strain. The evolutions of the free volume content and STZ nucleation energy are also used to demonstrate the effect of the strain rate, temperature, and thermal history of the sample on its post-yield behavior. The obtained results from the model are compared with the experimental observations on poly(methyl methacrylate) which show a satisfactory consonance.

  8. Enthalpy of formation of carbon-rich polymer-derived amorphous SiCN ceramics.

    SciTech Connect

    Morcos, R. M.; Mera, G.; Navrotsky, A.; Varga, T.; Riedel, R.; Poli, F.; Muller, K.; Materials Science Division; Univ. of California at Davis; Technische Univ. Darmstadt; Univ. of Stuttgart

    2008-10-01

    Carbon-rich silicon carbonitride (SiCN) ceramics derived from polysilylcarbodiimides represent a novel class of materials where the incorporation of a high amount of carbon was demonstrated to be beneficial for ultrahigh-temperature resistance against crystallization. Calorimetric measurements of heat of oxidative dissolution in a molten oxide solvent show that these amorphous SiCN ceramics produced at 1000 or 1100 C possess a small positive or near zero enthalpy of formation relative to their crystalline constituents, namely silicon nitride, silicon carbide, and graphite. The enthalpy of formation does not change strongly with increasing SiC mole fraction. Because the enthalpies of formation from crystalline constituents are at most slightly positive, and the entropies of formation are expected to be significantly positive because of disorder in the amorphous phase, it is likely that the free energies of formation from silicon carbide, silicon nitride, and graphite are negative and the high-temperature persistence of amorphous SiCN ceramics may originate from thermodynamic stabilization. However, this stabilization is less pronounced than that for SiCO polymer-derived ceramics studied earlier.

  9. Controlling Molecular Ordering in Solution-State Conjugated Polymers

    SciTech Connect

    Zhu, Jiahua; Han, Youngkyu; Kumar, Rajeev; Hong, Kunlun; Bonnesen, Peter V.; Sumpter, Bobby G.; Smith, Gregory Scott; Ivanov, Ilia N.; Do, Changwoo

    2015-07-17

    Rationally encoding molecular interactions that can control the assembly structure and functional expression in solution of conjugated polymers holds great potential for enabling optimal organic optoelectronic and sensory materials. In this work, we show that thermally-controlled and surfactant-guided assembly of water-soluble conjugated polymers in aqueous solution is a simple and effective strategy to generate optoelectronic materials with desired molecular ordering. We have studied a conjugated polymer consisting of a hydrophobic thiophene backbone and hydrophilic, thermo-responsive ethylene oxide side groups, which shows a step-wise, multi-dimensional assembly in water. By incorporating the polymer into phase-segregated domains of an amphiphilic surfactant in solution, we demonstrate that both chain conformation and degree of molecular ordering of the conjugated polymer can be tuned in hexagonal, micellar and lamellar phases of the surfactant solution. The controlled molecular ordering in conjugated polymer assembly is demonstrated as a key factor determining the electronic interaction and optical function.

  10. Effects of the Terminal Structure, Purity, and Molecular Weight of an Amorphous Conjugated Polymer on Its Photovoltaic Characteristics.

    PubMed

    Kuwabara, Junpei; Yasuda, Takeshi; Takase, Naoto; Kanbara, Takaki

    2016-01-27

    The photovoltaic characteristics of an amorphous polymer containing EDOT and fluorene units were investigated. In particular, the effects of the terminal structure, residual amount of Pd, and molecular weight were systematically investigated. Direct arylation polycondensation of EDOT followed by an established purification method readily afforded polymers with different terminal structures, Pd contents, and molecular weights. Of these factors, the terminal structure of the polymer was a crucial factor affecting the photovoltaic characteristics. For example, the polymer with a Br terminal had a PCE of 2.9% in bulk-heterojunction organic photovoltaics (BHJ OPVs) with a fullerene derivative, whereas the polymer without a Br terminal had a PCE of 4.6% in the same cell configuration. The decreased Pd residues and high molecular weights of the polymers increased the long-term stability of the devices. Moreover, BHJ OPVs containing the high-molecular-weight polymer could be fabricated with an environmentally friendly nonhalogenated solvent.

  11. Gelation in Physically Associating Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Kumar, Sanat

    2001-03-01

    Macromolecules, which possess moieties capable of physical association, commonly form reversible gels when dissolved in solvents. This unusual state of matter, which displays weakly elastic character at short times, is ubiquitous in contexts ranging from foods, viscosity modifiers and the cytoskeleton of living organisms. Gel formation in these systems is currently modeled by assuming that the ``sticker" pairing times are long, thus suggesting a connection to percolation concepts developed in the 1940's. We have performed computer simulations on solutions of chains with ``weak" stickers, i.e., in a realistic limit where sticker pairing energies are comparable to thermal energy, and find that gelation is not synonymous with percolation. Rather, as the temperature is lowered below a threshold value, the stickers cluster into multiplets, thus dramatically slowing the relaxation processes in these materials. The similarity of polymer physical gelation to vitrification suggests that reversible gelation and the glass transition should be describable by a common language. This view accords with recent suggestions that gelation in colloid solutions is a nonergodicity transition, comparable to the glass transition.

  12. Optimising Drug Solubilisation in Amorphous Polymer Dispersions: Rational Selection of Hot-melt Extrusion Processing Parameters.

    PubMed

    Li, Shu; Tian, Yiwei; Jones, David S; Andrews, Gavin P

    2016-02-01

    The aim of this article was to construct a T-ϕ phase diagram for a model drug (FD) and amorphous polymer (Eudragit® EPO) and to use this information to understand the impact of how temperature-composition coordinates influenced the final properties of the extrudate. Defining process boundaries and understanding drug solubility in polymeric carriers is of utmost importance and will help in the successful manufacture of new delivery platforms for BCS class II drugs. Physically mixed felodipine (FD)-Eudragit(®) EPO (EPO) binary mixtures with pre-determined weight fractions were analysed using DSC to measure the endset of melting and glass transition temperature. Extrudates of 10 wt% FD-EPO were processed using temperatures (110°C, 126°C, 140°C and 150°C) selected from the temperature-composition (T-ϕ) phase diagrams and processing screw speed of 20, 100 and 200rpm. Extrudates were characterised using powder X-ray diffraction (PXRD), optical, polarised light and Raman microscopy. To ensure formation of a binary amorphous drug dispersion (ADD) at a specific composition, HME processing temperatures should at least be equal to, or exceed, the corresponding temperature value on the liquid-solid curve in a F-H T-ϕ phase diagram. If extruded between the spinodal and liquid-solid curve, the lack of thermodynamic forces to attain complete drug amorphisation may be compensated for through the use of an increased screw speed. Constructing F-H T-ϕ phase diagrams are valuable not only in the understanding drug-polymer miscibility behaviour but also in rationalising the selection of important processing parameters for HME to ensure miscibility of drug and polymer.

  13. Performance of dielectric nanocomposites: matrix-free, hairy nanoparticle assemblies and amorphous polymer-nanoparticle blends.

    PubMed

    Grabowski, Christopher A; Koerner, Hilmar; Meth, Jeffrey S; Dang, Alei; Hui, Chin Ming; Matyjaszewski, Krzysztof; Bockstaller, Michael R; Durstock, Michael F; Vaia, Richard A

    2014-12-10

    Demands to increase the stored energy density of electrostatic capacitors have spurred the development of materials with enhanced dielectric breakdown, improved permittivity, and reduced dielectric loss. Polymer nanocomposites (PNCs), consisting of a blend of amorphous polymer and dielectric nanofillers, have been studied intensely to satisfy these goals; however, nanoparticle aggregates, field localization due to dielectric mismatch between particle and matrix, and the poorly understood role of interface compatibilization have challenged progress. To expand the understanding of the inter-relation between these factors and, thus, enable rational optimization of low and high contrast PNC dielectrics, we compare the dielectric performance of matrix-free hairy nanoparticle assemblies (aHNPs) to blended PNCs in the regime of low dielectric contrast to establish how morphology and interface impact energy storage and breakdown across different polymer matrices (polystyrene, PS, and poly(methyl methacrylate), PMMA) and nanoparticle loadings (0-50% (v/v) silica). The findings indicate that the route (aHNP versus blending) to well-dispersed morphology has, at most, a minor impact on breakdown strength trends with nanoparticle volume fraction; the only exception being at intermediate loadings of silica in PMMA (15% (v/v)). Conversely, aHNPs show substantial improvements in reducing dielectric loss and maintaining charge/discharge efficiency. For example, low-frequency dielectric loss (1 Hz-1 kHz) of PS and PMMA aHNP films was essentially unchanged up to a silica content of 50% (v/v), whereas traditional blends showed a monotonically increasing loss with silica loading. Similar benefits are seen via high-field polarization loop measurements where energy storage for ∼15% (v/v) silica loaded PMMA and PS aHNPs were 50% and 200% greater than respective comparable PNC blends. Overall, these findings on low dielectric contrast PNCs clearly point to the performance benefits of

  14. Relationships between Architectures and Properties of Highly Branched Polymers: The Cases of Amorphous Poly(trimethylene carbonate) and Crystalline Poly(ε-caprolactone).

    PubMed

    Ren, Yingying; Wei, Zhiyong; Leng, Xuefei; Wu, Tong; Bian, Yufei; Li, Yang

    2016-05-01

    Highly branched polymers (HBPs) are a special class of functional polymeric materials and possess unique properties due to their unique topological structure. A new series of highly branched linear-comb and star-comb amorphous poly(trimethylene carbonate)s (PTMC) and crystalline poly(ε-caprolactone)s (PCL) with well-defined structure and high molecular weight were first synthesized using hydroxylated polybutadiene (HPB) as macroinitiators by simple "one-step" and "graft from" strategies. It is expected that the impact of long-chain, highly branched architecture on the properties of amorphous and crystalline polymers, respectively, is different. We explored systematically for the first time the effect and comparison of branched architectures on the physical and chemical properties of highly branched PTMCs and PCLs, including the intrinsic viscosity, glass transition, thermal degradation, creep property, rheological property, and crystallization and melting behaviors. It is found that the intrinsic viscosities in solution for both comb-branched PTMCs and PCLs were much lower compared with their linear and star counterparts arise from more compact structure and smaller hydrodynamic volumes. For amorphous PTMC, the creep strain and rate increased remarkably with degree of branching increasing due to the shorter side chains making it difficult for the highly branched molecules to entangle. For crystalline PCL, both WAXD and DSC analysis of PCLs with different topological structures indicated that the comb branched architectures have no significant influence on the crystal structure of PCL, but greatly promote the crystallization behavior, e.g., higher crystallinities. The deep understanding of structure-property relationship expects to guide the synthesis of designed functional polymer materials and the processing of polymer products.

  15. Relationships between Architectures and Properties of Highly Branched Polymers: The Cases of Amorphous Poly(trimethylene carbonate) and Crystalline Poly(ε-caprolactone).

    PubMed

    Ren, Yingying; Wei, Zhiyong; Leng, Xuefei; Wu, Tong; Bian, Yufei; Li, Yang

    2016-05-01

    Highly branched polymers (HBPs) are a special class of functional polymeric materials and possess unique properties due to their unique topological structure. A new series of highly branched linear-comb and star-comb amorphous poly(trimethylene carbonate)s (PTMC) and crystalline poly(ε-caprolactone)s (PCL) with well-defined structure and high molecular weight were first synthesized using hydroxylated polybutadiene (HPB) as macroinitiators by simple "one-step" and "graft from" strategies. It is expected that the impact of long-chain, highly branched architecture on the properties of amorphous and crystalline polymers, respectively, is different. We explored systematically for the first time the effect and comparison of branched architectures on the physical and chemical properties of highly branched PTMCs and PCLs, including the intrinsic viscosity, glass transition, thermal degradation, creep property, rheological property, and crystallization and melting behaviors. It is found that the intrinsic viscosities in solution for both comb-branched PTMCs and PCLs were much lower compared with their linear and star counterparts arise from more compact structure and smaller hydrodynamic volumes. For amorphous PTMC, the creep strain and rate increased remarkably with degree of branching increasing due to the shorter side chains making it difficult for the highly branched molecules to entangle. For crystalline PCL, both WAXD and DSC analysis of PCLs with different topological structures indicated that the comb branched architectures have no significant influence on the crystal structure of PCL, but greatly promote the crystallization behavior, e.g., higher crystallinities. The deep understanding of structure-property relationship expects to guide the synthesis of designed functional polymer materials and the processing of polymer products. PMID:27064385

  16. Effect of polymer type and drug dose on the in vitro and in vivo behavior of amorphous solid dispersions.

    PubMed

    Knopp, Matthias Manne; Chourak, Nabil; Khan, Fauzan; Wendelboe, Johan; Langguth, Peter; Rades, Thomas; Holm, René

    2016-08-01

    This study investigated the non-sink in vitro dissolution behavior and in vivo performance in rats of celecoxib (CCX) amorphous solid dispersions with polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP) and hydroxypropyl methylcellulose (HPMC) at different drug doses. Both in vitro and in vivo, the amorphous solid dispersions with the hydrophilic polymers PVP and HPMC led to higher areas under both, the in vitro dissolution and the plasma concentration-time curves (AUC) compared to crystalline and amorphous CCX for all doses. In contrast, the amorphous solid dispersion with the hydrophobic polymer PVA showed a lower AUC both in vitro and in vivo than crystalline CCX. For crystalline CCX and CCX:PVA, the in vitro AUC was limited by the low solubility of the drug and the slow release of the drug from the hydrophobic polymer, respectively. For the supersaturating formulations, amorphous CCX, CCX:PVP and CCX:HPMC, the in vitro performance was mainly dependent on the dissolution rate and precipitation/crystallization inhibition of the polymer. As expected, the crystallization tendency increased with increasing dose, and therefore the in vitro AUCs did not increase proportionally with dose. Even though the in vivo AUC for all formulations increased with increasing dose, the relative bioavailability decreased significantly, indicating that the supersaturating formulations also crystallized in vivo and that the absorption of CCX was solubility-limited. These findings underline the importance of evaluating relevant in vitro doses, in order to rationally assess the performance of amorphous solid dispersions and avoid confusion in early in vivo studies.

  17. Effect of polymer type and drug dose on the in vitro and in vivo behavior of amorphous solid dispersions.

    PubMed

    Knopp, Matthias Manne; Chourak, Nabil; Khan, Fauzan; Wendelboe, Johan; Langguth, Peter; Rades, Thomas; Holm, René

    2016-08-01

    This study investigated the non-sink in vitro dissolution behavior and in vivo performance in rats of celecoxib (CCX) amorphous solid dispersions with polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP) and hydroxypropyl methylcellulose (HPMC) at different drug doses. Both in vitro and in vivo, the amorphous solid dispersions with the hydrophilic polymers PVP and HPMC led to higher areas under both, the in vitro dissolution and the plasma concentration-time curves (AUC) compared to crystalline and amorphous CCX for all doses. In contrast, the amorphous solid dispersion with the hydrophobic polymer PVA showed a lower AUC both in vitro and in vivo than crystalline CCX. For crystalline CCX and CCX:PVA, the in vitro AUC was limited by the low solubility of the drug and the slow release of the drug from the hydrophobic polymer, respectively. For the supersaturating formulations, amorphous CCX, CCX:PVP and CCX:HPMC, the in vitro performance was mainly dependent on the dissolution rate and precipitation/crystallization inhibition of the polymer. As expected, the crystallization tendency increased with increasing dose, and therefore the in vitro AUCs did not increase proportionally with dose. Even though the in vivo AUC for all formulations increased with increasing dose, the relative bioavailability decreased significantly, indicating that the supersaturating formulations also crystallized in vivo and that the absorption of CCX was solubility-limited. These findings underline the importance of evaluating relevant in vitro doses, in order to rationally assess the performance of amorphous solid dispersions and avoid confusion in early in vivo studies. PMID:27212472

  18. The peculiar behavior of the glass transition temperature of amorphous drug-polymer films coated on inert sugar spheres.

    PubMed

    Dereymaker, Aswin; Van Den Mooter, Guy

    2015-05-01

    Fluid bed coating has been proposed in the past as an alternative technology for manufacturing of drug-polymer amorphous solid dispersions, or so-called glass solutions. It has the advantage of being a one-step process, and thus omitting separate drying steps, addition of excipients, or manipulation of the dosage form. In search of an adequate sample preparation method for modulated differential scanning calorimetry analysis of beads coated with glass solutions, glass transition broadening and decrease of the glass transition temperature (Tg ) were observed with increasing particle size of crushed coated beads and crushed isolated films of indomethacin (INDO) and polyvinylpyrrolidone (PVP). Substituting INDO with naproxen gave comparable results. When ketoconazole was probed or the solvent in INDO-PVP films was switched to dichloromethane (DCM) or a methanol-DCM mixture, two distinct Tg regions were observed. Small particle sizes had a glass transition in the high Tg region, and large particle sizes had a glass transition in the low Tg region. This particle size-dependent glass transition was ascribed to different residual solvent amounts in the bulk and at the surface of the particles. A correlation was observed between the deviation of the Tg from that calculated from the Gordon-Taylor equation and the amount of residual solvent at the Tg of particles with different sizes.

  19. Dehydration and crystallization of amorphous calcium carbonate in solution and in air.

    PubMed

    Ihli, Johannes; Wong, Wai Ching; Noel, Elizabeth H; Kim, Yi-Yeoun; Kulak, Alexander N; Christenson, Hugo K; Duer, Melinda J; Meldrum, Fiona C

    2014-01-01

    The mechanisms by which amorphous intermediates transform into crystalline materials are poorly understood. Currently, attracting enormous interest is the crystallization of amorphous calcium carbonate, a key intermediary in synthetic, biological and environmental systems. Here we attempt to unify many contrasting and apparently contradictory studies by investigating this process in detail. We show that amorphous calcium carbonate can dehydrate before crystallizing, both in solution and in air, while thermal analyses and solid-state nuclear magnetic resonance measurements reveal that its water is present in distinct environments. Loss of the final water fraction--comprising less than 15% of the total--then triggers crystallization. The high activation energy of this step suggests that it occurs by partial dissolution/recrystallization, mediated by surface water, and the majority of the particle then crystallizes by a solid-state transformation. Such mechanisms are likely to be widespread in solid-state reactions and their characterization will facilitate greater control over these processes.

  20. Stimuli-responsive supramolecular polymers in aqueous solution.

    PubMed

    Ma, Xiang; Tian, He

    2014-07-15

    CONSPECTUS: Aiming to construct various novel supramolecular polymeric structures in aqueous solution beyond small supramolecular self-assembly molecules and develop functional supramolecular polymeric materials, research interest on functional supramolecular polymers has been prevailing in recent years. Supramolecular polymers are formed by bridging monomers or components together via highly directional noncovalent interactions such as hydrogen bonding, hydrophobic interaction, π-π interaction, metal-ligand coordination, electrostatic interaction, and so forth. They can be easily functionalized by employing diverse building components with specific functions besides the traditional polymeric properties, a number of which are responsive to such external stimuli as pH variance, photoirradiation, chemically or electrochemically redox with the controllable conformation or construction switching, polymerization building and rebuilding, and function adjustment reversibly owing to the reversibility of noncovalent interactions. Supramolecular polymers are "soft matters" and can be functionalized with specific properties such as morphology adjustment, controllable luminescence, shape memory, self-healing, and so forth. Supramolecular polymers constructed based on macrocycle recognition and interlocked structures represent one typical branch of the supramolecular polymer family. Cyclodextrin (CD), cucurbituril (CB), and hydrophilic calixarene derivatives are usually employed to construct hydrophilic supramolecular polymers in aqueous solution. Stimuli-responsive hydrophilic supramolecular polymers, constructed in aqueous solution particularly, can be promising candidates for mimicking biocompatible or vital functional materials. This Account mainly focuses on the recent stimuli-responsive supramolecular polymers based on the host-guest interaction in aqueous solution. We describe the hydrophilic supramolecular polymers constructed via hydrophobic effects, electrostatic

  1. Controlling molecular ordering in solution-state conjugated polymers

    NASA Astrophysics Data System (ADS)

    Zhu, J.; Han, Y.; Kumar, R.; He, Y.; Hong, K.; Bonnesen, P. V.; Sumpter, B. G.; Smith, S. C.; Smith, G. S.; Ivanov, I. N.; Do, C.

    2015-09-01

    Rationally encoding molecular interactions that can control the assembly structure and functional expression in a solution of conjugated polymers hold great potential for enabling optimal organic optoelectronic and sensory materials. In this work, we show that thermally-controlled and surfactant-guided assembly of water-soluble conjugated polymers in aqueous solution is a simple and effective strategy to generate optoelectronic materials with the desired molecular ordering. We have studied a conjugated polymer consisting of a hydrophobic thiophene backbone and hydrophilic, thermo-responsive ethylene oxide side groups, which shows a step-wise, multi-dimensional assembly in water. By incorporating the polymer into phase-segregated domains of an amphiphilic surfactant in solution, we demonstrate that both chain conformation and degree of molecular ordering of the conjugated polymer can be tuned in hexagonal, micellar and lamellar phases of the surfactant solution. The controlled molecular ordering in conjugated polymer assembly is demonstrated as a key factor determining the electronic interaction and optical function.Rationally encoding molecular interactions that can control the assembly structure and functional expression in a solution of conjugated polymers hold great potential for enabling optimal organic optoelectronic and sensory materials. In this work, we show that thermally-controlled and surfactant-guided assembly of water-soluble conjugated polymers in aqueous solution is a simple and effective strategy to generate optoelectronic materials with the desired molecular ordering. We have studied a conjugated polymer consisting of a hydrophobic thiophene backbone and hydrophilic, thermo-responsive ethylene oxide side groups, which shows a step-wise, multi-dimensional assembly in water. By incorporating the polymer into phase-segregated domains of an amphiphilic surfactant in solution, we demonstrate that both chain conformation and degree of molecular ordering

  2. Direct Uniaxial Alignment of a Donor-Acceptor Semiconducting Polymer Using Single-Step Solution Shearing.

    PubMed

    Shaw, Leo; Hayoz, Pascal; Diao, Ying; Reinspach, Julia Antonia; To, John W F; Toney, Michael F; Weitz, R Thomas; Bao, Zhenan

    2016-04-13

    The alignment of organic semiconductors (OSCs) in the active layers of electronic devices can confer desirable properties, such as enhanced charge transport properties due to better ordering, charge transport anisotropy for reduced device cross-talk, and polarized light emission or absorption. The solution-based deposition of highly aligned small molecule OSCs has been widely demonstrated, but the alignment of polymeric OSCs in thin films deposited directly from solution has typically required surface templating or complex pre- or postdeposition processing. Therefore, single-step solution processing and the charge transport enhancement afforded by alignment continue to be attractive. We report here the use of solution shearing to tune the degree of alignment in poly(diketopyrrolopyrrole-terthiophene) thin films by controlling the coating speed. A maximum dichroic ratio of ∼7 was achieved on unpatterned substrates without any additional pre- or postdeposition processing. The degree of polymer alignment was found to be a competition between the shear alignment of polymer chains in solution and the complex thin film drying process. Contrary to previous reports, no charge transport anisotropy was observed because of the small crystallite size relative to the channel length, a meshlike morphology, and the likelihood of increased grain boundaries in the direction transverse to coating. In fact, the lack of aligned morphological structures, coupled with observed anisotropy in X-ray diffraction data, suggests the alignment of polymer molecules in both the crystalline and the amorphous regions of the films. The shear speed at which maximum dichroism is achieved can be controlled by altering deposition parameters such as temperature and substrate treatment. Modest changes in molecular weight showed negligible effects on alignment, while longer polymer alkyl side chains were found to reduce the degree of alignment. This work demonstrates that solution shearing can be used

  3. Direct Uniaxial Alignment of a Donor-Acceptor Semiconducting Polymer Using Single-Step Solution Shearing.

    PubMed

    Shaw, Leo; Hayoz, Pascal; Diao, Ying; Reinspach, Julia Antonia; To, John W F; Toney, Michael F; Weitz, R Thomas; Bao, Zhenan

    2016-04-13

    The alignment of organic semiconductors (OSCs) in the active layers of electronic devices can confer desirable properties, such as enhanced charge transport properties due to better ordering, charge transport anisotropy for reduced device cross-talk, and polarized light emission or absorption. The solution-based deposition of highly aligned small molecule OSCs has been widely demonstrated, but the alignment of polymeric OSCs in thin films deposited directly from solution has typically required surface templating or complex pre- or postdeposition processing. Therefore, single-step solution processing and the charge transport enhancement afforded by alignment continue to be attractive. We report here the use of solution shearing to tune the degree of alignment in poly(diketopyrrolopyrrole-terthiophene) thin films by controlling the coating speed. A maximum dichroic ratio of ∼7 was achieved on unpatterned substrates without any additional pre- or postdeposition processing. The degree of polymer alignment was found to be a competition between the shear alignment of polymer chains in solution and the complex thin film drying process. Contrary to previous reports, no charge transport anisotropy was observed because of the small crystallite size relative to the channel length, a meshlike morphology, and the likelihood of increased grain boundaries in the direction transverse to coating. In fact, the lack of aligned morphological structures, coupled with observed anisotropy in X-ray diffraction data, suggests the alignment of polymer molecules in both the crystalline and the amorphous regions of the films. The shear speed at which maximum dichroism is achieved can be controlled by altering deposition parameters such as temperature and substrate treatment. Modest changes in molecular weight showed negligible effects on alignment, while longer polymer alkyl side chains were found to reduce the degree of alignment. This work demonstrates that solution shearing can be used

  4. Investigations into crazing in glassy amorphous polymers through molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Venkatesan, Sudarkodi; Basu, Sumit

    2015-04-01

    In many glassy amorphous polymers, localisation of deformation during loading leads to crazes. Crazes are crack like features whose faces are bridged either by fibrils or a cellular network of voids and fibrils. While formation of crazes is aided by the presence of surface imperfections and embedded dust particles, in this work, we focus on intrinsic crazes that form spontaneously in the volume of the material. We perform carefully designed molecular dynamics simulations on well equilibrated samples of a model polymer with a view to gaining insights into certain incompletely understood aspects of the crazing process. These include genesis of the early nanovoids leading to craze nucleation, mechanisms of stabilising the cellular or fibrillar structure and the competition between chain scission and chain disentanglement in causing the final breakdown of the craze. Additionally, we identify and enumerate clusters of entanglement points with high functionality as effective topological constraints on macromolecular chains. We show that regions with low density of entanglement clusters serve as sites for nanovoid nucleation under high mean stress. Growth occurs by the repeated triggering of cavitation instabilities above a growing void. The growth of the void is aided by disentanglement in and flow of entanglements away from the cavitating region. Finally, for the chain lengths chosen, scission serves to supply short chains to the growing craze but breakdown occurs by complete disentanglement of the chains. In fact, most of the energy supplied to the material seems to be used in causing disentanglements and very little energy is required to create a stable fibril.

  5. Modelling multi-scale deformation of amorphous glassy polymers with experimentally motivated evolution of the microstructure

    NASA Astrophysics Data System (ADS)

    Engqvist, Jonas; Wallin, Mathias; Ristinmaa, Matti; Hall, Stephen A.; Plivelic, Tomás S.

    2016-11-01

    Novel experimental data, obtained recently using advanced multi-scale experiments, have been used to develop a micro-mechanically motivated constitutive model for amorphous glassy polymers. Taking advantage of the experiments, the model makes use of a microstructural deformation gradient to incorporate the experimentally obtained deformation of the microstructure, as well as its evolving orientation. By comparing results from the model to experimental data, it is shown that the proposed approach is able to accurately predict glassy polymer deformation over a wide range of length-scales, from the macroscopic response (mm range) down to the deformation of the microstructure (nm range). The proposed model is evaluated by comparing the numerical response to experimental results on multiple scales from an inhomogeneous cold drawing experiment of glassy polycarbonate. Besides the macroscopic force-displacement response, a qualitative comparison of the deformation field at the surface of the specimen is performed. Furthermore, the predicted evolution of the fabric orientation is compared to experimental results obtained from X-ray scattering experiments. The model shows very good agreement with the experimental data over a wide range of length scales.

  6. Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide

    NASA Astrophysics Data System (ADS)

    Tran, Phong D.; Tran, Thu V.; Orio, Maylis; Torelli, Stephane; Truong, Quang Duc; Nayuki, Keiichiro; Sasaki, Yoshikazu; Chiam, Sing Yang; Yi, Ren; Honma, Itaru; Barber, James; Artero, Vincent

    2016-06-01

    Molybdenum sulfides are very attractive noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) from water. The atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx), which exhibits significantly higher HER activity compared to its crystalline counterpart. Here we show that HER-active a-MoSx, prepared either as nanoparticles or as films, is a molecular-based coordination polymer consisting of discrete [Mo3S13]2- building blocks. Of the three terminal disulfide (S22-) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimization of this HER electrocatalyst as an alternative to platinum.

  7. 10.5% efficient polymer and amorphous silicon hybrid tandem photovoltaic cell.

    PubMed

    Kim, Jeehwan; Hong, Ziruo; Li, Gang; Song, Tze-bin; Chey, Jay; Lee, Yun Seog; You, Jingbi; Chen, Chun-Chao; Sadana, Devendra K; Yang, Yang

    2015-01-01

    Thin-film solar cells made with amorphous silicon (a-Si:H) or organic semiconductors are considered as promising renewable energy sources due to their low manufacturing cost and light weight. However, the efficiency of single-junction a-Si:H or organic solar cells is typically <10%, insufficient for achieving grid parity. Here we demonstrate an efficient double-junction photovoltaic cell by employing an a-Si:H film as a front sub-cell and a low band gap polymer:fullerene blend film as a back cell on planar glass substrates. Monolithic integration of 6.0% efficienct a-Si:H and 7.5% efficient polymer:fullerene blend solar cells results in a power conversion efficiency of 10.5%. Such high-efficiency thin-film tandem cells can be achieved by optical management and interface engineering of fully optimized high-performance front and back cells without sacrificing photovoltaic performance in both cells. PMID:25736823

  8. Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide.

    PubMed

    Tran, Phong D; Tran, Thu V; Orio, Maylis; Torelli, Stephane; Truong, Quang Duc; Nayuki, Keiichiro; Sasaki, Yoshikazu; Chiam, Sing Yang; Yi, Ren; Honma, Itaru; Barber, James; Artero, Vincent

    2016-06-01

    Molybdenum sulfides are very attractive noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) from water. The atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx), which exhibits significantly higher HER activity compared to its crystalline counterpart. Here we show that HER-active a-MoSx, prepared either as nanoparticles or as films, is a molecular-based coordination polymer consisting of discrete [Mo3S13](2-) building blocks. Of the three terminal disulfide (S2(2-)) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimization of this HER electrocatalyst as an alternative to platinum. PMID:26974410

  9. Investigation of Phase Mixing in Amorphous Solid Dispersions of AMG 517 in HPMC-AS Using DSC, Solid-State NMR, and Solution Calorimetry.

    PubMed

    Calahan, Julie L; Azali, Stephanie C; Munson, Eric J; Nagapudi, Karthik

    2015-11-01

    Intimate phase mixing between the drug and the polymer is considered a prerequisite to achieve good physical stability for amorphous solid dispersions. In this article, spray dried amorphous dispersions (ASDs) of AMG 517 and HPMC-as were studied by differential scanning calorimetry (DSC), solid-state NMR (SSNMR), and solution calorimetry. DSC analysis showed a weakly asymmetric (ΔTg ≈ 13.5) system with a single glass transition for blends of different compositions indicating phase mixing. The Tg-composition data was modeled using the BKCV equation to accommodate the observed negative deviation from ideality. Proton spin-lattice relaxation times in the laboratory and rotating frames ((1)H T1 and T1ρ), as measured by SSNMR, were consistent with the observation that the components of the dispersion were in intimate contact over a 10-20 nm length scale. Based on the heat of mixing calculated from solution calorimetry and the entropy of mixing calculated from the Flory-Huggins theory, the free energy of mixing was calculated. The free energy of mixing was found to be positive for all ASDs, indicating that the drug and polymer are thermodynamically predisposed to phase separation at 25 °C. This suggests that miscibility measured by DSC and SSNMR is achieved kinetically as the result of intimate mixing between drug and polymer during the spray drying process. This kinetic phase mixing is responsible for the physical stability of the ASD.

  10. Extensional instability in electro-osmotic microflows of polymer solutions

    NASA Astrophysics Data System (ADS)

    Bryce, R. M.; Freeman, M. R.

    2010-03-01

    Fluid transport in microfluidic systems typically is laminar due to the low Reynolds number characteristic of the flow. The inclusion of suspended polymers imparts elasticity to fluids, allowing instabilities to be excited when substantial polymer stretching occurs. For high molecular weight polymer chains we find that flow velocities achievable by standard electro-osmotic pumping are sufficient to excite extensional instabilities in dilute polymer solutions. We observe a dependence in measured fluctuations on polymer concentration which plateaus at a threshold corresponding to the onset of significant molecular crowding in macromolecular solutions; plateauing occurs well below the overlap concentration. Our results show that electro-osmotic flows of complex fluids are disturbed from the steady regime, suggesting potential for enhanced mixing and requiring care in modeling the flow of complex liquids such as biopolymer suspensions.

  11. Hydrophilization and hydrophobic recovery in polymers obtained by casting of polymer solutions on water surface.

    PubMed

    Bormashenko, Edward; Chaniel, Gilad; Gendelman, Oleg

    2014-12-01

    We demonstrate the possibility of hydrophilization of polymer films in situ under the process of their preparation. The polymer surface is hydrophilized when the polymer solution is spread on the water surface and the solvent is evaporated. Essential hydrophilization of the polymer surface is achieved under this process. We relate the observed hydrophilization of polymer films to the dipole-dipole interaction of the polar moieties of polymer chains with highly polar water molecules. The dipole-dipole interaction between water molecules and polar groups of polymer chains, orienting the polar groups of a polymer, may prevail over the London dispersion forces. The process, reported in the paper, allows to manufacture the films in which the hydrophilic moieties of the polymer molecule are oriented toward the polymer/air interface. It is demonstrated that even such traditionally extremely hydrophobic polymers as polydimethylsiloxane can be markedly hydrophilized. This hydrophilization, however, does not persist forever. After removal from the water surface, hydrophobic recovery was observed, i.e. polymer films restored their hydrophobicity with time. The characteristic time of the hydrophobic recovery is on the order of magnitude of hours.

  12. Coordination polymers built from 1,4-bis(imidazol-1-ylmethyl)benzene: from crystalline to amorphous.

    PubMed

    Adarsh, N N; Novio, Fernando; Ruiz-Molina, Daniel

    2016-07-28

    The supramolecular chemistry of the bis-imidazole ligand 1,4-bis(imidazol-1-ylmethyl)benzene, popularly known as bix, has been explored by various researchers in order to synthesize functional coordination polymers (CPs). The flexibility of the bix ligand, its unpredictable conformation and its coordination behaviour with transition metal ions have resulted in a huge number of structurally diverse and functionally intriguing CPs. In this perspective review we discuss the progress in CPs of bix between 1997 and today. More precisely, this review emphasizes the developments in functional supramolecular coordination polymers built from the bix ligand, from crystalline materials to amorphous nanomaterials. PMID:27335273

  13. Rapid decolorization of acid orange II aqueous solution by amorphous zero-valent iron.

    PubMed

    Zhang, Changqin; Zhu, Zhengwang; Zhang, Haifeng; Hu, Zhuangqi

    2012-01-01

    Some problems including low treatment capacity, agglomeration and clogging phenomena, and short working life, limit the application of pre-treatment methods involving zero-valent iron (ZVI). In this article, ZVI was frozen in an amorphous state through a melt-spinning technique, and the decolorization effect of amorphous ZVI on Acid Orange II solution was investigated under varied conditions of experimental variables such as reaction temperature, ribbon dosage, and initial pH. Batch experiments suggested that the decolorization rate was enhanced with the increase of reaction temperature and ribbon dosage, but decreased with increasing initial solution pH. Kinetic analyses indicated that the decolorization process followed a first order exponential kinetic model, and the surface-normalized decolorization rate could reach 2.09 L/(m2 x min) at room temperature, which was about ten times larger than any previously reported under similar conditions. Recycling experiments also proved that the ribbons could be reused at least four times without obvious decay of decolorization rate and efficiency. This study suggests a tremendous application potential for amorphous ZVI in remediation of groundwater or wastewater contaminated with azo dyes.

  14. Amorphous metal composites

    DOEpatents

    Byrne, Martin A.; Lupinski, John H.

    1984-01-01

    An improved amorphous metal composite and process of making the composite. The amorphous metal composite comprises amorphous metal (e.g. iron) and a low molecular weight thermosetting polymer binder. The process comprises placing an amorphous metal in particulate form and a thermosetting polymer binder powder into a container, mixing these materials, and applying heat and pressure to convert the mixture into an amorphous metal composite.

  15. New development of large-area direct conversion detector for digital radiography using amorphous selenium with a C60-doped polymer layer

    NASA Astrophysics Data System (ADS)

    Nariyuki, F.; Imai, S.; Watano, H.; Nabeta, T.; Hosoi, Y.

    2010-04-01

    We have developed a novel direct conversion detector for digital radiography by using a fullerene (C60)-doped polymer layer added on a thick amorphous selenium (a-Se) layer coupled to an amorphous silicon thin-film transistor (a-Si TFT) array. This detector exhibits considerable improvement in the lag characteristics and durability in high ambient temperatures. The C60-doped polymer layer, which is directly and uniformly solution cast on the a-Se layer and followed by an inorganic electron-transporting layer, smoothly changes the electronic junction between the a-Se layer and the inorganic layer. It lubricates the emission of photocurrents from the a-Se photo-conversion layer and leads to the improved lag characteristics. Another merit of using a C60-doped polymer is that it is stabile in high-temperature ambient conditions and is not degraded by humidity or a large amount of X-ray exposure. The polymer layer prevents the crystallization of a-Se, which otherwise occurs on exposure of a-Se to high temperature not only during the deposition of the inorganic layer or the metal electrode layer in the manufacturing process but also in actual use. A prototype detector, with a size of 17 in × 17 in and a pixel pitch of 150 μm, exhibited a good resolution; its DQE is approximately 48% at 1 cy/mm in 258 μC/kg (RQA5). This new development can simplify cooling apparatus and detector modules and also make a wide range of operational environments available. In addition, the improved lag characteristics make it possible to reduce the exposure intervals for static imaging, tomosynthesis, and other various exposure techniques.

  16. Controlling molecular ordering in solution-state conjugated polymers.

    PubMed

    Zhu, J; Han, Y; Kumar, R; He, Y; Hong, K; Bonnesen, P V; Sumpter, B G; Smith, S C; Smith, G S; Ivanov, I N; Do, C

    2015-10-01

    Rationally encoding molecular interactions that can control the assembly structure and functional expression in a solution of conjugated polymers hold great potential for enabling optimal organic optoelectronic and sensory materials. In this work, we show that thermally-controlled and surfactant-guided assembly of water-soluble conjugated polymers in aqueous solution is a simple and effective strategy to generate optoelectronic materials with the desired molecular ordering. We have studied a conjugated polymer consisting of a hydrophobic thiophene backbone and hydrophilic, thermo-responsive ethylene oxide side groups, which shows a step-wise, multi-dimensional assembly in water. By incorporating the polymer into phase-segregated domains of an amphiphilic surfactant in solution, we demonstrate that both chain conformation and degree of molecular ordering of the conjugated polymer can be tuned in hexagonal, micellar and lamellar phases of the surfactant solution. The controlled molecular ordering in conjugated polymer assembly is demonstrated as a key factor determining the electronic interaction and optical function.

  17. Solution behavior of PEO : the ultimate biocompatible polymer.

    SciTech Connect

    Curro, John G.; Frischknecht, Amalie Lucile

    2004-11-01

    Poly(ethylene oxide) (PEO) is the quintessential biocompatible polymer. Due to its ability to form hydrogen bonds, it is soluble in water, and yet is uncharged and relatively inert. It is being investigated for use in a wide range of biomedical and biotechnical applications, including the prevention of protein adhesion (biofouling), controlled drug delivery, and tissue scaffolds. PEO has also been proposed for use in novel polymer hydrogel nanocomposites with superior mechanical properties. However, the phase behavior of PEO in water is highly anomalous and is not addressed by current theories of polymer solutions. The effective interactions between PEO and water are very concentration dependent, unlike other polymer/solvent systems, due to water-water and water-PEO hydrogen bonds. An understanding of this anomalous behavior requires a careful examination of PEO liquids and solutions on the molecular level. We performed massively parallel molecular dynamics simulations and self-consistent Polymer Reference Interaction Site Model (PRISM) calculations on PEO liquids. We also initiated MD studies on PEO/water solutions with and without an applied electric field. This work is summarized in three parts devoted to: (1) A comparison of MD simulations, theory and experiment on PEO liquids; (2) The implementation of water potentials into the LAMMPS MD code; and (3) A theoretical analysis of the effect of an applied electric field on the phase diagram of polymer solutions.

  18. Controlling Molecular Ordering in Solution-State Conjugated Polymers

    DOE PAGES

    Zhu, Jiahua; Han, Youngkyu; Kumar, Rajeev; Hong, Kunlun; Bonnesen, Peter V.; Sumpter, Bobby G.; Smith, Gregory Scott; Ivanov, Ilia N.; Do, Changwoo

    2015-07-17

    Rationally encoding molecular interactions that can control the assembly structure and functional expression in solution of conjugated polymers holds great potential for enabling optimal organic optoelectronic and sensory materials. In this work, we show that thermally-controlled and surfactant-guided assembly of water-soluble conjugated polymers in aqueous solution is a simple and effective strategy to generate optoelectronic materials with desired molecular ordering. We have studied a conjugated polymer consisting of a hydrophobic thiophene backbone and hydrophilic, thermo-responsive ethylene oxide side groups, which shows a step-wise, multi-dimensional assembly in water. By incorporating the polymer into phase-segregated domains of an amphiphilic surfactant in solution,more » we demonstrate that both chain conformation and degree of molecular ordering of the conjugated polymer can be tuned in hexagonal, micellar and lamellar phases of the surfactant solution. The controlled molecular ordering in conjugated polymer assembly is demonstrated as a key factor determining the electronic interaction and optical function.« less

  19. Dispersive Non-Geminate Recombination in an Amorphous Polymer:Fullerene Blend

    PubMed Central

    Kurpiers, Jona; Neher, Dieter

    2016-01-01

    Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions. PMID:27225584

  20. Electrical analysis of amorphous corn starch-based polymer electrolyte membranes doped with LiI

    NASA Astrophysics Data System (ADS)

    Shukur, M. F.; Ibrahim, F. M.; Majid, N. A.; Ithnin, R.; Kadir, M. F. Z.

    2013-08-01

    In this work, polymer electrolytes have been prepared by doping starch with lithium iodide (LiI). The incorporation of 30 wt% LiI optimizes the room temperature conductivity of the electrolyte at (1.83 ± 0.47) × 10-4 S cm-1. Further conductivity enhancement to (9.56 ± 1.19) × 10-4 S cm-1 is obtained with the addition of 30 wt% glycerol. X-ray diffraction analysis indicates that the conductivity enhancement is due to the increase in amorphous content. The activation energy, Ea, of 70 wt% starch-30 wt% LiI electrolyte is 0.26 eV, while 49 wt% starch-21 wt% LiI-30 wt% glycerol electrolyte exhibits an Ea of 0.16 eV. Dielectric studies show that all the electrolytes obey non-Debye behavior. The power law exponent s is obtained from the variation of dielectric loss, ɛi, with frequency at different temperatures. The conduction mechanism of 70 wt% starch-30 wt% LiI electrolyte can be explained by the correlated barrier hopping model, while the conduction mechanism for 49 wt% starch-21 wt% LiI-30 wt% glycerol electrolyte can be represented by the quantum mechanical tunneling model.

  1. Dispersive Non-Geminate Recombination in an Amorphous Polymer:Fullerene Blend

    NASA Astrophysics Data System (ADS)

    Kurpiers, Jona; Neher, Dieter

    2016-05-01

    Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.

  2. Disappearance of high frequency modes in polymer dilute solution viscoelasticity

    NASA Astrophysics Data System (ADS)

    Larson, Ronald; Jain, Semant

    2009-03-01

    We address the problem of the ``missing modes'' in the high frequency rheology of dilute polymer solutions. According to the Rouse-Zimm theory, the slow viscoelastic response of dilute polymers is dominated by the collective motion of the chain, as described by a bead-spring model. However, one expects this description to break down at high frequencies at which chain motion on scales too small to be represented by beads and springs should be evident; this motion should be controlled by rotations of individual backbone bonds of the polymer. The viscoelastic response produced by these ``local modes'' is observable in polymer melts; however, for dilute polymer solutions, the ``local modes'' are absent from viscoelastic spectra, as shown by Schrag and coworkers (Peterson, et al., J. Polym. Sci. B, 39:2860 (2001)). Here we address this problem by directly simulating single polymer chains using Brownian dynamics simulations, with realistic bending and torsional potentials. We show using these simulations that the ``missing modes'' result from barriers to bond rotation that make the chain ``dynamically rigid'' at high frequencies. As a result, the ``dynamical Kuhn length'' of the chain exceeds the static one, and the chain at high frequencies is not able to explore local conformations as fast as would be needed for their relaxation to contribute to the mechanical relaxation spectrum.

  3. Submicron flow of polymer solutions: slippage reduction due to confinement.

    PubMed

    Cuenca, Amandine; Bodiguel, Hugues

    2013-03-01

    Pressure-driven flows of high molecular weight polyacrylamide solutions are examined in nanoslits using fluorescence photobleaching. The effective viscosity of polymer solutions decreases when the channel height decreases below the micron scale. In addition, the apparent slippage of the solutions is characterized macroscopically on similar surfaces. Though slippage can explain qualitatively the effective viscosity reduction, a quantitative comparison shows that the slip length is greatly reduced below the micron scale. This result indicates that chain migration is suppressed in confined geometries.

  4. Depletion-mediated red blood cell aggregation in polymer solutions.

    PubMed

    Neu, Björn; Meiselman, Herbert J

    2002-11-01

    Polymer-induced red blood cell (RBC) aggregation is of current basic science and clinical interest, and a depletion-mediated model for this phenomenon has been suggested; to date, however, analytical approaches to this model are lacking. An approach is thus described for calculating the interaction energy between RBC in polymer solutions. The model combines electrostatic repulsion due to RBC surface charge with osmotic attractive forces due to polymer depletion near the RBC surface. The effects of polymer concentration and polymer physicochemical properties on depletion layer thickness and on polymer penetration into the RBC glycocalyx are considered for 40 to 500 kDa dextran and for 18 to 35 kDa poly (ethylene glycol). The calculated results are in excellent agreement with literature data for cell-cell affinities and with RBC aggregation-polymer concentration relations. These findings thus lend strong support to depletion interactions as the basis for polymer-induced RBC aggregation and suggest the usefulness of this approach for exploring interactions between macromolecules and the RBC glycocalyx. PMID:12414682

  5. Amorphous RE–Fe–B–Na colloidal nanoparticles: High temperature solution synthesis and magnetic properties

    SciTech Connect

    Jia, Li-Ping; Yan, Bing

    2015-04-15

    Graphical abstract: RE–Fe–B–Na (RE = Nd–Er) colloidal nanoparticles by high-temperature solution synthesis are ultra-small monodisperse and air-stable amorphous, whose size and magnetic dependence are studied. - Highlights: • RE–Fe–B–Na nanoparticles are obtained by high-temperature solution synthesis. • These colloidal nanoparticles are monodisperse and size controlled. • The magnetism dependence and possible magnetic coupling mechanism are studied. - Abstract: RE–Fe–B–Na (RE = Nd–Er) colloidal nanoparticles are prepared by high-temperature solution synthesis. These nanoparticles are ultra-small monodisperse, air-stable and amorphous, whose particle size and magnetic property are characterized by transmission electron microscope and superconducting quantum interference device. Taking Nd–Fe–B–Na nanoparticle as an example, it is found that the particle size can be controlled in less than 7 nm. Besides, the magnetic properties of RE–Fe–B–Na colloidal nanoparticles can be compared for different rare earth elements. Based on the bulk ferromagnetic coupling, other possible magnetic coupling mechanism is discussed.

  6. A lattice Boltzmann method for dilute polymer solutions.

    PubMed

    Singh, Shiwani; Subramanian, Ganesh; Ansumali, Santosh

    2011-06-13

    We present a lattice Boltzmann approach for the simulation of non-Newtonian fluids. The method is illustrated for the specific case of dilute polymer solutions. With the appropriate local equilibrium distribution, phase-space dynamics on a lattice, driven by a Bhatnagar-Gross-Krook (BGK) relaxation term, leads to a solution of the Fokker-Planck equation governing the probability density of polymer configurations. Results for the bulk rheological characteristics for steady and start-up shear flow are presented, and compare favourably with those obtained using Brownian dynamics simulations. The new method is less expensive than stochastic simulation techniques, particularly in the range of small to moderate Weissenberg numbers (Wi).

  7. Phase behaviors of polymer solutions using molecular simulation technique.

    PubMed

    Yang, Jung Ho; Bae, Young Chan

    2008-08-14

    Phase behaviors of polymer solutions are estimated using a combination of thermodynamic models and molecular simulation technique. In general, many parameters of binary systems are determined by fitting a thermodynamic model with experimental data. In this study, we obtained all parameters using molecular simulation. To take the specific interaction into account, we assume that it only occurs between a solvent molecule and a specific group. Our results show that the theoretical treatment accounting for the specific interaction gives more accurate predictions than those without consideration of specific interaction. Also, our approach describes the phase equilibria of various polymer solutions over the entire concentration remarkably well.

  8. Segment Orientation and Optical Birefringence of Amorphous Polymers Under Tensile Deformation: Novel Computational Method applied to Different Glassy Polycarbonates

    NASA Astrophysics Data System (ADS)

    Natarajan, Upendra; Sulatha, M. S.

    2005-03-01

    Orientation dependent optical properties of Bisphenol A polycarbonate and two aliphatic substituted polycarbonates in glassy phase have been studied by atomistic modeling using molecular mechanics simulations under tensile deformation. Probability distributions and orientation functions show that phenylene rings and carbonate groups vectors along the main chain orient towards stretching direction following deformation. Interchain packing of rings and carbonates become ordered with strain. Efficient computational approach for calculation of optical birefringence of amorphous polymers is presented and applied to the polycarbonates in detail. Polarizability anisotropy of the polymer segments and chain as a function of deformation is calculated by combining information on the conformations and group polarizabilities, and used to estimate birefringence during deformation. Simulated and experimental values for segment orientation and bulk birefringence are in very good agreement. Effect of the optical properties of atomic groups on bulk birefringence is brought forth for the first time by molecular simulation for polymers other than polyethylene.

  9. CORROSION OF AMORPHOUS AND NANOCRYSTALLINE Fe-BASED ALLOYS IN NaCl AND H2SO4 SOLUTIONS

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Lu, Wei; Wang, Yuxin; Yan, Biao; Pan, Deng

    2013-07-01

    Corrosion resistance of nanocrystalline Fe73.5Si13.5B9Nb3Cu1 alloy was investigated and compared to its amorphous counterpart. Low-temperature crystallization occurred during the annealing of amorphous tapes was used to obtain a nanocrystalline structure. The influence of annealing condition on the structure and corrosion resistance of the alloy in NaCl and H2SO4 solutions was investigated. Based on the testing results, it was found that nanocrystalline tapes have higher corrosion resistance than amorphous counterpart and H2SO4 can promote the occurrence of corrosion compared with NaCl.

  10. External field-assisted solution synthesis and selectively catalytic properties of amorphous iron nanoplatelets

    SciTech Connect

    Guan, Jianguo; Yan, Gongqin; Wang, Wei; Liu, Jun

    2012-03-07

    This work describes an easy and flexible approach for the synthesis of 2D nanostructures by external composite field-induced self-assembly. Amorphous iron nanoplatelets with a large aspect ratio were prepared by reducing a concentrated FeSO4 solution with NaBH4 without any templates or surfactants under a magnetic field and a shear field, and characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). Based on the morphological dependence of the resultant iron nanostructures on the kinetic parameters such as reactant concentration, reaction temperature, external fields as well as reaction time, etc., a novel conceivable formation mechanism of the iron nanoplatelets was substantiated to be a self-assembly of concentrated iron nuclei induced by the synergistic effect of both a magnetic field and a shear field. Due to the amorphous nature and shape anisotropy, the as-synthesized iron nanoplatelets exhibit quite different magnetic properties with an enhanced coercivity of >220 Oe from isotropic iron nanoparticles. In the oxidation of cyclohexane with hydrogen peroxide as a 'green' oxidant, the as-obtained amorphous iron nanoplatelets show a conversion more than 84% and a complete selectivity for cyclohexanol and cyclohexanone due to the unique structure. Moreover, their catalytic performances are strongly influenced by their morphology, and the iron atoms located on the faces tend to catalyze the formation of cyclohexanol while those on the sides tend to catalyze the formation of cyclohexanone. The external composite field-induced solution synthesis reported here can be readily explored for fabricating other 2D magnetic nanoplatelets, and the resulting iron nanoplatelets are promising for a number of applications such as high efficient selective catalysis, energy, environment fields and so forth.

  11. Study on degradation process of polymer electrolyte by solution analysis

    NASA Astrophysics Data System (ADS)

    Akiyama, Yoko; Sodaye, Hemant; Shibahara, Yuji; Honda, Yoshihide; Tagawa, Seiichi; Nishijima, Shigehiro

    Degradation process of Nafion which is one of the polymer electrolyte generally used for polymer electrolyte membrane fuel cell was investigated by solution analysis and structural analysis of eluted species. Nafion degraded by gamma-ray irradiation and heat treatment was immersed in distilled water and the solutions were analyzed using ion chromatograph, total organic carbon (TOC) analyzer, and inductively coupled plasma atomic emission spectrometer (ICP-AES). The solutions after the Fenton reaction were also analyzed with the same methods. Proton, sulfide ion, fluorine ion and organic carbon were eliminated into the solution, and their ratio was changed depending on the degradation method. To determine the eliminated species to the solution, structural analysis of concentrated dissolved species was performed using FT-IR. As the results, the initial process of degradation was detected sensitively in solution analysis compared with membrane analysis, and difference of the degradation process under different conditions was clearly observed. It was also found that new functional group COOH was formed in the eliminated species. These results showed that solution analysis are very simple yet powerful methods to elucidate the degradation process, which can also be applied to actual fuel cell operation to track minute changes in the polymer electrolyte.

  12. Efficient field-theoretic simulation of polymer solutions

    SciTech Connect

    Villet, Michael C.; Fredrickson, Glenn H.

    2014-12-14

    We present several developments that facilitate the efficient field-theoretic simulation of polymers by complex Langevin sampling. A regularization scheme using finite Gaussian excluded volume interactions is used to derive a polymer solution model that appears free of ultraviolet divergences and hence is well-suited for lattice-discretized field theoretic simulation. We show that such models can exhibit ultraviolet sensitivity, a numerical pathology that dramatically increases sampling error in the continuum lattice limit, and further show that this pathology can be eliminated by appropriate model reformulation by variable transformation. We present an exponential time differencing algorithm for integrating complex Langevin equations for field theoretic simulation, and show that the algorithm exhibits excellent accuracy and stability properties for our regularized polymer model. These developments collectively enable substantially more efficient field-theoretic simulation of polymers, and illustrate the importance of simultaneously addressing analytical and numerical pathologies when implementing such computations.

  13. Precipitation of Co(2+) carbonates from aqueous solution: insights on the amorphous to crystalline transformation.

    NASA Astrophysics Data System (ADS)

    González-López, Jorge; Fernández-González, Ángeles; Jiménez, Amalia

    2016-04-01

    Cobalt is toxic metal that is present only as a trace in the Earth crust. However, Co might concentrate on specific areas due to both natural and anthropogenic factors and thus, soils and groundwater can be contaminated. It is from this perspective that we are interested in the precipitation of cobalt carbonates, since co-precipitation with minerals phases is a well-known method for metal immobilization in the environment. In particular, the carbonates are widely used due to its reactivity and natural abundance. In order to evaluate the cobalt carbonate precipitation at room temperature, a simple experimental work was carried out in this work. The precipitation occurred via reaction of two common salts: 0.05M of CoCl2 and 0.05M of Na2CO3 in aqueous solution. After reaction, the precipitated solid was kept in the remaining water at 25 oC and under constant stirring for different aging times of 5 min, 1 and 5 hours, 1, 2, 4, 7, 30 and 60 days. In addition to the aging and precipitation experiments, we carried out experiments to determine the solubility of the solids. In these experiments each precipitate was dissolved in Milli-Q water until equilibrium was reached and then the aqueous solution was analyzed regarding Co2+ and total alkalinity. Furthermore, acid solution calorimetry of the products were attained. Finally, we modeled the results using the PHREEQC code. Solid and aqueous phase identification and characterization have been extensively reported in a previous work (González-López et al., 2015). The main results of our investigation were the initial precipitation of an amorphous cobalt carbonate that evolve towards a poorly crystalline cobalt hydroxide carbonate with aging treatment. Solubility of both phases have been calculated under two different approaches: precipitation and dissolution. Values of solubility from each approach were obtained with a general error due to differences in experiment conditions, for instance, ionic strength, temperature and

  14. Alumina nanoparticle/polymer nanocomposite dielectric for flexible amorphous indium-gallium-zinc oxide thin film transistors on plastic substrate with superior stability

    SciTech Connect

    Lai, Hsin-Cheng; Pei, Zingway; Jian, Jyun-Ruri; Tzeng, Bo-Jie

    2014-07-21

    In this study, the Al{sub 2}O{sub 3} nanoparticles were incorporated into polymer as a nono-composite dielectric for used in a flexible amorphous Indium-Gallium-Zinc Oxide (a-IGZO) thin-film transistor (TFT) on a polyethylene naphthalate substrate by solution process. The process temperature was well below 100 °C. The a-IGZO TFT exhibit a mobility of 5.13 cm{sup 2}/V s on the flexible substrate. After bending at a radius of 4 mm (strain = 1.56%) for more than 100 times, the performance of this a-IGZO TFT was nearly unchanged. In addition, the electrical characteristics are less altered after positive gate bias stress at 10 V for 1500 s. Thus, this technology is suitable for use in flexible displays.

  15. Amphipols: Polymers that Keep Membrane Proteins Soluble in Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Tribet, Christophe; Audebert, Roland; Popot, Jean-Luc

    1996-12-01

    Amphipols are a new class of surfactants that make it possible to handle membrane proteins in detergent-free aqueous solution as though they were soluble proteins. The strongly hydrophilic backbone of these polymers is grafted with hydrophobic chains, making them amphiphilic. Amphipols are able to stabilize in aqueous solution under their native state four well-characterized integral membrane proteins: (i) bacteriorhodopsin, (ii) a bacterial photosynthetic reaction center, (iii) cytochrome b6f, and (iv) matrix porin.

  16. Enhancement of flagellated bacterial motility in polymer solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Wenyu; Sha, Sha; Pelcovits, Robert; Tang, Jay

    2015-11-01

    Measurements of the swimming speed of many species of flagellated bacteria in polymer solutions have shown that with the addition of high molecular weight polymers, the speed initially increases as a function of the kinematic viscosity. It peaks at around 1.5-2 cP with typically 10-30% higher values than in cell media without added polymers (~ 1 cP). Past the peak, the average speed gradually decreases as the solution becomes more viscous. Swimming motility persists until solution viscosity reaches 5-10 cP. Models have been proposed to account for this behavior, and the magnitude of the peak becomes a crucial test of theoretical predictions. The status of the field is complicated in light of a recent report (Martinez et al., PNAS, 2014), stressing that low-molecular weight impurities account for the peaked speed-viscosity curves in some cases. We measured the swimming speed of a uni-flagellated bacterium, caulobacter crescentus, in solutions of a number of polymers of several different sizes. Our findings confirm the peaked speed-viscosity curve, only as the molecular weight of the flexible polymers used surpassed ~ 50,000 da. The threshold molecular weight required to augment swimming speed varies somewhat with the polymer species, but it generally corresponds to radius of gyration over tens of nanometers. This general feature is consistent with the model of Powers et al. (Physics of Fluid, 2009), predicting that nonlinear viscoelasticity of the fluid enhances swimming motility. Work Supported by the NSF Fluid Physics Program (Award number CBET 1438033).

  17. Characterization of amorphous yttria layers deposited by aqueous solutions of Y-chelate alkoxides complex

    NASA Astrophysics Data System (ADS)

    Kim, Young-Soon; Lee, Yu-Ri; Kim, Byeong-Joo; Lee, Jae-Hun; Moon, Seung-Hyun; Lee, Hunju

    2015-01-01

    Crack-free amorphous yttria layers were deposited by dip coating in solutions of different Y-chelate alkoxides complex. Three Y-chelate solutions of different concentrations were prepared using yttrium acetate tetrahydrate, yttrium stearic acid as Y source materials. PEG, diethanolamine were used as chelating agents, while ethanol, methanol and tetradecane were used as solvent. Three different combinations of chelating and solvents were used to prepare solutions for Y2O3 dip coating on SUS, electropolished and non-electropolished Hastelloy C-276 substrates. The thickness of the films was varied by changing the number of dipping cycles. At an optimized condition, the substrate surface roughness (rms) value was reduced from ∼50 nm to ∼1 nm over a 10 × 10 μm2 area. After Y2O3 deposition, MgO was deposited using ion-beam assisted deposition (IBAD), then LaMnO3 (LMO) was deposited using sputtering and GdBCO was deposited using reactive co-evaporation by deposition and reaction (RCE-DR). Detailed X-ray study indicates that LMO/MgO/Y2O3 and GdBCO/LMO/MgO/Y2O3 stack films have good out-of-plane and in-plane textures with strong c-axis alignment. The critical current (Ic) of GdBCO/LMO/MgO/Y2O3 multilayer structure varied from 190 to 420 A/cm with different solutions, when measured at 77 K. These results demonstrated that amorphous yttria can be easily deposited by dip coating using Y-chelates complex as a diffusion barrier and nucleation layer.

  18. Cake Filtration in Viscoelastic Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Surý, Alexander; Machač, Ivan

    2009-07-01

    In this contribution, the filtration equations for a cake filtration in viscoelastic fluids are presented. They are based on a capillary hybrid model for the flow of a power law fluid. In order to express the elastic pressure drop excess in the flow of viscoelastic filtrate through the filter cake and filter screen, modified Deborah number correction functions are included into these equations. Their validity was examined experimentally. Filtration experiments with suspensions of hardened polystyrene particles (Krasten) in viscoelastic aqueous solutions of polyacryl amides (0.4% and 0.6%wt. Kerafloc) were carried out at a constant pressure on a cylindrical filtration unit using filter screens of different resistance.

  19. Structure, Dynamic and Photophysical Properties of a Fluorescent Dye Incorporated in an Amorphous Hydrophobic Polymer Bundle

    PubMed Central

    De Mitri, N.; Monti, S.; Barone, V.

    2015-01-01

    The properties of a low molecular weight organic dye, namely 4-naphtoyloxy-1-methoxy-2,2,6,6-tetramethylpiperidine, covalently bound to an apolar polyolefin are investigated by means of a multi-level approach, combining classical molecular dynamics simulations, based on an purposely parameterized force fields, and quantum mechanical calculations, based on density functional theory (DFT) and its time-dependent extension (TD-DFT). The structure and dynamics of the dye in its embedding medium is analyzed and discussed in the light of the entangling effect of the surrounding polymer, also by comparing it to the results obtained for a different environment, i.e. toluene solution. The influence on photophysical properties of long lived cages, found in the polymeric embedding is eventually investigated in terms of slow and fast dye’s internal dynamics, by comparing computed IR and UV spectra with their experimental counterparts. PMID:24988373

  20. Nonequilibrium thermodynamics of dilute polymer solutions in flow

    SciTech Connect

    Latinwo, Folarin; Hsiao, Kai-Wen; Schroeder, Charles M.

    2014-11-07

    Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

  1. Electrospining Solutions of Associating Polymers -- the Case of Stereocomplex PMMA

    NASA Astrophysics Data System (ADS)

    Crne, Matija; Park, Jung; Srinivasarao, Mohan

    2008-03-01

    A mixture of isotactic and syndiotactic PMMA polymers (also called a ``stereocomplex PMMA'') forms a supramolecular helical structure, which is held together by non-covalent bonding. This association is thermoreversible and solvent-sensitive. If the concentration of stereocomplex PMMA is high enough, the solutions form thermoreversible physical gels. We have examined the influence this associating behavior has on the process of electrospinning. In our work, we have used solutions of stereocomplex PMMA to study the effect of physical gelation interaction on the fiber morphology and compared it to the solutions of atactic PMMA of similar molecular weight. We have found that the stereocomplex PMMA solutions do not follow the same empirical rules that are applicable for linear polymers in solution. Instead, the concentration necessary for the production of smooth, continous fibers is much lower. We ascribe this extraordinary behavior to the ability of these polymers to associate and form a network during the electrospinning process. The elasticity of the fluid jet thus rises and results in a more stable jet. The resulting fibers are interesting, as they have greater temperature stability than regular atactic PMMA. Therefore they have a bigger processing window for making composites with better mechanical properties.

  2. Monte Carlo simulations of single crystals from polymer solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Jianing; Muthukumar, M.

    2007-06-01

    A novel "anisotropic aggregation" model is proposed to simulate nucleation and growth of polymer single crystals as functions of temperature and polymer concentration in dilute solutions. Prefolded chains in a dilute solution are assumed to aggregate at a seed nucleus with an anisotropic interaction by a reversible adsorption/desorption mechanism, with temperature, concentration, and seed size being the control variables. The Monte Carlo results of this model resolve the long-standing dilemma regarding the kinetic and thermal roughenings, by producing a rough-flat-rough transition in the crystal morphology with increasing temperature. It is found that the crystal growth rate varies nonlinearly with temperature and concentration without any marked transitions among any regimes of polymer crystallization kinetics. The induction time increases with decreasing the seed nucleus size, increasing temperature, or decreasing concentration. The apparent critical nucleus size is found to increase exponentially with increasing temperature or decreasing concentration, leading to a critical nucleus diagram composed in the temperature-concentration plane with three regions of different nucleation barriers: no growth, nucleation and growth, and spontaneous growth. Melting temperatures as functions of the crystal size, heating rate, and concentration are also reported. The present model, falling in the same category of small molecular crystallization with anisotropic interactions, captures most of the phenomenology of polymer crystallization in dilute solutions.

  3. Study on Mixing Field of Salt Tolerant Polymer Solution

    NASA Astrophysics Data System (ADS)

    Zhang, L. H.; Zhang, M. G.; Li, X. G.; Zhang, D.; Jiang, B.

    The salt tolerant polymer (PAM) solution is a kind of viscoelastic fluid. The polymer. whose molecular weight is more than 2.5x107g/mol, is apt to form ultra-molecular structures in solution with pretty high viscoelasticity. These characteristics considerably affect the flow patterns and the mixing process. It is far more difficult to mix viscoelastic fluid homogeneously than Newtonian fluid. Because the molecular diffusion rate of viscoelastic fluid in mixing process is very low, improving the circulating performance of the agitator is the main path to increase the mixing velocity of the viscoelastic fluid. In this study, structure and operation parameters of new type agitator—double helical ribbon screw agitator designed for the salt tolerant polymer are optimized via laboratory experiment. The experiment results show that, compared with the screw propeller, the new type agitator improves circulation of fluid field effectively and increases the homogenized rate. It reduces the mixing time from 4h to 2h. And the viscosity of the polymer solution increases by 10%. However, the energy consumption does not increase.

  4. Entanglement-Controlled Subdiffusion of Nanoparticles within Concentrated Polymer Solutions

    SciTech Connect

    Guo, Hongyu; Bourret, Gilles; Lennox, R. Bruce; Sutton, Mark; Harden, James L.; Leheny, Robert L.

    2012-10-23

    We describe x-ray photon correlation spectroscopy (XPCS) experiments tracking the motion of gold nanoparticles within solutions of high-molecular-weight polystyrene. Over displacements from nanometers to tens of nanometers, the particles undergo subdiffusive motion that is dictated by the temporal evolution of the entangled polymer mesh in the immediate vicinity of the particles. The results thus provide a novel microscopic dynamical characterization of this key structural property of polymers and more broadly demonstrate the capability of XPCS-based microrheology to interrogate heterogeneous mechanical environments in nanostructured soft materials.

  5. Dynamics of polymer solutions and polymer/vesicle mixtures during microchannel flow

    NASA Astrophysics Data System (ADS)

    Graham, Michael; Anekal, Samartha; Hernandez-Ortiz, Juan

    2008-11-01

    Addition of small amounts of long-chain polymers to blood has been found to have dramatic effects on its flow in the microcirculation. To address the mechanisms underlying these phenomena, we use a real-space P^3M method for Stokes flow including Brownian fluctuations to study the dynamics of polymer solutions and polymer/vesicle mixtures in microscale flows. Both a simple slit geometry and a grooved cavity flow are studied and polymer concentrations from ultradilute up to near the overlap concentration are considered. As concentration increases, the hydrodynamic migration effects observed in dilute solution unidirectional flows become less prominent, virtually vanishing as the overlap concentration is approached. In a grooved channel geometry, the groove is almost completely depleted of polymer chains at high Weissenberg number in the dilute limit, but at finite concentration this depletion effect is dramatically reduced. In suspensions of vesicles, the presence of polymer molecules has a substantial effect on the dynamics of pair collisions and on migration of the vesicles from microchannel walls.

  6. Spontaneous unilamellar polymer vesicles in aqueous solution.

    PubMed

    Kim, Tae-Hwan; Song, Chaeyeon; Han, Young-Soo; Jang, Jong-Dae; Choi, Myung Chul

    2014-01-21

    A unilamellar polymeric vesicle is a self-assembled structure of a block copolymer that forms a spherical single bilayer structure with a hydrophobic interlayer and a hydrophilic surface. Due to their enhanced colloidal stability and mechanical property, controllable surface functionality, or tunable membrane thickness, polymeric vesicles are useful in nano and bio-science, providing potential applications as nanosized carriers for catalysts, drugs, and enzymes. For fabrication of a unilamellar vesicle, however, preparative procedures with a few steps are inherently required. Herein, without complicated preparative procedures, we report spontaneous unilamellar polymeric vesicles with nanometer sizes (<100 nm), which are prepared by simply mixing a triblock copolymer, Pluronic P85 (PEO26PPO40PEO26), and an organic derivative, 5-methyl salicylic acid (5mS), in aqueous solution. Depending on the 5mS concentration and the temperature, the P85-5mS mixtures presented various self-assembled nanostructures such as spherical and cylindrical micelles or vesicles, which were characterized by small angle neutron scattering and cryo-TEM, resulting in a phase diagram drawn as a function of temperature and the 5mS concentration. Interestingly the critical temperature for the micelle-to-vesicle phase transition was easily controlled by varying the 5mS concentration, i.e. it was decreased with increasing the 5mS concentration. PMID:24652418

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

    PubMed Central

    Mendels, Dan; Tessler, Nir

    2016-01-01

    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. PMID:27405103

  8. 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.

  9. Optical coatings of variable refractive index and high laser-resistance from physical-vapor-deposited perfluorinated amorphous polymer

    DOEpatents

    Chow, Robert; Loomis, Gary E.; Thomas, Ian M.

    1999-01-01

    Variable index optical single-layers, optical multilayer, and laser-resistant coatings were made from a perfluorinated amorphous polymer material by physical vapor deposition. This was accomplished by physically vapor depositing a polymer material, such as bulk Teflon AF2400, for example, to form thin layers that have a very low refractive index (.about.1.10-1.31) and are highly transparent from the ultra-violet through the near infrared regime, and maintain the low refractive index of the bulk material. The refractive index can be varied by simply varying one process parameter, either the deposition rate or the substrate temperature. The thus forming coatings may be utilized in anti-reflectors and graded anti-reflection coatings, as well as in optical layers for laser-resistant coatings at optical wavelengths of less than about 2000 nm.

  10. Optical coatings of variable refractive index and high laser-resistance from physical-vapor-deposited perfluorinated amorphous polymer

    DOEpatents

    Chow, R.; Loomis, G.E.; Thomas, I.M.

    1999-03-16

    Variable index optical single-layers, optical multilayer, and laser-resistant coatings were made from a perfluorinated amorphous polymer material by physical vapor deposition. This was accomplished by physically vapor depositing a polymer material, such as bulk Teflon AF2400, for example, to form thin layers that have a very low refractive index (ca. 1.10--1.31) and are highly transparent from the ultra-violet through the near infrared regime, and maintain the low refractive index of the bulk material. The refractive index can be varied by simply varying one process parameter, either the deposition rate or the substrate temperature. The thus forming coatings may be utilized in anti-reflectors and graded anti-reflection coatings, as well as in optical layers for laser-resistant coatings at optical wavelengths of less than about 2000 nm. 2 figs.

  11. Removing iron from concentrated alum solutions by polymer filtrations

    SciTech Connect

    Trujillo, S.M.

    1997-12-31

    The Forest Product Industry is the ninth largest industry in the United States, yet it is ranked third in energy consumption among all U.S. industries. From the environmental point of view, paper manufacturing is a complex business, with a wide range of impacts. Its use of natural raw materials, large amounts of energy, chemicals and water, coupled with a wide range of emissions ensure that it has a high environmental profile. Any new technology that is introduced to into pulp and paper mills to reduce energy consumption will have a major impact on the environment. Polymer Filtration, A membrane-based technology, was successful in making the electroplating industry recycle its rinse wastestream and was recognize for this achievement with a 1995 R&D 100 Award. We would like extend the applications of Polymer Filtration to the Forest Products in the following area: Removing Iron From Concentrated Alum Solutions by Polymer Filtration.

  12. Role of Polymer Segment-Particle Surface Interactions in Controlling Nanoparticle Dispersions in Concentrated Polymer Solutions

    SciTech Connect

    Kim, So Youn; Zukoski, Charles F.

    2014-09-24

    The microstructure of particles suspended in concentrated polymer solutions is examined with small-angle X-ray scattering and small-angle neutron scattering. Of interest are changes to long wavelength particle density fluctuations in ternary mixtures of silica nanoparticles suspended in concentrated solutions of poly(ethylene glycol). The results are understood in terms of application of the pseudo-two-component polymer reference interaction site model (PRISM) theory modified to account for solvent addition via effective contact strength of interfacial attraction, εpc, in an implicit manner. The combined experimental-theoretical study emphasizes the complex interactions between solvent, polymer, and particle surface that control particle miscibility but also demonstrate that these factors can all be understood in terms of variations of εpc.

  13. Modeling the Rheology of Polymer Melts and Solutions

    NASA Astrophysics Data System (ADS)

    Larson, R. G.; Desai, Priyanka S.

    2015-01-01

    We review constitutive modeling of solutions and melts of linear polymers, focusing on changes in rheological behavior in shear and extensional flow as the concentration increases from unentangled dilute, to entangled, to dense melt. The rheological changes are captured by constitutive equations, prototypes of which are the FENE-P model for unentangled solutions and the DEMG model for entangled solutions and melts. From these equations, and supporting experimental data, for dilute solutions, the extensional viscosity increases with the strain rate from the low-strain rate to the high-strain rate asymptote, but in the densely entangled state, the high-strain rate viscosity is lower than the low-shear rate value, especially when orientation-dependent friction is accounted for. In shearing flow, shear thinning increases dramatically as the entanglement density increases, which can eventually lead to a shear-banding inhomogeneity. Recent improvements in constitutive modeling are paving the way for robust and accurate numerical simulations of polymer fluid mechanics and industrial processing of polymers.

  14. Multi-blob coarse graining for ring polymer solutions.

    PubMed

    Narros, Arturo; Likos, Christos N; Moreno, Angel J; Capone, Barbara

    2014-12-28

    We present a multi-scale molecular modeling of concentrated solutions of unknotted and non-concatenated ring polymers under good solvent conditions. The approach is based on a multi-blob representation of each ring polymer, which is capable of overcoming the shortcomings of single-blob approaches that lose their validity at concentrations exceeding the overlap density of the solution [A. Narros, A. J. Moreno, and C. N. Likos, Soft Matter, 2010, 6, 2435]. By means of a first principles coarse-graining strategy based on analytically determined effective pair potentials between the blobs, computed at zero density, we quantitatively reproduce the single molecule and solution properties of a system with well-defined topological constraints. Detailed comparisons with the underlying, monomer-resolved model demonstrate the validity of our approach, which employs fully transferable pair potentials between connected and unconnected blobs. We demonstrate that the pair structure between the centers of mass of the rings is accurately reproduced by the multi-blob approach, thus opening the way for simulation of arbitrarily long polymers. Finally, we show the importance of the topological constraint of non-concatenation on the structure of the concentrated solution and in particular on the size of the correlation hole and the shrinkage of the rings as melt concentrations are approached.

  15. Infrared optical constants of H2O ice, amorphous nitric acid solutions, and nitric acid hydrates

    NASA Technical Reports Server (NTRS)

    Toon, Owen B.; Koehler, Birgit G.; Middlebrook, Ann M.; Tolbert, Margaret A.; Jordon, Joseph

    1994-01-01

    We determined the infrared optical constants of nitric acid trihydrate, nitric acid dihydrate, nitric acid monohydrate, and solid amorphous nitric acid solutions which crystallize to form these hydrates. We have also found the infrared optical constants of H2O ice. We measured the transmission of infrared light throught thin films of varying thickness over the frequency range from about 7000 to 500/cm at temperatures below 200 K. We developed a theory for the transmission of light through a substrate that has thin films on both sides. We used an iterative Kramers-Kronig technique to determine the optical constants which gave the best match between measured transmission spectra and those calculated for a variety of films of different thickness. These optical constants should be useful for calculations of the infrared spectrum of polar stratospheric clouds.

  16. Solution processed polymer tandem solar cell using efficient small and wide bandgap polymer:fullerene blends.

    PubMed

    Gevaerts, Veronique S; Furlan, Alice; Wienk, Martijn M; Turbiez, Mathieu; Janssen, René A J

    2012-04-24

    Solution processed polymer tandem solar cells that combine wide and small bandgap absorber layers reach a power conversion efficiency of 7% in a series configuration. This represents a 20% increase compared to the best single junction cells made with the individual active layers and shows that the tandem configuration reduces transmission and thermalization losses in converting sunlight. PMID:22438114

  17. The Dynamics of Nanoparticles in Polymer Solutions and Melts

    NASA Astrophysics Data System (ADS)

    Mukhopadhyay, Ashis; Alam, Sharmine; Kohli, Indermeet

    2014-03-01

    Polymer nanocomposites (PNCs) has received a lot of attention in the recent years because of their potential applications in fabricating materials with novel mechanical, electrical, and photonic properties. The mobility of nanoparticles (NPs) play crucial role in determining various properties of PNC systems. Computer simulations and recent experiments have suggested that properties such as the toughness of a composite depend upon particle mobility. Even nanocomposites with ``self-healing'' properties that can restore strength in damaged regions have been proposed and some early work of their feasibility has been demonstrated. In this talk I will present some of our experimental work on the diffusion of nano-sized gold particles in polymer solutions and melt. Unusually fast diffusion of NPs when their size is smaller than the tube diameter in an entangled polymer was observed. Comparison with current theories and simulations will be shown. If time permits, our recent results on gold nanorod diffusion in polymer solution using polarized fluorescence correlation spectroscopy will be presented. Acknowledgements are made to the Donors of the American Chemical Society Petroleum Research fund (PRF # 51694-ND10) for support of this research.

  18. Small Angle Neutron Scattering of Solutions of Arborescent Graft Polymers

    NASA Astrophysics Data System (ADS)

    Choi, Sangwook; Briber, R. M.; Bauer, B. J.; Topp, Andreas; Gauthier, Mario

    1998-03-01

    Arborescent graft polymers are branched macromolecules resulting from successive cycles of chloromethylation and anionic grafting reactions. Small angle neutron scattering (SANS) was used to measure the size and shape of arborescent graft polymers in solution. Guinier plots were used to analyze the data at small q. The radius of gyration of arborescent graft polymers was found to be almost independent of temperature as the solution was cooled towards the phase separation temperature. The optical cloud point temperature was found to be 15 ^0C. At the phase separation temperature two peaks were observed in the I versus q SANS data. The first peak is due to the interference between molecules while the second peak comes from the single particle form factor. The value of q at the peak from the form factor was almost constant as temperature was changed from 40 ^0C to 20 ^0C. The peak position shifted to higher q at the phase separation temperature. This indicates that the size of molecules decreased as the molecules began to aggregate below the phase separation temperature. The value of A2 for arborescent graft polymers was found to be independent of temperature and close to zero.

  19. Instabilities in stagnation point flows of polymer solutions

    NASA Astrophysics Data System (ADS)

    Haward, S. J.; McKinley, G. H.

    2013-08-01

    A recently developed microfluidic device, the optimized shape cross-slot extensional rheometer or OSCER [S. J. Haward, M. S. N. Oliveira, M. A. Alves, and G. H. McKinley, "Optimized cross-slot flow geometry for microfluidic extensional rheometry," Phys. Rev. Lett. 109, 128301 (2012), 10.1103/PhysRevLett.109.128301], is used to investigate the stability of viscoelastic polymer solutions in an idealized planar stagnation point flow. Aqueous polymer solutions, consisting of poly(ethylene oxide) and of hyaluronic acid with various molecular weights and concentrations, are formulated in order to provide fluids with a wide range of rheological properties. Semi-dilute solutions of high molecular weight polymers provide highly viscoelastic fluids with long relaxation times, which achieve a high Weissenberg number (Wi) at flow rates for which the Reynolds number (Re) remains low; hence the elasticity number El = Wi/Re is high. Lower concentration solutions of moderate molecular weight polymers provide only weakly viscoelastic fluids in which inertia remains important and El is relatively low. Flow birefringence observations are used to visualize the nature of flow instabilities in the fluids as the volumetric flow rate through the OSCER device is steadily incremented. At low Wi and Re, all of the fluids display a steady, symmetric, and uniform "birefringent strand" of highly oriented polymer molecules aligned along the outflowing symmetry axis of the test geometry, indicating the stability of the flow field under such conditions. In fluids of El > 1, we observe steady elastic flow asymmetries beyond a critical Weissenberg number,Wicrit, that are similar in character to those already reported in standard cross-slot geometries [e.g., P. E. Arratia, C. C. Thomas, J. Diorio, and J. P. Gollub, "Elastic instabilities of polymer solutions in cross-channel flow," Phys. Rev. Lett. 96, 144502 (2006), 10.1103/PhysRevLett.96.144502]. However, in fluids with El < 1 we observe a sequence

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

    PubMed

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

    2015-10-20

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

  1. Limitations of amorphous content quantification by isothermal calorimetry using saturated salt solutions to control relative humidity: alternative methods.

    PubMed

    Khalef, Nawel; Pinal, Rodolfo; Bakri, Aziz

    2010-04-01

    Despite the high sensitivity of isothermal calorimetry (IC), reported measurements of amorphous content by this technique show significant variability even for the same compound. An investigation into the reasons behind such variability is presented using amorphous lactose and salbutamol sulfate as model compounds. An analysis was carried out on the heat evolved as a result of the exchange of water vapor between the solid sample during crystallization and the saline solution reservoir. The use of saturated salt solutions as means of control of the vapor pressure of water within sealed ampoules bears inherent limitations that lead in turn to the variability associated with the IC technique. We present an alternative IC method, based on an open cell configuration that effectively addresses the limitations encountered with the sealed ampoule system. The proposed approach yields an integral whose value is proportional to the amorphous content in the sample, thus enabling reliable and consistent quantifications. PMID:19774655

  2. All-solution processed polymer light-emitting diode displays

    NASA Astrophysics Data System (ADS)

    Zheng, Hua; Zheng, Yina; Liu, Nanliu; Ai, Na; Wang, Qing; Wu, Sha; Zhou, Junhong; Hu, Diangang; Yu, Shufu; Han, Shaohu; Xu, Wei; Luo, Chan; Meng, Yanhong; Jiang, Zhixiong; Chen, Yawen; Li, Dongyun; Huang, Fei; Wang, Jian; Peng, Junbiao; Cao, Yong

    2013-06-01

    Adopting the emerging technology of printed electronics in manufacturing novel ultrathin flat panel displays attracts both academic and industrial interests because of the challenge in the device physics and the potential of reducing production costs. Here we produce all-solution processed polymer light-emitting diode displays by solution-depositing the cathode and utilizing a multifunctional buffer layer between the cathode and the organic layers. The use of ink-jetted conducting nanoparticles as the cathode yields high-resolution cathode patterns without any mechanical stress on the organic layers. The buffer layer, which offers the functions of solvent-proof electron injection and proper affinity, is fabricated by mixing the water/alcohol-soluble polymer and a curable epoxy adhesive. Our 1.5-inch polymer light-emitting diode displays are fabricated without any dead pixels or dead lines. The all-solution process eliminates the need for high vacuum for thermal evaporation of the cathode, which paves the way to industrial roll-to-roll manufacturing of flat panel displays.

  3. Measurement of cloud point temperature in polymer solutions.

    PubMed

    Mannella, G A; La Carrubba, V; Brucato, V

    2013-07-01

    A temperature-controlled turbidity measurement apparatus for the characterization of polymer solutions has been instrumented and set up. The main features are the coupled temperature-light transmittance measurement and the accurate temperature control, achieved by means of peltier cells. The apparatus allows to measure cloud point temperatures by adopting different cooling protocols: low rate for quasi-equilibrium measurements and high rate for detect kinetic effects. A ternary polymeric solution was adopted as case study system showing that cooling rate affects the measured cloud point temperature.

  4. Structure of polymer layers adsorbed from concentrated solutions

    NASA Astrophysics Data System (ADS)

    Auvray, Loïc; Auroy, Philippe; Cruz, Margarida

    1992-06-01

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

  5. Polymer Encapsulation of an Amorphous Pharmaceutical by initiated Chemical Vapor Deposition for Enhanced Stability.

    PubMed

    Christian, Paul; Ehmann, Heike M A; Coclite, Anna Maria; Werzer, Oliver

    2016-08-24

    The usage of amorphous solids in practical applications, such as in medication, is commonly limited by the poor long-term stability of this state, because unwanted crystalline transitions occur. In this study, three different polymeric coatings are investigated for their ability to stabilize amorphous films of the model drug clotrimazole and to protect against thermally induced transitions. For this, drop cast films of clotrimazole are encapsulated by initiated chemical vapor deposition (iCVD), using perfluorodecyl acrylate (PFDA), hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA). The iCVD technique operates under solvent-free conditions at low temperatures, thus leaving the solid state of the encapsulated layer unaffected. Optical microscopy and X-ray diffraction data reveal that at ambient conditions of about 22 °C, any of these iCVD layers extends the lifetime of the amorphous state significantly. At higher temperatures (50 or 70 °C), the p-PFDA coating is unable to provide protection, while the p-HEMA and p-MAA strongly reduce the crystallization rate. Furthermore, p-HEMA and p-MAA selectively facilitate a preferential alignment of clotrimazole and, interestingly, even suppress crystallization upon a temporary, rapid temperature increase (3 °C/min, up to 150 °C). The results of this study demonstrate how a polymeric coating, synthesized directly on top of an amorphous phase, can act as a stabilizing agent against crystalline transitions, which makes this approach interesting for a variety of applications. PMID:27467099

  6. Polymer Encapsulation of an Amorphous Pharmaceutical by initiated Chemical Vapor Deposition for Enhanced Stability

    PubMed Central

    2016-01-01

    The usage of amorphous solids in practical applications, such as in medication, is commonly limited by the poor long-term stability of this state, because unwanted crystalline transitions occur. In this study, three different polymeric coatings are investigated for their ability to stabilize amorphous films of the model drug clotrimazole and to protect against thermally induced transitions. For this, drop cast films of clotrimazole are encapsulated by initiated chemical vapor deposition (iCVD), using perfluorodecyl acrylate (PFDA), hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA). The iCVD technique operates under solvent-free conditions at low temperatures, thus leaving the solid state of the encapsulated layer unaffected. Optical microscopy and X-ray diffraction data reveal that at ambient conditions of about 22 °C, any of these iCVD layers extends the lifetime of the amorphous state significantly. At higher temperatures (50 or 70 °C), the p-PFDA coating is unable to provide protection, while the p-HEMA and p-MAA strongly reduce the crystallization rate. Furthermore, p-HEMA and p-MAA selectively facilitate a preferential alignment of clotrimazole and, interestingly, even suppress crystallization upon a temporary, rapid temperature increase (3 °C/min, up to 150 °C). The results of this study demonstrate how a polymeric coating, synthesized directly on top of an amorphous phase, can act as a stabilizing agent against crystalline transitions, which makes this approach interesting for a variety of applications. PMID:27467099

  7. Influence of polymer molecular weight on in vitro dissolution behavior and in vivo performance of celecoxib:PVP amorphous solid dispersions.

    PubMed

    Knopp, Matthias Manne; Nguyen, Julia Hoang; Becker, Christian; Francke, Nadine Monika; Jørgensen, Erling B; Holm, Per; Holm, René; Mu, Huiling; Rades, Thomas; Langguth, Peter

    2016-04-01

    In this study, the influence of the molecular weight of polyvinylpyrrolidone (PVP) on the non-sink in vitro dissolution and in vivo performance of celecoxib (CCX):PVP amorphous solid dispersions were investigated. The dissolution rate of CCX from the amorphous solid dispersions increased with decreasing PVP molecular weight and crystallization inhibition was increased with increasing molecular weight of PVP, but reached a maximum for PVP K30. This suggested that the crystallization inhibition was not proportional with molecular weight of the polymer, but rather there was an optimal molecular weight where the crystallization inhibition was strongest. Consistent with the findings from the non-sink in vitro dissolution tests, the amorphous solid dispersions with the highest molecular weight PVPs (K30 and K60) resulted in significantly higher in vivo bioavailability (AUC0-24h) compared with pure amorphous and crystalline CCX. A linear relationship between the in vitro and in vivo parameter AUC0-24h indicated that the simple non-sink in vitro dissolution method used in this study could be used to predict the in vivo performance of amorphous solid dispersion with good precision, which enabled a ranking between the different formulations. In conclusion, the findings of this study demonstrated that the in vitro and in vivo performance of CCX:PVP amorphous solid dispersions were significantly controlled by the molecular weight of the polymer.

  8. Adsorption of catechol from aqueous solution by aminated hypercrosslinked polymers.

    PubMed

    Sun, Yue; Li, Xiao-Tao; Xu, Chao; Chen, Jin-Long; Li, Ai-Min; Zhang, Quan-Xing

    2005-01-01

    Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1, AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly basic anion exchanger resin D301 was compared. It was found that the aminated hypercrosslinked resins had the highest adsorption capacities among the tested polymers. The empirical Freundlich equation was successfully employed to describe the adsorption process. Specific surface area and micropore structure of the adsorbent, in company with tertiary amino groups on matrix affected the adsorption performance towards catechol. In addition, thermodynamic study was carried out to interpret the adsorption mechanism. Kinetic study testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate and increase the adsorption apparent activation energy.

  9. Demixing kinetics of phase separated polymer solutions in microgravity

    NASA Technical Reports Server (NTRS)

    Brooks, D. E.; Bamberger, S. B.; Harris, J. M.; Vanalstine, J.; Snyder, R. S.

    1988-01-01

    Phase separated solutions of two neutral polymers in buffer provide a useful and versatile medium for the partition separation of biological cells. However, the efficiency of such separations is orders of magnitude lower than the thermodynamic limit. To test the hypothesis that this inefficiency is at least partially due to the convection and sedimentation that occur during the gravity driven demixing that follows introduction of cells to the systems, a series of experiments were begun aimed at performing cell partition in a low g environment. Demixing of isopycnic three polymer solvent systems was studied, experiments were performed on KC-135 aircraft and one shuttle middeck experiment was completed. Analysis of the results of these experiments and comparisons with the predictions of scaling relations for the dependence of phase domain size on time, derived for a number of possible demixing mechanisms, are presented.

  10. Tuning the critical solution temperature of polymers by copolymerization

    SciTech Connect

    Schulz, Bernhard; Chudoba, Richard; Dzubiella, Joachim; Heyda, Jan

    2015-12-28

    We study statistical copolymerization effects on the upper critical solution temperature (CST) of generic homopolymers by means of coarse-grained Langevin dynamics computer simulations and mean-field theory. Our systematic investigation reveals that the CST can change monotonically or non-monotonically with copolymerization, as observed in experimental studies, depending on the degree of non-additivity of the monomer (A-B) cross-interactions. The simulation findings are confirmed and qualitatively explained by a combination of a two-component Flory-de Gennes model for polymer collapse and a simple thermodynamic expansion approach. Our findings provide some rationale behind the effects of copolymerization and may be helpful for tuning CST behavior of polymers in soft material design.

  11. Mesoscale modeling of shear-thinning polymer solutions.

    PubMed

    Santos de Oliveira, I S; Fitzgerald, B W; den Otter, W K; Briels, W J

    2014-03-14

    We simulate the linear and nonlinear rheology of two different viscoelastic polymer solutions, a polyisobutylene solution in pristane and an aqueous solution of hydroxypropylcellulose, using a highly coarse-grained approach known as Responsive Particle Dynamics (RaPiD) model. In RaPiD, each polymer has originally been depicted as a spherical particle with the effects of the eliminated degrees of freedom accounted for by an appropriate free energy and transient pairwise forces. Motivated by the inability of this spherical particle representation to entirely capture the nonlinear rheology of both fluids, we extended the RaPiD model by introducing a deformable particle capable of elongation. A Finite-Extensible Non-Linear Elastic potential provides a free energy penalty for particle elongation. Upon disentangling, this deformability allows more time for particles to re-entangle with neighbouring particles. We show this process to be integral towards recovering the experimental nonlinear rheology, obtaining excellent agreement. We show that the nonlinear rheology is crucially dependent upon the maximum elongation and less so on the elasticity of the particles. In addition, the description of the linear rheology has been retained in the process.

  12. Diffusion behavior of lipid vesicles in entangled polymer solutions.

    PubMed Central

    Cao, X; Bansil, R; Gantz, D; Moore, E W; Niu, N; Afdhal, N H

    1997-01-01

    Dynamic light scattering was used to follow the tracer diffusion of phospholipid/cholesterol vesicles in aqueous polyacrylamide solutions and compared with the diffusive behavior of polystyrene (PS) latex spheres of comparable diameters. Over the range of the matrix concentration examined (Cp = 0.1-10 mg/ml), the diffusivities of the PS spheres and the large multilamellar vesicles exhibited the Stokes-Einstein (SE) relation, while the diffusivity of the unilamellar vesicles did not follow the increase of the solution's viscosity caused by the presence of the matrix molecules. The difference between the diffusion behaviors of unilamellar vesicles and hard PS spheres of similar size is possibly due to the flexibility of the lipid bilayer of the vesicles. The unilamellar vesicles are capable of changing their shape to move through the entangled polymer solution so that the hindrance to their diffusion due to the presence of the polymer chains is reduced, while the rigid PS spheres have little flexibility and they encounter greater resistance. The multilamellar vesicles are less flexible, thus their diffusion is similar to the hard PS spheres of similar diameter. Images FIGURE 2 PMID:9336189

  13. Separation of Ionic Solutes Using Nanoparticle-Crosslinked Polymer Hydrogels

    NASA Astrophysics Data System (ADS)

    Thomas, Peter; Cipriano, Bani; Raghavan, Srinivasa

    2007-03-01

    Polymer hydrogels are usually made by crosslinking a monomer such as N-isopropylacrylamide (NIPAAm) with a multifunctional crosslinker. Recently, gels have been shown to be formed even in the absence of monomer by using clay nanoparticles as crosslinkers. These particle-crosslinked gels tend to have larger pore sizes and higher gel strengths compared to conventional NIPAAm gels. In this talk, we will show that particle-crosslinked gels are also suited for use as separation matrices. In particular, we will describe the extraordinary ability of these gels to soak up a cationic solute from a solution. We speculate that cationic molecules can be adsorbed on the anionic surface of the clay platelets inside the gel, akin to a process of ion exchange. An additional unique property of these gels is that they can be disassembled in the presence of organic solvents -- due to the non-covalent interaction between polymer and particles (there is no counterpart for this behavior in conventional covalently-linked gels). By exploiting this property, cationic solutes adsorbed on the particles within our gel can be released and recovered.

  14. Gigantic enhancement in the dielectric properties of polymer-based composites using core/shell MWCNT/amorphous carbon nanohybrids

    NASA Astrophysics Data System (ADS)

    Guo, Qikai; Xue, Qingzhong; Sun, Jin; Dong, Mingdong; Xia, Fujun; Zhang, Zhongyang

    2015-02-01

    Novel core/shell structured multi-walled carbon nanotube/amorphous carbon (MWCNT@AC) nanohybrids were successfully prepared using a simple and novel method. Subsequently, the MWCNT@AC nanohybrids were used as fillers to enhance the dielectric properties of poly(vinylidene fluoride) (PVDF) based composites. It is found that the dielectric constant of the MWCNT@AC/PVDF composites can reach 5910 (the dielectric loss is ~2), which is considerably better than that of MWCNT/PVDF composites. The uniform amorphous carbon shell provides an insulative layer between adjacent MWCNTs in the polymer matrix, which not only prevents the direct contact of MWCNTs but also improves the dispersibility of the MWCNTs. Therefore, a surprising number of microcapacitors could be formed in the composites before the formation of a conductive network, leading to a gigantic enhancement in the dielectric properties. Our strategy provides a new approach to fabricate excellent dielectric materials for energy storage capacitors. In addition, the design concept used in this work can be extended to other carbon materials.

  15. Hot melt extrusion for amorphous solid dispersions: temperature and moisture activated drug-polymer interactions for enhanced stability.

    PubMed

    Sarode, Ashish L; Sandhu, Harpreet; Shah, Navnit; Malick, Waseem; Zia, Hossein

    2013-10-01

    Hot melt extrudates (HMEs) of indomethacin (IND) with Eudragit EPO and Kollidon VA 64 and those of itraconazole (ITZ) with HPMCAS-LF and Kollidon VA 64 were manufactured using a Leistritz twin screw extruder. The milled HMEs were stored at controlled temperature and humidity conditions. The samples were collected after specified time periods for 3 months. The stability of amorphous HMEs was assessed using moisture analysis, thermal evaluation, powder X-ray diffraction, FTIR, HPLC, and dissolution study. In general, the moisture content increased with time, temperature, and humidity levels. Amorphous ITZ was physically unstable at very high temperature and humidity levels, and its recrystallization was detected in the HMEs manufactured using Kollidon VA 64. Although physical stability of IND was better sustained by both Eudragit EPO and Kollidon VA 64, chemical degradation of the drug was identified in the stability samples of HMEs with Eudragit EPO stored at 50 °C. The dissolution rates and the supersaturation levels were significantly decreased for the stability samples in which crystallization was detected. Interestingly, the supersaturation was improved for the stability samples of IND:Eudragit EPO and ITZ:HPMCAS-LF, in which no physical or chemical instability was observed. This enhancement in supersaturation was attributed to the temperature and moisture activated electrostatic interactions between the drugs and their counterionic polymers. PMID:23961978

  16. Gigantic enhancement in the dielectric properties of polymer-based composites using core/shell MWCNT/amorphous carbon nanohybrids.

    PubMed

    Guo, Qikai; Xue, Qingzhong; Sun, Jin; Dong, Mingdong; Xia, Fujun; Zhang, Zhongyang

    2015-02-28

    Novel core/shell structured multi-walled carbon nanotube/amorphous carbon (MWCNT@AC) nanohybrids were successfully prepared using a simple and novel method. Subsequently, the MWCNT@AC nanohybrids were used as fillers to enhance the dielectric properties of poly(vinylidene fluoride) (PVDF) based composites. It is found that the dielectric constant of the MWCNT@AC/PVDF composites can reach 5910 (the dielectric loss is ∼2), which is considerably better than that of MWCNT/PVDF composites. The uniform amorphous carbon shell provides an insulative layer between adjacent MWCNTs in the polymer matrix, which not only prevents the direct contact of MWCNTs but also improves the dispersibility of the MWCNTs. Therefore, a surprising number of microcapacitors could be formed in the composites before the formation of a conductive network, leading to a gigantic enhancement in the dielectric properties. Our strategy provides a new approach to fabricate excellent dielectric materials for energy storage capacitors. In addition, the design concept used in this work can be extended to other carbon materials.

  17. Temperature Gradients Induce Phase Separation in a Miscible Polymer Solution

    NASA Astrophysics Data System (ADS)

    Kumaki, Jiro; Hashimoto, Takeji; Granick, Steve

    1996-09-01

    Phase separation occurred up to 20 °C above the coexistence temperature in a polymer solution (polystyrene-polybutadiene-dioctylphthalate) to which small temperature gradients ( ~2 °C) were applied. Before convection began, spinodal-like patterns with characteristic spacing that grew in proportion to time elapsed persisted for times up to hours. The cause appears to be thermally driven concentration gradients normal to the surface, large enough to induce phase separation parallel to the surface, although temperatures throughout the mixture exceeded the thermodynamic coexistence temperature.

  18. Polymer monoliths synthesized by radiation co-polymerization in solution

    NASA Astrophysics Data System (ADS)

    Beiler, Barbara; Sáfrány, Ágnes

    2007-08-01

    Hydrophilic co-polymer monoliths were prepared by irradiating alcoholic solutions containing diethyleneglycol dimethacrylate (DEGDMA) and 2-hydroxyethylacrylate (HEA) monomers. The effect of monomer ratio, solvent properties and radiation dose on the porous properties of the monoliths was studied in detail and compared to the monolith prepared from DEGDMA. Increase of the HEA content in the co-monomer mixture (up to 18 vol%) resulted in monoliths with increased pore size and hydrophilic character. The biggest pores were obtained when methanol was used as solvent. The use of the monoliths as chromatographic columns for separation of proteins, amino and nucleic acids is also reported.

  19. Low-temperature solution-processed amorphous indium tin oxide field-effect transistors.

    PubMed

    Kim, Hyun Sung; Kim, Myung-Gil; Ha, Young-Geun; Kanatzidis, Mercouri G; Marks, Tobin J; Facchetti, Antonio

    2009-08-12

    Amorphous indium tin oxide (ITO)-based thin-film transistors (TFTs) were fabricated on various dielectrics [SiO(2) and self-assembled nanodielectrics (SANDs)] by spin-coating an ITO film precursor solution consisting of InCl(3) and SnCl(4) as the sources of In(3+) and Sn(4+), respectively, methoxyethanol (solvent), and ethanolamine (base). These films can be annealed at temperatures T(a) < or = 250 degrees C and afford devices with excellent electrical characteristics. The optimized [In(3+)]/[In(3+) + Sn(4+)] molar ratio (0.7) and annealing temperature (T(a) = 250 degrees C) afford TFTs exhibiting electron mobilities of approximately 2 and approximately 10-20 cm(2) V(-1) s(-1) with SiO(2) and SAND, respectively, as the gate dielectric. Remarkably, ITO TFTs processed at 220 degrees C still exhibit electron mobilities of >0.2 cm(2) V(-1) s(-1), which is encouraging for processing on plastic substrates.

  20. Solution and Melt Rheology of Polypropylene Comb and Star Polymers

    NASA Astrophysics Data System (ADS)

    Ghosh, Arnav; Colby, Ralph H.; Rose, Jeffrey M.; Cherian, Anna E.; Coates, Geoffrey W.

    2006-03-01

    Syndiotactic polypropylene macromonomer arms have been prepared by coordination-insertion polymerization. These arms have been made into polypropylene star polymers by the homopolymerization of the syndiotactic arms with a living alkene polymerization catalyst. The macromonomer arms have also been randomly copolymerized with propylene using rac-dimethylsilyl(2-methyl-4-phenylindenyl) zirconium dichloride catalysts to make polypropylene combs. Consequently we have star polymers and a series of comb polymers with different backbone lengths that are all made from the same macromonomer arms. We compare linear viscoelastic data on star and comb polypropylene melts and solutions in squalane to predictions of the tube dilation model and the tube model without tube dilation. The ratio of comb terminal relaxation time to star terminal relaxation time eliminates the friction coefficient and allows determination of the extent of tube dilation the backbone experiences when it relaxes. The concentration dependence of the comb/star terminal relaxation time ratio can be described by either model, owing to adjustable parameters that are not known apriori, so independent means to evaluate those parameters will be discussed.

  1. Polymer Dynamics Effects on Solute Transport in Hairy Nanoparticle Membranes

    NASA Astrophysics Data System (ADS)

    Buenning, Eileen; Bilchak, Connor; Durning, Christopher; Benicewicz, Brian; Sokolov, Alexei; Kumar, Sanat

    Molecular transport measurements in matrix-free grafted nanoparticle (MFGNP) films have shown remarkable enhancement of permeability and ideal selectivity of small condensable molecules and simple gases over the neat polymer melts and conventional, dispersed nanoparticle composites. Films comprised of covalently-attached poly(methyl acrylate) PMA chains to the surface of 14nm silica particles self-assemble into ordered arrays, and we postulate this structure plays an important role in regulating solute transport. This self-assembly creates interstitial spaces between the nanoparticle cores, which the polymer chains can only fill by stretching. Here we use small-angle neutron scattering (SANS), broadband dielectric spectroscopy (BDS), rheology and temperature-modulated differential scanning calorimetry (TMDSC) to probe polymer chain and segmental dynamics and investigate this hypothesis of chain stretching in MFGNP materials. We found that grafting slows both chain and segmental relaxation, and increases fragility, indicating that the chains are more ``frustrated'' in the grafted systems. We propose that the effects of the chain/surface interactions on chain dynamics leads to an increase in available free volume and thus enhances transport properties in MFGNP systems. Special thanks to the NSF GRFP and the DOE SCGSR programs.

  2. Structure and dynamics of polymers: From bulk solutions to single polymer translocation

    NASA Astrophysics Data System (ADS)

    Guo, Lei

    This thesis covers the research work that has been done during my Ph.D. study, which focuses on studying polymeric systems by means of computational methods. The research topics include the study of the critical phase transition in ternary homopolymer solutions, the sol-gel transition of triblock copolymers, and single polymer translocation through nanopores. Specifically, the study of the critical phase transition in ternary solutions is aimed at verifying the theoretical predictions for such systems. Due to the finite polymer concentration, mean-field theory fails and the phase transition is described by a sophisticated renormalization approach. Phase separation also induces strong variation of the shape of linear chains, which is investigated as well. The study of the sol-gel transition of triblock copolymers aims to clarify the relationship between the structure and the dynamcal and mechanical properties of triblock copolymers. This is important for the design of new materials that have desired properties. Single DNA translocation through a nanopore presents another interesting and important problem. Understanding the DNA translocation process is beneficial for the design of an efficient DNA-sequencing device, the feasibility of which has been demonstrated in experiments. Moreover, simulations can reveal the complicated nature of the translocation dynamics, which is influenced by many factors, including the external driving force. Another interesting problem related to the translocation process is the distribution of ions and water molecules inside the nanopore, which is important for understanding the phenomena observed in the experiments, such as the screening of DNA inside the pore and the sometimes enhanced ionic current during translocation. It is of particular interest to study how the distribution of ions and water molecules is changed as the pore becomes polarizable, a feature displayed by certain types of nanopores. The thesis is organized as follows

  3. Mathematical models of polymer solutions motion and their symmetries

    NASA Astrophysics Data System (ADS)

    Bozhkov, Yu. D.; Pukhnachev, V. V.; Pukhnacheva, T. P.

    2015-10-01

    We consider three mathematical models describing motion of aqueous polymer solutions. All of them are derived from equations of Maxwell type viscoelastic medium at small relaxation time. Distinction consists in the choice of time derivative in the rheological constitutive law. Namely, we can choose (a) connective, (b) partial or (c) objective derivative of the strain tensor in time. We found widest symmetry groups admitted by each of these models. Systems (a) and (c) admit the extended Galilei group containing four arbitrary functions of time while the group admitted by system (b) is rather poor. Wide classes of exact solutions are obtained and their behaviors are analyzed if the relaxation viscosity tends to zero. Asymptotic expansion in this solution's parameter describing the flow near a critical point in planar and axially symmetric cases is derived. Analogs of the classical Hagen-Poiseuille and Nusselt solutions are studied too. We found difference in the pressure distribution between solutions calculated on the base of model (c) and two other models.

  4. Molecular degradation, injectivity, and elastic properties of polymer solutions

    SciTech Connect

    Southwick, J.G. ); Manke, C.W. )

    1988-11-01

    New features of polymer rheology in porous media were observed when hydrolyzed polyacrylamide (HPAM) solutions were flowed through sandstone, gravel packs, and glass-bead packs at high rates. Independent measurement of elongational viscosity, /sub e/, with a ductless-siphon technique demonstrates that the enhanced resistance seen at high flow rates is not directly proportional to /sub e/. Furthermore, significant permeability trends in resistance factor and mechanical degradation are observed when plotted vs. strain rate. When these results are translated to field flow rates and geometries, they indicate that HPAM solutions can be injected at reasonable injection pressures with minimal viscosity losses, provided that perforated completions are designed with either sufficient perforation density or perforation size.

  5. Divergent Shear Thinning and Shear Thickening Behavior of Supramolecular Polymer Networks in Semidilute Entangled Polymer Solutions

    PubMed Central

    Xu, Donghua; Liu, Chen-Yang; Craig, Stephen L.

    2011-01-01

    The steady shear behavior of metallo-supramolecular polymer networks formed by bis-Pd(II) cross-linkers and semidilute entangled solutions of poly(4-vinylpyridine) (PVP) in dimethyl sulfoxide (DMSO) or N,N-dimethyl formamide (DMF) is reported. The steady shear behavior of the networks depends on the dissociation rate and association rate of the cross-linkers, the concentration of cross-linkers, and the concentration of the polymer solution. The divergent steady shear behavior—shear thinning versus shear thickening—of samples with identical structure but different cross-linker dynamics (J. Phys. Chem. Lett. 2010, 1, 1683-1686) is further explored in this paper. The divergent steady shear behavior for networks with different cross-linkers is connected to a competition between different time scales: the average time that a cross-linker remains open (τ1) and the local relaxation time of a segment of polymer chain (τsegment). When τ1 is larger than τsegment, shear thickening is observed. When τ1 is smaller than τsegment, only shear thinning is observed. PMID:21547008

  6. A thermodynamic study of shear banding in polymer solutions

    NASA Astrophysics Data System (ADS)

    Hooshyar, Soroush; Germann, Natalie

    2016-06-01

    Although shear banding is a ubiquitous phenomenon observed in soft materials, the mechanisms that give rise to shear-band formation are not always the same. In this work, we develop a new two-fluid model for semi-dilute entangled polymer solutions using the generalized bracket approach of nonequilibrium thermodynamics. The model is based on the hypothesis that the direct coupling between polymer stress and concentration is the driving mechanism of steady shear-band formation. To obtain smooth banded profiles in the two-fluid framework, a new stress-diffusive term is added to the time evolution equation for the conformation tensor. The advantage of the new model is that the differential velocity is treated as a state variable. This allows a straightforward implementation of the additional boundary conditions arising from the derivative diffusive terms with respect to this new state variable. To capture the overshoot of the shear stress during the start of a simple shear flow, we utilize a nonlinear Giesekus relaxation. Moreover, we include an additional relaxation term that resembles the term used in the Rouse linear entangled polymer model to account for convective constraint release and chain stretch to generate the upturn of the flow curve at large shear rates. Numerical calculations performed for cylindrical Couette flow confirm the independency of the solution from the deformation history and initial conditions. Furthermore, we find that stress-induced migration is the responsible diffusive term for steady-state shear banding. Because of its simplicity, the new model is an ideal candidate for the use in the simulation of more complex flows.

  7. Hot Melt Extruded Amorphous Solid Dispersion of Posaconazole with Improved Bioavailability: Investigating Drug-Polymer Miscibility with Advanced Characterisation

    PubMed Central

    Amin, Purnima

    2014-01-01

    Invasive antifungal infections are reasons for morbidity and mortality in immunogenic patients worldwide. Posaconazole is a most promising antifungal agent against all types of invasive infections with high % of cure rate. The marketed suspension formulation has low bioavailability and is needed to be taken with food. In this paper, PCZ hot melt extruded amorphous solid dispersion (SD) with immediate release and improved bioavailability was prepared using Soluplus (Sol) as primary carrier for solubilization. Surfactants such as PEG 400, Lutrol F27, Lutrol F68, and TPGS are also used in combination with Soluplus to improve the physicochemical performance of the formulation when it comes in contact with GI (gastrointestinal) fluid. Drug-polymer miscibility of SD was investigated using advanced techniques. In the in vivo study, the AUC(0–72) and Cmax of PCZ/Soluplus were 11.5 and 11.74 time higher than those of pure PCZ. The formulation of the extrudate SD had an AUC(0–72) and Cmax higher than those with the commercial capsule (Noxafil). Molecular dynamic (MD) simulation studies were carried out using in silico molecular modelling to understand the drug-polymer intermolecular behaviour. The results of this research ensure enhanced dissolution and bioavailability of the solid dispersion of PCZ prepared by HME compared with the PCZ suspension. PMID:25143935

  8. Hot melt extruded amorphous solid dispersion of posaconazole with improved bioavailability: investigating drug-polymer miscibility with advanced characterisation.

    PubMed

    Fule, Ritesh; Amin, Purnima

    2014-01-01

    Invasive antifungal infections are reasons for morbidity and mortality in immunogenic patients worldwide. Posaconazole is a most promising antifungal agent against all types of invasive infections with high % of cure rate. The marketed suspension formulation has low bioavailability and is needed to be taken with food. In this paper, PCZ hot melt extruded amorphous solid dispersion (SD) with immediate release and improved bioavailability was prepared using Soluplus (Sol) as primary carrier for solubilization. Surfactants such as PEG 400, Lutrol F27, Lutrol F68, and TPGS are also used in combination with Soluplus to improve the physicochemical performance of the formulation when it comes in contact with GI (gastrointestinal) fluid. Drug-polymer miscibility of SD was investigated using advanced techniques. In the in vivo study, the AUC(0-72) and C(max) of PCZ/Soluplus were 11.5 and 11.74 time higher than those of pure PCZ. The formulation of the extrudate SD had an AUC(0-72) and C(max) higher than those with the commercial capsule (Noxafil). Molecular dynamic (MD) simulation studies were carried out using in silico molecular modelling to understand the drug-polymer intermolecular behaviour. The results of this research ensure enhanced dissolution and bioavailability of the solid dispersion of PCZ prepared by HME compared with the PCZ suspension.

  9. Wetting and spreading of long-chain ZDOL polymer nanodroplet on graphene-coated amorphous carbon

    NASA Astrophysics Data System (ADS)

    Sorkin, V.; Zhang, Y. W.

    2014-12-01

    Wetting transparency/translucency/opacity of graphene recently has attracted great interest. The underlying mechanisms and physics for simple liquid droplets containing small molecules on graphene coated crystalline substrates have been studied extensively. However, the behavior of more complicated polymeric droplets on graphene coated amorphous substrates has not been explored. In this work, we perform molecular dynamics simulations to examine the wetting of long-chain ZDOL polymeric droplet on graphene coated amorphous hydrogenated diamond-like carbon or DLCH. We find that at room temperature, the droplet adopts a nearly spherical cap shape with no protruding foot on bare DLCH, and a complex multi-layered structure is formed at the droplet-substrate interface. With addition of graphene layers, externally, the height of the droplet decreases and the protruding foot at the droplet edge appears and grows in size; while internally, the complex multi-layered structure near the droplet-substrate interface remains, but the density distribution for the formed layers becomes increasingly non-uniform. A steady state of the droplet is attained when the number of graphene layers reaches three. These changes can be explained by the interactions between the droplet and substrate across the number of graphene layers. Therefore, it is concluded that the graphene monolayer and bilayer are translucent, while trilayer and above are opaque from the wetting point of view.

  10. Mechanical behavior of linear amorphous polymers: Comparison between molecular dynamics and finite-element simulations

    NASA Astrophysics Data System (ADS)

    Solar, Mathieu; Meyer, Hendrik; Gauthier, Christian; Fond, Christophe; Benzerara, Olivier; Schirrer, Robert; Baschnagel, Jörg

    2012-02-01

    This paper studies the rheology of weakly entangled polymer melts and films in the glassy domain and near the rubbery domain using two different methods: molecular dynamics (MD) and finite element (FE) simulations. In a first step, the uniaxial mechanical behavior of a bulk polymer sample is studied by means of particle-based MD simulations. The results are in good agreement with experimental data, and mechanical properties may be computed from the simulations. This uniaxial mechanical behavior is then implemented in FE simulations using an elasto-viscoelasto-viscoplastic constitutive law in a continuum mechanics (CM) approach. In a second step, the mechanical response of a polymer film during an indentation test is modeled with the MD method and with the FE simulations using the same constitutive law. Good agreement is found between the MD and CM results. This work provides evidence in favor of using MD simulations to investigate the local physics of contact mechanics, since the volume elements studied are representative and thus contain enough information about the microstructure of the polymer model, while surface phenomena (adhesion and surface tension) are naturally included in the MD approach.

  11. Mechanical behavior of linear amorphous polymers: comparison between molecular dynamics and finite-element simulations.

    PubMed

    Solar, Mathieu; Meyer, Hendrik; Gauthier, Christian; Fond, Christophe; Benzerara, Olivier; Schirrer, Robert; Baschnagel, Jörg

    2012-02-01

    This paper studies the rheology of weakly entangled polymer melts and films in the glassy domain and near the rubbery domain using two different methods: molecular dynamics (MD) and finite element (FE) simulations. In a first step, the uniaxial mechanical behavior of a bulk polymer sample is studied by means of particle-based MD simulations. The results are in good agreement with experimental data, and mechanical properties may be computed from the simulations. This uniaxial mechanical behavior is then implemented in FE simulations using an elasto-viscoelasto-viscoplastic constitutive law in a continuum mechanics (CM) approach. In a second step, the mechanical response of a polymer film during an indentation test is modeled with the MD method and with the FE simulations using the same constitutive law. Good agreement is found between the MD and CM results. This work provides evidence in favor of using MD simulations to investigate the local physics of contact mechanics, since the volume elements studied are representative and thus contain enough information about the microstructure of the polymer model, while surface phenomena (adhesion and surface tension) are naturally included in the MD approach. PMID:22463237

  12. Method of solution preparation of polyolefin class polymers for electrospinning processing included

    NASA Technical Reports Server (NTRS)

    Rabolt, John F. (Inventor); Lee, Keun-Hyung (Inventor); Givens, Steven R. (Inventor)

    2011-01-01

    A process to make a polyolefin fiber which has the following steps: mixing at least one polyolefin into a solution at room temperature or a slightly elevated temperature to form a polymer solution and electrospinning at room temperature said polymer solution to form a fiber.

  13. Phosphorylcholine substituted polyolefins: New syntheses, solution assemblies, and polymer vesicles

    NASA Astrophysics Data System (ADS)

    Kratz, Katrina A.

    This thesis describes the synthesis and applications of a new series of amphiphilic homopolymers and copolymers consisting of hydrophobic polyolefin backbone and hydrophilic phosphorylcholine (PC) pendant groups. These polymers are synthesized by ring opening metathesis polymerization (ROMP) of a novel PC- cyclooctene monomer, and copolymerization of various functionalized cyclooctene comonomers. Incorporation of different comonomers into the PC-polyolefin backbone affords copolymers with different functionalities, including crosslinkers, fluorophores, and other reactive groups, that tune the range of applications of these polymers, and their hydrophobic/hydrophilic balance. The amphiphilic nature of PC-polyolefins was exploited in oil-water interfacial assembly, providing robust polymer capsules to encapsulate and deliver nanoparticles to damaged regions of a substrate in a project termed `repair-and-go.' In repair-and-go, a flexible microcapsule filled with a solution of nanoparticles probes an imperfection-riddled substrate as it rolls over the surface. The thin capsule wall allows the nanoparticles to escape the capsules and enter into the cracks, driven in part by favorable interactions between the nanoparticle ligands and the cracked surface (i.e., hydrophobic-hydrophobic interactions). The capsules then continue their transport along the surface, filling more cracks and depositing particles into them. The amphiphilic nature of PC-polyolefins was also exploited in aqueous assembly, forming novel polymer vesicles in water. PC-polyolefin vesicles ranged in size from 50 nm to 30 µm. The mechanical properties of PC-polyolefin vesicles were measured by micropipette aspiration techniques, and found to be more robust than conventional liposomes or polymersomes prepared from block copolymers. PC-polyolefin vesicles have potential use in drug delivery; it was found that the cancer drug doxorubicin could be encapsulated efficiently in PC-polyolefin vesicles. In

  14. Novel technique for phosphorus recovery from aqueous solutions using amorphous calcium silicate hydrates (A-CSHs).

    PubMed

    Okano, Kenji; Uemoto, Masahide; Kagami, Jumpei; Miura, Keiichi; Aketo, Tsuyoshi; Toda, Masaya; Honda, Kohsuke; Ohtake, Hisao

    2013-05-01

    A novel technique for phosphorus (P) recovery from aqueous solutions was developed using amorphous calcium silicate hydrates (A-CSHs). A-CSHs, which have a high Ca/Si molar ratio of 2.0 or greater, could be synthesized using unlimitedly available, inexpensive materials such as siliceous shale and calcium hydroxide. A-CSHs showed high performance for P recovery from an anaerobic sludge digestion liquor (ASDL) and the synthetic model liquor (s-ASDL) containing 89 mg PO4-P/L. After 20 min mixing, 1.5 g/L A-CSHs could remove approximately 69 and 73% PO4-P from ASDL and s-ASDL, respectively. By contrast, autoclaved lightweight concrete particles, which contained crystalline calcium silicate hydrates as a principal component, removed only 10 and 6% PO4-P from ASDL and s-ASDL, respectively, under the same experimental conditions. When A-CSHs were washed with deionized water to remove free Ca(OH)2, P removability was significantly improved (up to 82%) despite the reduction in the amount of Ca(2+) released. Unlike in the case of Ca(OH)2, no significant carbonate inhibition was observed with P removal by A-CSHs. Moreover, P removed by A-CSHs showed better settleability, filterability, and dewaterability than P precipitated with conventional CaCl2 and Ca(OH)2. The present study demonstrated that A-CSHs have great potential as a novel, beneficial material for P recovery and recycling. PMID:23497975

  15. Improvement of impact strength in linear low density polyethylene (LLDPE) by blending with amorphous polymers

    SciTech Connect

    Mirabella, F.M. Jr.

    1996-12-31

    The objective of the current work was to improve the film impact strength of commercial linear low density polyethylene (LLDPE) resins, while maintaining or improving other desirable properties. The approach used was to blend rubber-like (i.e. essentially noncrystalline) polymer resins with the base resin LLDPE. The choice of the rubber-like components was largely dictated by their commercial availability. The rubber-like polymers chosen were poly (ethylene-vinyl acetate) [EVA], poly (ethylene-n-butyl acrylate) [EnBA], and poly (ethylene-propylene) rubber [EPR]. The weight percent range of addition of the rubber-like component was restricted to 5% - 20%. The preferred range was only up to 10%. The structure of the base LLDPE resin, rubber-like components and the blends thereof was characterized. The physical and mechanical properties of the blown films of the resin blends were measured and correlations between structure and properties were determined.

  16. Morphological and mechanical properties of carbon-nanotube-reinforced semicrystalline and amorphous polymer composites

    NASA Astrophysics Data System (ADS)

    Cadek, M.; Coleman, J. N.; Barron, V.; Hedicke, K.; Blau, W. J.

    2002-12-01

    In this work, multiwalled carbon nanotubes were investigated as potential mechanical reinforcement agents in two hosts, polyvinyl alcohol (PVA) and poly(9-vinyl carbazole) (PVK). It was found that, by adding various concentrations of nanotubes, both Young's modulus and hardness increased by factors of 1.8 and 1.6 at 1 wt % in PVA and 2.8 and 2.0 at 8 wt % in PVK, in reasonable agreement with the Halpin-Tsai theory. Furthermore, the presence of the nanotubes was found to nucleate crystallization of the PVA. This crystal growth is thought to enhance matrix-nanotube stress transfer. In addition, microscopy studies suggest extremely strong interfacial bonding in the PVA-based composite. This is manifested by the fracture of the polymer rather that the polymer-nanotube interface.

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

    PubMed

    Toshchevikov, V; Saphiannikova, M; Heinrich, G

    2009-04-16

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

  18. Nonlinear signatures of entangled polymer solutions in active microbead rheology

    PubMed Central

    Cribb, J. A.; Vasquez, P. A.; Moore, P.; Norris, S.; Shah, S.; Forest, M. G.; Superfine, R.

    2014-01-01

    We present experimental data and numerical modeling of a nonlinear phenomenon in active magnetic microbead rheology that appears to be common to entangled polymer solutions (EPS). Dynamic experiments in a modest range of magnetic forces show: 1. a short-lived high viscosity plateau, followed by 2. a bead acceleration phase with a sharp drop in apparent viscosity, and 3. a terminal steady state that we show resides on the shear-thinning slope of the steady-state flow curve from cone and plate data. This latter feature implies a new protocol to access the nonlinear steady-state flow curve for many biological EPS only available in microliter-scale volumes. We solve the moment-closure form of the Rolie-Poly kinetic model for EPS hydrodynamics, together with a decoupling approximation that obviates the need for a full 3D flow solver, and show that the model qualitatively reproduces the dynamic experimental sequence above. In this way, we explain the phenomenon in terms of entangled polymer physics, and show how the nonlinear event (acceleration and termination on the shear-thinning response curve) is tunable by the interplay between molecular-scale mechanisms (relaxation via reptation and chain retraction) and magnetic force controls. The experimental conditions mimic movement of cilia tips, bacteria, and sperm in mucus barriers, implying a physiological relevance of the phenomenon, and compelling further development of the fully coupled, 3D flow-microstructure model to achieve quantitative accuracy. PMID:24526800

  19. Elasticity and Extensibility Determine Printability and Spinnability of Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Dinic, Jelena; Nallely Jimenez, Leidy; Mei, Vicky; Zhang, Yiran; Sharma, Vivek

    2015-03-01

    Many advanced manufacturing technologies like inkjet printing, 3D printing, nano-fiber spinning, gravure printing and nanoimprint lithography involve complex free-surface flows, where both shear and extensional rheology affect processability. In applications that involve progressive thinning and break-up of a fluid column or sheet into drops, the dominant flow within the filament is extensional in nature. Polymeric fluids exhibit a much larger resistance to flow in an elongational flow field than Newtonian fluids with same shear viscosity. Characterizing the filament thinning and break-up kinetics in jetting, dripping and stretching liquid bridge provides invaluable insight into the interplay of elastic, viscous, capillary and inertial stresses relevant for these applications. In this talk, we elucidate how polymer composition, flexibility and molecular weight determine the kinetics of capillary-driven thinning and pinch-off in our experiments. Both effective relaxation time and transient extensional viscosity are found to be strongly concentration dependent even for dilute solutions. Further, we show how finite extensibility of polymers dramatically changes the kinematics from elastocapillary to viscocapillary under strong extensional flow fields that can lead to coil-stretch transition.

  20. Early turbulence in von Karman swirling flow of polymer solutions

    NASA Astrophysics Data System (ADS)

    Burnishev, Yuri; Steinberg, Victor

    2015-01-01

    We present quantitative experimental results on the transition to early turbulence in von Karman swirling flow of water- and water-sugar-based polymer solutions compared to the transition to turbulence in their Newtonian solvents by measurements of solely global quantities as torque Γ(t) and pressure p(t) with large statistics as a function of Re. For the first time the transition values of Re_c\\textit{turb} to fully developed turbulence and turbulent drag reduction regime Re_c\\textit{TDR} are obtained as functions of elasticity El by using the solvents with different viscosities and polymer concentrations ϕ. Two scaling regions for fundamental turbulent characteristics are identified and they correspond to the turbulent and TDR regimes. Both Re_c\\textit{turb} and Re_c\\textit{TDR} are found via the dependence of the friction coefficient Cf and Cp, defined through scaled average torque \\barΓ and rms pressure fluctuations p\\textit{rms} , respectively, on Re for different El and ϕ and via the limits of the two scaling regions.

  1. Ordering phenomena of star polymer solutions approaching the Θ state

    NASA Astrophysics Data System (ADS)

    Likos, C. N.; Löwen, H.; Poppe, A.; Willner, L.; Roovers, J.; Cubitt, B.; Richter, D.

    1998-11-01

    The liquid-state ordering phenomena of a semidilute polybutadiene 64-arm star polymer solution were investigated by small-angle neutron scattering. For this purpose, we used deuterated 1,4-dioxane, which is a Θ solvent for the star at 31.5 °C. Its quality was modified by varying the temperature in the range between 40 °C and 80 °C. Besides a swelling of the star, with increasing temperature the development of a strong correlation peak was observed in the experiment. The experimental data were described theoretically by employing an effective pair potential between stars which was introduced earlier by Mewis et al. [J. Mewis, W. J. Frith, T. A. Strivens, and W. B. Russel, AIChE J. 35, 415 (1989)].

  2. Charging Mechanism for Polymer Particles in Nonpolar Surfactant Solutions: Influence of Polymer Type and Surface Functionality.

    PubMed

    Lee, Joohyung; Zhou, Zhang-Lin; Behrens, Sven Holger

    2016-05-17

    Surface charging phenomena in nonpolar dispersions are exploited in a wide range of industrial applications, but their mechanistic understanding lags far behind. We investigate the surface charging of a variety of polymer particles with different surface functionality in alkane solutions of a custom-synthesized and purified polyisobutylene succinimide (PIBS) polyamine surfactant and a related commercial surfactant mixture commonly used to control particle charge. We find that the observed electrophoretic particle mobility cannot be explained exclusively by donor-acceptor interactions between surface functional groups and surfactant polar moieties. Our results instead suggest an interplay of multiple charging pathways, which likely include the competitive adsorption of ions generated among inverse micelles in the solution bulk. We discuss possible factors affecting the competitive adsorption of micellar ions, such as the chemical nature of the particle bulk material and the size asymmetry between inverse micelles of opposite charge. PMID:27135950

  3. Engineering solutions for polymer composites solar water heaters production

    NASA Astrophysics Data System (ADS)

    Frid, S. E.; Arsatov, A. V.; Oshchepkov, M. Yu.

    2016-06-01

    Analysis of engineering solutions aimed at a considerable decrease of solar water heaters cost via the use of polymer composites in heaters construction and solar collector and heat storage integration into a single device representing an integrated unit results are considered. Possibilities of creating solar water heaters of only three components and changing welding, soldering, mechanical treatment, and assembly of a complicate construction for large components molding of polymer composites and their gluing are demonstrated. Materials of unit components and engineering solutions for their manufacturing are analyzed with consideration for construction requirements of solar water heaters. Optimal materials are fiber glass and carbon-filled plastics based on hot-cure thermosets, and an optimal molding technology is hot molding. It is necessary to manufacture the absorbing panel as corrugated and to use a special paint as its selective coating. Parameters of the unit have been optimized by calculation. Developed two-dimensional numerical model of the unit demonstrates good agreement with the experiment. Optimal ratio of daily load to receiving surface area of a solar water heater operating on a clear summer day in the midland of Russia is 130‒150 L/m2. Storage tank volume and load schedule have a slight effect on solar water heater output. A thermal insulation layer of 35‒40 mm is sufficient to provide an efficient thermal insulation of the back and side walls. An experimental model layout representing a solar water heater prototype of a prime cost of 70‒90/(m2 receiving surface) has been developed for a manufacturing volume of no less than 5000 pieces per year.

  4. Constraints in Semicrystalline Polymers: Using Quasi-isothermal Analysis to Investigate the Mechanisms of Formation and Loss of the Rigid Amorphous Fraction

    SciTech Connect

    Q Ma; G Georgiev; P Cebe

    2011-12-31

    The nanoscale phase behavior of a semicrystalline polymer is important for mechanical, thermal, optical and other macroscopic properties and can be analyzed well by thermal methods. Using quasi-isothermal (QI) heat capacity measurements, we investigate the formation behavior of the crystalline, mobile amorphous, and rigid amorphous fractions in poly(trimethylene terephthalate), PTT. The crystal and rigid amorphous phases comprise the total solid fraction in PTT at temperatures above T{sub g}, the glass transition temperature of the mobile amorphous fraction. PTT was quasi-isothermally cooled step-wise from the melt which causes its crystalline fraction to be fixed below 451 K. Between the high temperature fulfillment of the T{sub g} step and 451 K, the temperature dependent rigid amorphous fraction (RAF) is completely determined. For PTT, most of the RAF vitrifies between 451 K and T{sub g} step by step during QI cooling after the crystals have formed. The constraints imposed by the crystal surfaces reduce the mobility of the highly entangled polymer chains. We suggest the vitrification of RAF proceeds outward away from the lamellar surfaces in a step by step manner during QI cooling. Upon reheating, devitrification of RAF occurs at a temperature above its previous vitrification temperature, due to the effects of densification brought by physical aging during the long period of quasi-isothermal treatment. Finally, we consider recent concepts related to jamming, which have been suggested to apply to filled polymer systems, and may also be applicable in describing constraints exerted by crystal lamellae upon the RAF.

  5. Triple-junction hybrid tandem solar cells with amorphous silicon and polymer-fullerene blends.

    PubMed

    Kim, Taehee; Kim, Hyeok; Park, Jinjoo; Kim, Hyungchae; Yoon, Youngwoon; Kim, Sung-Min; Shin, Chonghoon; Jung, Heesuk; Kim, Inho; Jeong, Doo Seok; Kim, Honggon; Kim, Jin Young; Kim, BongSoo; Ko, Min Jae; Son, Hae Jung; Kim, Changsoon; Yi, Junsin; Han, Seunghee; Lee, Doh-Kwon

    2014-11-21

    Organic-inorganic hybrid tandem solar cells attract a considerable amount of attention due to their potential for realizing high efficiency photovoltaic devices at a low cost. Here, highly efficient triple-junction (TJ) hybrid tandem solar cells consisting of a double-junction (DJ) amorphous silicon (a-Si) cell and an organic photovoltaic (OPV) rear cell were developed. In order to design the TJ device in a logical manner, a simulation was carried out based on optical absorption and internal quantum efficiency. In the TJ architecture, the high-energy photons were utilized in a more efficient way than in the previously reported a-Si/OPV DJ devices, leading to a significant improvement in the overall efficiency by means of a voltage gain. The interface engineering such as tin-doped In2O3 deposition as an interlayer and its UV-ozone treatment resulted in the further improvement in the performance of the TJ solar cells. As a result, a power conversion efficiency of 7.81% was achieved with an open-circuit voltage of 2.35 V. The wavelength-resolved absorption profile provides deeper insight into the detailed optical response of the TJ hybrid solar cells.

  6. Triple-Junction Hybrid Tandem Solar Cells with Amorphous Silicon and Polymer-Fullerene Blends

    PubMed Central

    Kim, Taehee; Kim, Hyeok; Park, Jinjoo; Kim, Hyungchae; Yoon, Youngwoon; Kim, Sung-Min; Shin, Chonghoon; Jung, Heesuk; Kim, Inho; Jeong, Doo Seok; Kim, Honggon; Kim, Jin Young; Kim, BongSoo; Ko, Min Jae; Son, Hae Jung; Kim, Changsoon; Yi, Junsin; Han, Seunghee; Lee, Doh-Kwon

    2014-01-01

    Organic-inorganic hybrid tandem solar cells attract a considerable amount of attention due to their potential for realizing high efficiency photovoltaic devices at a low cost. Here, highly efficient triple-junction (TJ) hybrid tandem solar cells consisting of a double-junction (DJ) amorphous silicon (a-Si) cell and an organic photovoltaic (OPV) rear cell were developed. In order to design the TJ device in a logical manner, a simulation was carried out based on optical absorption and internal quantum efficiency. In the TJ architecture, the high-energy photons were utilized in a more efficient way than in the previously reported a-Si/OPV DJ devices, leading to a significant improvement in the overall efficiency by means of a voltage gain. The interface engineering such as tin-doped In2O3 deposition as an interlayer and its UV-ozone treatment resulted in the further improvement in the performance of the TJ solar cells. As a result, a power conversion efficiency of 7.81% was achieved with an open-circuit voltage of 2.35 V. The wavelength-resolved absorption profile provides deeper insight into the detailed optical response of the TJ hybrid solar cells. PMID:25412648

  7. Triple-junction hybrid tandem solar cells with amorphous silicon and polymer-fullerene blends.

    PubMed

    Kim, Taehee; Kim, Hyeok; Park, Jinjoo; Kim, Hyungchae; Yoon, Youngwoon; Kim, Sung-Min; Shin, Chonghoon; Jung, Heesuk; Kim, Inho; Jeong, Doo Seok; Kim, Honggon; Kim, Jin Young; Kim, BongSoo; Ko, Min Jae; Son, Hae Jung; Kim, Changsoon; Yi, Junsin; Han, Seunghee; Lee, Doh-Kwon

    2014-01-01

    Organic-inorganic hybrid tandem solar cells attract a considerable amount of attention due to their potential for realizing high efficiency photovoltaic devices at a low cost. Here, highly efficient triple-junction (TJ) hybrid tandem solar cells consisting of a double-junction (DJ) amorphous silicon (a-Si) cell and an organic photovoltaic (OPV) rear cell were developed. In order to design the TJ device in a logical manner, a simulation was carried out based on optical absorption and internal quantum efficiency. In the TJ architecture, the high-energy photons were utilized in a more efficient way than in the previously reported a-Si/OPV DJ devices, leading to a significant improvement in the overall efficiency by means of a voltage gain. The interface engineering such as tin-doped In2O3 deposition as an interlayer and its UV-ozone treatment resulted in the further improvement in the performance of the TJ solar cells. As a result, a power conversion efficiency of 7.81% was achieved with an open-circuit voltage of 2.35 V. The wavelength-resolved absorption profile provides deeper insight into the detailed optical response of the TJ hybrid solar cells. PMID:25412648

  8. Performance of SuSi: a method for generating atomistic models of amorphous polymers based on a random search of energy minima.

    PubMed

    Curcó, David; Alemán, Carlos

    2004-04-30

    The performance of a recently developed method to generate representative atomistic models of amorphous polymers has been investigated. This method, which is denoted SuSi, can be defined as a random generator of energy minima. The effects produced by different parameters used to define the size of the system and the characteristics of the generation algorithm have been examined. Calculations have been performed on poly(L,D-lactic) acid (rho = 1.25 g/cm3) and nylon 6 (rho = 1.084 g/cm(3)), which are important commercial polymers.

  9. Thermodynamic theory of light-induced material transport in amorphous azobenzene polymer films.

    PubMed

    Saphiannikova, Marina; Neher, Dieter

    2005-10-20

    It was discovered 10 years ago that the exposure of an initially flat layer of an azobenzene-containing polymer to an inhomogeneous light pattern leads to the formation of surface relief structures, accompanied by a mass transport over several micrometers. However, the driving force of this process is still unclear. We propose a new thermodynamic approach that explains a number of experimental findings including the light-induced deformation of free-standing films and the formation of surface relief gratings for main inscription geometries. Our basic assumption is that under homogeneous illumination, an initially isotropic sample should stretch itself along the polarization direction to compensate the entropy decrease produced by the photoinduced reorientation of azobenzene chromophores. The magnitude of the elastic stress, estimated by taking the derivative of the free energy over the sample deformation, is shown to be sufficient to induce plastic deformation of the polymer film. Orientational distributions of chromophores predicted by our model are compared with those deduced from Raman intensity measurements.

  10. Solvent-shift strategy to identify suitable polymers to inhibit humidity-induced solid-state crystallization of lacidipine amorphous solid dispersions.

    PubMed

    Sun, Mengchi; Wu, Chunnuan; Fu, Qiang; Di, Donghua; Kuang, Xiao; Wang, Chao; He, Zhonggui; Wang, Jian; Sun, Jin

    2016-04-30

    The solvent-shift strategy was used to identify appropriate polymers that inhibit humidity-induced solid-state crystallization of amorphous solid dispersions (ASDs). Lacidipine with the polymers, PVP-K30, HPMC-E5 or Soluplus, were combined to form amorphous solid dispersions prepared by solvent evaporation. The formulations were characterized by differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and Fourier-transform infrared spectroscopy (FT-IR) and were subjected to in vitro dissolution testing. The moisture had a significant impact on the amount dissolved for the solid dispersions. Molecular docking studies established that hydrogen bonding was critical for the stabilization of the solid dispersions. The rank order of the binding energy of the drug-polymer association was Soluplus (-6.21 kcal/mol)>HPMC-E5 (-3.21 kcal/mol)>PVP-K30 (-2.31 kcal/mol). PVP-K30 had the highest water uptake among the polymers, as did ASD system of lacidipine-PVP-K30 ASDs. In the Soluplus ASDs, with its strong drug-polymer interactions and low water uptake, moisture-induced solid-state crystallization was not observed.

  11. Single polymer dynamics of linear and architecturally complex chains in semi-dilute solutions

    NASA Astrophysics Data System (ADS)

    Hsiao, Kaiwen; Li, Yanfei; McKenna, Gregory; Schroeder, Charles

    The interplay between polymer topology and concentration gives rise to complex dynamics due to inter- and intramolecular interactions. We use a molecular level approach to study the threading behavior for linear and ring polymers near equilibrium and in non-linear flows. A semi-dilute solution of linear DNA chains is doped with fluorescently labeled ring polymers (circular DNA plasmids), and this material is used to study the dynamics of rings in semi-dilute solutions of linear chains. Single molecule fluorescence microscopy in combination with a custom-built microfluidic trapping system is used to study collective polymer dynamics at the molecular level, which allows us to precisely control flow rates and accumulated fluid strain applied to single polymer. We performed step-strain experiments on ring polymer in linear semi-dilute polymer solutions undergoing deformation in planar extensional flow. In comparison to our previous work on semi-dilute linear chains, ring polymers exhibit large fluctuations in fractional extension at steady state extension, indicating strong interactions with the background polymer solution. Transient stretching dynamics of ring polymer is inhibited in semi-dilute linear background, similar to our previous observation in linear systems. Our findings show that topology and concentration play a strong role on polymer chain dynamics in non-equilibrium flow.

  12. Electrostatics of polymer translocation events in electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Buyukdagli, Sahin; Ala-Nissila, T.

    2016-07-01

    We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ≈10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution.

  13. Long Range Bond-Bond Correlations in Dense Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Wittmer, J. P.; Meyer, H.; Baschnagel, J.; Johner, A.; Obukhov, S.; Mattioni, L.; Müller, M.; Semenov, A. N.

    2004-09-01

    The scaling of the bond-bond correlation function P1(s) along linear polymer chains is investigated with respect to the curvilinear distance s along the flexible chain and the monomer density ρ via Monte Carlo and molecular dynamics simulations. Surprisingly, the correlations in dense three-dimensional solutions are found to decay with a power law P1(s)˜s-ω with ω=3/2 and the exponential behavior commonly assumed is clearly ruled out for long chains. In semidilute solutions, the density dependent scaling of P1(s)≈g-ω0(s/g)-ω with ω0=2-2ν=0.824 (ν=0.588 being Flory's exponent) is set by the number of monomers g(ρ) in an excluded volume blob. Our computational findings compare well with simple scaling arguments and perturbation calculation. The power-law behavior is due to self-interactions of chains caused by the chain connectivity and the incompressibility of the melt.

  14. Electrostatics of polymer translocation events in electrolyte solutions.

    PubMed

    Buyukdagli, Sahin; Ala-Nissila, T

    2016-07-01

    We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ≈10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution.

  15. Electrostatics of polymer translocation events in electrolyte solutions.

    PubMed

    Buyukdagli, Sahin; Ala-Nissila, T

    2016-07-01

    We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ≈10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution. PMID:27394120

  16. Improving battery safety by reducing the formation of Li dendrites with the use of amorphous silicon polymer anodes

    PubMed Central

    Maruyama, Hitoshi; Nakano, Hideyuki; Ogawa, Masahiro; Nakamoto, Masaaki; Ohta, Toshiaki; Sekiguchi, Akira

    2015-01-01

    To provide safe lithium-ion batteries (LIBs) at low cost, battery materials which lead to reduced Li dendrite formation are needed. The currently used anode materials have low redox voltages that are very close to the redox potential for the formation of Li metal, which leads to severe short circuiting. Herein, we report that when the three-dimensional amorphous silicon polymers poly(methylsilyne) and poly(phenylsilyne) are used as anode materials, dendritic Li formation on the anode surface is avoided up to a practical current density of 10 mA·g−1 at 5 °C. Equally as significant, poly(methylsilyne) and poly(phenylsilyne) are capable of reacting with 0.45 and 0.9 Li atoms per formula unit, respectively, at an average voltage of approximately 1.0 V, affording reversible capacities of 244 mAh·g−1 and 180 mAh·g−1. Moreover, noteworthy is the fact that polysilynes are suitable for practical applications because they can be prepared through a simple and low-cost process and are easy to handle. PMID:26249325

  17. CO2 switchable dual responsive polymers as draw solutes for forward osmosis desalination.

    PubMed

    Cai, Yufeng; Shen, Wenming; Wang, Rong; Krantz, William B; Fane, Anthony G; Hu, Xiao

    2013-09-28

    Low molecular weight dual responsive polymers, after purging with CO2, become polyelectrolytes with high osmolality, which can be used as draw solutes for seawater desalination. These polymers precipitate above their Lower Critical Solution Temperature (LCST) after removal of CO2 via purging with inert gas for ease of recovery and reuse.

  18. Microfluidics Meets Dilute Solution Viscometry: An Undergraduate Laboratory to Determine Polymer Molecular Weight Using a Microviscometer

    ERIC Educational Resources Information Center

    Pety, Stephen J.; Lu, Hang; Thio, Yonathan S.

    2011-01-01

    This paper describes a student laboratory experiment to determine the molecular weight of a polymer sample by measuring the viscosity of dilute polymer solutions in a PDMS microfluidic viscometer. Sample data are given for aqueous solutions of poly(ethylene oxide) (PEO). A demonstration of shear thinning behavior using the microviscometer is…

  19. Strong stabilization of amorphous calcium carbonate emulsion by ovalbumin: gaining insight into the mechanism of 'polymer-induced liquid precursor' processes.

    PubMed

    Wolf, Stephan E; Leiterer, Jork; Pipich, Vitaliy; Barrea, Raul; Emmerling, Franziska; Tremel, Wolfgang

    2011-08-17

    The impact of the ovo proteins ovalbumin and lysozyme--present in the first stage of egg shell formation--on the homogeneous formation of the liquid amorphous calcium carbonate (LACC) precursor, was studied by a combination of complementing methods: in situ WAXS, SANS, XANES, TEM, and immunogold labeling. Lysozyme (pI = 9.3) destabilizes the LACC emulsion whereas the glycoprotein ovalbumin (pI = 4.7) extends the lifespan of the emulsified state remarkably. In the light of the presented data: (a) Ovalbumin is shown to behave commensurable to the 'polymer-induced liquid precursor' (PILP) process proposed by Gower et al. Ovalbumin can be assumed to take a key role during eggshell formation where it serves as an effective stabilization agent for transient precursors and prevents undirected mineralization of the eggshell. (b) It is further shown that the emulsified LACC carries a negative surface charge and is electrostatically stabilized. (c) We propose that the liquid amorphous calcium carbonate is affected by polymers by depletion stabilization and de-emulsification rather than 'induced' by acidic proteins and polymers during a so-called polymer-induced liquid-precursor process. The original PILP coating effect, first reported by Gower et al., appears to be a result of a de-emulsification process of a stabilized LACC phase. The behavior of the liquid amorphous carbonate phase and the polymer-induced liquid-precursor phase itself can be well described by colloid chemical terms: electrostatic and depletion stabilization and de-emulsification by depletion destabilization.

  20. Strong stabilization of liquid amorphous calcium carbonate by ovalbumin: gaining insight into the mechanism of ‘polymer-induced liquid precursor’ processes

    PubMed Central

    Leiterer, Jork; Pipich, Vitaliy; Barrea, Raul; Tremel, Wolfgang

    2011-01-01

    The impact of the ovo-proteins ovalbumin and lysozyme—present in the first stage of egg shell formation—on the homogeneous formation of the liquid-amorphous calcium carbonate (LACC) precursor, was studied by a combination of complementing methods: in situ WAXS, SANS, XANES, TEM, and immunogold labeling. Lysozyme (pI = 9.3) destabilizes the LACC emulsion whereas the glycoprotein ovalbumin (pI = 4.7) extends the lifespan of the emulsified state remarkably. In the light of the presented data: (a) Ovalbumin is shown to behave commensurable to the ‘polymer-induced liquid precursor’ (PILP) process proposed by Gower et al. Ovalbumin can be assumed to take a key role during eggshell formation where it serves as an effective stabilization agent for transient precursors and prevents undirected mineralization of the eggshell. (b) It is further shown that the emulsified LACC carries a negative surface charge and is electrostatically stabilized. (c) We propose that the liquid amorphous calcium carbonate is affected by polymers by depletion stabilization and de-emulsification rather than ‘induced’ by acidic proteins and polymers during a polymer-induced liquid-precursor process. The original PILP coating effect, first reported by Gower et al., appears to be a result of a de-emulsification process of a stabilized LACC phase. The behavior of the liquid amorphous carbonate phase and the polymer-induced liquid-precursor phase itself can be well described by colloid chemical terms: electrostatic and depletion stabilization and de-emulsification by depletion destabilization. PMID:21736300

  1. Structure and interaction in the polymer-dependent reentrant phase behavior of a charged nanoparticle solution

    NASA Astrophysics Data System (ADS)

    Kumar, Sugam; Ray, D.; Aswal, V. K.; Kohlbrecher, J.

    2014-10-01

    Small-angle neutron scattering (SANS) studies have been carried out to examine the evolution of interaction and structure in a nanoparticle (silica)-polymer (polyethylene glycol) system. The nanoparticle-polymer solution interestingly shows a reentrant phase behavior where the one-phase charged stabilized nanoparticles go through a two-phase system (nanoparticle aggregation) and back to one-phase as a function of polymer concentration. Such phase behavior arises because of the nonadsorption of polymer on nanoparticles and is governed by the interplay of polymer-induced attractive depletion with repulsive nanoparticle-nanoparticle electrostatic and polymer-polymer interactions in different polymer concentration regimes. At low polymer concentrations, the electrostatic repulsion dominates over the depletion attraction. However, the increase in polymer concentration enhances the depletion attraction to give rise to the nanoparticle aggregation in the two-phase system. Further, the polymer-polymer repulsion at high polymer concentrations is believed to be responsible for the reentrance to one-phase behavior. The SANS data in polymer contrast-matched conditions have been modeled by a two-Yukawa potential accounting for both repulsive and attractive parts of total interaction potential between nanoparticles. Both of these interactions (repulsive and attractive) are found to be long range. The magnitude and the range of the depletion interaction increase with the polymer concentration leading to nanoparticle clustering. At higher polymer concentrations, the increased polymer-polymer repulsion reduces the depletion interaction leading to reentrant phase behavior. The nanoparticle clusters in the two-phase system are characterized by the surface fractal with simple cubic packing of nanoparticles within the clusters. The effect of varying ionic strength and polymer size in tuning the interaction has also been examined.

  2. Structure and interaction in the polymer-dependent reentrant phase behavior of a charged nanoparticle solution.

    PubMed

    Kumar, Sugam; Ray, D; Aswal, V K; Kohlbrecher, J

    2014-10-01

    Small-angle neutron scattering (SANS) studies have been carried out to examine the evolution of interaction and structure in a nanoparticle (silica)-polymer (polyethylene glycol) system. The nanoparticle-polymer solution interestingly shows a reentrant phase behavior where the one-phase charged stabilized nanoparticles go through a two-phase system (nanoparticle aggregation) and back to one-phase as a function of polymer concentration. Such phase behavior arises because of the nonadsorption of polymer on nanoparticles and is governed by the interplay of polymer-induced attractive depletion with repulsive nanoparticle-nanoparticle electrostatic and polymer-polymer interactions in different polymer concentration regimes. At low polymer concentrations, the electrostatic repulsion dominates over the depletion attraction. However, the increase in polymer concentration enhances the depletion attraction to give rise to the nanoparticle aggregation in the two-phase system. Further, the polymer-polymer repulsion at high polymer concentrations is believed to be responsible for the reentrance to one-phase behavior. The SANS data in polymer contrast-matched conditions have been modeled by a two-Yukawa potential accounting for both repulsive and attractive parts of total interaction potential between nanoparticles. Both of these interactions (repulsive and attractive) are found to be long range. The magnitude and the range of the depletion interaction increase with the polymer concentration leading to nanoparticle clustering. At higher polymer concentrations, the increased polymer-polymer repulsion reduces the depletion interaction leading to reentrant phase behavior. The nanoparticle clusters in the two-phase system are characterized by the surface fractal with simple cubic packing of nanoparticles within the clusters. The effect of varying ionic strength and polymer size in tuning the interaction has also been examined.

  3. Inhibiting the transport of hazardous spores using polymer-based solutions.

    PubMed

    Krauter, Paula A; Hoffman, D Mark; Vu, Alexander K; Keating, Garrett A; Zalk, David M

    2007-11-01

    A series of polymer solutions were developed for the purpose of immobilizing aerosolized 1-10 mu m sized hazardous biological particles. The polymer solutions were designed as tools for emergency response and remediation personnel. The inhibition of secondary aerosolization and migration of biothreat particles has important implications for public health protection and contamination cleanup. Limiting further dispersion of particles such as Bacillus anthracis spores may reduce inhalation hazards and enhance remediation efficiencies. This study evaluated film-forming polymers that have multiple functional groups capable of attracting and binding particles; these included acrylates, cellulosics, vinyl polymers, and polyurethanes. The selected polymers were combined with appropriate solvents to design solutions that met specific performance objectives. The polymer solutions were then evaluated for key characteristics, such as high adhesion, high elasticity, low density, short drying time, low viscosity, and low surface tension. These solutions were also evaluated for their adhesion to biothreat agent in a series of wind tunnel experiments using highly refined aerosolized Bacillus atrophaeus spores (a simulant for anthrax, 1-3 mu m). Results demonstrated that a polymer solution, an amphoteric acrylate identified as NS-2, was the best candidate for attaching to spores and inhibiting reaerosolization. This polymer solution was anionic, thus providing the electrostatic (coulombic) attraction to cationic spores, had low surface tension, and performed well in wind tunnel tests.

  4. Low-Temperature Solution Processing of Amorphous Metal Oxide Semiconductors for High-Performance Thin-Film Transistors

    NASA Astrophysics Data System (ADS)

    Hennek, Jonathan W.

    The growing field of large-area flexible electronics presents the need for amorphous materials with electrical performances superior to amorphous hydrogenated silicon (a-Si:H). Metal oxide semiconductors show great promise in thin film transistors (TFTs) due to their high electron mobility (micro, 1--100 cm2V-1s-1), mechanical flexibility, and electrical stability. However, most oxide semiconductor fabrication still relies on expensive, inflexible and energy intensive vacuum deposition methods. To overcome these limitations, my thesis work has focused on developing low-temperature solution processing routes to functional metal oxide materials. In Chapter 2, we demonstrate an optimized "ink" and printing process for inkjet patterning of amorphous indium gallium zinc oxide (a-IGZO) and investigate the effects of device structure on derived electron mobility. Bottom-gate top-contact (BGTC) TFTs are fabricated and shown to exhibit electron mobilities comparable to a-Si:H. Furthermore, a record micro of 2.5 cm 2V-1s-1 is demonstrated for bottom-gate bottom-contact (BGBC) TFTs. The mechanism underlying such impressive performance is investigated using transmission line techniques, and it is shown that the semiconductor-source/drain electrode interface contact resistance is nearly an order of magnitude lower for BGBC transistors versus BGTC devices. In Chapter 3, we report the implementation of amorphous indium yttrium oxide (a-IYO) as a TFT semiconductor for the first time. Amorphous and polycrystalline IYO films are grown via a low-temperature solution process utilizing exothermic "combustion" precursors. Precursor transformation and the IYO films are analyzed by DTA, TGA, XRD, AFM, XPS, and optical transmission, revealing efficient conversion to the metal-oxide lattice, and smooth, transparent films. a-IYO TFTs fabricated with a hybrid nanodielectric exhibit impressive electron mobilities of 7.3 cm2V-1s-1 (Tanneal = 300 °C) and 5.0 cm2V-1s -1 (Tanneal = 250 °C) for 2

  5. Nanoscale Concentration Quantification of Pharmaceutical Actives in Amorphous Polymer Matrices by Electron Energy-Loss Spectroscopy.

    PubMed

    Ricarte, Ralm G; Lodge, Timothy P; Hillmyer, Marc A

    2016-07-26

    We demonstrated the use of electron energy-loss spectroscopy (EELS) to evaluate the composition of phenytoin:hydroxypropyl methylcellulose acetate succinate (HPMCAS) spin-coated solid dispersions (SDs). To overcome the inability of bright-field and high-angle annular dark-field TEM imaging to distinguish between glassy drug and polymer, we used the π-π* transition peak in the EELS spectrum to detect phenytoin within the HPMCAS matrix of the SD. The concentration of phenytoin within SDs of 10, 25, and 50 wt % drug loading was quantified by a multiple least-squares analysis. Evaluating the concentration of 50 different regions in each SD, we determined that phenytoin and HPMCAS are intimately mixed at a length scale of 200 nm, even for drug loadings up to 50 wt %. At length scales below 100 nm, the variance of the measured phenytoin concentration increases; we speculate that this increase is due to statistical fluctuations in local concentration and chemical changes induced by electron irradiation. We also performed EELS analysis of an annealed 25 wt % phenytoin SD and showed that the technique can resolve concentration differences between regions that are less than 50 nm apart. Our findings indicate that EELS is a useful tool for quantifying, with high accuracy and sub-100 nm spatial resolution, the composition of many pharmaceutical and soft matter systems. PMID:27419264

  6. Characterization of nanoscale spatial distribution of small molecules in amorphous polymer matrices

    NASA Astrophysics Data System (ADS)

    Ricarte, Ralm; Hillmyer, Marc; Lodge, Timothy

    Hydroxypropyl methylcellulose acetate succinate (HPMCAS) can significantly enhance the efficacy of active pharmaceutical ingredients (APIs). Yet, the interactions between species in HPMCAS-API blends are not understood. Elucidating these interactions is difficult because the spatial distributions of HPMCAS and API in the blends are ambiguous; the polymer and drug may be molecularly mixed or the species may form phase separated domains. As these phase separated domains may be less than 100 nm in size, traditional characterization techniques may not accurately evaluate the spatial distribution. To address this challenge, we explore the use of electron energy-loss spectroscopy (EELS) for detecting the model API phenytoin in an HPMCAS-phenytoin blend. Using EELS, we directly measured with high accuracy and precision the phenytoin concentrations in several blends. We present evidence that suggests phase separation occurs in blends that have a phenytoin loading of approximately 50 wt percent. Finally, we demonstrate that this technique achieves a sub-100 nm spatial resolution and can detect several other APIs.

  7. Understanding API-polymer proximities in amorphous stabilized composite drug products using fluorine-carbon 2D HETCOR solid-state NMR.

    PubMed

    Abraham, Anuji; Crull, George

    2014-10-01

    A simple and robust method for obtaining fluorine-carbon proximities was established using a (19)F-(13)C heteronuclear correlation (HETCOR) two-dimensional (2D) solid-state nuclear magnetic resonance (ssNMR) experiment under magic-angle spinning (MAS). The method was applied to study a crystalline active pharmaceutical ingredient (API), avagacestat, containing two types of fluorine atoms and its API-polymer composite drug product. These results provide insight into the molecular structure, aid with assigning the carbon resonances, and probe API-polymer proximities in amorphous spray dried dispersions (SDD). This method has an advantage over the commonly used (1)H-(13)C HETCOR because of the large chemical shift dispersion in the fluorine dimension. In the present study, fluorine-carbon distances up to 8 Å were probed, giving insight into the API structure, crystal packing, and assignments. Most importantly, the study demonstrates a method for probing an intimate molecular level contact between an amorphous API and a polymer in an SDD, giving insights into molecular association and understanding of the role of the polymer in API stability (such as recrystallization, degradation, etc.) in such novel composite drug products.

  8. Supersaturation, nucleation, and crystal growth during single- and biphasic dissolution of amorphous solid dispersions: polymer effects and implications for oral bioavailability enhancement of poorly water soluble drugs.

    PubMed

    Sarode, Ashish L; Wang, Peng; Obara, Sakae; Worthen, David R

    2014-04-01

    The influence of polymers on the dissolution, supersaturation, crystallization, and partitioning of poorly water soluble compounds in biphasic media was evaluated. Amorphous solid dispersions (ASDs) containing felodipine (FLD) and itraconazole (ITZ) were prepared by hot melt mixing (HMM) using various polymers. The ASDs were analyzed using powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), and HPLC. Amorphous drug conversion was confirmed using DSC and PXRD, and drug stability by HPLC. Single- and biphasic dissolution studies of the ASDs with concurrent dynamic light scattering (DLS) and polarized light microscopic (PLM) analysis of precipitated drugs were performed. HPLC revealed no HMM-induced drug degradation. Maximum partitioning into the organic phase was dependent upon the degree of supersaturation. Although the highest supersaturation of FLD was attained using Eudragit® EPO and AQOAT® AS-LF with better nucleation and crystal growth inhibition using the latter, higher partitioning of the drug into the organic phase was achieved using Pharmacoat® 603 and Kollidon® VA-64 by maintaining supersaturation below critical nucleation. Critical supersaturation for ITZ was surpassed using all of the polymers, and partitioning was dependent upon nucleation and crystal growth inhibition in the order of Pharmacoat® 603>Eudragit® L-100-55>AQOAT® AS-LF. HMM drug-polymer systems that prevent drug nucleation by staying below critical supersaturation are more effective for partitioning than those that achieve the highest supersaturation.

  9. Elastic turbulence in curvilinear flows of polymer solutions

    NASA Astrophysics Data System (ADS)

    Groisman, Alexander; Steinberg, Victor

    2004-03-01

    Following our first report (A Groisman and V Steinberg 2000 Nature 405 53), we present an extended account of experimental observations of elasticity-induced turbulence in three different systems: a swirling flow between two plates, a Couette-Taylor (CT) flow between two cylinders, and a flow in a curvilinear channel (Dean flow). All three set-ups had a high ratio of the width of the region available for flow to the radius of curvature of the streamlines. The experiments were carried out with dilute solutions of high-molecular-weight polyacrylamide in concentrated sugar syrups. High polymer relaxation time and solution viscosity ensured prevalence of non-linear elastic effects over inertial non-linearity, and development of purely elastic instabilities at low Reynolds number (Re) in all three flows. Above the elastic instability threshold, flows in all three systems exhibit features of developed turbulence. They include: (i) randomly fluctuating fluid motion excited in a broad range of spatial and temporal scales and (ii) significant increase in the rates of momentum and mass transfer (compared with those expected for a steady flow with a smooth velocity profile). Phenomenology, driving mechanisms and parameter dependence of the elastic turbulence are compared with those of the conventional high-Re hydrodynamic turbulence in Newtonian fluids. Some similarities as well as multiple principal differences were found. In two out of three systems (swirling flow between two plates and flow in the curvilinear channel), power spectra of velocity fluctuations decayed rather quickly, following power laws with exponents of about -3.5. It suggests that, being random in time, the flow is rather smooth in space, in the sense that the main contribution to deformation and mixing (and, possibly, elastic energy) is coming from flow at the largest scale of the system. This situation, random in time and smooth in space, is analogous to flows at small scales (below the Kolmogorov

  10. Shock wave emission from laser-induced cavitation bubbles in polymer solutions.

    PubMed

    Brujan, Emil-Alexandru

    2008-09-01

    The role of extensional viscosity on the acoustic emission from laser-induced cavitation bubbles in polymer solutions and near a rigid boundary is investigated by acoustic measurements. The polymer solutions consist of a 0.5% polyacrylamide (PAM) aqueous solution with a strong elastic component and a 0.5% carboxymethylcellulose (CMC) aqueous solution with a weak elastic component. A reduction of the maximum amplitude of the shock wave pressure and a prolongation of the oscillation period of the bubble were found in the elastic PAM solution. It might be caused by an increased resistance to extensional flow which is conferred upon the liquid by the polymer additive. In both polymer solutions, however, the shock pressure decays proportionally to r(-1) with increasing distance r from the emission centre.

  11. Elastic instabilities in planar elongational flow of monodisperse polymer solutions

    PubMed Central

    Haward, Simon J.; McKinley, Gareth H.; Shen, Amy Q.

    2016-01-01

    We investigate purely elastic flow instabilities in the almost ideal planar stagnation point elongational flow field generated by a microfluidic optimized-shape cross-slot extensional rheometer (OSCER). We use time-resolved flow velocimetry and full-field birefringence microscopy to study the behavior of a series of well-characterized viscoelastic polymer solutions under conditions of low fluid inertia and over a wide range of imposed deformation rates. At low deformation rates the flow is steady and symmetric and appears Newtonian-like, while at high deformation rates we observe the onset of a flow asymmetry resembling the purely elastic instabilities reported in standard-shaped cross-slot devices. However, for intermediate rates, we observe a new type of elastic instability characterized by a lateral displacement and time-dependent motion of the stagnation point. At the onset of this new instability, we evaluate a well-known dimensionless criterion M that predicts the onset of elastic instabilities based on geometric and rheological scaling parameters. The criterion yields maximum values of M which compare well with critical values of M for the onset of elastic instabilities in viscometric torsional flows. We conclude that the same mechanism of tension acting along curved streamlines governs the onset of elastic instabilities in both extensional (irrotational) and torsional (rotational) viscoelastic flows. PMID:27616181

  12. Elastic instabilities in planar elongational flow of monodisperse polymer solutions

    NASA Astrophysics Data System (ADS)

    Haward, Simon J.; McKinley, Gareth H.; Shen, Amy Q.

    2016-09-01

    We investigate purely elastic flow instabilities in the almost ideal planar stagnation point elongational flow field generated by a microfluidic optimized-shape cross-slot extensional rheometer (OSCER). We use time-resolved flow velocimetry and full-field birefringence microscopy to study the behavior of a series of well-characterized viscoelastic polymer solutions under conditions of low fluid inertia and over a wide range of imposed deformation rates. At low deformation rates the flow is steady and symmetric and appears Newtonian-like, while at high deformation rates we observe the onset of a flow asymmetry resembling the purely elastic instabilities reported in standard-shaped cross-slot devices. However, for intermediate rates, we observe a new type of elastic instability characterized by a lateral displacement and time-dependent motion of the stagnation point. At the onset of this new instability, we evaluate a well-known dimensionless criterion M that predicts the onset of elastic instabilities based on geometric and rheological scaling parameters. The criterion yields maximum values of M which compare well with critical values of M for the onset of elastic instabilities in viscometric torsional flows. We conclude that the same mechanism of tension acting along curved streamlines governs the onset of elastic instabilities in both extensional (irrotational) and torsional (rotational) viscoelastic flows.

  13. Elasticity and Extensibility Determine Printability and Spinnability of Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Dinic, Jelena; Jimenez, Leidy; Sharma, Vivek

    Many advanced manufacturing technologies like inkjet and 3D printing, nano-fiber spinning involve complex free-surface flows, and the formation of columnar necks that undergo spontaneous capillary-driven thinning and pinch-off. The progressive self-thinning of neck is often characterized by self-similar profiles and scaling laws that depend on the relative magnitude of capillary, inertial and viscous stresses for simple (Newtonian and inelastic) fluids. Stream-wise velocity gradients that arise within the thinning columnar neck create an extensional flow field that can orient and stretch macromolecules, contributing extra elastic stresses and extensional viscosity that change thinning and pinch-off dynamics for polymeric complex fluids. Characterizing the filament thinning and break-up kinetics in jetting, dripping and stretching liquid bridge provides invaluable insight into the interplay of elastic, viscous, capillary and inertial stresses relevant for these applications. We elucidate how polymer composition, flexibility and molecular weight determine the thinning and pinch-off kinetics in our experiments. Both effective relaxation time and transient extensional viscosity are found to be strongly concentration dependent even for dilute solutions.

  14. Elastic instabilities in planar elongational flow of monodisperse polymer solutions.

    PubMed

    Haward, Simon J; McKinley, Gareth H; Shen, Amy Q

    2016-01-01

    We investigate purely elastic flow instabilities in the almost ideal planar stagnation point elongational flow field generated by a microfluidic optimized-shape cross-slot extensional rheometer (OSCER). We use time-resolved flow velocimetry and full-field birefringence microscopy to study the behavior of a series of well-characterized viscoelastic polymer solutions under conditions of low fluid inertia and over a wide range of imposed deformation rates. At low deformation rates the flow is steady and symmetric and appears Newtonian-like, while at high deformation rates we observe the onset of a flow asymmetry resembling the purely elastic instabilities reported in standard-shaped cross-slot devices. However, for intermediate rates, we observe a new type of elastic instability characterized by a lateral displacement and time-dependent motion of the stagnation point. At the onset of this new instability, we evaluate a well-known dimensionless criterion M that predicts the onset of elastic instabilities based on geometric and rheological scaling parameters. The criterion yields maximum values of M which compare well with critical values of M for the onset of elastic instabilities in viscometric torsional flows. We conclude that the same mechanism of tension acting along curved streamlines governs the onset of elastic instabilities in both extensional (irrotational) and torsional (rotational) viscoelastic flows. PMID:27616181

  15. 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.

  16. Hydro-gel environment and solution additives modify calcite growth mechanism to an accretion process of amorphous nanospheres

    NASA Astrophysics Data System (ADS)

    Gal, A.; Kahil, K.; Habraken, W.; Gur, D.; Fratzl, P.; Addadi, L.; Weiner, S.

    2013-12-01

    Various biominerals form via the transformation of a transient amorphous precursor phase into a mature crystalline phase. The mature biominerals usually exhibit morphology reminiscent of aggregated nanoparticles. Although these observations suggest an accretion-based growth process consisting on nanoparticles, the key factors that control the accretion process are unknown. We investigated the transformation of solid amorphous calcium carbonate (ACC) into calcite. When plant cystoliths, a biogenic stable ACC phase, are transformed into calcite in vitro by immersion in water, calcite crystals grow in two distinct steps (Gal et al., Angewandte Chemie, 2013). First, rhombohedral crystals grow that show flat facets as expected from ion-by-ion growth. These crystals then grow by the aggregation and crystallization of the original ACC nanospheres leading to a surface morphology dominated by aggregated spheres. The transformation process occurs within an organic hydro-gel that originates from inside the cystoliths. We tested the importance of the gel phase to the transformation process by transforming synthetic ACC into calcite inside various gels. In all the investigated systems: in gelatin, agarose, and pectin gels, calcite crystals grew that showed the nanosphere aggregation morphology. In additional experiments we demonstrated that also other additives, such as phosphate ions and biogenic macromolecules, that slow down ACC dissolution and calcite precipitation from ions can induce the accretion process dominance (see figure attached). These experiments show that although in solution the dominant process is dissolution to ions of the ACC and crystal growth by ion-by-ion mechanism, the presence of an additive that slows the ion-mediated processes makes the ACC nanospheres stable long enough to interact with the crystal surface. As a result, the metastable ACC nanospheres undergo secondary nucleation on the crystal surface without dissolving. These experiments highlight

  17. Comparative analysis of zaleplon complexation with cyclodextrins and hydrophilic polymers in solution and in solid state.

    PubMed

    Jablan, Jasna; Szalontai, Gábor; Jug, Mario

    2012-12-01

    The aim of this work was to investigate the potential synergistic effect of water-soluble polymers (hypromellose, HPMC and polyvinylpyrrolidone, PVP) on zaleplon (ZAL) complexation with parent β-cyclodextrin (βCD) and its randomly methylated derivative (RAMEB) in solution and in solid state. The addition of HPMC to the complexation medium improved ZAL complexation and solubilization with RAMEB (K(ZAL/RAMEB)=156±5M(-1) and K(ZAL/RAMEB/HPMC)=189±8M(-1); p<0.01), while such effect was not observed for βCD (K(ZAL/βCD)=112±2M(-1) and K(ZAL/βCD/HPMC)=119±8M(-1); p>0.05). Although PVP increased the ZAL aqueous solubility from 0.22 to 0.27mg/mL, it did not show any synergistic effects on ZAL solubilization with the cyclodextrins tested. Binary and ternary systems of ZAL with βCD, RAMEB and HPMC were prepared by spray-drying. Differential scanning calorimetry, X-ray powder diffraction and scanning electron microscopy demonstrated a partial ZAL amorphization in spray-dried binary and ternary systems with βCD, while the drug was completely amorphous in all samples with RAMEB. Furthermore, inclusion complex formation in all systems prepared was confirmed by solid-state NMR spectroscopy. The in vitro dissolution rate followed the rank order ZAL/RAMEB/HPMC>ZAL/RAMEB=ZAL/βCD/HPMC>ZAL/βCD≫ZAL, clearly demonstrating the superior performance of RAMEB on ZAL complexation in the solid state and its synergistic effect with HPMC on drug solubility. Surprisingly, when loaded into tablets made with insoluble microcrystalline cellulose, RAMEB complexes had no positive effect on drug dissolution, because HPMC and RAMEB acted as a binders inside the tablets, prolonging their disintegration. Oppositely, the formulation with mannitol, a soluble excipient, containing a ternary RAMEB system, released the complete drug-dose in only 5min, clearly demonstrating its suitability for the development of immediate-release oral formulation of ZAL.

  18. Variation of persistence length with concentration in a hydrogen bonding polymer solution

    NASA Astrophysics Data System (ADS)

    Sukumaran, S.; Beaucage, G.

    2000-03-01

    Miscibility of some polymers in water is usually attributed to the ability of the polymer to hydrogen bond with water. Hydrogen bonding contributes a strong interaction component to the free energy that enhances mixing between the polymer and water. It is widely known that certain conformations of the polymer have significantly higher dipole moment and consequently higher affinity for water. If the solvent alters the bond rotation energetics of the polymer it is natural to expect the average local structure of the chain to be affected leading to a change in the persistence length. Small angle neutron scattering experiments were performed on aqueous (D2O) solutions of a polymer (PEO or PVME) at different concentrations to investigate the microscopic structure of these solutions. The persistence length was strongly dependent on concentration. A simple physical explanation for this phenomenon will be provided. Possible ramifications of such a phenomenon in understanding phase behavior will be indicated.

  19. Interactions and Aggregation of Charged Nanoparticles in Uncharged Polymer Solutions.

    PubMed

    Pandav, Gunja; Pryamitsyn, Victor; Ganesan, Venkat

    2015-11-17

    We employ an extension of the single chain in mean field simulation method to study mixtures of charged particles and uncharged polymers. We examine the effect of particle charge, polymer concentration, and particle volume fraction on the resulting particle aggregates. The structures of aggregates were characterized using particle-particle radial distribution functions and cluster size distributions. We observe that the level of aggregation between particles increases with increasing particle volume fraction and polymer concentration and decreasing particle charge. At intermediate regimes of particle volume fraction and polymer concentrations, we observe the formation of equilibrium clusters with a preferred size. We also examined the influence of manybody effects on the structure of a charged particle-polymer system. Our results indicate that the effective two-body approximation overpredicts the aggregation between particles even at dilute particle concentrations. Such effects are thought to be a consequence of the interplay between the respective manybody effects on the depletion and electrostatic interactions.

  20. Salting-in and salting-out of water-soluble polymers in aqueous salt solutions.

    PubMed

    Sadeghi, Rahmat; Jahani, Farahnaz

    2012-05-01

    To obtain further experimental evidence for the mechanisms of the salting effect produced by the addition of salting-out or sating-in inducing electrolytes to aqueous solutions of water-soluble polymers, systematic studies on the vapor-liquid equilibria and liquid-liquid equilibria of aqueous solutions of several polymers are performed in the presence of a large series of electrolytes. Polymers are polyethylene glycol 400 (PEG400), polyethylene glycol dimethyl ether 250 (PEGDME250), polyethylene glycol dimethyl ether 2000 (PEGDME2000), and polypropylene glycol 400 (PPG400), and the investigated electrolytes are KCl, NH(4)Cl, MgCl(2), (CH(3))(4)NCl, NaCl, NaNO(3), Na(2)CO(3), Na(2)SO(4), and Na(3)Cit (tri-sodium citrate). Aqueous solutions of PPG400 form aqueous two-phase systems with all the investigated salts; however, other investigated polymers form aqueous two-phase systems only with Na(2)CO(3), Na(2)SO(4), and Na(3)Cit. A relation was found between the salting-out or sating-in effects of electrolyte on the polymer aqueous solutions and the slopes of the constant water activity lines of ternary polymer-salt aqueous solutions, so that, in the case of the salting-out effect, the constant water activity lines had a concave slope, but in the case of the salting-in effects, the constant water activity lines had a convex slope. The effect of temperature, anion of electrolyte, cation of electrolyte, and type and molar mass of polymers were studied and the results interpreted in terms of the solute-water and solute-solute interactions. The salting-out effect results from the formation of ion (specially anion)-water hydration complexes, which, in turn, decreases hydration, and hence, the solubility of the polymer and the salting-in effect results from a direct binding of the cations to the ether oxygens of the polymers.

  1. Sorption of Ochratoxin A from aqueous solutions using beta-cyclodextrin-polyurethane polymer

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The ability of a cyclodextrin-polyurethane polymer to remove ochratoxin A from aqueous solutions, including wine, was examined by batch rebinding assays and equilibrium sorption isotherms. The results were fit to two parameter models. Freundlich analysis of the sorption isotherm indicates the polyme...

  2. A Transition to a Compact Form of DNA in Polymer Solutions

    PubMed Central

    Lerman, L. S.

    1971-01-01

    In the presence of over-threshold concentrations of simple neutral polymers and salts, DNA undergoes a cooperative change in its solution structure. Sedimentation studies at low DNA concentrations show that phage DNA molecules collapse into particles approaching the compactness of the contents of phage heads. The interaction between DNA and polymers is thought to be nonspecifically replusive. PMID:5288774

  3. A photochromic supramolecular polymer based on bis-p-sulfonatocalix[4]arene recognition in aqueous solution.

    PubMed

    Yao, Xuyang; Li, Teng; Wang, Sheng; Ma, Xiang; Tian, He

    2014-07-11

    A photochromic supramolecular polymer based on bis-p-sulfonatocalix[4]arene recognition with a dithienylethene derivative in aqueous solution was fabricated. The resultant polymer showed good photochromic behaviour with obvious colour switching and a morphology change under alternative UV/Vis light stimuli. PMID:24853232

  4. Elastic Energy Transfer in Turbulence of Dilute Polymer Solution

    NASA Astrophysics Data System (ADS)

    Xi, Heng-Dong; Bodenschatz, Eberhard; Xu, Haitao

    2012-11-01

    We present an experimental study of the energy transfer in the bulk of a turbulent flow with small amount long-chain polymer additives. By varying the Reynolds numbers Rλ, Wissenberg number Wi and polymer concentration φ. We test quantitively the elastic theory proposed by de Gennes and Tabor (Europhys. Lett., 1986; Physica A, 1986). The rate of energy transfer by polymer elasticity as inferred from the theory is consistent with that measured from the second order Eulerian structure functions. The unknown parameter n in the theory, which represents the flow topology of the stretching field, is found to be nearly 1. Based on energy transfer rate balance, We propose an elastic length scale, rɛ, which describes the effect of polymer elasticity on turbulence energy cascade and captures the scale dependence of the elastic energy transfer rate. We are grateful to the Max Planck Society, the Alexander von Humboldt Foundation and the Deutsche Forschungsgemeinschaft for their support.

  5. Synthesis and Evaluation of Cyclodextrin-based Polymers for Patulin Extraction from Aqueous Solutions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Patulin is a mycotoxin produced by fungi that contaminate fruits, juices, and other agricultural commodities. Sorption properties of polyurethane-beta-cyclodextrin polymers were evaluated for the ability to remove patulin from solutions, including apple juice. Freundlich isotherm analysis determin...

  6. Amorphous ZnAlSnO thin-film transistors by a combustion solution process for future displays

    SciTech Connect

    Jiang, Qingjun; Feng, Lisha; Wu, Chuanjia; Sun, Rujie; Lu, Bin; Ye, Zhizhen; Lu, Jianguo; Li, Xifeng

    2015-02-02

    A combustion solution method was developed to fabricate amorphous ZnAlSnO (a-ZATO) for thin-film transistors (TFTs). The properties of a-ZATO films and behaviors of a-ZATO TFTs were studied in detail. An appropriate Al content in the matrix could suppress the formation of oxygen vacancies efficiently and achieve densely amorphous films. The a-ZATO TFTs exhibited acceptable performances, with an on/off current ratio of ∼10{sup 6}, field-effect mobility of 2.33 cm{sup 2}·V{sup −1}·S{sup −1}, threshold voltage of 2.39 V, and subthreshold swing of 0.52 V/decade at an optimal Al content (0.5). The relation between on- and off-resistance of the ZATO TFT was also within the range expected for fast switching devices. More importantly, the introduced Al with an appropriate content had the ability to evidently enhance the device long-term stability under working bias stress and storage durations. The obtained indium- and gallium-free a-ZATO TFTs are very promising for the next-generation displays.

  7. Amorphous and nanocrystalline titanium nitride and carbonitride materials obtained by solution phase ammonolysis of Ti(NMe 2) 4

    NASA Astrophysics Data System (ADS)

    Jackson, Andrew W.; Shebanova, Olga; Hector, Andrew L.; McMillan, Paul F.

    2006-05-01

    Solution phase reactions between tetrakisdimethylamidotitanium (Ti(NMe 2) 4) and ammonia yield precipitates with composition TiC 0.5N 1.1H 2.3. Thermogravimetric analysis (TGA) indicates that decomposition of these precursor materials proceeds in two steps to yield rocksalt-structured TiN or Ti(C,N), depending upon the gas atmosphere. Heating to above 700 °C in NH 3 yields nearly stoichiometric TiN. However, heating in N 2 atmosphere leads to isostructural carbonitrides, approximately TiC 0.2N 0.8 in composition. The particle sizes of these materials range between 4-12 nm. Heating to a temperature that corresponds to the intermediate plateau in the TGA curve (450 °C) results in a black powder that is X-ray amorphous and is electrically conducting. The bulk chemical composition of this material is found to be TiC 0.22N 1.01H 0.07, or Ti 3(C 0.17N 0.78H 0.05) 3.96, close to Ti 3(C,N) 4. Previous workers have suggested that the intermediate compound was an amorphous form of Ti 3N 4. TEM investigation of the material indicates the presence of nanocrystalline regions <5 nm in dimension embedded in an amorphous matrix. Raman and IR reflectance data indicate some structural similarity with the rocksalt-structured TiN and Ti(C,N) phases, but with disorder and substantial vacancies or other defects. XAS indicates that the local structure of the amorphous solid is based on the rocksalt structure, but with a large proportion of vacancies on both the cation (Ti) and anion (C,N) sites. The first shell Ti coordination is approximately 4.5 and the second-shell coordination ˜5.5 compared with expected values of 6 and 12, respectively, for the ideal rocksalt structure. The material is thus approximately 50% less dense than known Ti x(C,N) y crystalline phases.

  8. Fabrication of gold nanoparticle-polymer composite particles with raspberry, core-shell and amorphous morphologies at room temperature via electrostatic interactions and diffusion.

    PubMed

    Kanahara, Masaaki; Shimomura, Masatsugu; Yabu, Hiroshi

    2014-01-14

    Composite particles with varying morphologies composed of gold nanoparticles (Au NPs) and polymers were fabricated based on a combination of electrostatic interactions between the polymer particles and Au NPs and diffusion processes. The positively charged polymer particles were prepared from amino-terminated polystyrene (PS-NH2) and amino-terminated 1,2-polybutadiene (PB-NH2). Adsorption of citrate-stabilized Au NPs resulted in three different distribution states of Au NPs in the polymer particles, depending on the glass transition temperature (Tg) and molecular weight of the polymer. The adsorption of Au NPs onto PS-NH2 particles produced raspberry-like composite particle morphologies, while the NPs instead diffused into the PB-NH2 particles, since the Tg of PB-NH2 is below room temperature. The diffusion of Au NPs could be controlled by varying the molecular weight of the PB-NH2 and the diameter of the NPs, and both core-shell and amorphous distributions were successfully achieved. PMID:24651763

  9. Thermally Activated Delayed Fluorescence Polymers for Efficient Solution-Processed Organic Light-Emitting Diodes.

    PubMed

    Lee, Sae Youn; Yasuda, Takuma; Komiyama, Hideaki; Lee, Jiyoung; Adachi, Chihaya

    2016-06-01

    Thermally activated delayed fluorescence (TADF) π-conjugated polymers are developed for solution-processed TADF-OLEDs. Benzophenone-based alternating donor-acceptor structures contribute to the small ∆EST , enabling efficient exciton-harvesting through TADF. Solution-processed OLEDs using the TADF polymers as emitters can achieve high maximum external electroluminescence efficiencies of up to 9.3%. PMID:27001891

  10. Structural Properties and Phase Behavior of Crosslinked Networks in Polymer Solutions

    PubMed Central

    Benmouna, Farida; Zemmour, Samira; Benmouna, Mustapha

    2016-01-01

    ABSTRACT Structural properties and phase behavior of crosslinked networks embedded in polymer solutions are theoretically investigated. The partial structure factor of the network is calculated using a matrix formulation of the random phase approximation and the forward scattering limit is correlated with the phase behavior. Swelling and deswelling processes are analyzed in terms of the polymer concentration, the mismatch of solvent quality with respect to polymer and network, the polymers incompatibility and their characteristic sizes. Most studies reported so far in the literature have focussed on the swelling of crosslinked networks and gels in pure solvents but the correlation of the structural properties with the phase behavior in the presence of high molecular weight polymers in solution has not been given sufficient attention. The present work is intended to fill this gap in view of the current efforts to develop novel drug encapsulating and targeted delivery devices. PMID:27134310

  11. Sub-100 °C solution processed amorphous titania nanowire thin films for high-performance perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Wu, Wu-Qiang; Chen, Dehong; Huang, Fuzhi; Cheng, Yi-Bing; Caruso, Rachel A.

    2016-10-01

    The present work demonstrates a facile one-step process to fabricate thin films of amorphous titania nanowires on transparent conducting oxide substrates via hydrolysis of potassium titanium oxide oxalate in an aqueous solution at 90 °C. The resultant titania nanowire thin films (that have not undergone further annealing) are efficient electron transport layers in CH3NH3PbI3 perovskite solar cells, yielding full sun solar-to-electricity conversion efficiencies of up to 14.67% and a stabilized efficiency of 14.00% under AM 1.5G one sun illumination, comparable to high temperature sintered TiO2 counterparts. The high photovoltaic performance is attributed to the porous nanowire network that facilitates perovskite infiltration, its unique 1D geometry and excellent surface coverage for efficient electron transport, as well as suppressed charge recombination between FTO and perovskite.

  12. Morphology of crystalline–amorphous olefin block copolymers in solution characterized by small-angle neutron scattering and microscopy

    PubMed Central

    Radulescu, Aurel; Goerigk, Günter; Fetters, Lewis; Richter, Dieter

    2015-01-01

    The single-chain properties and self-assembly behavior in dilute solution of olefin block copolymers obtained by chain-shuttling technology and consisting of alternating crystallizable and amorphous ethylene/1-octene blocks were investigated by pinhole and focusing small-angle neutron scattering techniques, optical microscopy in bright-field and crossed-polarizer modes, and differential scanning calorimetry. The complex hydrocarbon soluble (precipitant free) macro-aggregates formed with decreasing temperature are characterized by spherulitic textures. The spherulites yield, on one hand, a morphology that depends on the chain structure properties and, on the other hand, multiple structural levels with a hierarchical organization that ranges from 10 Å up to tens of micrometres. This morphology displays peculiarities dictated by the polydisperse character of these materials. PMID:26664344

  13. Effect of polymer matrix on structure of Se particles formed in aqueous solutions during redox process

    SciTech Connect

    Suvorova, E. I. Klechkovskaya, V. V.

    2010-12-15

    Transmission electron microscopy and X-ray energy dispersive microanalysis study of the structure of particles formed during the reduction of Se(IV) to Se(0) in aqueous solutions in the presence of amphiphilic polymers showed the formation of Se/polymer composite particles. The content of carbon inside the particles can be as large as 80 at %. Polymers deeply influence the structure of particles. Depending on polymers, the composite particles may be unstable with time and they spontaneously evolve from Se/polymer composite particles to crystalline particles of monoclinic Se. For the stable ones, addition of bacterial cellulose Acetobacter xylinum gel-film can induce crystallization in the particles which expel the polymeric material. The Se/polymer composite particles and Se crystalline particles exhibit different sensitivity to electron irradiation and stiffness.

  14. Hybrid light emitting diodes based on solution processed polymers, colloidal quantum dots, and colloidal metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Ma, Xin

    This dissertation focuses on solution-processed light-emitting devices based on polymer, polymer/PbS quantum dot, and polymer/silver nanoparticle hybrid materials. Solution based materials and organic/inorganic hybrid light emitting diodes attracted significant interest recently due to many of their advantages over conventional light emitting diodes (LEDs) including low fabrication cost, flexible, high substrate compatibility, as well as tunable emission wavelength of the quantum dot materials. However, the application of these novel solution processed materials based devices is still limited due to their low performances. Material properties and fabrication parameters need to be carefully examined and understood for further device improvement. This thesis first investigates the impact of solvent property and evaporation rate on the polymer molecular chain morphology and packaging in device structures. Solvent is a key component to make the active material solution for spin coating fabrication process. Their impacts are observed and examined on both polymer blend system and mono-polymer device. Secondly, PbS colloidal quantum dot are introduced to form hybrid device with polymer and to migrate the device emission into near-IR range. As we show, the dithiol molecules used to cross-link quantum dots determine the optical and electrical property of the resulting thin films. By choosing a proper ligand for quantum dot ligand exchange, a high performance polymer/quantum dot hybrid LED is fabricated. In the end, the interaction of polymer exciton with surface plasmon mode in colloidal silver nanoparticles and the use of this effect to enhance solution processed LEDs' performances are investigated.

  15. Liquid-liquid equilibria for polymer solutions and blends, including copolymers

    SciTech Connect

    Song, Y.; Hino, T.; Lambert, S.M.; Prausnitz, J.M.

    1995-02-01

    A simplified perturbed hard-sphere-chain (PHSC) theory is applied to interpret, correlate, and (in part) predict liquid-liquid equilibria (LLE) for polymer solutions and blends, including copolymers. The PHSC equation of state uses a hard-sphere-chain reference system plus a van der Waals attractive perturbation. Three pure-component parameters are obtained from readily available thermodynamic properties. Mixture parameters are obtained using pure-component parameters, conventional combining rules, and one or two binary constants. Theoretical and experimental coexistence curves and miscibility maps show good agreement for selected blends containing polymers and copolymers. For LLE of dilute or semi-dilute solvent/polymer solutions, it is necessary to decrease the pure-component polymer chain length, probably because the mean-field approximation is not suitable for such solutions.

  16. Investigating the Influence of Polymers on Supersaturated Flufenamic Acid Cocrystal Solutions.

    PubMed

    Guo, Minshan; Wang, Ke; Hamill, Noel; Lorimer, Keith; Li, Mingzhong

    2016-09-01

    The development of enabling formulations is a key stage when demonstrating the effectiveness of pharmaceutical cocrystals to maximize the oral bioavailability for poorly water soluble drugs. Inhibition of drug crystallization from a supersaturated cocrystal solution through a fundamental understanding of the nucleation and crystal growth is important. In this study, the influence of the three polymers of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and a copolymer of N-vinly-2-pyrrodidone (60%) and vinyl acetate (40%) (PVP-VA) on the flufenamic acid (FFA) crystallization from three different supersaturated solutions of the pure FFA and two cocrystals of FFA-NIC CO and FFA-TP CO has been investigated by measuring nucleation induction times and desupersaturation rates in the presence and absence of seed crystals. It was found that the competition of intermolecular hydrogen bonding among drug/coformer, drug/polymer, and coformer/polymer was a key factor responsible for maintaining supersaturation through nucleation inhibition and crystal growth modification in a cocrystal solution. The supersaturated cocrystal solutions with predissolved PEG demonstrated more effective stabilization in comparison to the pure FFA in the presence of the same polymer. In contrast, neither of the two cocrystal solutions, in the presence of PVP or PVP-VA, exhibited a better performance than the pure FFA with the same predissolved polymer. The study suggests that the selection of a polymeric excipient in a cocrystal formulation should not be solely dependent on the interplay of the parent drug and polymer without considering the coformer effects. PMID:27494289

  17. CONDENSED MATTER: STRUCTURE, MECHANICAL AND THERMAL PROPERTIES: Molecular Dynamics Study of Stability of Solid Solutions and Amorphous Phase in the Cu-Al System

    NASA Astrophysics Data System (ADS)

    Yang, Bin; Lai, Wen-Sheng

    2009-06-01

    The relative stability of fcc and bcc solid solutions and amorphous phase with different compositions in the Cu-Al system is studied by molecular dynamics simulations with n-body potentials. For Cu1-xAlx alloys, the calculations show that the fcc solid solution has the lowest energies in the composition region with x < 0.32 or x > 0.72, while the bee solid solution has the lowest energies in the central composition range, in agreement with the ball-milling experiments that a single bcc solid solution with 0.30 < x < 0.70 is obtained. The evolution of structures in solid solutions and amorphous phase is studied by the coordination number (CN) and bond-length analysis so as to unveil the underlying physics. It is found that the energy sequence among three phases is determined by the competition in energy change originating from the bond length and CNs (or the number of bonds).

  18. Tribocorrosion Behavior of Fe-Based Amorphous Composite Coating Reinforced by Al2O3 in 3.5% NaCl Solution

    NASA Astrophysics Data System (ADS)

    Yasir, Muhammad; Zhang, Cheng; Wang, Wei; Zhang, Zhi-Wei; Liu, Lin

    2016-09-01

    Although corrosion and friction/wear behavior of Fe-based amorphous coatings and their composites has been extensively studied during the past decade, there is very limited work related to tribocorrosion behavior. In this paper, the tribocorrosion behavior of a Fe-based amorphous composite coating reinforced with 20 wt.% Al2O3 particles was investigated in a 3.5% NaCl solution on a ball-on-disk tester and was compared to the monolithic amorphous coating and 316L stainless steel (SS). The results showed that the amorphous composite coating exhibited the highest tribocorrosion resistance among the three materials tested, as evidenced by the lowest coefficient of friction (~0.3) and tribocorrosion wear rate (~1.2 × 10-5 mm3/N·m). In addition, potentiodynamic polarization measurements before and during tribocorrosion testing demonstrated that corrosion resistance of the amorphous composite coating was not influenced so much by mechanical loading compared to the amorphous coating and the 316L SS. Observations on the worn surface revealed a corrosion-wear- and oxidational-wear-dominated tribocorrosion mechanism for the composite coatings. The excellent tribocorrosion resistance of the composite coating results from the effect of chemically stable Al2O3 phase which resists oxidation and delamination during sliding, along with poor wettability with corrosive NaCl droplets.

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

    SciTech Connect

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

    2015-11-28

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

  20. Functionalized Polymers-Emerging Versatile Tools for Solution-Phase Chemistry and Automated Parallel Synthesis.

    PubMed

    Kirschning, Andreas; Monenschein, Holger; Wittenberg, Rüdiger

    2001-02-16

    As part of the dramatic changes associated with the need for preparing compound libraries in pharmaceutical and agrochemical research laboratories, industry searches for new technologies that allow for the automation of synthetic processes. Since the pioneering work by Merrifield polymeric supports have been identified to play a key role in this field however, polymer-assisted solution-phase synthesis which utilizes immobilized reagents and catalysts has only recently begun to flourish. Polymer-assisted solution-phase synthesis has various advantages over conventional solution-phase chemistry, such as the ease of separation of the supported species from a reaction mixture by filtration and washing, the opportunity to use an excess of the reagent to force the reaction to completion without causing workup problems, and the adaptability to continuous-flow processes. Various strategies for employing functionalized polymers stoichiometrically have been developed. Apart from reagents that are covalently or ionically attached to the polymeric backbone and which are released into solution in the presence of a suitable substrate, scavenger reagents play an increasingly important role in purifying reaction mixtures. Employing functionalized polymers in solution-phase synthesis has been shown to be extremely useful in automated parallel synthesis and multistep sequences. So far, compound libraries containing as many as 88 members have been generated by using several polymer-bound reagents one after another. Furthermore, it has been demonstrated that complex natural products like the alkaloids (+/-)-oxomaritidine and (+/-)-epimaritidine can be prepared by a sequence of five and six consecutive polymer-assisted steps, respectively, and the potent analgesic compound (+/-)-epibatidine in twelve linear steps ten of which are based on functionalized polymers. These developments reveal the great future prospects of polymer-assisted solution-phase synthesis.

  1. On the origin of Gaussian network theory in the thermo/chemo-responsive shape memory effect of amorphous polymers undergoing photo-elastic transition

    NASA Astrophysics Data System (ADS)

    Lu, Haibao; Huang, Wei Min; Leng, Jinsong

    2016-06-01

    Amorphous polymers are normally isotropic in their physical properties, however, upon stress their structural randomness is disturbed and they become anisotropic. There is a close connection between the optical anisotropy and the elastic (or mechanical) anisotropy, since both are related to the type of symmetry exhibited by the molecular structure. On the origin of Gaussian network theory, a phenomenological constitutive framework was proposed to study the photo-elastic transition and working mechanism of the thermo-/chemo-responsive shape-memory effect (SME) in amorphous shape memory polymers (SMPs). Optically refractive index was initially employed to couple the stress, strain and the anisotropy of the random link in macromolecule chain. Based on the Arrhenius law, a constitutive framework was then applied for the temperature dependence of optical (or elastic or mechanical) anisotropy according to the fictive temperature parameter. Finally, the phenomenological photo-elastic model was proposed to quantitatively identify the influential factors behind the thermo-/chemo-responsive SME in SMPs, of which the shape recovery behavior is predicted and verified by the available experimental data reported in the literature.

  2. Holey polymer films templated by growth and self-assembly of water drops over evaporating polymer solutions

    NASA Astrophysics Data System (ADS)

    Sharma, Vivek; Srinivasarao, Mohan

    2010-03-01

    Water drops that nucleate and grow over evaporating polymer solutions exhibit non-coalescence and pack like hard spheres. In this study, we elucidate how the growth and self-organization of a population of close packed drops occur in response to the heat and mass fluxes involved in water condensation and evaporation of organic solvent. We examine the role of solvent and polymer in controlling the kinetics of growth and assembly of droplets, which eventually evaporate away, producing a polymer film with ordered array of pores. We describe a rich array of experimental observations and theoretical considerations about water droplet growth, noncoalescence and assembly that have not been reported in the published literature so far. Most importantly, we provide insights into how the porous, microstructure is generated and how the size of pore can be controlled.

  3. Hot melt extrusion (HME) for amorphous solid dispersions: predictive tools for processing and impact of drug-polymer interactions on supersaturation.

    PubMed

    Sarode, Ashish L; Sandhu, Harpreet; Shah, Navnit; Malick, Waseem; Zia, Hossein

    2013-02-14

    The processing parameters for HME have been evaluated and the impact of solid state intermolecular drug-polymer interactions on supersaturation has been investigated. Poorly water soluble drugs Indomethacin (IND), Itraconazole (ITZ), and Griseofulvin (GSF) and hydrophilic polymers - Eudragit EPO, Eudragit L-100-55, Eudragit L-100, HPMCAS-LF, HPMCAS-MF, Pharmacoat 603, and Kollidon VA-64 were selected for this study. Solubility parameters calculations (SPCs), differential scanning calorimetry (DSC), and rheological analysis of drug-polymer physical mixtures (PMs) was performed. The solid dispersions were manufactured using HME and characterized by powder X-ray diffraction (PXRD), polarized light microscopy (PLM), Fourier transform infra-red (FTIR) Spectroscopy, and dissolution study. Results obtained by DSC correlated well with SPC, showing single glass transition temperatures for all the PMs except ITZ in Eudragit EPO that depicted the highest difference in solubility parameters. The zero rate viscosity (η₀) was dependent on the melting point and consequently the state of the drug in the polymer at the softening temperature. The η₀ of PMs was useful to estimate the processing conditions for HME and to produce transparent glassy HMEs from most of the PMs. The amorphous conversion due to HME was confirmed by PXRD and PLM. The solid state drug-polymer interactions occurred during HME could be confirmed by FTIR analysis. Highest supersaturation could be achieved for IND, ITZ, and GSF using Eudragit EPO, HPMCAS-LF, and Eudragit L-100-55, respectively where relatively higher stretching of the carbonyl peaks was observed by FTIR. Thus, the highest dissolution rate and supersaturation of poorly water soluble drugs could be attributed to drug-polymer interactions occurred during HME.

  4. Sonochemical precipitation of amorphous uranium phosphates from trialkyl phosphate solutions and their thermal conversion to UP2O7.

    PubMed

    Doroshenko, Iaroslav; Zurkova, Jana; Moravec, Zdenek; Bezdicka, Petr; Pinkas, Jiri

    2015-09-01

    Insoluble amorphous precipitates containing uranyl and phosphate ions are obtained by sonication of solutions of three uranyl precursors, UO2(X)2, X=NO3, CH3COO, CH3C(O)CHC(O)CH3 (acetylacetonate, acac), in triesters of phosphoric acid, OP(OR)3, R=Me (trimethyl phosphate, TMP), Et (triethyl phosphate, TEP). TMP and TEP are used as high-boiling solvents and they serve also as a source of phosphate anions. Sonolysis experiments were carried out under flow of Ar at 40°C on a Sonics and Materials VXC 500W system (f=20 kHz, Pac=0.49 W cm(-3)). Powder X-ray diffraction (PXRD) reveals amorphous character of all obtained precipitates. The presence of uranyl and phosphate is evidenced by IR spectroscopy and ICP-OES analysis reveals the content of both U (38.6-43.4 wt%) and P (11.0-13.6 wt%). The thermal behavior of the substances was studied by TG/DSC analysis, which shows weight losses in the range of 19.21-24.08%. On heating the amorphous precipitates to 1000°C, crystalline uranium diphosphate UP2O7 is obtained in all cases as the only crystalline phase. Uranyl(VI) is reduced during thermolysis to U(IV) as there is no characteristic vibration of UO2(2+) in the IR spectra of solid UP2O7 products. The ICP-OES analysis of U and P content in precipitates allowed us to calculate the efficiency of precipitation of uranium from mother liquor and to compare it with the efficiency calculated from the data received by the PXRD and TG/DSC analyses. The efficiency of the uranium removal attained by our sonoprecipitation procedure was typically 30-35%. These sonochemical precipitation reactions providing insoluble uranium phosphates may be potentially interesting models for the description of behavior of uranium-containing waste or reprocessing streams.

  5. Effect of hydrodynamic correlations on the dynamics of polymers in dilute solution

    NASA Astrophysics Data System (ADS)

    Huang, Chien-Cheng; Gompper, Gerhard; Winkler, Roland G.

    2013-04-01

    We analyze the effect of time-dependent hydrodynamic interactions on the dynamics of flexible polymers in dilute solution. In analytical calculations, the fluctuating hydrodynamics approach is adopted to describe the fluid, and a Gaussian model to represented the polymer. Simulations are performed exploiting the multiparticle collision dynamics approach, a mesoscale hydrodynamic simulation technique, to explicitly describe the fluid. Polymer center-of-mass velocity correlation functions are calculated for various polymer lengths. Similarly, segment mean square displacements are discussed and polymer diffusion coefficients are determined. Particular attention is paid to the influence of sound propagation on the various properties. The simulations reveal a strong effect of hydrodynamic interactions. Specifically, the time dependence of the center-of-mass velocity correlation functions is determined by polymer properties over a length-dependent time window, but are asymptotically solely governed by fluid correlations, with a long-time tail decaying as t-3/2. The correlation functions are heavily influenced by sound modes for short polymers, an effect which gradually disappears with increasing polymer length. We find excellent agreement between analytical and simulation results. This allows us to provide a theory-based asymptotic value for the polymer diffusion coefficient in the limit of large system sizes, which is based on a single finite-system-size simulation.

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

    SciTech Connect

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

    1996-09-01

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

  7. Ultrafast photogeneration of charged polarons on conjugated polymer chains in dilute solution

    NASA Astrophysics Data System (ADS)

    Miranda, Paulo B.; Moses, Daniel; Heeger, Alan J.

    2004-08-01

    Ultrafast photoinduced absorption by infrared-active vibrational modes is used to study the photogeneration of polarons on semiconducting polymer chains in dilute solutions and in solid films of a soluble derivative of poly(para-phenylene vinylene). In dilute solutions, polaron pairs are photogenerated on the conjugated polymer within less than 250fs with quantum efficiencies ϕch˜3% , about one-third of that for solid films of the same polymer. The excitation spectra of ϕch for both solutions and films show that ϕch is weakly dependent on photon energy between 2.2eV (the onset of absorption) and 4.7eV . The recombination dynamics of polarons is very fast and highly dependent on the excitation density for polymer films, but it is significantly slower and less sensitive to pump intensity for the semiconducting polymer in dilute solution. We conclude that the positive and negative polarons on a single chain in solution are typically separated by hundreds of monomer repeat units and that their one-dimensional diffusion along the chain is inhibited by the intervening excitons. This, together with the suppression of interchain recombination, explains the surprisingly slower polaron recombination in isolated chains.

  8. Apparatus for and method of producing monodisperse submicron polymer powders from solution

    DOEpatents

    Noid, Donald W.; Otaigbe, Joshua U.; Barnes, Michael D.; Sumpter, Bobby G.; Kung, Chung-Yi

    2002-01-01

    This invention describes a method of producing polymer powders from solution in a compatible solvent using a new device referred to as a microdroplets on demand generator (MODG). The embodiment of this invention is the MODG apparatus and its relevance as a method to extensive application in materials science and technology. Proof of concept is demonstrated using poly(ethylene) glycol polymer microparticles generated with the MODG and captured in a microparticle levitation device.

  9. Vapor-Liquid Equilibria for Some Concentrated Aqueous PolymerSolutions

    SciTech Connect

    Striolo, Alberto; Prausnitz, John M.

    1999-07-01

    Vapor-liquid-equilibrium data were obtained for binary aqueous solutions of six water-soluble linear polymers in the range 70-95 C. A classical gravimetric sorption method was used to measure the amount of solvent absorbed as a function of vapor-phase water pressure. Polymers studied were polyvinylpyrrolidone, polyethyleneoxide, polyvinylalcohol, hydroxyethylcellulose, polyethylenimine, polymethylvinylether. The experimental data were reduced with Hino's lattice model that distinguished the interactions due to London dispersion forces and those due to hydrogen bonding.

  10. Visualizing phase transition behavior of dilute stimuli responsive polymer solutions via Mueller matrix polarimetry.

    PubMed

    Narayanan, Amal; Chandel, Shubham; Ghosh, Nirmalya; De, Priyadarsi

    2015-09-15

    Probing volume phase transition behavior of superdiluted polymer solutions both micro- and macroscopically still persists as an outstanding challenge. In this regard, we have explored 4 × 4 spectral Mueller matrix measurement and its inverse analysis for excavating the microarchitectural facts about stimuli responsiveness of "smart" polymers. Phase separation behavior of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) and pH responsive poly(N,N-(dimethylamino)ethyl methacrylate) (PDMAEMA) and their copolymers were analyzed in terms of Mueller matrix derived polarization parameters, namely, depolarization (Δ), diattenuation (d), and linear retardance (δ). The Δ, d, and δ parameters provided useful information on both macro- and microstructural alterations during the phase separation. Additionally, the two step action ((i) breakage of polymer-water hydrogen bonding and (ii) polymer-polymer aggregation) at the molecular microenvironment during the cloud point generation was successfully probed via these parameters. It is demonstrated that, in comparison to the present techniques available for assessing the hydrophobic-hydrophilic switch over of simple stimuli-responsive polymers, Mueller matrix polarimetry offers an important advantage requiring a few hundred times dilute polymer solution (0.01 mg/mL, 1.1-1.4 μM) at a low-volume format. PMID:26287499

  11. Liquid filament instability due to stretch-induced phase separation in polymer solutions

    NASA Astrophysics Data System (ADS)

    Arinstein, Arkadii; Kulichikhin, Valery; Malkin, Alexander; Technion-Israel Institute of Technology Collaboration; Institute of Petrochemical Synthesis, Russian Academy of Sciences Team

    2015-03-01

    The instability in a jet of a viscoelastic semi-dilute entangled polymer solution under high stretching is discussed. Initially, the variation in osmotic pressure can compensate for decrease in the capillary force, and the jet is stable. The further evolution of the polymer solution along the jet results in formation of a filament in the jet center and of a near-surface solvent layer. Such a redistribution of polymer seems like a ``phase separation'', but it is related to stretching of the jet. The viscous liquid shell demonstrates Raleigh-type instability resulting in the formation of individual droplets on the oriented filament. Experimental observations showed that this separation is starting during few first seconds, and continues of about 10 -15 seconds. The modeling shows that a jet stretching results in a radial gradient in the polymer distribution: the polymer is concentrated in the jet center, whereas the solvent is remaining near the surface. The key point of this model is that a large longitudinal stretching of a polymer network results in its lateral contraction, so a solvent is pressed out of this polymer network because of the decrease in its volume. V.K. and A.M. acknowledge the financial support of the Russian Scientific Foundation (Grant 4-23-00003).

  12. Electric field-mediated processing of polymer blend solutions

    NASA Technical Reports Server (NTRS)

    Wnek, G. E.; Krause, S.

    1993-01-01

    Multiphase polymer blends in which the minor phases are oriented in a desired direction may demonstrate unique optical, electrical, and mechanical properties. While morphology development in shear fields was studied extensively, little work has focused on effects of electric fields on phase structure. The use of electric fields for blend morphology modulation with particular attention given to solvent casting of blends in d.c. fields was explored. Both homopolymer blends (average phase sizes of several microns) and diblock copolymer/homopolymer blends (average phase sizes of hundreds of Angstroms) were investigated. Summarized are important observations and conclusions.

  13. Sorption of ochratoxin A from aqueous solutions using β-cyclodextrin-polyurethane polymer.

    PubMed

    Appell, Michael; Jackson, Michael A

    2012-02-01

    The ability of a cyclodextrin-polyurethane polymer to remove ochratoxin A from aqueous solutions was examined by batch rebinding assays. The results from the aqueous binding studies were fit to two parameter models to gain insight into the interaction of ochratoxin A with the nanosponge material. The ochratoxin A sorption data fit well to the heterogeneous Freundlich isotherm model. The polymer was less effective at binding ochratoxin A in high pH buffer (9.5) under conditions where ochratoxin A exists predominantly in the dianionic state. Batch rebinding assays in red wine indicate the polymer is able to remove significant levels of ochratoxin A from spiked solutions between 1-10 μg·L(-1). These results suggest cyclodextrin nanosponge materials are suitable to reduce levels of ochratoxin A from spiked aqueous solutions and red wine samples.

  14. Correlating polymer solution conformation and thin film nanostructure: Implications for BHJ processing

    NASA Astrophysics Data System (ADS)

    Dattani, Rajeev; Nedoma, Alisyn; Stingelin, Natalie; Nelson, Jenny; Cabral, Joao

    2013-03-01

    We study the solution properties of polymer-fullerene mixtures by a combination of dynamic light scattering, viscometry, small angle neutron scattering and microscopy. Specifically, the kinetics of polymer conformation (Rg and Rh) and interaction changes are mapped as function of polymer-particle concentration, overall concentration in solution and age. A model system of polystyrene and C60 fullerene was selected for this study, in addition to the P3HT/PCBM pair, which is currently explored in photovoltaic applications. The solution properties show a clear correlation to the resulting thin film nanostructured composite morphology. Our future work will further link it to bulk heterojunction solar cell performance. EPSRC and Plastic Electronics DTC

  15. Consistent and transferable coarse-grained model for semidilute polymer solutions in good solvent.

    PubMed

    D'Adamo, Giuseppe; Pelissetto, Andrea; Pierleoni, Carlo

    2012-07-14

    We present a coarse-grained model for linear polymers with a tunable number of effective atoms (blobs) per chain interacting by intra- and intermolecular potentials obtained at zero density. We show how this model is able to accurately reproduce the universal properties of the underlying solution of athermal linear chains at various levels of coarse-graining and in a range of chain densities which can be widened by increasing the spatial resolution of the multiblob representation, i.e., the number of blobs per chain. The present model is unique in its ability to quantitatively predict thermodynamic and large scale structural properties of polymer solutions deep in the semidilute regime with a very limited computational effort, overcoming most of the problems related to the simulations of semidilute polymer solutions in good solvent conditions.

  16. Thermal analysis of frozen solutions: multiple glass transitions in amorphous systems.

    PubMed

    Sacha, Gregory A; Nail, Steven L

    2009-09-01

    Frozen aqueous solutions of sucrose exhibit two "glass transition-like" thermal events below the melting endotherm of ice when examined by DSC, but the physical basis of these events has been a source of some disagreement. In this study, a series of sugars, including sucrose, lactose, trehalose, maltose, fructose, galactose, fucose, mannose, and glucose were studied by modulated DSC and freeze-dry microscopy in order to better understand whether sucrose is unique in any way with respect to this behavior, as well as to explore the physical basis, and the pharmaceutical significance of these multiple transitions. Double transitions were found to be a common feature of all sugars examined. The results are consistent with both thermal events being glass transitions in that (1) both events have second-order characteristics that appear in the reversing signals, (2) annealing experiments reveal that enthalpy recovery is associated with each transition, and (3) Lissajous plots indicate that no detectable latent heat of melting is associated with either transition. The data in this study are consistent with the idea that the lower temperature transition arises from a metastable glassy mixture containing more water than that in the maximally freeze-concentrated solute. Freeze-dry microscopy observations show that for all of the sugars examined, it is the higher temperature transition that is associated with structural collapse during freeze-drying. There is no apparent pharmaceutical significance associated with the lower-temperature transition. PMID:19384925

  17. Kinetics of microphase separation in interpenetrated polymer networks in solution.

    PubMed

    Derouiche, A; Benhamou, M; Bettachy, A

    2005-04-01

    We present here a theoretical study of the early kinetics of the microphase separation in crosslinked polymer blends, made of two incompatible polymers A and B, dissolved in a common good solvent. Use is made of an extended blob model used previously for the investigation of the static properties of such a transition. We are interested in the variation of the relaxation rate, tau(q), versus the wave number q, in the vicinity of the spinodal temperature. We first show that kinetics is entirely dominated by local motions, which are of Rouse type. Slow motions are absent, because of the permanent presence of crosslinks. Second, we find that the characteristic frequency, omega (q) = tau(q)(-1), increases with increasing wave number q according to a sixth power law, that is omega (q) approximately q6 phi(-9/4), where phi is the overall monomer volume fraction. Therefore, the swelling of strands due to the excluded-volume forces leads to a renormalization of the characteristic frequency by a multiplicative factor scaling as phi(-9/4). The main conclusion is that the presence of a good solvent necessitates relaxation rates less important than those relative to crosslinked mixtures in the molten state.

  18. Local, real-time measurement of drying films of aqueous polymer solutions using active microrheology.

    PubMed

    Komoda, Yoshiyuki; Leal, L Gary; Squires, Todd M

    2014-05-13

    Oscillatory microdisk rheometry was applied to evaluate the evolution of the viscoelastic properties at the surface of a film of an aqueous solution of poly(vinyl alcohol) (PVA) during drying. The drying rate was measured concurrently, based upon measurements of the variation of film thickness. A fully hydrolyzed PVA solution shows a constant drying rate, while a less hydrolyzed PVA solution exhibits a decreased drying rate in the latter part of the drying process, which occurred at the same time as an increase of the elastic modulus. We suggest that this difference in behavior is a consequence of the fact that both the configuration of the PVA molecule and the strength of interaction with water depend on the degree to which the PVA is hydrolyzed. The polymer concentration at the film surface can be estimated from the measured viscosity at the surface for the fully hydrolyzed PVA solution, and this result then can be compared with two theoretical calculations: one in which the polymer concentration is assumed to remain uniform throughout the film, and the other in which the polymer concentration distribution is determined via a one-dimensional diffusion model. This comparison suggests that the polymer is first concentrated locally near the surface but later in the drying process the distribution of polymer becomes increasingly uniform, possibly due to a spontaneously generated convective flow inside the film.

  19. Capillary electrophoretic separation of DNA restriction fragments using dilute polymer solutions

    SciTech Connect

    Braun, B.; Blanch, W.; Prausnitz, J.M.

    1997-02-01

    Because the mechanism of DNA separation in capillary electrophoresis is not well understood, selection of polymers is a {open_quotes}trial-and-error{close_quotes} procedure. We investigated dilute-solution DNA separations by capillary electrophoresis using solutions of four polymers that differ in size, shape and stiffness. Hydroxyethylcellulose of high molecular weight provides excellent separation of large DNA fragments (2027 bp - 23130 bp). Polyvinylpyrrolidone separates DNA from 72 bp to 23 kbp and star-(polyethylene oxide), like linear poly (ethylene oxide), provides separation of fragments up to 1353 bp.

  20. Effects of Chain Entanglement on Polymer Solutions and Their Rheological Properties.

    NASA Astrophysics Data System (ADS)

    Berger, Todd Patrick

    The diffusion coefficients (measured by dynamic light scattering) of poly(p-methylstyrene-graft-isoprene) of molecular weights 1.5 times 10 ^6, 4.7 times 10^6 and 10.0 times 10^6 g/mol were measured in dilute solution for concentrations ranging from 100ppm (c*/5) to 1000ppm (2c*), respectively. Both the diffusion coefficient at zero concentration and the first order concentration dependent term were determined. To establish the effect of the solvent on such diffusion coefficients, the measurements were made in THF (a good solvent for both the branches and the backbone) and in methylcyclohexane (a good solvent for the branches and a poor solvent for the backbone). The solutions were studied as a function of temperature from 25 to 50^circC. Coil collapse of the backbone was observed. The molecular weight dependence of the diffusion coefficient is discussed in terms of the power law dependence of the frictional coefficient which ranges from 0.4 to 0.5. The leading concentration dependent term of the frictional coefficient has a very strong molecular weight dependence. An attempt is made to relate this dependence to the entanglements of the structure for these very large molecules. In the second part of this study the entanglement behavior of this type of graft polymer was demonstrated using electron microscopy. The polymer was deposited onto grids from solution. The polymer formed aggregates of vary diameter ranging from 100 to 15,000A. This range corresponds to a lower limit of a few molecules per aggregate and to an upper limit of hundreds of molecules per aggregate. The entanglement behavior was examined as a function of temperature, concentration, volume of solution applied to the grid, and by applying a small shearing force to the solution. Entanglement was observed using THF as the solvent for concentrations of 100 and 1000ppm with or without applying shear to the solution. When methylcyclohexane was used as the solvent a distribution of particle sizes was

  1. Low percolation threshold of graphene/polymer composites prepared by solvothermal reduction of graphene oxide in the polymer solution

    PubMed Central

    2013-01-01

    Graphene/polyvinylidene fluoride (PVDF) composites were prepared using in-situ solvothermal reduction of graphene oxide in the PVDF solution. The electrical conductivity of the composites was greatly improved by doping with graphene sheets. The percolation threshold of such composite was determined to be 0.31 vol.%, being much smaller than that of the composites prepared via blending reduced graphene sheets with polymer matrix. This is attributed to the large aspect ratio of the SRG sheets and their uniform dispersion in the polymer matrix. The dielectric constant of PVDF showed a marked increase from 7 to about 105 with only 0.5 vol.% loading of SRG content. Like the other conductor-insulator systems, the AC conductivity of the system also obeyed the universal dynamic response. In addition, the SRG/PVDF composite shows a much stronger nonlinear conduction behavior than carbon nanotube/nanofiber based polymer composite, owing to intense Zener tunneling between the SRG sheets. The strong electrical nonlinearity provides further support for a homogeneous dispersion of SRG sheets in the polymer matrix. PMID:23522102

  2. Low-Temperature and Solution-Processed Amorphous WO(x) as Electron-Selective Layer for Perovskite Solar Cells.

    PubMed

    Wang, Kai; Shi, Yantao; Dong, Qingshun; Li, Yu; Wang, Shufeng; Yu, Xufeng; Wu, Mengyao; Ma, Tingli

    2015-03-01

    The electron-selective layer (ESL) is an indispensable component of perovskite solar cells (PSCs) and is responsible for the collection of photogenerated electrons. Preparing ESL at a low temperature is significant for future fabrication of flexible PSCs. In this work, solution-processed amorphous WO(x) thin film was prepared facilely at low temperature and used as ESL in PSCs. Results indicated that a large quantity of nanocaves were observed in the WO(x) thin film. In comparison with the conventional TiO2 ESL, the WO(x) ESL exhibited comparable light transmittance but higher electrical conductivity. Compared with the TiO2-based PSCs, PSCs that use WO(x) ESL exhibited comparable photoelectric conversion efficiency, larger short-circuit current density, but lower open-circuit voltage. Electrochemical characterization indicated that the unsatisfied open-circuit voltage and fill factor were caused by the inherent charge recombination. This study demonstrated that this material is an excellent candidate for ESL.

  3. Low-Temperature and Solution-Processed Amorphous WO(x) as Electron-Selective Layer for Perovskite Solar Cells.

    PubMed

    Wang, Kai; Shi, Yantao; Dong, Qingshun; Li, Yu; Wang, Shufeng; Yu, Xufeng; Wu, Mengyao; Ma, Tingli

    2015-03-01

    The electron-selective layer (ESL) is an indispensable component of perovskite solar cells (PSCs) and is responsible for the collection of photogenerated electrons. Preparing ESL at a low temperature is significant for future fabrication of flexible PSCs. In this work, solution-processed amorphous WO(x) thin film was prepared facilely at low temperature and used as ESL in PSCs. Results indicated that a large quantity of nanocaves were observed in the WO(x) thin film. In comparison with the conventional TiO2 ESL, the WO(x) ESL exhibited comparable light transmittance but higher electrical conductivity. Compared with the TiO2-based PSCs, PSCs that use WO(x) ESL exhibited comparable photoelectric conversion efficiency, larger short-circuit current density, but lower open-circuit voltage. Electrochemical characterization indicated that the unsatisfied open-circuit voltage and fill factor were caused by the inherent charge recombination. This study demonstrated that this material is an excellent candidate for ESL. PMID:26262648

  4. Pseudo-one-dimensional nucleation in dilute polymer solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Lingyun; Schmit, Jeremy D.

    2016-06-01

    Pathogenic protein fibrils have been shown in vitro to have nucleation-dependent kinetics despite the fact that one-dimensional structures do not have the size-dependent surface energy responsible for the lag time in classical theory. We present a theory showing that the conformational entropy of the peptide chains creates a free-energy barrier that is analogous to the translational entropy barrier in higher dimensions. We find that the dynamics of polymer rearrangement make it very unlikely for nucleation to succeed along the lowest free-energy trajectory, meaning that most of the nucleation flux avoids the free-energy saddle point. We use these results to construct a three-dimensional model for amyloid nucleation that accounts for conformational entropy, backbone H bonds, and side-chain interactions to compute nucleation rates as a function of concentration.

  5. Pseudo-one-dimensional nucleation in dilute polymer solutions.

    PubMed

    Zhang, Lingyun; Schmit, Jeremy D

    2016-06-01

    Pathogenic protein fibrils have been shown in vitro to have nucleation-dependent kinetics despite the fact that one-dimensional structures do not have the size-dependent surface energy responsible for the lag time in classical theory. We present a theory showing that the conformational entropy of the peptide chains creates a free-energy barrier that is analogous to the translational entropy barrier in higher dimensions. We find that the dynamics of polymer rearrangement make it very unlikely for nucleation to succeed along the lowest free-energy trajectory, meaning that most of the nucleation flux avoids the free-energy saddle point. We use these results to construct a three-dimensional model for amyloid nucleation that accounts for conformational entropy, backbone H bonds, and side-chain interactions to compute nucleation rates as a function of concentration. PMID:27415194

  6. Tuning electrical properties in amorphous zinc tin oxide thin films for solution processed electronics.

    PubMed

    Chandra, R Devi; Rao, Manohar; Zhang, Keke; Prabhakar, Rajiv Ramanujam; Shi, Chen; Zhang, Jie; Mhaisalkar, Subodh G; Mathews, Nripan

    2014-01-22

    Solution processed zinc tin oxide (ZTO) thin film transistors (TFTs) were fabricated by varying the Zn/Sn composition. The addition of Sn to the zinc oxide (ZnO) films resulted in improved electrical characteristics, with devices of Zn0.7Sn0.3O composition showing the highest mobility of 7.7 cm(2)/(V s). An improvement in subthreshold swings was also observed, indicative of a reduction of the interfacial trap densities. Mobility studies at low temperature have been carried out, which indicated that the activation energy was reduced with Sn incorporation. Kelvin probe force microscopy was performed on the films to evaluate work function and correlated to the metal-semiconductor barrier indicating Zn0.7Sn0.3O films had the smallest barrier for charge injection. Organic-inorganic hybrid complementary inverters with a maximum gain of 10 were fabricated by integrating ZTO TFTs with poly-3-hexylthiophene (P3HT) transistors. PMID:24380364

  7. Solidification Behavior of Polymer Solution during Membrane Preparation by Thermally Induced Phase Separation

    PubMed Central

    Ishigami, Toru; Nii, Yoko; Ohmukai, Yoshikage; Rajabzadeh, Saeid; Matsuyama, Hideto

    2014-01-01

    The solidification behavior of poly(vinylidene fluoride) (PVDF) solution during membrane preparation by thermally induced phase separation (TIPS) was investigated. Apparatus newly developed in our laboratory was used to quantitatively measure membrane stiffness during phase separation. In this apparatus, a cooling polymer solution, placed on a stage, is moved upwards and the surface of the polymer solution contacts a sphere attached to the tip of a needle. The displacement of a blade spring attached to the needle is then measured by a laser displacement sensor. Different phase separation modes, such as liquid-liquid (L-L) phase separation and solid-liquid (S-L) phase separation (polymer crystallization) were investigated. In the case of S-L phase separation, the stiffness of the solution surface began to increase significantly just before termination of crystallization. In contrast, L-L phase separation delayed solidification of the solution. This was because mutual contact of the spherulites was obstructed by droplets of polymer-lean phase formed during L-L phase separation. Thus, the solidification rate was slower for the L-L phase separation system than for the S-L phase separation system. PMID:24957124

  8. Solidification Behavior of Polymer Solution during Membrane Preparation by Thermally Induced Phase Separation.

    PubMed

    Ishigami, Toru; Nii, Yoko; Ohmukai, Yoshikage; Rajabzadeh, Saeid; Matsuyama, Hideto

    2014-01-01

    The solidification behavior of poly(vinylidene fluoride) (PVDF) solution during membrane preparation by thermally induced phase separation (TIPS) was investigated. Apparatus newly developed in our laboratory was used to quantitatively measure membrane stiffness during phase separation. In this apparatus, a cooling polymer solution, placed on a stage, is moved upwards and the surface of the polymer solution contacts a sphere attached to the tip of a needle. The displacement of a blade spring attached to the needle is then measured by a laser displacement sensor. Different phase separation modes, such as liquid-liquid (L-L) phase separation and solid-liquid (S-L) phase separation (polymer crystallization) were investigated. In the case of S-L phase separation, the stiffness of the solution surface began to increase significantly just before termination of crystallization. In contrast, L-L phase separation delayed solidification of the solution. This was because mutual contact of the spherulites was obstructed by droplets of polymer-lean phase formed during L-L phase separation. Thus, the solidification rate was slower for the L-L phase separation system than for the S-L phase separation system. PMID:24957124

  9. Thermodynamically stable Si{sub w}C{sub x}N{sub y}O{sub z} polymer-like, amorphous ceramics made from organic precursors.

    SciTech Connect

    Morcos, R. M.; Navrotsky, A.; Varga, T.; Ahn, D.; Saha, S.; Poli, F.; Muller, K.; Raj, R.

    2008-07-01

    This communication reports new results on the enthalpy of formation of pseudo-amorphous ceramic compounds constituted from silicon, carbon, oxygen, and nitrogen (SiCNO), made from the polymer route. Again, like the SiCO materials, although with one exception, the enthalpy of formation from crystalline components (SiO{sub 2} cristobalite, {beta}-Si{sub 3}N{sub 4}, SiC, and excess C) is negative. Some of the alloyed oxygen-nitrogen compositions yield enthalpies that are much more negative ({approx}100 kJ/g {center_dot} atom) in comparison with compositions that contain mainly oxygen or nitrogen ({approx}20 kJ/g {center_dot} atom). The exception, having a N/O ratio near 2, has a positive value for the enthalpy. This may reflect the presence of nanoclusters of stoichiometric Si{sub 2}N{sub 2}O instead of the pseudo-amorphous nanodomain structure seen for the other samples.

  10. Diagnostics of Apparent Wall Slip in Aqueous Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Wein, Ondřej; Tovčigrečko, Valentin V.; Sobolík, Václav; Večeř, Marek

    2009-07-01

    Two experimental methods, apparent-wall-slip (AWS) rotational viscometry with "Morse-taper" sensors and electrodiffusion (ED) flow diagnostics with auto-calibrated friction probes, are used to study velocity profiles in aqueous solutions of high-molecular polysaccharides. By comparing the velocity data from the both methods, estimates are obtained of depleted layer thickness in dependence on wall shear stress.

  11. Flow-enhanced solution printing of all-polymer solar cells.

    PubMed

    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

    2015-08-12

    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 ∼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.

  12. Flow-enhanced solution printing of all-polymer solar cells

    SciTech Connect

    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

    2015-08-12

    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 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. However, we expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility.

  13. 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

  14. Particle manipulation through polymer solutions in microfluidic processes

    NASA Astrophysics Data System (ADS)

    Del Giudice, F.; D'Avino, G.; Villone, M. M.; Greco, F.; Maffettone, P. L.

    2015-12-01

    Manipulation of particles suspended in fluids flowing in microfluidic channels is required in a variety of biological, diagnostic and therapeutic applications. For instance, alignment of particles into a tight stream is a necessary step prior to counting, detecting, and sorting. Generally, this task is accomplished by using a Newtonian fluid as suspending medium and by properly fabricating a complex device aimed to displace particle trajectories. In the last years, however, the use of polymeric liquids in microfluidic processes has received a growing interest. Indeed, the addition of a small amount of polymer in a Newtonian suspension flowing in a channel promotes "internal" forces that can be exploited to manipulate the trajectories of suspended particles in simple devices. In this work, we show the possibility to align particles in simple square-shaped microfluidic channels by exploiting viscoelastic forces in flowing suspending liquids. Experiments have been performed to investigate the effect of the channel length, flow rate, confinement ratio (i.e., the ratio between the particle and channel size) and fluid rheology on the particle alignment. Finally, we present experimental results where particle alignment induced by fluid viscoelasticity is combined with magnetophoresis to deflect magnetic beads in a H-shaped channel. High-efficiency separation of magnetic and non-magnetic beads is demonstrated.

  15. Prediction of Solution Properties of Flexible-Chain Polymers: A Computer Simulation Undergraduate Experiment

    ERIC Educational Resources Information Center

    de la Torre, Jose Garcia; Cifre, Jose G. Hernandez; Martinez, M. Carmen Lopez

    2008-01-01

    This paper describes a computational exercise at undergraduate level that demonstrates the employment of Monte Carlo simulation to study the conformational statistics of flexible polymer chains, and to predict solution properties. Three simple chain models, including excluded volume interactions, have been implemented in a public-domain computer…

  16. High energy and power density capacitors from solution-processed ternary ferroelectric polymer nanocomposites.

    PubMed

    Li, Qi; Han, Kuo; Gadinski, Matthew Robert; Zhang, Guangzu; Wang, Qing

    2014-09-01

    Concurrent improvements in dielectric constant and breakdown strength are attained in a solution-processed ternary ferroelectric polymer nanocomposite incorporated with two-dimensional boron nitride nanosheets and zero-dimensional barium titanate nanoparticles that synergistically interact to enable a remarkable energy-storage capability, including large discharged energy density, high charge-discharge efficiency, and great power density.

  17. Universal Scaling of Linear and Nonlinear Rheological Properties of Semidilute and Concentrated Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Larson, Ronald; Heo, Youngsuk

    2008-03-01

    We examine the validity of the de Gennes ``blob'' concept in predicting linear and nonlinear rheological properties of semidilute polystyrene solutions in tricresyl phosphate (TCP). At a fixed value of rescaled concentration c/ce where ce is the entanglement concentration, below a critical value of around 2.0 for our polystyrene/TCP solutions, linear and nonlinear rheological functions superimpose after the modulus and the frequency (or shear rate) of each solution are respectively normalized with the concentration-dependent plateau modulus and the equilibration time obtained from the de Gennes scaling relationships using the literature value of the solvent-quality exponent 0.53. However, once the polymer volume fraction exceeds the ``swelling volume fraction, above which the polymer takes on a random walk configuration on all length scales even in a good solvent, this universal scaling breaks down and the polymer conformation appears to be governed by Colby-Rubinstein's scaling laws for theta solutions. We estimate that all polybutadiene solutions in phenyl octane (a good solvent) from the work of Colby et al. are above the swelling concentration and can be scaled using theta solvent scaling laws for concentrations ranging all the way up to the melt, showing universal behavior of melts and solutions above the swelling concentration.

  18. Skin formation and bubble growth during drying process of polymer solution.

    PubMed

    Arai, S; Doi, M

    2012-07-01

    When a polymer solution with volatile solvent is dried, skins are often formed at the surface of the solution. It has been observed that after the skin is formed, bubbles often appear in the solution. We conducted experiments to clarify the relation between the skin formation and the bubble formation. We measured the time dependence of the thickness of the skin layer, the size of the bubbles, and the pressure in the solution. From our experiments, we concluded that i) the gas in the bubble is a mixture of solvent vapor and air dissolved in the solution, ii) the bubble nucleation is assisted by the pressure decrease in the solution covered by the skin layer, and iii) the growth of the bubbles is diffusion limited, mainly limited by the diffusion of air molecules dissolved in the solution.

  19. Amorphous silica solubilities—III. Activity coefficient relations and predictions of solubility behavior in salt solutions, 0-350°C

    NASA Astrophysics Data System (ADS)

    Marshall, William L.

    1980-07-01

    Activity coefficients of amorphous silica in added salt solutions, obtained from solubility measurements, were calculated on the basis of concentration (molarity) and composition (molality). The logarithm of the activity coefficients based on concentration when plotted against molarity of added salt, as previous observations would dictate, yielded straight line relations even to 6 M. The use of composition units produced instead curves at the highest molalities and caused divergences in behavior from the single straight lines for 1-1 salts of a common cation. Introduction of the activity of water also caused divergences in behavior. Thus, it might appear that amorphous silica is fully hydrated at 25°C as a solid in equilibrium with solution. Lack of densities of aqueous sodium nitrate necessitated using units of molality in interpretations at high temperatures. Nevertheless, approximately straight line behavior of log activity coefficient vs m was still observed to reasonably high molalities, and allowed a simple equation to describe activity coefficient behavior as a function of both molality of sodium nitrate and temperature. The simplicity of the relation, with some assumptions, might be used to predict solubility of amorphous silica at high temperatures in other added aqueous salt solutions.

  20. Phase behavior and second osmotic virial coefficient for competitive polymer solvation in mixed solvent solutions.

    PubMed

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

    2015-11-21

    We apply our recently developed generalized Flory-Huggins (FH) type theory for the competitive solvation of polymers by two mixed solvents to explain general trends in the variation of phase boundaries and solvent quality (quantified by the second osmotic virial coefficient B2) with solvent composition. The complexity of the theoretically predicted miscibility patterns for these ternary mixtures arises from the competitive association between the polymer and the solvents and from the interplay of these associative interactions with the weak van der Waals interactions between all components of the mixture. The main focus here lies in determining the influence of the free energy parameters for polymer-solvent association (solvation) and the effective FH interaction parameters {χαβ} (driving phase separation) on the phase boundaries (specifically the spinodals), the second osmotic virial coefficient B2, and the relation between the positions of the spinodal curves and the theta temperatures at which B2 vanishes. Our classification of the predicted miscibility patterns is relevant to numerous applications of ternary polymer solutions in industrial formulations and the use of mixed solvent systems for polymer characterization, such as chromatographic separation where mixed solvents are commonly employed. A favorable comparison of B2 with experimental data for poly(methyl methacrylate)/acetonitrile/methanol (or 1-propanol) solutions only partially supports the validity of our theoretical predictions due to the lack of enough experimental data and the neglect of the self and mutual association of the solvents.

  1. Phase behavior and second osmotic virial coefficient for competitive polymer solvation in mixed solvent solutions

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    We apply our recently developed generalized Flory-Huggins (FH) type theory for the competitive solvation of polymers by two mixed solvents to explain general trends in the variation of phase boundaries and solvent quality (quantified by the second osmotic virial coefficient B 2 ) with solvent composition. The complexity of the theoretically predicted miscibility patterns for these ternary mixtures arises from the competitive association between the polymer and the solvents and from the interplay of these associative interactions with the weak van der Waals interactions between all components of the mixture. The main focus here lies in determining the influence of the free energy parameters for polymer-solvent association (solvation) and the effective FH interaction parameters {χαβ} (driving phase separation) on the phase boundaries (specifically the spinodals), the second osmotic virial coefficient B 2 , and the relation between the positions of the spinodal curves and the theta temperatures at which B 2 vanishes. Our classification of the predicted miscibility patterns is relevant to numerous applications of ternary polymer solutions in industrial formulations and the use of mixed solvent systems for polymer characterization, such as chromatographic separation where mixed solvents are commonly employed. A favorable comparison of B 2 with experimental data for poly(methyl methacrylate)/acetonitrile/methanol (or 1-propanol) solutions only partially supports the validity of our theoretical predictions due to the lack of enough experimental data and the neglect of the self and mutual association of the solvents.

  2. Current applications of foams formed from mixed surfactant-polymer solutions.

    PubMed

    Bureiko, Andrei; Trybala, Anna; Kovalchuk, Nina; Starov, Victor

    2015-08-01

    Foams cannot be generated without the use of special foaming agents, as pure liquids do not foam. The most common foaming agents are surfactants, however often for foam stability one active agent is not enough, it is necessary to add other component to increase foam lifetime. Foams on everyday use are mostly made from mixture of different components. Properly chosen combinations of two active ingredients lead to a faster foam formation and increased foam stability. During the last decade polymers (mainly polyelectrolytes and proteins) have become frequently used additives to foaming solutions. Mixtures of surfactants and polymers often demonstrate different foaming properties in comparison to surfactant only or polymer only solutions. The nature of surfactant-polymer interactions is complicated and prediction of resulting foaming properties of such formulations is not straightforward. Properties and foaming of surfactant-polymer mixtures are discussed as well as current applications of foams and foaming agents as foams are widely used in cosmetics, pharmaceutics, medicine and the food industry.

  3. Removal of parabens from aqueous solution using β-cyclodextrin cross-linked polymer.

    PubMed

    Chin, Yuk Ping; Mohamad, Sharifah; Abas, Mhd Radzi Bin

    2010-01-01

    The removal of four parabens, methyl-, ethyl-, propyl-, and benzyl-paraben, by β-cyclodextrin (β-CD) polymer from aqueous solution was studied. Different β-CD polymers were prepared by using two cross-linkers, i.e., hexamethylene diisocyanate (HMDI) and toluene-2,6-diisocyanate (TDI), with various molar ratios of cross-linker. β-CD-HMDI polymer with molar ratio of 1:7 and β-CD-TDI polymer with ratio 1:4 gave the highest adsorption of parabens among the β-CD-HMDI and β-CD-TDI series, and were subsequently used for further studies. The adsorption capacity of β-CD-HMDI is 0.0305, 0.0376, 0.1854 and 0.3026 mmol/g for methyl-, ethyl-, propyl-, and benzyl-paraben, respectively. β-CD-TDI have higher adsorption capacities compared with β-CD-HMDI, the adsorption capacity are 0.1019, 0.1286, 0.2551, and 0.3699 mmol/g methyl-, ethyl-, propyl-, and benzyl-paraben respectively. The parameters studied were adsorption capacity, water retention, and reusability. Role of both cross-linker in adsorption, hydrophobicity of polymers, and adsorption capacity of different parabens were compared and discussed. All experiments were conducted in batch adsorption technique. These polymers were applied to real samples and showed positive results. PMID:20957106

  4. Removal of Parabens from Aqueous Solution Using β-Cyclodextrin Cross-Linked Polymer

    PubMed Central

    Chin, Yuk Ping; Mohamad, Sharifah; Abas, Mhd Radzi Bin

    2010-01-01

    The removal of four parabens, methyl-, ethyl-, propyl-, and benzyl-paraben, by β-cyclodextrin (β-CD) polymer from aqueous solution was studied. Different β-CD polymers were prepared by using two cross-linkers, i.e., hexamethylene diisocyanate (HMDI) and toluene-2,6-diisocyanate (TDI), with various molar ratios of cross-linker. β-CD-HMDI polymer with molar ratio of 1:7 and β-CD-TDI polymer with ratio 1:4 gave the highest adsorption of parabens among the β-CD-HMDI and β-CD-TDI series, and were subsequently used for further studies. The adsorption capacity of β-CD-HMDI is 0.0305, 0.0376, 0.1854 and 0.3026 mmol/g for methyl-, ethyl-, propyl-, and benzyl-paraben, respectively. β-CD-TDI have higher adsorption capacities compared with β-CD-HMDI, the adsorption capacity are 0.1019, 0.1286, 0.2551, and 0.3699 mmol/g methyl-, ethyl-, propyl-, and benzyl-paraben respectively. The parameters studied were adsorption capacity, water retention, and reusability. Role of both cross-linker in adsorption, hydrophobicity of polymers, and adsorption capacity of different parabens were compared and discussed. All experiments were conducted in batch adsorption technique. These polymers were applied to real samples and showed positive results. PMID:20957106

  5. Preliminary investigation of elongational flow of dilute polymer solutions

    NASA Technical Reports Server (NTRS)

    Peng, S. T. J.; Landel, R. F.

    1976-01-01

    A tubeless siphon apparatus has been set up to measure extensional flow. In this apparatus, the liquid is continuously drawn into a capillary and, after steady flow has been established, the tube is raised above the liquid surface. With viscoelastic liquids, the flow continues and a column can be lifted from the reservoir. At the capillary entrance, an oscillating bead of excess liquid collects which interferes with both the flow and the measurements. This can be minimized by careful control of the liquid-column height. For homogeneous solutions, the column is symmetrical and tapers steadily from the liquid surface to the capillary entrance, with no bulging. Preliminary results show tensile viscosities 1000 times that of the Trouton coefficient and having a very strong dependence on deformation rate. A concentration-stretch rate-reduced variable scheme is proposed.

  6. The relevance of molecular weight in the design of amorphous biodegradable polymers with optimized shape memory effect.

    PubMed

    Petisco-Ferrero, S; Fernández, J; Fernández San Martín, M M; Santamaría Ibarburu, P A; Sarasua Oiz, J R

    2016-08-01

    The shape memory effect (SME) has long been the focus of interest of many research groups that have studied many facets of it, yet to the authors' knowledge some molecular parameters, such as the molecular weight, have been skipped. Thus, the aim of this work is to offer further insight into the shape memory effect, by disclosing the importance of the molecular weight as the relevant parameter dictating the extension of the rubbery plateau, which is the scenario where the entropic network of entanglements manifests. For this, a set of biodegradable amorphous poly(rac-d,l)lactides have been synthesised by ring opening copolymerization of a racemic mixture of L-and D-lactide. The analysis performed on the synthesised enantiomeric copolylactides includes the determination of molecular weights by means of Gel Permeation Chromatography (GPC), thermal properties by Differential Scanning Calorimetry (DSC), dynamic mechanical analysis (DMA) and rheological tests using small amplitude oscillatory flow analysis. Shape memory properties have been determined by means of specific cyclic thermo-mechanic test protocol. It has been shown that the recovery capacity of amorphous PDLLA is linked to the disentanglement time through an exponential law.

  7. Solution Behavior of Modified Polyethylenimine (PEI) Polymers by Light Scattering Investigations

    SciTech Connect

    Sonny A. Ekhorutomwen; Samuel P. Sawan; Barbara F. Smith; Thomas W. Robison; Kennard V. Wilson

    2004-03-18

    The eight average molecular weights, as well as other characteristics such as the second virial coefficients and root-mean-square (RMS) radii of gyration of poly (ethyleneimine) (PEI) and various derivatives, have been determined in solution light scattering studies. The solution dynamics of PEI and carboxylated and phosphorylated derivatives were studied a pH of 3.3, 7.0 and 10.0. Measurements were made in freshly distilled and de-ionized water as well as in 0.1 M, 1 M and 5-M solutions of sodium chloride in water. Molecular weights were calculated from Berry plots. The purified polymer, PEI-1, gave a molecular weight of 39,600 g/mol., while the same polymer, which was not purified, PEI-2, has MW of 43,100 g/mol.

  8. Mechanical properties of melt-processed polymer blend of amorphous corn flour composite filler and styrene-butadiene rubber

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The corn flour composite fillers were prepared by blending corn flour with rubber latex, dried, and cryogenically ground into powders, which were then melt-blended with rubber polymers in an internal mixer to form composites with enhanced mechanical properties. The composites prepared with melt-blen...

  9. Molecular Packing and Electronic Processes in Amorphous-like Polymer Bulk Heterojunction Solar Cells with Fullerene Intercalation

    NASA Astrophysics Data System (ADS)

    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

    2014-06-01

    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.

  10. Effect of water structure on adsorption of thermosensitive polymer hydrogel in salt solutions

    SciTech Connect

    Nakano, Yoshio; Seida, Yoshimi

    1996-12-31

    Effects of temperature and additive salt on an adsorption property of thermosensitive polymer hydrogel were studied in terms of (1) phase transition temperature of the gel, (2) hydration structure of network of the gel in the various salt solutions, and (3) structure of water in the solutions. The adsorption properties of the gel were correlated fairly well with the phase transition temperature of the gel and the structure of water both on the network of the gel and in the bulk solution. 2 refs., 5 figs.

  11. Efficient tandem polymer solar cells fabricated by all-solution processing.

    PubMed

    Kim, Jin Young; Lee, Kwanghee; Coates, Nelson E; Moses, Daniel; Nguyen, Thuc-Quyen; Dante, Mark; Heeger, Alan J

    2007-07-13

    Tandem solar cells, in which two solar cells with different absorption characteristics are linked to use a wider range of the solar spectrum, were fabricated with each layer processed from solution with the use of bulk heterojunction materials comprising semiconducting polymers and fullerene derivatives. A transparent titanium oxide (TiO(x)) layer separates and connects the front cell and the back cell. The TiO(x) layer serves as an electron transport and collecting layer for the first cell and as a stable foundation that enables the fabrication of the second cell to complete the tandem cell architecture. We use an inverted structure with the low band-gap polymer-fullerene composite as the charge-separating layer in the front cell and the high band-gap polymer composite as that in the back cell. Power-conversion efficiencies of more than 6% were achieved at illuminations of 200 milliwatts per square centimeter. PMID:17626879

  12. Sodium chloride methanol solution spin-coating process for bulk-heterojunction polymer solar cells

    NASA Astrophysics Data System (ADS)

    Liu, Tong-Fang; Hu, Yu-Feng; Deng, Zhen-Bo; Li, Xiong; Zhu, Li-Jie; Wang, Yue; Lv, Long-Feng; Wang, Tie-Ning; Lou, Zhi-Dong; Hou, Yan-Bing; Teng, Feng

    2016-08-01

    The sodium chloride methanol solution process is conducted on the conventional poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) polymer bulk heterojunction solar cells. The device exhibits a power conversion efficiency of up to 3.36%, 18% higher than that of the device without the solution process. The measurements of the active layer by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and ultraviolet photoelectron spectroscopy (UPS) indicate a slight phase separation in the vertical direction and a sodium chloride distributed island-like interface between the active layer and the cathode. The capacitance–voltage (C–V) and impedance spectroscopy measurements prove that the sodium chloride methanol process can reduce the electron injection barrier and improve the interfacial contact of polymer solar cells. Therefore, this one-step solution process not only optimizes the phase separation in the active layers but also forms a cathode buffer layer, which can enhance the generation, transport, and collection of photogenerated charge carriers in the device simultaneously. This work indicates that the inexpensive and non-toxic sodium chloride methanol solution process is an efficient one-step method for the low cost manufacturing of polymer solar cells. Project supported by the Fundamental Research Funds for the Central Universities, China (Grant No. 2014JBZ009) and the National Natural Science Foundation of China (Grant Nos. 61274063, 61377028, 61475014, and 61475017).

  13. Sodium chloride methanol solution spin-coating process for bulk-heterojunction polymer solar cells

    NASA Astrophysics Data System (ADS)

    Liu, Tong-Fang; Hu, Yu-Feng; Deng, Zhen-Bo; Li, Xiong; Zhu, Li-Jie; Wang, Yue; Lv, Long-Feng; Wang, Tie-Ning; Lou, Zhi-Dong; Hou, Yan-Bing; Teng, Feng

    2016-08-01

    The sodium chloride methanol solution process is conducted on the conventional poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) polymer bulk heterojunction solar cells. The device exhibits a power conversion efficiency of up to 3.36%, 18% higher than that of the device without the solution process. The measurements of the active layer by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and ultraviolet photoelectron spectroscopy (UPS) indicate a slight phase separation in the vertical direction and a sodium chloride distributed island-like interface between the active layer and the cathode. The capacitance-voltage (C-V) and impedance spectroscopy measurements prove that the sodium chloride methanol process can reduce the electron injection barrier and improve the interfacial contact of polymer solar cells. Therefore, this one-step solution process not only optimizes the phase separation in the active layers but also forms a cathode buffer layer, which can enhance the generation, transport, and collection of photogenerated charge carriers in the device simultaneously. This work indicates that the inexpensive and non-toxic sodium chloride methanol solution process is an efficient one-step method for the low cost manufacturing of polymer solar cells. Project supported by the Fundamental Research Funds for the Central Universities, China (Grant No. 2014JBZ009) and the National Natural Science Foundation of China (Grant Nos. 61274063, 61377028, 61475014, and 61475017).

  14. Terahertz Time-Domain Spectroscopy of Thermoresponsive Polymers in Aqueous Solution.

    PubMed

    Serin, Guillaume; Nguyen, Hong Hanh; Marty, Jean-Daniel; Micheau, Jean-Claude; Gernigon, Véronique; Mingotaud, Anne-Françoise; Bajon, Damienne; Soulet, Thierry; Massenot, Sébastien; Coudret, Christophe

    2016-09-15

    The behavior of highly concentrated aqueous solutions of two thermoresponsive polymers poly(N-isopropylacrylamide) (PNIPAm) and poly(N-vinylcaprolactam) (PVCL) have been investigated by terahertz time-domain spectroscopy (THz-TDS). Measurements have been performed for concentrations up to 20 wt %, over a frequency range from 0.3 to 1.5 THz and for temperatures from 20 to 45 °C including the zone for lower critical solution temperature (LCST). THz-TDS enables the study of the behavior of water present in the solution (i.e., free or bound to the polymer). From these measurements, in addition to phase transition temperature, thermodynamic data such as variation of enthalpy and entropy can be inferred. Thanks to these data, further insights upon the mechanism involved during the dehydration phenomenon were obtained. These results were compared to the ones issued from dynamic light scattering, spectroscopy, or microscopy techniques to underline the interest to use THz-TDS as a powerful tool to characterize the behavior of thermoresponsive polymers in highly concentrated solutions. PMID:27490372

  15. Bubble fractionation of enantiomers from solution using molecularly imprinted polymers as collectors.

    PubMed

    Armstrong, D W; Schneiderheinze, J M; Hwang, Y S; Sellergren, B

    1998-09-01

    Adsorptive bubble separation methods have been used to enrich components from both heterogeneous and homogeneous solutions. These methods are particularly effective for processing large solution volumes at low cost. Previous work demonstrated that chiral, surface-active collectors could be used to enrich enantiomers from homogeneous solution in a foam fractionation process. In a significant extension of this work, the use of highly selective molecularly imprinted polymers (MIPs) and heterogeneous solutions for the bubble flotation of enantiomers was evaluated. The high selectivity and ease of recycling of the MIP make this a potentially powerful approach for process-scale separations from large-volume bulk solutions. New MIPs were produced with low swelling properties which allowed them to retain enantioselectivity after numerous recyclings.

  16. Stabilization of hot-melt extrusion formulations containing solid solutions using polymer blends.

    PubMed

    Prodduturi, Suneela; Urman, Kevin L; Otaigbe, Joshua U; Repka, Michael A

    2007-06-29

    This study was aimed at enhancing the physical stability of the drug clotrimazole (CT) and the polymer contained within hot-melt extrusion (HME) films using polymer blends of hydroxypropyl cellulose (HPC) and poly(ethylene oxide) (PEO). The HME films were investigated for solid-state characteristics, moisture sorption, bioadhesivity, mechanical properties, glass transition temperature, release characteristics, and physical and chemical stability of the drug and the polymer within the HME films. The solid-state characterization of the drug and the polymer was performed using differential scanning calorimetry, x-ray diffractometry, and dynamic mechanical analysis. A texture analyzer was used to study the bioadhesive and mechanical properties of the HME films. The physical and chemical stability of the films, stored at 25 degrees C/60% relative humidity or in a desiccator, was studied for up to 12 months. CT was found to be in solid solution within all of the formulations extruded. The physical stability of the drug and PEO in the HME films increased with increasing HPC concentration, but the bioadhesivity and flexibility of the PEO films decreased with increasing HPC concentration. Films containing HPC:PEO:CT in the ratio of 55:35:10 demonstrated optimum physical-mechanical, bioadhesive, and release properties. In conclusion, polymer blends of HPC and PEO were used successfully to tailor the drug release, mechanical and bioadhesive properties, and stability of the HME films.

  17. Thickness Dependent Effective Viscosity of a Polymer Solution near an Interface Probed by a Quartz Crystal Microbalance with Dissipation Method

    PubMed Central

    Fang, Jiajie; Zhu, Tao; Sheng, Jie; Jiang, Zhongying; Ma, Yuqiang

    2015-01-01

    The solution viscosity near an interface, which affects the solution behavior and the molecular dynamics in the solution, differs from the bulk. This paper measured the effective viscosity of a dilute poly (ethylene glycol) (PEG) solution adjacent to a Au electrode using the quartz crystal microbalance with dissipation (QCM-D) technique. We evidenced that the effect of an adsorbed PEG layer can be ignored, and calculated the zero shear rate effective viscosity to remove attenuation of high shear frequency oscillations. By increasing the overtone n from 3 to 13, the thickness of the sensed polymer solution decreased from ~70 to 30 nm. The zero shear rate effective viscosity of the polymer solution and longest relaxation time of PEG chains within it decrease with increasing solution thickness. The change trends are independent of the relation between the apparent viscosity and shear frequency and the values of the involved parameter, suggesting that the polymer solution and polymer chains closer to a solid substrate have a greater effective viscosity and slower relaxation mode, respectively. This method can study the effect of an interface presence on behavior and phenomena relating to the effective viscosity of polymer solutions, including the dynamics of discrete polymer chains. PMID:25684747

  18. Thickness Dependent Effective Viscosity of a Polymer Solution near an Interface Probed by a Quartz Crystal Microbalance with Dissipation Method

    NASA Astrophysics Data System (ADS)

    Fang, Jiajie; Zhu, Tao; Sheng, Jie; Jiang, Zhongying; Ma, Yuqiang

    2015-02-01

    The solution viscosity near an interface, which affects the solution behavior and the molecular dynamics in the solution, differs from the bulk. This paper measured the effective viscosity of a dilute poly (ethylene glycol) (PEG) solution adjacent to a Au electrode using the quartz crystal microbalance with dissipation (QCM-D) technique. We evidenced that the effect of an adsorbed PEG layer can be ignored, and calculated the zero shear rate effective viscosity to remove attenuation of high shear frequency oscillations. By increasing the overtone n from 3 to 13, the thickness of the sensed polymer solution decreased from ~70 to 30 nm. The zero shear rate effective viscosity of the polymer solution and longest relaxation time of PEG chains within it decrease with increasing solution thickness. The change trends are independent of the relation between the apparent viscosity and shear frequency and the values of the involved parameter, suggesting that the polymer solution and polymer chains closer to a solid substrate have a greater effective viscosity and slower relaxation mode, respectively. This method can study the effect of an interface presence on behavior and phenomena relating to the effective viscosity of polymer solutions, including the dynamics of discrete polymer chains.

  19. Coarse-graining polymer solutions: A critical appraisal of single- and multi-site models

    NASA Astrophysics Data System (ADS)

    D'Adamo, G.; Menichetti, R.; Pelissetto, A.; Pierleoni, C.

    2015-09-01

    We critically discuss and review the general ideas behind single- and multi-site coarse-grained (CG) models as applied to macromolecular solutions in the dilute and semi-dilute regime. We first consider single-site models with zero-density and density-dependent pair potentials. We highlight advantages and limitations of each option in reproducing the thermodynamic behavior and the large-scale structure of the underlying reference model. As a case study we consider solutions of linear homopolymers in a solvent of variable quality. Secondly, we extend the discussion to multi-component systems presenting, as a test case, results for mixtures of colloids and polymers. Specifically, we found the CG model with zero-density potentials to be unable to predict fluid-fluid demixing in a reasonable range of densities for mixtures of colloids and polymers of equal size. For larger colloids, the polymer volume fractions at which phase separation occurs are largely overestimated. CG models with density-dependent potentials are somewhat less accurate than models with zero-density potentials in reproducing the thermodynamics of the system and, although they present a phase separation, they significantly underestimate the polymer volume fractions along the binodal. Finally, we discuss a general multi-site strategy, which is thermodynamically consistent and fully transferable with the number of sites, and that allows us to overcome most of the limitations discussed for single-site models.

  20. Solution Properties of 1,3-Cyclohexadiene Polymers by Small Angle Neutron and Light Scattering

    SciTech Connect

    Yun, Seok I; Melnichenko, Yuri B; Wignall, George D; Hong, Kunlun; Mays, Jimmy; Britt, Phillip F; Terao, Ken; Nakamura, Yo

    2006-01-01

    1,3-Cyclohexdiene polymers (PCHD) and their derivatives are of interest due to the six-member rings in the main chain, which are expected to impart higher mechanical strength and better thermal and chemical stability, as compared to common vinyl polymers. For example, hydrogenated PCHD has the highest glass transition temperature (T{sub g} {approx} 231 C) of all hydrocarbon polymers, and it also shows good heat, weather, impact, abrasion, and chemical resistance as well as low water absorption. In addition, PCHD has unique photochemical properties, such as excellent transparency, due to the isolated double bonds in the main chain. Also, block copolymers containing PCHD show unusual phase separation behavior. For example, a styrene/1,3-CHD block copolymer (PS-b-PCHD) with 50 vol % CHD (1,4/1,2 {approx} 95/5) exhibits a core-shell or hollow cylinder morphology, while a typical styrene/acyclic diene (isoprene or butadiene) block copolymer with similar composition exhibits a lamellar structure. Such phase behavior and many other properties strongly depend on the conformation of the polymer in solution or bulk. However, almost no data have been reported on the conformation of PCHD, probably because of the lack of well-defined and well-characterized samples. Here we report solution properties of PCHD in tetrahydrofuran (THF) and chloroform by multiangle laser light scattering, viscometry, and small-angle neutron scattering (SANS).

  1. Multiresolution Modeling of Polymer Solutions: Wavelet-Based Coarse-Graining and Reverse-Mapping

    NASA Astrophysics Data System (ADS)

    Ismail, Ahmed; Adorf, Carl Simon; Agarwal, Animesh; Iacovella, Christopher R.

    2014-03-01

    Unlike multiscale methods, which encompass multiple simulation techniques, multiresolution models uses one modeling technique at different length and time scales. We present a combined coarse-graining and reverse-mapping framework for modeling of semidilute polymer solutions, based on the wavelet-accelerated Monte Carlo (WAMC) method, which forms a hierarchy of resolutions to model polymers at length scales that cannot be reached via atomistic or even ``standard'' coarse-grained simulations. A universal scaling function is obtained so that potentials do not need to be recomputed as the scale of the system is changed. We show that coarse-grained polymer solutions can reproduce results obtained from the simulations of the more detailed atomistic system to a reasonable degree of accuracy. Reverse mapping proceeds similarly: using probability distributions obtained from coarse-graining the bond lengths, angles, torsions, and the non-bonded potentials, we can reconstruct a more detailed polymer consistent with both geometric constraints and energetic considerations. Using a ``convergence factor'' within a Monte Carlo-based energy optimization scheme, we can successfully reconstruct entire atomistic configurations from coarse-grained descriptions.

  2. Direct measurement of depletion and hydrodynamic forces in solutions of a reversible supramolecular polymer.

    PubMed

    Knoben, W; Besseling, N A M; Stuart, M A Cohen

    2007-05-22

    In this paper, the investigation of surface forces in semidilute solutions of a nonadsorbing hydrogen-bonded reversible supramolecular polymer is described. Colloidal probe atomic force microscopy was used for direct measurement of depletion forces. Hydrodynamic drag on the AFM cantilever with the colloidal probe was measured both far away from and close to the planar substrate surface. The results indicate that the presence of the depletion layer causes slip at the surfaces with a large apparent slip length. Our analysis explains how the presence of slip enables the measurement of (relatively weak) depletion forces in solutions with a high viscosity by significantly reducing the hydrodynamic forces. The range and magnitude of the measured depletion forces are qualitatively in agreement with previous experiments and theoretical predictions. Due to the relatively large experimental error, no quantitative conclusions can be drawn. Depletion-induced phase separation of suspensions of stearylated silica particles was also observed. Phase separation becomes more pronounced with increasing polymer concentration.

  3. Convective depletion during the fast propagation of a nanosphere through a polymer solution

    NASA Astrophysics Data System (ADS)

    Odijk, Theo

    2004-06-01

    A theory of nonlinear convective depletion is set up as a nanosphere translates fast through a semidilute polymer solution. For nanospheres a self-consistent field theory in the Rouse approximation is often legitimate. A self-similar solution of the convective depletion equation is argued to be feasible at high velocities. The nature of the thin boundary layer in front of the propagating particle is analyzed. One example of convective depletion is when a charged protein moves through a semidilute polymer under the influence of a high electric field. The protein velocity is then proportional to the fifth power of the field. The theory could be useful in interpreting the separation of protein mixtures by microchip electrophoresis.

  4. Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

    SciTech Connect

    Minelli, Matteo; Doghieri, Ferruccio

    2014-05-15

    Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps.

  5. Mechanism of anomalously increased oil displacement with aqueous viscoelastic polymer solutions.

    PubMed

    Clarke, Andrew; Howe, Andrew M; Mitchell, Jonathan; Staniland, John; Hawkes, Laurence; Leeper, Katherine

    2015-05-14

    Single-phase flows of viscoelastic polymer solutions in both microfluidic devices and rock cores exhibit apparent flow thickening. We demonstrate that this thickening occurs above a critical Deborah number corresponding to the onset of spatio-temporal fluctuations. These fluctuations are observed to occur over a broad range of spatial and temporal scales consistent with elastic turbulence. The fluctuations provide a previously unreported mechanism for enhancing the displacement of a second, capillary trapped, immiscible phase. PMID:25797578

  6. Mechanism of anomalously increased oil displacement with aqueous viscoelastic polymer solutions.

    PubMed

    Clarke, Andrew; Howe, Andrew M; Mitchell, Jonathan; Staniland, John; Hawkes, Laurence; Leeper, Katherine

    2015-05-14

    Single-phase flows of viscoelastic polymer solutions in both microfluidic devices and rock cores exhibit apparent flow thickening. We demonstrate that this thickening occurs above a critical Deborah number corresponding to the onset of spatio-temporal fluctuations. These fluctuations are observed to occur over a broad range of spatial and temporal scales consistent with elastic turbulence. The fluctuations provide a previously unreported mechanism for enhancing the displacement of a second, capillary trapped, immiscible phase.

  7. Simultaneous heat and mass transfer in polymer solutions exposed to intermittent infrared radiation heating

    SciTech Connect

    Chen, J.J.; Lin, J.D.

    1998-06-01

    Drying is one of the essential steps in a number of industrial applications, such as the preserving of food and the drying of paint, pulp, and paper. The quality of paper tubes is significantly affected by the heat and mass transfer process. The drying of polymer solution plays a crucial role in the manufacturer of photographic film, synthetic fibers, adhesives, and a variety of other polymeric products. During drying of wet materials, simultaneous heat and mass transfer occurs both inside the medium and in the boundary layer of the drying agent. Drying is one of the most energy-consuming processes in the industrial sector and can also be very time consuming as, for example, in conventional convective drying by hot air, while minimum cost and energy consumption and maximum product quality are among the main concerns in industry today. Here, a theoretical study is performed that describes heat transfer and moisture variation while a polymer solution is exposed to high-intensity infrared radiation flux and/or an airflow. While the intermittent heating is considered, the authors investigate the influences of various radiation and convection parameters on the transfer of heat and moisture variation of coated layers on an optically thick substrate. During the tempering stage in the intermittent heating process, the convective mass transfer is included to simulate the ambient air in reality. The effects of radiation and convection parameters on the transfer processes are presented in terms of the rate of water content removal, heat transfer, and moisture distributions. Numerical results show that the rate of water removal from the polymer solution is dominated by both the adsorbed radiative heat energy and the distributions of water mass fraction in the polymer solution.

  8. Solution-based single molecule imaging of surface-immobilized conjugated polymers.

    PubMed

    Dalgarno, Paul A; Traina, Christopher A; Penedo, J Carlos; Bazan, Guillermo C; Samuel, Ifor D W

    2013-05-15

    The photophysical behavior of conjugated polymers used in modern optoelectronic devices is strongly influenced by their structural dynamics and conformational heterogeneity, both of which are dependent on solvent properties. Single molecule studies of these polymer systems embedded in a host matrix have proven to be very powerful to investigate the fundamental fluorescent properties. However, such studies lack the possibility of examining the relationship between conformational dynamics and photophysical response in solution, which is the phase from which films for devices are deposited. By developing a synthetic strategy to incorporate a biotin moiety as a surface attachment point at one end of a polyalkylthiophene, we immobilize it, enabling us to make the first single molecule fluorescence measurements of conjugated polymers for long periods of time in solution. We identify fluctuation patterns in the fluorescence signal that can be rationalized in terms of photobleaching and stochastic transitions to reversible dark states. Moreover, by using the advantages of solution-based imaging, we demonstrate that the addition of oxygen scavengers improves optical stability by significantly decreasing the photobleaching rates.

  9. Theory of DNA electrophoresis in physical gels and entangled polymer solutions

    NASA Astrophysics Data System (ADS)

    Duke, Thomas; Viovy, Jean Louis

    1994-03-01

    A scaling theory is presented for the electrophoretic mobility of DNA in sieving media that form dynamically evolving meshworks, such as physical gels and solutions of entangled polymers. In such media, the topological constraints on the DNA's motion are perpetually changing as cross links break and rejoin or as the polymers diffuse. It is shown that if the rate of constraint release falls within a certain range (which depends on the field strength), fractionation can be extended to higher molecular weights than would be feasible using a permanent gel of equivalent pore size. This improvement is a consequence of the disruptive effect that constraint release has on the mechanism of molecular orientation. Numerical simulations support the predictions of the theory. The possibility of realizing such a system in practice, with the aim of improving on current electrophoresis methods, is commented upon. It is suggested that semidilute polymer solutions may be a versatile medium for the rapid separation of long single-stranded DNA molecules, and the particular quality of solution required is identified.

  10. Dynamics of associative polymer solutions: Capillary break-up, jetting and rheology

    NASA Astrophysics Data System (ADS)

    Sharma, Vivek; Serdy, James G.; Threfall-Holmes, Phil; McKinley, Gareth H.

    2010-03-01

    Associative polymer solutions are used in extensively in the formulations for water-borne paints, food, inks, cosmetics, etc to control the rheology and processing behavior of multi-component dispersions. The commercially relevant formulations use dilute solutions of associative polymers, which have low viscosity and short relaxation times, and hence their non-Newtonian response is not apparent in a conventional rheometer. In this talk, we explore several methods for systematically exploring the linear and nonlinear solution rheology of associative polymer dispersions, including: high frequency oscillatory tests at frequencies up to 10 kHz, microfluidic shear rheometry at deformation rates up to 10^6 s-1 and the influence of transientextensional rheology in the jet breakup. The presence of inertial, elastic and viscous effects typically leads to complex dynamics in a necking fluid thread. We show that by carefully controlling the excitation frequency, it is possible to drive the break-up in a particularly simple and symmetric mode, which can be used to extract extensional viscosity information using capillary thinning analysis.

  11. Dynamics of associative polymer solutions: Capillary break-up, jetting and rheology

    NASA Astrophysics Data System (ADS)

    Sharma, Vivek; Serdy, James G.; Threfall-Holmes, Phil; McKinley, Gareth H.

    2011-11-01

    Associative polymer solutions are used in extensively in the formulations for water-borne paints, food, inks, cosmetics, etc to control the rheology and processing behavior of multi-component dispersions. These complex dispersions are processed and used over a broad range of shear and extensional rates. Furthermore, the commercially relevant formulations use dilute solutions of associative polymers, which have low viscosity and short relaxation times, and hence their non-Newtonian response is not apparent in a conventional rheometer. In this talk, we explore several methods for systematically exploring the linear and nonlinear solution rheology of associative polymer dispersions, including: fractional model description of physical gelation, high frequency oscillatory tests at frequencies up to 10 kHz, microfluidic shear rheometry at deformation rates up to 1000000 /s and the influence of transient extensional rheology in the jet breakup. We show that high deformation rates can be obtained in jetting flows, and the growth and evolution of instability during jetting and break-up of these viscoelastic fluids shows the influence of both elasticity and extensibility.

  12. Photoinduced processes in solid polymer solutions of dyes in an interference field of laser radiation

    SciTech Connect

    Sizykh, A G; Tarakanova, E A

    1998-12-31

    An investigation was made of the relationships governing the photochemical mechanism of formation of light-induced gratings in solid polymer solutions of a dye with a high quantum yield of the triplet states. The combined analysis of the results of real and numerical experiments was made for a solution of eosin K in gelatin. The protonation rate constant of the dye was measured and the dependence of the diffraction efficiency on the duration of irradiation was explained taking diffusion of the dye into account. A method was proposed for determination of the duffusion coefficient in a spatially modified interference field of the laser radiation. The diffusion coefficients were found. (nonlinear optical phenomena)

  13. The effect of heat developed during high strain rate deformation on the constitutive modeling of amorphous polymers

    NASA Astrophysics Data System (ADS)

    Safari, Keivan H.; Zamani, Jamal; Guedes, Rui M.; Ferreira, Fernando J.

    2016-02-01

    An adiabatic constitutive model is proposed for large strain deformation of polycarbonate (PC) at high strain rates. When the strain rate is sufficiently high such that the heat generated does not have time to transfer to the surroundings, temperature of material rises. The high strain rate deformation behavior of polymers is significantly affected by temperature-dependent constants and thermal softening. Based on the isothermal model which first was introduced by Mulliken and Boyce et al. (Int. J. Solids Struct. 43:1331-1356, 2006), an adiabatic model is proposed to predict the yield and post-yield behavior of glassy polymers at high strain rates. When calculating the heat generated and the temperature changes during the step by step simulation of the deformation, temperature-dependent elastic constants are incorporated to the constitutive equations. Moreover, better prediction of softening phenomena is achieved by the new definition for softening parameters of the proposed model. The constitutive model has been implemented numerically into a commercial finite element code through a user material subroutine (VUMAT). The experimental results, obtained using a split Hopkinson pressure bar, are supported by dynamic mechanical thermal analysis (DMTA) and Decompose/Shift/Reconstruct (DSR) method. Comparison of adiabatic model predictions with experimental data demonstrates the ability of the model to capture the characteristic features of stress-strain curve of the material at very high strain rates.

  14. Concentration-dependent self-diffusion coefficients in amorphous Si{sub 1−x}Ge{sub x} solid solutions: An interdiffusion study

    SciTech Connect

    Noah, Martin A. Flötotto, David; Wang, Zumin; Mittemeijer, Eric J.

    2015-04-28

    Self-diffusion coefficients of Si and Ge in amorphous Si{sub 1−x}Ge{sub x} (a-Si{sub 1−x}Ge{sub x}) solid solutions were determined quantitatively in the temperature range of 440 °C – 460 °C by the investigation of interdiffusion in amorphous Si/Si{sub 0.52}Ge{sub 0.48} multilayers using Auger electron spectroscopy sputter-depth profiling. The determined concentration dependent self-diffusion coefficients of Si and Ge in a-Si{sub 1−x}Ge{sub x} with 0 ≤ x ≤ 0.48 at. % Ge are about ten orders of magnitude larger than in the corresponding crystalline phases, due to the inherent, excess free volume in the amorphous phase. The self-diffusion coefficient of Si (or Ge) in a-Si{sub 1−x}Ge{sub x} increases in association with a decreasing activation enthalpy with increasing Ge concentration. This concentration dependence has been related to an overall decrease of the average bond strength with increasing Ge concentration.

  15. High-performance fully amorphous bilayer metal-oxide thin film transistors using ultra-thin solution-processed ZrOx dielectric

    NASA Astrophysics Data System (ADS)

    Liu, G. X.; Liu, A.; Shan, F. K.; Meng, Y.; Shin, B. C.; Fortunato, E.; Martins, R.

    2014-09-01

    In this study, we report high-performance amorphous In2O3/InZnO bilayer metal-oxide (BMO) thin-film transistor (TFT) using an ultra-thin solution-processed amorphous ZrOx dielectric. A thin layer of In2O3 offers a higher carrier concentration, thereby maximizing the charge accumulation and yielding high carrier mobility. A thick amorphous layer of InZnO controls the charge conductance resulting in low off-state current and suitable threshold voltage. As a consequence, the BMO TFT showed higher filed-effect mobility (37.9 cm2/V s) than single-layer InZnO TFT (7.6 cm2/V s). Apart from that we obtain an on/off current ratio of 109, a subthreshold swing voltage of 120 mV/decade, and a voltage shift ≤ 0.4 V under positive bias stress for 2.5 h, for a gate voltage of 3 V and drain voltage of 1 V. These data demonstrate that the BMO TFT has great potential for a broad range of applications as switching low-power transistors.

  16. The behavior of acoustic bubbles in aqueous solutions containing soluble polymers.

    PubMed

    Tronson, Rohan; Tchea, Michelle F; Ashokkumar, Muthupandian; Grieser, Franz

    2012-11-26

    The effects of the water-soluble polymer polyvinylpyrrolidone (PVP) on the multibubble sonoluminescence (MBSL) intensity generated in aqueous solutions exposed to ultrasound at the two ultrasound frequencies of 20 and 363 kHz have been examined. In both cases, the presence of PVP, at concentrations of up to 2 g/100 mL, was found to enhance the MBSL intensity emitted from the solutions. On the basis of the intensity behavior of the SL observed from aqueous solutions containing PVP/surfactant and PVP/alcohol mixtures, it is suggested that PVP enhances MBSL by increasing the number of active bubbles in the system by hindering bubble-bubble coalescence processes and probably also by changing the structure of the bubble "clouds" formed at the acoustic antinodes in solution. The influence of PVP on bubble-bubble coalescence rates was also measured to support the interpretation of the MBSL emission experiments.

  17. Size distribution of linear and helical polymers in actin solution analyzed by photon counting histogram.

    PubMed

    Terada, Naofumi; Shimozawa, Togo; Ishiwata, Shin'ichi; Funatsu, Takashi

    2007-03-15

    Actin is a ubiquitous protein that is a major component of the cytoskeleton, playing an important role in muscle contraction and cell motility. At steady state, actin monomers and filaments (F-actin) coexist, and actin subunits continuously attach and detach at the filament ends. However, the size distribution of actin oligomers in F-actin solution has never been clarified. In this study, we investigated the size distribution of actin oligomers using photon-counting histograms. For this purpose, actin was labeled with a fluorescent dye, and the emitted photons were detected by confocal optics (the detection volume was of femtoliter (fL) order). Photon-counting histograms were analyzed to obtain the number distribution of actin oligomers in the detection area from their brightness, assuming that the brightness of an oligomer was proportional to the number of protomers. We found that the major populations at physiological ionic strength were 1-5mers. For data analysis, we successfully applied the theory of linear and helical aggregations of macromolecules. The model postulates three states of actin, i.e., monomers, linear polymers, and helical polymers. Here we obtained three parameters: the equilibrium constants for polymerization of linear polymers, K(l)=(5.2 +/- 1.1) x 10(6) M(-1), and helical polymers, K(h)=(1.6 +/- 0.5) x 10(7) M(-1); and the ratio of helical to linear trimers, gamma = (3.6 +/- 2.3) x 10(-2). The excess free energy of transforming a linear trimer to a helical trimer, which is assumed to be a nucleus for helical polymers, was calculated to be 2.0 kcal/mol. These analyses demonstrate that the oligomeric phase at steady state is predominantly composed of linear 1-5mers, and the transition from linear to helical polymers occurs on the level of 5-7mers. PMID:17172301

  18. Photovoltaic manufacturing technology monolithic amorphous silicon modules on continuous polymer substrates: Final technical report, July 5, 1995--December 31, 1999

    SciTech Connect

    Jeffrey, F.

    2000-03-28

    Iowa Thin Film Technologies is completing a three-phase program that has increased throughput and decreased costs in nearly all aspects of its thin-film photovoltaic manufacturing process. The overall manufacturing costs have been reduced by 61 percent through implementation of the improvements developed under this program. Development of the ability to use a 1-mil substrate, rather than the standard 2-mil substrate, results in a 50 percent cost-saving for this material. Process development on a single-pass amorphous silicon deposition system has resulted in a 37 percent throughput improvement. A wide range of process and machine improvements have been implemented on the transparent conducting oxide deposition system. These include detailed parameter optimization of deposition temperatures, process gas flows, carrier gas flows, and web speeds. An overall process throughput improvement of 275 percent was achieved based on this work. The new alignment technique was developed for the laser scriber and printer systems, which improved registration accuracy from 100 microns to 10 microns. The new technique also reduced alignment time for these registration systems significantly. This resulted in a throughput increase of 75 percent on the scriber and 600 percent on the printer. Automated techniques were designed and implemented for the module assembly processes. These include automated busbar attachment, roll-based lamination, and automated die cutting of finished modules. These processes were previously done by hand labor. Throughput improvements ranged from 200 percent to 1200 percent, relative to hand labor rates. A wide range of potential encapsulation materials were evaluated for suitability in a roll lamination process and for cost-effectiveness. A combination material was found that has a cost that is only 10 percent of the standard EVA/Tefzel cost and is suitable for medium-lifetime applications. The 20-year lifetime applications still require the more expensive

  19. Continuum theory of critical phenomena in polymer solutions: Formalism and mean field approximation

    NASA Astrophysics Data System (ADS)

    Goldstein, Raymond E.; Cherayil, Binny J.

    1989-06-01

    A theoretical description of the critical point of a polymer solution is formulated directly from the Edwards continuum model of polymers with two- and three-body excluded-volume interactions. A Hubbard-Stratonovich transformation analogous to that used in recent work on the liquid-vapor critical point of simple fluids is used to recast the grand partition function of the polymer solution as a functional integral over continuous fields. The resulting Landau-Ginzburg-Wilson (LGW) Hamiltonian is of the form of a generalized nonsymmetric n=1 component vector model, with operators directly related to certain connected correlation functions of a reference system. The latter is taken to be an ensemble of Gaussian chains with three-body excluded-volume repulsions, and the operators are computed in three dimensions by means of a perturbation theory that is rapidly convergent for long chains. A mean field theory of the functional integral yields a description of the critical point in which the power-law variations of the critical polymer volume fraction φc, critical temperature Tc, and critical amplitudes on polymerization index N are essentially identical to those found in the Flory-Huggins theory. In particular, we find φc ˜N-1/2, Tθ-Tc˜N-1/2 with (Tθ the theta temperature), and that the composition difference between coexisting phases varies with reduced temperature t as N-1/4t1/2. The mean field theory of the interfacial tension σ between coexisting phases near the critical point, developed by considering the LGW Hamiltonian for a weakly inhomogeneous solution, yields σ˜N-1/4t3/2, with the correlation length diverging as ξ˜N1/4t-1/2 within the same approximation, consistent with the mean field limit of de Gennes' scaling form. Generalizations to polydisperse systems are discussed.

  20. Does nitrogen gas bubbled through a low density polymer gel dosimeter solution affect the polymerization process?

    PubMed Central

    Shahbazi-Gahrouei, Daryoush; Gholami, Mehrdad; Pourfallah, Tayyeb Allahverdi; Keshtkar, Mohammad

    2015-01-01

    Background: On account of the lower electron density in the lung tissue, the dose distribution in the lung cannot be verified with the existing polymer gel dosimeters. Thus, the aims of this study are to make a low density polymer gel dosimeter and investigate the effect of nitrogen gas bubbles on the R2 responses and its homogeneity. Materials and Methods: Two different types of low density polymer gel dosimeters were prepared according to a composition proposed by De Deene, with some modifications. In the first type, no nitrogen gas was perfused through the gel solution and water. In the second type, to expel the dissolved oxygen, nitrogen gas was perfused through the water and gel solution. The post-irradiation times in the gels were 24 and 5 hours, respectively, with and without perfusion of nitrogen gas through the water and gel solution. Results: In the first type of gel, there was a linear correlation between the doses and R2 responses from 0 to 12 Gy. The fabricated gel had a higher dynamic range than the other low density polymer gel dosimeter; but its background R2 response was higher. In the second type, no difference in R2 response was seen in the dose ranges from 0 to 18 Gy. Both gels had a mass density between 0.35 and 0.45 g.cm-3 and CT values of about -650 to -750 Hounsfield units. Conclusion: It appeared that reactions between gelatin-free radicals and monomers, due to an increase in the gel temperature during rotation in the household mixer, led to a higher R2-background response. In the second type of gel, it seemed that the collapse of the nitrogen bubbles was the main factor that affected the R2-responses. PMID:26015914

  1. Data on energy-band-gap characteristics of composite nanoparticles obtained by modification of the amorphous potassium polytitanate in aqueous solutions of transition metal salts.

    PubMed

    Zimnyakov, D A; Sevrugin, A V; Yuvchenko, S A; Fedorov, F S; Tretyachenko, E V; Vikulova, M A; Kovaleva, D S; Krugova, E Y; Gorokhovsky, A V

    2016-06-01

    Here we present the data on the energy-band-gap characteristics of composite nanoparticles produced by modification of the amorphous potassium polytitanate in aqueous solutions of different transition metal salts. Band gap characteristics are investigated using diffuse reflection spectra of the obtained powders. Calculated logarithmic derivative quantity of the Kubelka-Munk function reveals a presence of local maxima in the regions 0.5-1.5 eV and 1.6-3.0 eV which correspond to band gap values of the investigated materials. The values might be related to the constituents of the composite nanoparticles and intermediate products of their chemical interaction. PMID:27158654

  2. Wetting Kinetics: an Alternative Approach Towards Understanding the Enhanced Dissolution Rate for Amorphous Solid Dispersion of a Poorly Soluble Drug.

    PubMed

    Verma, Sanjay; Rudraraju, Varma S

    2015-10-01

    Developing amorphous solid dispersions of water-insoluble molecules using polymeric materials is a well-defined approach to improve the dissolution rate and bioavailability. While the selected polymer plays a vital role in stabilizing the amorphous solid dispersion physically, it is equally important to improve the dissolution profile by inhibiting crystallization from the supersaturated solution generated by dissolution of the amorphous material. Furthermore, understanding the mechanism of dissolution rate enhancement is of vital importance. In this work, wetting kinetics was taken up as an alternative approach for understanding the enhanced dissolution rate for amorphous solid dispersion of a poorly soluble drug. While cilostazol (CIL) was selected as the model drug, povidone (PVP), copovidone, and hypromellose (HPMC) were the polymers of choice. The concentrations against time profiles were evaluated for the supersaturated solutions of CIL in the presence and absence of the selected polymers. The degree of supersaturation increased significantly with increase in polymer content within the solid dispersion. While povidone was found to maintain the highest level of supersaturation for the greatest length of time both in dissolution and solution crystallization experiments, copovidone and hypromellose were found to be the less effective as crystallization inhibitor. The ability of polymers to generate and maintain supersaturated drug solutions was assessed by dissolution studies. The wetting kinetics was compared against the solid dispersion composition to establish a correlation with enhanced dissolution rate.

  3. The effect of injection molding conditions on the near-surface rubber morphology, surface chemistry, and adhesion performance of semi-crystalline and amorphous polymers

    NASA Astrophysics Data System (ADS)

    Weakley-Bollin, Shannon Christine

    This thesis investigated the effect of injection molding processing variables, resin formulation and mold material on the resulting morphology and properties of semi-crystalline and amorphous polymers in parts molded on large presses with fully developed flow. Five different polymer resins and two different coating types were investigated, and the near-surface morphology was found to be dependent on material formulation, processing parameters, and geometry. For painted TPO, changes in the near-surface rubber morphology and surface chemistry based on material and processing conditions had no significant effect on the adhesion performance. For metal plated ABS, the adhesion performance was found to be heavily dependent on the rubber surface morphology, which varied with material formulation and processing conditions. One of the most significant findings was that forged aluminum injection molding tooling had little effect on the surface morphology or adhesion performance of either polypropylene or the two TPO formulations examined, despite the five-fold increase in thermal conductivity over traditional tool steel. Surface chemistry, however, was found to be affected by cooling rate, depending on material formulation. A UV stabilizer additive was found concentrated at 2.5 atomic percent on the surface of the aluminum molded part, but not the steel molded part, demonstrating a possible opportunity for using additives and aluminum tooling to create "designer surfaces". Processing conditions were found to have a competing role in metal plated ABS, where conditions that lowered surface stress and improved adhesion by a factor of 15 also increased the amount of bulk molded-in stress by nearly 7%. Both factors were found to play an important role in adhesion performance due to the effect of surface stress on the quality of the resulting etch structure. The bulk stress must be minimized to due to the large mechanical and thermal mismatch between the polymer and metal layers

  4. A many-body Hamiltonian for nanoparticles immersed in a polymer solution.

    PubMed

    Woodward, Clifford E; Forsman, Jan

    2015-01-13

    We developed an analytical theory for the many-body potential of mean force (POMF) between N spheres immersed in a continuum chain fluid. The theory is almost exact for a Θ polymer solution in the protein limit (small particles, long polymers), where N-body effects are important. Polydispersity in polymer length according to a Schulz-Flory distribution emerges naturally from our analysis, as does the transition to the monodisperse limit. The analytical expression for the POMF allows for computer simulations employing the complete N-body potential (i.e., without n-body truncation; n < N). These are compared with simulations of an explicit particle/polymer mixture. We show that the theory produces fluid structure in excellent agreement with the explicit model simulations even when the system is strongly fluctuating, e.g., at or near the spinodal region. We also demonstrate that other commonly used theoretical approaches, such as truncation of the POMF at the pair level or the Asakura Oosawa model, are extremely inaccurate for these systems. PMID:25547161

  5. Polymer Diffusion in Microgels with Upper Critical Solution Temperature as Studied by Incoherent Neutron Scattering

    NASA Astrophysics Data System (ADS)

    Serrano Ruiz, D.; Alonso Cristobal, P.; Laurenti, M.; Rubio Retama, J.; Lopez-Cabarcos, E.

    2014-11-01

    Poly(acrylic-acrylamide) interpenetrated microgels present continuous phase transition from collapsed to swollen state around 42 °C. The upper critical solution temperature (UCST) of this polymeric system has prompted scientists to consider them candidates for its use in biological applications such as smart drug delivery devices since the swelling of the polymer matrix would permit the release of the drug previously entrapped within the microgels. In these systems the increment of the temperature can break inter-chain interactions, mainly hydrogen bonds, which reduce the elastic tension that stabilizes the microgel, favoring the polymer swelling. The microgel molecular dynamics at the UCST can be investigated using Incoherent Elastic (IENS) and Quasielastic Neutron Scattering (IQNS). From the analysis of the IQNS data we obtained that the diffusion coefficient of the polymer segments depends on the composition of the interpenetrated matrix. Thus, at room temperature, microgels with a polymer composition of 50% of each component present a diffusion coefficient 1·10-12 m2/s, while for the microgels formed by only one component the diffusion coefficient is 5.10-10 m2/s. This huge difference in the diffusion coefficient is conspicuously reduced when temperature increases, and we attribute this effect to the breaking of the inter-chain interaction. By means of FTIR-ATR analysis we have identified the groups that are involved in this phenomenon and we associate the breaking of the polyacrylic-polyacrylamide interactions with the swelling of the microgels.

  6. Carrier Transport Enhancement in Conjugated Polymers through Interfacial Self-Assembly of Solution-State Aggregates.

    PubMed

    Zhao, Kui; Khan, Hadayat Ullah; Li, Ruipeng; Hu, Hanlin; Amassian, Aram

    2016-08-01

    We demonstrate that local and long-range orders of poly(3-hexylthiophene) (P3HT) semicrystalline films can be synergistically improved by combining chemical functionalization of the substrate with solution-state disentanglement and preaggregation of P3HT in a θ solvent, leading to a very significant enhancement of the field effect carrier mobility. The preaggregation and surface functionalization effects combine to enhance the carrier mobility nearly 100-fold as compared with standard film preparation by spin-coating, and nearly 10-fold increase over the benefits of preaggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of preaggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to unaggregated polymer chains in the same conditions. Additional measurements reveal the combined preaggregation and surface functionalization significantly enhances local order of the conjugated polymer through planarization and extension of the conjugated backbone of the polymer which clearly translate to significant improvements of carrier transport at the semiconductor-dielectric interface in organic thin film transistors. This study points to opportunities in combining complementary routes, such as well-known preaggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties. PMID:27410517

  7. Ketjenblack carbon supported amorphous manganese oxides nanowires as highly efficient electrocatalyst for oxygen reduction reaction in alkaline solutions.

    PubMed

    Lee, Jang-Soo; Park, Gi Su; Lee, Ho Il; Kim, Sun Tai; Cao, Ruiguo; Liu, Meilin; Cho, Jaephil

    2011-12-14

    A composite air electrode consisting of Ketjenblack carbon (KB) supported amorphous manganese oxide (MnOx) nanowires, synthesized via a polyol method, is highly efficient for the oxygen reduction reaction (ORR) in a Zn-air battery. The low-cost and highly conductive KB in this composite electrode overcomes the limitations due to low electrical conductivity of MnOx while acting as a supporting matrix for the catalyst. The large surface area of the amorphous MnOx nanowires, together with other microscopic features (e.g., high density of surface defects), potentially offers more active sites for oxygen adsorption, thus significantly enhancing ORR activity. In particular, a Zn-air battery based on this composite air electrode exhibits a peak power density of ∼190 mW/cm2, which is far superior to those based on a commercial air cathode with Mn3O4 catalysts. PMID:22050041

  8. Flow-enhanced solution printing of all-polymer solar cells

    DOE PAGES

    Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; Shaw, Leo; Wang, Cheng; Park, Steve; Guo, Yikun; Reinspach, Julia A.; Gu, Kevin; Gu, Xiaodan; et al

    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

  9. Recent Developments in Fully Fluctuating Field-Theoretic Simulations of Polymer Melts and Solutions.

    PubMed

    Delaney, Kris T; Fredrickson, Glenn H

    2016-08-11

    We review the latest developments in computational methods for direct simulation of fully fluctuating field theories of polymeric assemblies. In this context, we describe a newly developed theoretical and computational framework for accurately computing fluctuation-corrected phase diagrams of mesostructured polymer systems and report the first such complete phase diagram for a diblock copolymer melt. The method is based on complex Langevin sampling of a UV regularized field-theoretic model, with Helmholtz free energies computed using thermodynamic integration. UV regularization ensures that the free energies do not have an arbitrary reference; they can be compared between incommensurate phases, permitting for the first time the computation of order-order transitions with fluctuation corrections. We further demonstrate that computed free energies are accurate in the disordered phase by comparison to perturbation theory on the one-loop level. Importantly, we note that our method uses no uncontrolled approximations beyond the initial definition of a coarse-grained molecular model for the polymer melt or solution. The method can be applied straightforwardly to melts and solutions containing multiple species with diverse polymer architectures. PMID:27414265

  10. Solution-Processed p-Dopant as Interlayer in Polymer Solar Cells.

    PubMed

    Guillain, F; Endres, J; Bourgeois, L; Kahn, A; Vignau, L; Wantz, G

    2016-04-13

    We report here an original approach to dope the semiconducting polymer-metal interface in an inverted bulk-heterojunction (BHJ) organic solar cell. Solution-processed 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), is deposited on top of a P3HT:PC61BM layer before deposition of the top electrode. Doping of P3HT by F4-TCNQ occurs after thermally induced diffusion at 100 °C of the latter into the BHJ. Diffusion and doping are evidenced by XPS and UV-vis-NIR absorption. XPS highlights the decrease in Fluorine concentration on top of the BHJ after annealing. In the same time, a charge transfer band attributed to doping is observed in the UV-vis-NIR absorption spectrum. Inverted polymer solar cells using solution-processed F4-TCNQ exhibit power conversion efficiency of nearly 3.5% after annealing. This simple and efficient approach, together with the low annealing temperature required to allow diffusion and doping, leads to standard efficiency P3HT:PC61BM polymer solar cells, which are suitable for printing on plastic flexible substrate.

  11. Solution-Crystallization and Related Phenomena in 9,9-Dialkyl-Fluorene Polymers. I. Crystalline Polymer-Solvent Compound Formation for Poly(9,9-dioctylfluorene)

    PubMed Central

    Perevedentsev, Aleksandr; Stavrinou, Paul N; Bradley, Donal D C; Smith, Paul

    2015-01-01

    Polymer-solvent compound formation, occurring via co-crystallization of polymer chains and selected small-molecular species, is demonstrated for the conjugated polymer poly(9,9-dioctylfluorene) (PFO) and a range of organic solvents. The resulting crystallization and gelation processes in PFO solutions are studied by differential scanning calorimetry, with X-ray diffraction providing additional information on the resulting microstructure. It is shown that PFO-solvent compounds comprise an ultra-regular molecular-level arrangement of the semiconducting polymer host and small-molecular solvent guest. Crystals form following adoption of the planar-zigzag β-phase chain conformation, which, due to its geometry, creates periodic cavities that accommodate the ordered inclusion of solvent molecules of matching volume. The findings are formalized in terms of nonequilibrium temperature–composition phase diagrams. The potential applications of these compounds and the new functionalities that they might enable are also discussed. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 1481–1491 PMID:26435576

  12. The measurement of a complete set of transport properties for a concentrated solid polymer electrolyte solution

    SciTech Connect

    Ma, Y.; Doyle, M.; Doeff, M.M.; De Jonghe, L.C.; Newman, J.; Fuller, T.F.

    1995-06-01

    Polymer electrolytes based on alkali metal salts in poly(ethylene oxides) are important for possible use in rechargeable batteries for both electric vehicle and consumer electronics applications. The authors measure a complete set of transport properties for one particular binary salt solution: sodium trifluoromethanesulfonate in poly(ethylene oxide), over a wide range of salt concentrations (0.1 to 2.6M) at 85 C. The properties measured include the conductivity, the salt diffusion coefficient, and the Na ion transference number. The mean molar activity coefficient of the salt is also determined. The conductivity and diffusion coefficients of NaCF{sub 3}SO{sub 3} are similar in magnitude to those of LiCF{sub 3}SO{sub 3} in (polyethylene oxide). The transference number and thermodynamic factor are found by combining concentration cell data with the results of galvanostatic polarization experiments. A theoretical analysis of the experimental method based on concentrated-solution theory is given. The study verifies that the transference numbers derived from the experiments retain fundamental significance in applications involving both steady and transient processes and in systems coupling the polymer electrolyte with electrodes of all types (stoichiometries). The relevant transference numbers can be determined independently of any knowledge of speciation of the polymer electrolyte. The transference numbers found here for the sodium ion are much lower than those reported for the lithium ion, especially in the concentrated solutions. The transference number of the sodium ion is negative in the more concentrated solutions and levels off at its maximum value of 0.31 in the dilute concentration range. The transference number results are interpreted in terms of complexation of the sodium ion with the anionic species.

  13. Application of X-ray microtomography for the characterisation of hollow polymer-stabilised spray dried amorphous dispersion particles.

    PubMed

    Gamble, John F; Terada, Masako; Holzner, Christian; Lavery, Leah; Nicholson, Sarah J; Timmins, Peter; Tobyn, Mike

    2016-08-20

    The aim of this study was to investigate the capability of X-ray microtomography to obtain information relating to powder characteristics such as wall thickness and solid volume fraction for hollow, polymer-stabilised spray dried dispersion (SDD) particles. SDDs of varying particle properties, with respect to shell wall thickness and degree of particle collapse, were utilised to assess the capability of the approach. The results demonstrate that the approach can provide insight into the morphological characteristics of these hollow particles, and thereby a means to understand/predict the processability and performance characteristics of the bulk material. Quantitative assessments of particle wall thickness, particle/void volume and thereby solid volume fraction were also demonstrated to be achievable. The analysis was also shown to be able to qualitatively assess the impact of the drying rate on the morphological nature of the particle surfaces, thus providing further insight into the final particle shape. The approach demonstrated a practical means to access potentially important particle characteristics for SDD materials which, in addition to the standard bulk powder measurements such as particle size and bulk density, may enable a better understanding of such materials, and their impact on downstream processability and dosage form performance.

  14. Study of a smart polymer medical device, product development obstacles and innovative solutions

    NASA Astrophysics Data System (ADS)

    Banister, Mark; Clark, Ray; Coiner, Eric; Geronov, Yordan; McWilliams, Mark; Sias, Ralph; Walters, Gary; McGrath, Dominic

    2012-04-01

    The concept is simple, within the pump a pH responsive polymer actuator swells in volume under electrically controlled stimulus. As the actuator swells it presses against a drug reservoir, as the reservoir collapses the drug is metered out to the patient. From concept to finished product, engineering this smart system entailed integration across multiple fields of science and engineering. Materials science, nanotechnology, polymer chemistry, organic chemistry, electrochemistry, molecular engineering, electrical engineering, and mechanical engineering all played a part in solutions to multiple technical hurdles. Some of these hurdles where overcome by tried and true materials and component engineering, others where resolved by some very creative out of the box thinking and tinkering. This paper, hopefully, will serve to encourage others to venture into unfamiliar territory as we did, in order to overcome technical obstacles and successfully develop a low cost smart medical device that can truly change a patient's life.

  15. Trehalose amorphization and recrystallization.

    PubMed

    Sussich, Fabiana; Cesàro, Attilio

    2008-10-13

    The stability of the amorphous trehalose prepared by using several procedures is presented and discussed. Amorphization is shown to occur by melting (T(m)=215 degrees C) or milling (room temperature) the crystalline anhydrous form TRE-beta. Fast dehydration of the di-hydrate crystalline polymorph, TRE-h, also produces an amorphous phase. Other dehydration procedures of TRE-h, such as microwave treatment, supercritical extraction or gentle heating at low scan rates, give variable fractions of the polymorph TRE-alpha, that undergo amorphization upon melting (at lower temperature, T(m)=130 degrees C). Additional procedures for amorphization, such as freeze-drying, spray-drying or evaporation of trehalose solutions, are discussed. All these procedures are classified depending on the capability of the undercooled liquid phase to undergo cold crystallization upon heating the glassy state at temperatures above the glass transition temperature (T(g)=120 degrees C). The recrystallizable amorphous phase is invariably obtained by the melt of the polymorph TRE-alpha, while other procedures always give an amorphous phase that is unable to crystallize above T(g). The existence of two different categories is analyzed in terms of the transformation paths and the hypothesis that the systems may exhibit different molecular mobilities.

  16. Gold Nanorod Linking to Control Plasmonic Properties in Solution and Polymer Nanocomposites

    PubMed Central

    2015-01-01

    A novel, solution-based method is presented to prepare bifunctional gold nanorods (B-NRs), assemble B-NRs end-to-end in various solvents, and disperse linked B-NRs in a polymer matrix. The B-NRs have poly(ethylene glycol) grafted along its long axis and cysteine adsorbed to its ends. By controlling cysteine coverage, bifunctional ligands or polymer can be end-grafted to the AuNRs. Here, two dithiol ligands (C6DT and C9DT) are used to link the B-NRs in organic solvents. With increasing incubation time, the nanorod chain length increases linearly as the longitudinal surface plasmon resonance shifts toward lower adsorption wavelengths (i.e., red shift). Analogous to step-growth polymerization, the polydispersity in chain length also increases. Upon adding poly(ethylene glycol) or poly(methyl methacrylate) to chloroform solution with linked B-NR, the nanorod chains are shown to retain end-to-end linking upon spin-casting into PEO or PMMA films. Using quartz crystal microbalance with dissipation (QCM-D), the mechanism of nanorod linking is investigated on planar gold surfaces. At submonolayer coverage of cysteine, C6DT molecules can insert between cysteines and reach an areal density of 3.4 molecules per nm2. To mimic the linking of Au NRs, this planar surface is exposed to cysteine-coated Au nanoparticles, which graft at 7 NPs per μm2. This solution-based method to prepare, assemble, and disperse Au nanorods is applicable to other nanorod systems (e.g., CdSe) and presents a new strategy to assemble anisotropic particles in organic solvents and polymer coatings. PMID:24483622

  17. Gold nanorod linking to control plasmonic properties in solution and polymer nanocomposites.

    PubMed

    Ferrier, Robert C; Lee, Hyun-Su; Hore, Michael J A; Caporizzo, Matthew; Eckmann, David M; Composto, Russell J

    2014-02-25

    A novel, solution-based method is presented to prepare bifunctional gold nanorods (B-NRs), assemble B-NRs end-to-end in various solvents, and disperse linked B-NRs in a polymer matrix. The B-NRs have poly(ethylene glycol) grafted along its long axis and cysteine adsorbed to its ends. By controlling cysteine coverage, bifunctional ligands or polymer can be end-grafted to the AuNRs. Here, two dithiol ligands (C6DT and C9DT) are used to link the B-NRs in organic solvents. With increasing incubation time, the nanorod chain length increases linearly as the longitudinal surface plasmon resonance shifts toward lower adsorption wavelengths (i.e., red shift). Analogous to step-growth polymerization, the polydispersity in chain length also increases. Upon adding poly(ethylene glycol) or poly(methyl methacrylate) to chloroform solution with linked B-NR, the nanorod chains are shown to retain end-to-end linking upon spin-casting into PEO or PMMA films. Using quartz crystal microbalance with dissipation (QCM-D), the mechanism of nanorod linking is investigated on planar gold surfaces. At submonolayer coverage of cysteine, C6DT molecules can insert between cysteines and reach an areal density of 3.4 molecules per nm(2). To mimic the linking of Au NRs, this planar surface is exposed to cysteine-coated Au nanoparticles, which graft at 7 NPs per μm(2). This solution-based method to prepare, assemble, and disperse Au nanorods is applicable to other nanorod systems (e.g., CdSe) and presents a new strategy to assemble anisotropic particles in organic solvents and polymer coatings. PMID:24483622

  18. Rheology and microstructure of complex fluids: Dispersions, emulsions and polymer solutions

    NASA Astrophysics Data System (ADS)

    Vicic, Michael Allen

    1999-12-01

    The rheology and microstructure of complex fluids are intimately related, and this relationship is explored to gain a deeper understanding of the physics of colloidal dispersions, emulsions and polymer solutions. The nonequilibrium microstructure and rheological properties of dispersions in steady, simple shear flow are calculated by solving the Smoluchowski equation as a function of dimensionless shear rate. The particles have a purely repulsive interaction with an hydrodynamic radius, a, and a thermodynamic radius, b. For hard spheres, b/ a --> 1, shear thinning is caused by a decrease in the Brownian contribution since Brownian motion becomes less important with increasing shear. Shear thickening occurs because of an increase in the hydrodynamic viscosity caused by the increased probability of finding particles near contact with increasing shear when particles hydrodynamically interact. The first normal stress difference changes sign since Brownian and hydrodynamic contributions have opposite signs, while the second normal stress difference is always negative. Scaling arguments are made to extend these dilute results for concentrated dispersions. Similar calculations and analyses are performed to study the effects of hydrodynamic interactions and varying b/ a ratios on rheology and microstructure. Scaling arguments for the volume-fraction dependence of the bulk stress of emulsions at the critical capillary number are presented along with experimental evidence using an unstabilized emulsion of polymerized castor oil dispersed in polydimethylsiloxane. It is shown that the droplet contribution to both the relative shear viscosity and first normal stress difference is linear in volume fraction for a given viscosity ratio for dilute to moderately-concentrated emulsions in steady, simple shear flow. Stress jump measurements are performed for the first time for (i)shear startup and (ii)polymer solutions in shear. The startup viscosity of a polymer solution of

  19. Atomization and rheology of mixed non-ionic and ionic polymer solutions

    NASA Astrophysics Data System (ADS)

    Sun, Patricia B.

    2003-06-01

    Misting problem of metalworking fluids caused by liquid jets breakup under high shear and strong impact working conditions during machining processes brings about significant health hazard and air pollution in automotive plants. The use of high molecular polyethylene oxide (PEO) is very effective to reduce mist formation of low viscosity aqueous solutions by bestowing elasticity to the system. However, severe chain scission induced high replenishment cost is the biggest economical barrier of this method. In this study, mixed polymer solutions with physical associating structures were developed to improve PEO's cost effectiveness as anti-misting agent for water-based machining fluids through improved shear stability (due to structure regeneration) and reduced polymer molecular weight and concentrations (due to enhanced mist suppression effectiveness). The association of sodium poly(styrene sulfonate salt) (SPSS) with PEO, particularly its impact on dynamics, rheology and atomization behavior of aqueous solutions were systematically investigated, providing a more reliable and efficient means of enhancing PEO mist reduction performances relative to PEO-surfactant systems. Strong structure-forming interaction of the two components was detected by dynamic light scatting. It yields pronounced enlargement in PEO's coil size, and consequently magnificent enhancement on solution's elongational viscosity, which contributes most in retarding liquid jet disintegration and exhibits direct correlation with the resultant drop size distribution under atomization. The degree of their association is dependent on both molecular weight and concentration of each species and their molar ratio. By using mixed polymeric solutions, the optimum anti-misting effectiveness can be obtained throughout a broad concentration range.

  20. Solution and interfacial behavior of modified silicone polymers and their interactions with solid substrates

    NASA Astrophysics Data System (ADS)

    Purohit, Parag

    Surface treatment is very important step in many applications such as fabric finishing, coatings, cosmetics and personal care. Silicone polymers are a class of organic/inorganic materials that show unique properties such as weak intermolecular forces and high flexibility enabling even a very high molecular weight chain to achieve optimal orientation on surfaces. Material properties such as softness, repellency, bounciness and friction can therefore be tailored by using appropriately modified silicone polymers. Despite wide applications, the underlying mechanisms of material modification are unknown and tailoring silicones for applications remains mostly empirical. Thus the objective of this research is to understand the solution and interfacial behavior of functionalized silicone polymers, which govern their performance in material modification. Modified silicones are simultaneously hydrophobic and oleophobic in nature and due to this nearly universal non-compatibility, the studies of these polymers present unusual challenges. Due to this incompatible nature, the functionalized silicone polymers were emulsified into O/W emulsions to study their solution and interfacial properties. The colloidal properties such as electrokinetic and droplet distribution of these emulsions are assumed to play an important role in the observed surface and physical properties of solid substrates (in present study, cellulosic substrates) as well the stability of emulsions itself. To understand the effects of modified silicones on cellulosic substrates a variety of techniques such as frictional analysis, scanning electron microscopy and atomic force microscopy that can probe from macro to nano level were used. It is hypothesized that the size distribution and charge of silicone emulsions as well as the physiochemical conditions such as pH, control silicone conformation which in turn affect the modification of the substrate properties. With bimodal droplet distribution of silicone

  1. Fabrication of conductive polymer nanofibers through SWNT supramolecular functionalization and aqueous solution processing

    NASA Astrophysics Data System (ADS)

    Naeem, Fahim; Prestayko, Rachel; Saem, Sokunthearath; Nowicki, Lauren; Imit, Mokhtar; Adronov, Alex; Moran-Mirabal, Jose M.

    2015-10-01

    Polymeric thin films and nanostructured composites with excellent electrical properties are required for the development of advanced optoelectronic devices, flexible electronics, wearable sensors, and tissue engineering scaffolds. Because most polymers available for fabrication are insulating, one of the biggest challenges remains the preparation of inexpensive polymer composites with good electrical conductivity. Among the nanomaterials used to enhance composite performance, single walled carbon nanotubes (SWNTs) are ideal due to their unique physical and electrical properties. Yet, a barrier to their widespread application is that they do not readily disperse in solvents traditionally used for polymer processing. In this study, we employed supramolecular functionalization of SWNTs with a conjugated polyelectrolyte as a simple approach to produce stable aqueous nanotube suspensions, that could be effortlessly blended with the polymer poly(ethyleneoxide) (PEO). The homogeneous SWNT:PEO mixtures were used to fabricate conductive thin films and nanofibers with improved conductivities through drop casting and electrospinning. The physical characterization of electrospun nanofibers through Raman spectroscopy and SEM revealed that the SWNTs were uniformly incorporated throughout the composites. The electrical characterization of SWNT:PEO thin films allowed us to assess their conductivity and establish a percolation threshold of 0.1 wt% SWNT. Similarly, measurement of the nanofiber conductivity showed that the electrospinning process improved the contact between nanotube complexes, resulting in conductivities in the S m-1 range with much lower weight loading of SWNTs than their thin film counterparts. The methods reported for the fabrication of conductive nanofibers are simple, inexpensive, and enable SWNT processing in aqueous solutions, and offer great potential for nanofiber use in applications involving flexible electronics, sensing devices, and tissue engineering

  2. Fabrication of conductive polymer nanofibers through SWNT supramolecular functionalization and aqueous solution processing.

    PubMed

    Naeem, Fahim; Prestayko, Rachel; Saem, Sokunthearath; Nowicki, Lauren; Imit, Mokhtar; Adronov, Alex; Moran-Mirabal, Jose M

    2015-10-01

    Polymeric thin films and nanostructured composites with excellent electrical properties are required for the development of advanced optoelectronic devices, flexible electronics, wearable sensors, and tissue engineering scaffolds. Because most polymers available for fabrication are insulating, one of the biggest challenges remains the preparation of inexpensive polymer composites with good electrical conductivity. Among the nanomaterials used to enhance composite performance, single walled carbon nanotubes (SWNTs) are ideal due to their unique physical and electrical properties. Yet, a barrier to their widespread application is that they do not readily disperse in solvents traditionally used for polymer processing. In this study, we employed supramolecular functionalization of SWNTs with a conjugated polyelectrolyte as a simple approach to produce stable aqueous nanotube suspensions, that could be effortlessly blended with the polymer poly(ethyleneoxide) (PEO). The homogeneous SWNT:PEO mixtures were used to fabricate conductive thin films and nanofibers with improved conductivities through drop casting and electrospinning. The physical characterization of electrospun nanofibers through Raman spectroscopy and SEM revealed that the SWNTs were uniformly incorporated throughout the composites. The electrical characterization of SWNT:PEO thin films allowed us to assess their conductivity and establish a percolation threshold of 0.1 wt% SWNT. Similarly, measurement of the nanofiber conductivity showed that the electrospinning process improved the contact between nanotube complexes, resulting in conductivities in the S m(-1) range with much lower weight loading of SWNTs than their thin film counterparts. The methods reported for the fabrication of conductive nanofibers are simple, inexpensive, and enable SWNT processing in aqueous solutions, and offer great potential for nanofiber use in applications involving flexible electronics, sensing devices, and tissue engineering

  3. Simulation of bead-and-spring chain models for semidilute polymer solutions in shear flow

    NASA Astrophysics Data System (ADS)

    Fetsko, S. W.; Cummings, P. T.

    1994-11-01

    We report preliminary results of simulations of the steady-state rheological behavior for semidilute polymer solutions of head-and-spring chain models in planar Couette now. The simulations include examination of the effects of excluded volume. hydrodynamic interactions and density. Hydrodynamic interactions are modeled by the Rotne -Prager Yamakawa tensor. The simulations are based on the nonequilibrium Brownian dynamics algorithm of Ermak and McCammon. In addition to the spring potential between neighboring beads in the chain. the interaction between any two beads in the solution is modeled using a shifted, repulsive Leonard-Jones potential. Lees Edward sliding brick boundary conditions are used for consistency with the Couette flow field.

  4. Solution-processed parallel tandem polymer solar cells using silver nanowires as intermediate electrode.

    PubMed

    Guo, Fei; Kubis, Peter; Li, Ning; Przybilla, Thomas; Matt, Gebhard; Stubhan, Tobias; Ameri, Tayebeh; Butz, Benjamin; Spiecker, Erdmann; Forberich, Karen; Brabec, Christoph J

    2014-12-23

    Tandem architecture is the most relevant concept to overcome the efficiency limit of single-junction photovoltaic solar cells. Series-connected tandem polymer solar cells (PSCs) have advanced rapidly during the past decade. In contrast, the development of parallel-connected tandem cells is lagging far behind due to the big challenge in establishing an efficient interlayer with high transparency and high in-plane conductivity. Here, we report all-solution fabrication of parallel tandem PSCs using silver nanowires as intermediate charge collecting electrode. Through a rational interface design, a robust interlayer is established, enabling the efficient extraction and transport of electrons from subcells. The resulting parallel tandem cells exhibit high fill factors of ∼60% and enhanced current densities which are identical to the sum of the current densities of the subcells. These results suggest that solution-processed parallel tandem configuration provides an alternative avenue toward high performance photovoltaic devices. PMID:25405589

  5. The corrosion effect of ozonated seawater solution on titanium in polymer generated crevice environments

    SciTech Connect

    Leveillee, S.Y.

    1998-01-01

    Two different tests were designed to evaluate the reaction of various polymers and grade-2 titanium in ozonated seawater in conjunction with a comparative analysis in an aerated seawater solution. The first was a weight loss test measuring the weight change of Polyvinyl chloride (PVC), Polyethylene and Teflon{trademark} in both ozonated and aerated artificial seawater baths. The second test was designed to induce crevice corrosion on the titanium test samples using various crevice generating materials in both ozonated and aerated solutions. The materials used to create the crevices were grade-2 titanium washers, PVC, Polyethylene, Saran and Teflon{trademark}. The weight loss test showed that all three polymers lost weight in the ozonated bath. The results of the titanium washer crevice test provided no indication of corrosion or surface discoloration in either the ozonated or aerated solutions. Energy dispersive spectrometry (EDS) analysis found no fluorine, chlorine or other corrosion product. The PVC samples in the aerated bath also showed no signs of corrosion, but the PVC samples in the ozonated tank had light brown rings of surface discoloration. One of the ozonated PVC samples did show evidence of chlorine in the corrosion product. The outer circumference of the ozonated PVC washers exhibited the same type bleaching effect as in the weight loss samples, but the whitening of these samples were more pronounced. The polyethylene samples under aeration showed no discoloration or presence of fluorine or chlorine. The polyethylene crevice samples in the ozonated solution all exhibited the distinct brilliant blue color of titanium oxide. Fluorine was found in the corrosion product on only one of the samples. Chlorine was found on the surface of one of the other corrosion coupons. The results of the Teflon{trademark} crevice samples substantiated the previous Rensselaer study.

  6. Hydrodynamic effects on phase separation morphologies in evaporating thin films of polymer solutions

    NASA Astrophysics Data System (ADS)

    Zoumpouli, Garyfalia A.; Yiantsios, Stergios G.

    2016-08-01

    We examine effects of hydrodynamics on phase separation morphologies developed during drying of thin films containing a volatile solvent and two dissolved polymers. Cahn-Hilliard and Flory-Huggins theories are used to describe the free energy of the phase separating systems. The thin films, considered as Newtonian fluids, flow in response to Korteweg stresses arising due to concentration non-uniformities that develop during solvent evaporation. Numerical simulations are employed to investigate the effects of a Peclet number, defined in terms of system physical properties, as well as the effects of parameters characterizing the speed of evaporation and preferential wetting of the solutes at the gas interface. For systems exhibiting preferential wetting, diffusion alone is known to favor lamellar configurations for the separated phases in the dried film. However, a mechanism of hydrodynamic instability of a short length scale is revealed, which beyond a threshold Peclet number may deform and break the lamellae. The critical Peclet number tends to decrease as the evaporation rate increases and to increase with the tendency of the polymers to selectively wet the gas interface. As the Peclet number increases, the instability moves closer to the gas interface and induces the formation of a lateral segregation template that guides the subsequent evolution of the phase separation process. On the other hand, for systems with no preferential wetting or any other property asymmetries between the two polymers, diffusion alone favors the formation of laterally separated configurations. In this case, concentration perturbation modes that lead to enhanced Korteweg stresses may be favored for sufficiently large Peclet numbers. For such modes, a second mechanism is revealed, which is similar to the solutocapillary Marangoni instability observed in evaporating solutions when interfacial tension increases with the concentration of the non-volatile component. This mechanism may lead

  7. Polymers.

    ERIC Educational Resources Information Center

    Tucker, David C.

    1986-01-01

    Presents an open-ended experiment which has students exploring polymer chemistry and reverse osmosis. This activity involves construction of a polymer membrane, use of it in a simple osmosis experiment, and application of its principles in solving a science-technology-society problem. (ML)

  8. Simulating the dynamics of a single polymer chain in solution: Lattice Boltzmann vs Brownian dynamics

    NASA Astrophysics Data System (ADS)

    Duenweg, Burkhard

    2010-03-01

    Two well--established and complementary methodologies to simulate the dynamics of polymers in solution are (i) Brownian Dynamics (BD), and (ii) Molecular Dynamics coupled dissipatively to a lattice Boltzmann background (MD/LB). The talk gives a brief introduction into both methods, and then presents results of a recent comparative study that applied both methods to the same model of a single chain that moves in a solvent under the influence of thermal noise. Emphasis is put on the question how to map the parameters onto each other, in particular those that are crucial for the dynamics. The agreement of static properties is perfect, as it must be. The dynamic properties agree very well, if for the MD/LB case the effects of finite box size are eliminated by extrapolation. We also find that proper thermalization of all MD/LB degrees of freedom (including the so--called ``kinetic modes'') is necessary. Small deviations between BD and MD/LB remain as a result of the different simulation methodologies. Finally, the computational efficiency of the two methods is compared. For the single--chain system, BD is clearly much faster, while scaling estimates suggest that the opposite is true for semidilute solutions. References: *Tri T. Pham, Ulf D. Schiller, J. Ravi Prakash, and B. D"unweg, J. Chem. Phys. 131, 164114 (2009). *B. D"unweg and A. J. C. Ladd, Adv. Polym. Sci. 221, 89 (2009).

  9. Concentration Field Evolution during the Drying of a Thin Polymer Solution Film near the Contact Line.

    PubMed

    Babaie, A; Stoeber, B

    2015-08-25

    An experimental study is performed for polymer concentration field measurements during the drying of an aqueous poly(vinyl alcohol) solution inside a shallow cavity near a vertical side wall. The measurements are based on optical techniques such as 3D confocal microscopy for laser-induced fluorescence analysis. The results reveal a significant concentration heterogeneity across the film near the meniscus during the drying process. The concentration at the solution-air interface remains higher compared to the bulk, and it increases toward the pinned contact line and also over time. A skin layer starts forming as the surface concentration reaches the glass-transition concentration, after which the evaporation rate starts decreasing. Regardless of the cavity depth and the initial polymer concentration, the drying film undergoes a similar concentration evolution during the evaporation process, although minor differences can be recognized. For instance, a low local capillary number at the surface is associated with a wavy surface concentration profile while at higher capillary numbers disturbances are damped and a much more uniform concentration profile is observed.

  10. Microstructure Changes of Copper Nano Particles via Polymer Solution and Reduction Firing Processes.

    PubMed

    Han, Young-Min; Jung, Choong-Hwan; Lee, Sang-Jin

    2016-02-01

    Cu nano particles were fabricated at a very low temperature via polymer solution and reduction firing processes using a polyvinyl alcohol (PVA) and Ar-4%H2 gas mixture. In the process, copper nitrate and 5 wt% PVA solution were dissolved in D.I. water and the organic-inorganic precursor sols were dried to porous gels. The precursor gels were calcined in an air atmosphere, and then refired at 250 degrees C-300 degrees C under an Ar-4%H2 atmosphere for the reduction of CuO. The morphology of precursor gels and CuO and Cu powders was strongly dependent on the PVA content, and the as- calcined CuO readily deoxidized to Cu with minimal residual carbon. The polymer also contributed to an atomic-scale copper cation distribution, which resulted in nano-sized CuO and Cu powders. The Cu powder synthesized with PVA content in a 4:1 ratio showed a crystallite size of about 20 nm or less. In this paper, the microstructure changes of Cu nano particles at each set of processing conditions were examined by SEM and TEM observations.

  11. Acousto-spinodal decomposition of compressible polymer solutions: early stage analysis.

    PubMed

    Rasouli, Ghoncheh; Rey, Alejandro D

    2011-05-14

    The structure and dynamics of early stage kinetics of pressure-induced phase separation of compressible polymer solutions via spinodal decomposition is analyzed using a linear Euler-Cahn-Hilliard model and the modified Sanchez Lacombe equation of state. The integrated density wave and Cahn-Hilliard equations combine the kinetic and structural characteristics of spinodal decomposition with density waves arising from pressure-induced couplings. When mass transfer rate is slower that acoustic waves, concentration gradients generate density waves that cycle back into the spinodal decomposition dynamics, resulting in oscillatory demixing. The wave attenuation increases with increasing mass transfer rates eventually leading to nonoscillatory spinodal demixing. The novel aspects of acousto-spinodal decomposition arise from the coexistence of stable oscillatory density dynamics and the unstable monotonic concentration dynamics. Scaling laws for structure and dynamics indicate deviations from incompressible behavior, with a significant slowing down of demixing due to couplings with density waves. Partial structure factors for density and density-concentration reflect the oscillatory nature of acousto-spinodal modes at lower wave vectors, while the single maximum at a constant wave vector reflects the presence of a dominant mode in the linear regime. The computed total structure factor is in qualitative agreement with experimental data for a similar polymer solution. PMID:21568529

  12. Direct measurement of depletion and hydrodynamic forces in solutions of a reversible supramolecular polymer.

    PubMed

    Knoben, W; Besseling, N A M; Stuart, M A Cohen

    2007-05-22

    In this paper, the investigation of surface forces in semidilute solutions of a nonadsorbing hydrogen-bonded reversible supramolecular polymer is described. Colloidal probe atomic force microscopy was used for direct measurement of depletion forces. Hydrodynamic drag on the AFM cantilever with the colloidal probe was measured both far away from and close to the planar substrate surface. The results indicate that the presence of the depletion layer causes slip at the surfaces with a large apparent slip length. Our analysis explains how the presence of slip enables the measurement of (relatively weak) depletion forces in solutions with a high viscosity by significantly reducing the hydrodynamic forces. The range and magnitude of the measured depletion forces are qualitatively in agreement with previous experiments and theoretical predictions. Due to the relatively large experimental error, no quantitative conclusions can be drawn. Depletion-induced phase separation of suspensions of stearylated silica particles was also observed. Phase separation becomes more pronounced with increasing polymer concentration. PMID:17439251

  13. On the Role of Specific Interactions in the Diffusion of Nanoparticles in Aqueous Polymer Solutions

    PubMed Central

    2013-01-01

    Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(N-vinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions. PMID:24354390

  14. Equilibrium sampling of self-associating polymer solutions: A parallel selective tempering methodology

    NASA Astrophysics Data System (ADS)

    Ayyagari, Chakravarthy

    2005-11-01

    A novel simulation algorithm based on tempering a fraction of relaxation-limiting interactions to accelerate the process of obtaining uncorrelated equilibrium configurations of self-associating polymer solutions has been presented. This approach consists of tempering (turning off) the attractive interactions for a fraction of self-associating groups determined by a biasing field h. A number of independent configurations (replicas) with overlapping Hamiltonian distributions in the expanded (NVTh) ensemble with constant NVT but different biasing fields, forming a chain of Hamiltonians, were simulated in parallel with occasional attempts to exchange the replicas associated with adjacent fields. Each field had an associated distribution of tempered interactions, average fraction of tempered interactions and structural decorrelation time. Tempering parameters (number of replicas, fields and exchange frequencies) were chosen to obtain the highest efficiency in sampling equilibrium configurations of a self-association polymer solution based on short serial simulation runs and a statistical model. Depending on the strength of the relaxation limiting interactions, system size and thermodynamic conditions, the algorithm can be orders of magnitude more efficient than conventional canonical simulation and is superior to conventional temperature parallel tempering.

  15. A stable solution-processed polymer semiconductor with record high-mobility for printed transistors

    PubMed Central

    Li, Jun; Zhao, Yan; Tan, Huei Shuan; Guo, Yunlong; Di, Chong-An; Yu, Gui; Liu, Yunqi; Lin, Ming; Lim, Suo Hon; Zhou, Yuhua; Su, Haibin; Ong, Beng S.

    2012-01-01

    Microelectronic circuits/arrays produced via high-speed printing instead of traditional photolithographic processes offer an appealing approach to creating the long-sought after, low-cost, large-area flexible electronics. Foremost among critical enablers to propel this paradigm shift in manufacturing is a stable, solution-processable, high-performance semiconductor for printing functionally capable thin-film transistors — fundamental building blocks of microelectronics. We report herein the processing and optimisation of solution-processable polymer semiconductors for thin-film transistors, demonstrating very high field-effect mobility, high on/off ratio, and excellent shelf-life and operating stabilities under ambient conditions. Exceptionally high-gain inverters and functional ring oscillator devices on flexible substrates have been demonstrated. This optimised polymer semiconductor represents a significant progress in semiconductor development, dispelling prevalent skepticism surrounding practical usability of organic semiconductors for high-performance microelectronic devices, opening up application opportunities hitherto functionally or economically inaccessible with silicon technologies, and providing an excellent structural framework for fundamental studies of charge transport in organic systems. PMID:23082244

  16. Visualization of TCE recovery mechanisms using surfactant-polymer solutions in a two-dimensional heterogeneous sand model.

    PubMed

    Robert, Thomas; Martel, Richard; Conrad, Stephen H; Lefebvre, René; Gabriel, Uta

    2006-06-30

    This research focused on the optimization of TCE dissolution in a physical two-dimensional model providing a realistic representation of a heterogeneous granular aquifer. TCE was infiltrated in the sand pack where it resided both in pools and in zones of residual saturation. Surfactant was initially injected at low concentration to minimize TCE remobilization at first contact but was incrementally increased later during the experiment. Xanthan gum was added to the injected surfactant solution to optimize the sweep efficiency through the heterogeneous medium. Photographs and digital image analysis illustrated the interactions between TCE and the injected fluids. During the polymer flood, the effects of heterogeneities inside the sand pack were greatly reduced by the increased fluid viscosity and the shear-thinning effects of the polymer. The polymer also improved the contact between the TCE ganglia and the surfactant-polymer solution, thereby promoting dissolution. Surfactants interacted with the polymer reducing the overall viscosity of the solution. At first contact with a 0.5%(mass) surfactant solution, the TCE pools drained and some remobilization occurred. However, no TCE bank was formed and TCE did not penetrate into any previously uncontaminated areas. As a result, TCE surface area was increased. Subsequent surfactant floods at higher surfactant concentrations did not trigger more remobilization. TCE was mainly dissolved by the solution with the highest surfactant concentration. Plugging from bacterial growth or microgel formation associated to the polymer at the inflow screen prevented the full completion of the experiment. However, more than 90% of TCE was recovered with the circulation of less than 6 pore volumes of surfactant-polymer solution. PMID:16624443

  17. Solution preparation of the amorphous molybdenum oxysulfide MoOS{sub 2} and its use for catalysis

    SciTech Connect

    Genuit, Daisy; Bezverkhyy, Igor; Afanasiev, Pavel . E-mail: afanas@catalyse.univ-lyon1.fr

    2005-09-15

    Acid condensation of aqueous MoO{sub 2}S{sub 2} {sup 2-} anion yields amorphous MoOS{sub 2} oxysulfide. This compound possesses tubular morphology and when freshly precipitated is soluble in polar organics such as acetone and ethanol. The ensemble of characterizations (IR, UV-visible, EXAFS spectroscopy) suggests that it contains cyclic or short linear oligomers of neutral molybdenum (V) oxysulfide MoOS{sub 2} core. Thermal decomposition of MoOS{sub 2} under inert atmosphere leads to the formation of a mixture of MoO{sub 2} and MoS{sub 2} phases. Promotion of MoOS{sub 2} with cobalt followed by sulfidation leads to highly active HDS catalysts.

  18. Free-standing, single-monomer-thick two-dimensional polymers through covalent self-assembly in solution.

    PubMed

    Baek, Kangkyun; Yun, Gyeongwon; Kim, Youngkook; Kim, Dongwoo; Hota, Raghunandan; Hwang, Ilha; Xu, Dan; Ko, Young Ho; Gu, Gil Ho; Suh, Ju Hyung; Park, Chan Gyung; Sung, Bong June; Kim, Kimoon

    2013-05-01

    The design and synthesis of two-dimensional (2D) polymers is a challenging task, hitherto achieved in solution only through the aid of a solid surface "template" or preorganization of the building blocks in a 2D confined space. We present a novel approach for synthesizing free-standing, covalently bonded, single-monomer-thick 2D polymers in solution without any preorganization of building blocks on solid surfaces or interfaces by employing shape-directed covalent self-assembly of rigid, disk-shaped building blocks having laterally predisposed reactive groups on their periphery. We demonstrate our strategy through a thiol-ene "click" reaction between (allyloxy)12CB[6], a cucurbit[6]uril (CB[6]) derivative with 12 laterally predisposed reactive alkene groups, and 1,2-ethanedithiol to synthesize a robust and readily transferable 2D polymer. We can take advantage of the high binding affinity of fully protonated spermine (positive charges on both ends) to CB[6] to keep each individual polymer sheet separated from one another by electrostatic repulsion during synthesis, obtaining, for the first-time ever, a single-monomer-thick 2D polymer in solution. The arrangement of CB[6] repeating units in the resulting 2D polymer has been characterized using gold nanoparticle labeling and scanning transmission electron microscopy. Furthermore, we have confirmed the generality of our synthetic approach by applying it to different monomers to generate 2D polymers. Novel 2D polymers, such as our CB[6] derived polymer, may be useful in selective transport, controlled drug delivery, and chemical sensing and may even serve as well-defined 2D scaffolds for ordered functionalization and platforms for bottom-up 3D construction.

  19. Amorphous Silk Fibroin Membranes for Separation of CO2

    NASA Technical Reports Server (NTRS)

    Aberg, Christopher M.; Patel, Anand K.; Gil, Eun Seok; Spontak, Richard J.; Hagg, May-Britt

    2009-01-01

    Amorphous silk fibroin has shown promise as a polymeric material derivable from natural sources for making membranes for use in removing CO2 from mixed-gas streams. For most applications of silk fibroin, for purposes other than gas separation, this material is used in its highly crystalline, nearly natural form because this form has uncommonly high tensile strength. However, the crystalline phase of silk fibroin is impermeable, making it necessary to convert the material to amorphous form to obtain the high permeability needed for gas separation. Accordingly, one aspect of the present development is a process for generating amorphous silk fibroin by treating native silk fibroin in an aqueous methanol/salt solution. The resulting material remains self-standing and can be prepared as thin film suitable for permeation testing. The permeability of this material by pure CO2 has been found to be highly improved, and its mixed-gas permeability has been found to exceed the mixed-gas permeabilities of several ultrahigh-CO2-permeable synthetic polymers. Only one of the synthetic polymers poly(trimethylsilylpropyne) [PTMSP] may be more highly permeable by CO2. PTMSP becomes unstable with time, whereas amorphous silk should not, although at the time of this reporting this has not been conclusively proven.

  20. Inclusion of mPRISM potential for polymer-induced protein interactions enables modeling of second osmotic virial coefficients in aqueous polymer-salt solutions.

    PubMed

    Herhut, Marcel; Brandenbusch, Christoph; Sadowski, Gabriele

    2016-01-01

    The downstream processing of therapeutic proteins is a challenging task. Key information needed to estimate applicable workup strategies (e.g. crystallization) are the interactions of the proteins with other components in solution. This information can be deduced from the second osmotic virial coefficient B22 , measurable by static light scattering. Thermodynamic models are very valuable for predicting B22 data for different process conditions and thus decrease the experimental effort. Available B22 models consider aqueous salt solutions but fail for the prediction of B22 if an additional polymer is present in solution. This is due to the fact that depending on the polymer concentration protein-protein interactions are not rectified as assumed within these models. In this work, we developed an extension of the xDLVO model to predict B22 data of proteins in aqueous polymer-salt solutions. To show the broad applicability of the model, lysozyme, γ-globulin and D-xylose ketol isomerase in aqueous salt solution containing polyethylene glycol were considered. For all proteins considered, the modified xDLVO model was able to predict the experimentally observed non-monotonical course in B22 data with high accuracy. When used in an early stage in process development, the model will contribute to an efficient and cost effective downstream processing development.

  1. Mechanisms behind injecting the combination of nano-clay particles and polymer solution for enhanced oil recovery

    NASA Astrophysics Data System (ADS)

    Khalili Nezhad, Seyyed Shahram; Cheraghian, Goshtasp

    2016-08-01

    Laboratory investigations and field applications have proved injection of polymer solution to be an effective means to improve oil recovery for reservoirs of medium oil viscosity. The incremental oil produced in this case is the result of an increase in areal and vertical sweep efficiencies. Biopolymers and synthetic polymers are the major categories used in the petroleum industry for specific reasons. Biopolymers like xanthan are limited in their application as they are more susceptible to biodegradation. Synthetic polymers like Hydrolyzed PolyAcrylaMide (HPAM) have a much wider application as they are less susceptible to biodegradation. Furthermore, development of nanotechnology has successfully provided technical and economical viable alternatives for present materials. The objective of this study is to investigate the effect of combining clay nanoparticles with polymer solution on oil recovery. This paper includes a history match of both one-dimensional and two-dimensional polymer floods using a three-dimensional numerical model for fluid flow and mass transport. Results indicated that the amount of polymer adsorption decreased when clay nanoparticles were added to the PolyAcrylaMide solution; however, mobility ratio improvement is believed to be the main contributor for the proposed method in order to enhance much oil recovery compared to xanthan flood and HPAM flood.

  2. Data on energy-band-gap characteristics of composite nanoparticles obtained by modification of the amorphous potassium polytitanate in aqueous solutions of transition metal salts

    PubMed Central

    Zimnyakov, D.A.; Sevrugin, A.V.; Yuvchenko, S.A.; Fedorov, F.S.; Tretyachenko, E.V.; Vikulova, M.A.; Kovaleva, D.S.; Krugova, E.Y.; Gorokhovsky, A.V.

    2016-01-01

    Here we present the data on the energy-band-gap characteristics of composite nanoparticles produced by modification of the amorphous potassium polytitanate in aqueous solutions of different transition metal salts. Band gap characteristics are investigated using diffuse reflection spectra of the obtained powders. Calculated logarithmic derivative quantity of the Kubelka–Munk function reveals a presence of local maxima in the regions 0.5–1.5 eV and 1.6–3.0 eV which correspond to band gap values of the investigated materials. The values might be related to the constituents of the composite nanoparticles and intermediate products of their chemical interaction. PMID:27158654

  3. Method of making amorphous metal composites

    DOEpatents

    Byrne, Martin A.; Lupinski, John H.

    1982-01-01

    The process comprises placing an amorphous metal in particulate form and a low molecular weight (e.g., 1000-5000) thermosetting polymer binder powder into a container, mixing these materials, and applying heat and pressure to convert the mixture into an amorphous metal composite.

  4. Sorption properties of an amorphous hydroxo titanate towards Pb(2+), Ni(2+), and Cu(2+) ions in aqueous solution.

    PubMed

    Volpe, Angela; Pagano, Michele; Pastore, Carlo; Cuocci, Corrado; Milella, Antonella

    2016-11-01

    Titanates may be selectively used as inorganic adsorbents for heavy metal ions owing to their stability and fast adsorption kinetics. Nevertheless, the synthesis of such materials usually requires extreme reaction conditions. In this work, a new titanium-based material was rapidly synthesized under mild laboratory conditions. The obtained amorphous hydroxo titanate was tested for heavy metal sorption through kinetic and equilibrium batch tests, which indicated that the new material had high adsorption rates and adsorption capacities towards Cu(2+), Ni(2+) and Pb(2) ions. Adsorption kinetics were pseudo-second order, and equilibrium data fitted the Langmuir isotherm model. The calculated maximum adsorption capacities of Cu(2+), Ni(2+) and Pb(2+) in deionized water were around 1 mmol g(-1), and they decreased for Cu(2+) and Ni(2+) in the presence of Na(+), Ca(2+) and Mg(2+) ions, whereas the alkali metal ions did not influence Pb(2+) uptake. The efficiency of adsorption and recovery of lead ions were evaluated through column dynamic tests, by feeding the column with groundwater and tap water spiked with Pb(2+). The high performance of the hydroxo titanate over several cycles of retention and elution suggested that the product is potentially useful for the solid phase extraction of lead at trace levels in natural water samples, with potential use in metal pre-concentration for analytical applications. PMID:27419851

  5. Highly uniform resistive switching properties of amorphous InGaZnO thin films prepared by a low temperature photochemical solution deposition method.

    PubMed

    Hu, Wei; Zou, Lilan; Chen, Xinman; Qin, Ni; Li, Shuwei; Bao, Dinghua

    2014-04-01

    We report on highly uniform resistive switching properties of amorphous InGaZnO (a-IGZO) thin films. The thin films were fabricated by a low temperature photochemical solution deposition method, a simple process combining chemical solution deposition and ultraviolet (UV) irradiation treatment. The a-IGZO based resistive switching devices exhibit long retention, good endurance, uniform switching voltages, and stable distribution of low and high resistance states. Electrical conduction mechanisms were also discussed on the basis of the current-voltage characteristics and their temperature dependence. The excellent resistive switching properties can be attributed to the reduction of organic- and hydrogen-based elements and the formation of enhanced metal-oxide bonding and metal-hydroxide bonding networks by hydrogen bonding due to UV irradiation, based on Fourier-transform-infrared spectroscopy, X-ray photoelectron spectroscopy, and Field emission scanning electron microscopy analysis of the thin films. This study suggests that a-IGZO thin films have potential applications in resistive random access memory and the low temperature photochemical solution deposition method can find the opportunity for further achieving system on panel applications if the a-IGZO resistive switching cells were integrated with a-IGZO thin film transistors.

  6. Generation of multicomponent polymer blend microparticles using droplet evaporation technique and modeling evaporation of binary droplet containing nonvolatile solute

    NASA Astrophysics Data System (ADS)

    Rajagopalan, Venkat Narayan

    Recently, considerable attention has been focused on the generation of nano- and micrometer scale multicomponent polymer particles with specifically tailored mechanical, electrical and optical properties. As only a few polymer-polymer pairs are miscible, the set of multicomponent polymer systems achievable by conventional methods, such as melt blending, is severely limited in property ranges. Therefore, researchers have been evaluating synthesis methods that can arbitrarily blend immiscible solvent pairs, thus expanding the range of properties that are practical. The generation of blended microparticles by evaporating a co-solvent from aerosol droplets containing two dissolved immiscible polymers in solution seems likely to exhibit a high degree of phase uniformity. A second important advantage of this technique is the formation of nano- and microscale particulates with very low impurities, which are not attainable through conventional solution techniques. When the timescale of solvent evaporation is lower than that of polymer diffusion and self-organization, phase separation is inhibited within the atto- to femto-liter volume of the droplet, and homogeneous blends of immiscible polymers can be produced. We have studied multicomponent polymer particles generated from highly monodisperse micrordroplets that were produced using a Vibrating Orifice Aerosol Generator (VOAG). The particles are characterized for both external and internal morphology along with homogeneity of the blends. Ultra-thin slices of polymer particles were characterized by a Scanning Electron Microscope (SEM), and the degree of uniformity was examined using an Electron Dispersive X-ray Analysis (EDAX). To further establish the homogeneity of the polymer blend microparticles, differential scanning calorimeter was used to measure the glass transition temperature of the microparticles obtained. These results have its significance in the field of particulate encapsulation. Also, better control of the

  7. Mimicking Conjugated Polymer Thin Film Photophysics with a Well-Defined Triblock Copolymer in Solution

    SciTech Connect

    Brazard, Johanna; Ono, Robert J.; Bielawski, Christopher W.; Barbara, Paul F.; Vanden Bout, David A.

    2013-04-25

    Conjugated polymers (CPs) are promising materials for use in electronic applications, such as low-cost, easily processed organic photovoltaic (OPV) devices. Improving OPV efficiencies is hindered by a lack of a fundamental understanding of the photophysics in CP-based thin films that is complicated by their heterogeneous nanoscale morphologies. Here, we report on a poly(3-hexylthiophene)-block-poly(tert-butyl acrylate)-block-poly(3-hexylthiophene) rod–coil–rod triblock copolymer. In good solvents, this polymer resembles solutions of P3HT; however, upon the addition of a poor solvent, the two P3HT chains within the triblock copolymer collapse, affording a material with electronic spectra identical to those of a thin film of P3HT. Using this new system as a model for thin films of P3HT, we can attribute the low fluorescence quantum yield of films to the presence of a charge-transfer state, providing fundamental insights into the condensed phase photophysics that will help to guide the development of the next generation of materials for OPVs.

  8. [Removal of bisphenol A in aqueous solutions by core-shell magnetic molecularly imprinted polymers].

    PubMed

    Liu, Jian-Ming; Li, Hong-Hong; Xiong, Zhen-Hu

    2013-06-01

    This paper reports the preparation of surface-imprinted polymer core-shell magnetic material as adsorbent for separating bisphenol A in the environmental water. The adsorbent prepared easily achieved the magnetic separation under an external magnetic field. The structures of the resulting composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) analysis. The adsorption selectivity of Fe3O4@SiO2-MIPs for bisphenol A was demonstrated by equilibrium rebinding experiments and Scatchard analysis. Freundlich adsorption model can well describe the adsorption isothermals of bisphenol A with the correlation coefficients R2 = 0.995 2. The dynamics of bisphenol A adsorbed by Fe3O4@SiO2-MIPs can be well described by the pseudo second-order model (R2 = 0.999 9). In the solutions with weak acidity, the Fe3O4@SiO2-MIPs showed higher removal rate and rapid adsorption dynamical process, requiring only 40 min to reach a removal rate of 90%; the presence of ions did not affect the adsorption rate of bisphenol A; when compared with the non-imprinted polymer (Fe3O4@SiO2-NIPs), the Fe3O4@SiO2-MIPs showed outstanding affinity toward bisphenol A; the performance of the resulting composites (Fe3O4@SiO2-MIPs) without obvious deterioration was demonstrated in seven repeated cycles.

  9. Size-exclusion partitioning of neutral solutes in crosslinked polymer networks: a Monte Carlo simulation study.

    PubMed

    Quesada-Pérez, Manuel; Adroher-Benítez, Irene; Maroto-Centeno, José Alberto

    2014-05-28

    In this work, the size-exclusion partitioning of neutral solutes in crosslinked polymer networks has been studied through Monte Carlo simulations. Two models that provide user-friendly expressions to predict the partition coefficient have been tested over a wide range of volume fractions: Ogston's model (especially devised for fibrous media) and the pore model. The effects of crosslinking and bond stiffness have also been analyzed. Our results suggest that the fiber model can acceptably account for size-exclusion effects in crosslinked gels. Its predictions are good for large solutes if the fiber diameter is assumed to be the effective monomer diameter. For solutes sizes comparable to the monomer dimensions, a smaller fiber diameter must be used. Regarding the pore model, the partition coefficient is poorly predicted when the pore diameter is estimated as the distance between adjacent crosslinker molecules. On the other hand, our results prove that the pore sizes obtained from the pore model by fitting partitioning data of swollen gels are overestimated. PMID:24880328

  10. Solution processable organic polymers and small molecules for bulk-heterojunction solar cells: A review

    SciTech Connect

    Sharma, G. D.

    2011-10-20

    Solution processed bulk heterojunction (BHJ) organic solar cells (OSCs) have gained wide interest in past few years and are established as one of the leading next generation photovoltaic technologies for low cost power production. Power conversion efficiencies up to 6% and 6.5% have been reported in the literature for single layer and tandem solar cells, respectively using conjugated polymers. A recent record efficiency about 8.13% with active area of 1.13 cm{sup 2} has been reported. However Solution processable small molecules have been widely applied for photovoltaic (PV) devices in recent years because they show strong absorption properties, and they can be easily purified and deposited onto flexible substrates at low cost. Introducing different donor and acceptor groups to construct donor--acceptor (D--A) structure small molecules has proved to be an efficient way to improve the properties of organic solar cells (OSCs). The power conversion efficiency about 4.4 % has been reported for OSCs based on the small molecules. This review deals with the recent progress of solution processable D--A structure small molecules and discusses the key factors affecting the properties of OSCs based on D--A structure small molecules: sunlight absorption, charge transport and the energy level of the molecules.

  11. Size-exclusion partitioning of neutral solutes in crosslinked polymer networks: A Monte Carlo simulation study

    SciTech Connect

    Quesada-Pérez, Manuel; Maroto-Centeno, José Alberto; Adroher-Benítez, Irene

    2014-05-28

    In this work, the size-exclusion partitioning of neutral solutes in crosslinked polymer networks has been studied through Monte Carlo simulations. Two models that provide user-friendly expressions to predict the partition coefficient have been tested over a wide range of volume fractions: Ogston's model (especially devised for fibrous media) and the pore model. The effects of crosslinking and bond stiffness have also been analyzed. Our results suggest that the fiber model can acceptably account for size-exclusion effects in crosslinked gels. Its predictions are good for large solutes if the fiber diameter is assumed to be the effective monomer diameter. For solutes sizes comparable to the monomer dimensions, a smaller fiber diameter must be used. Regarding the pore model, the partition coefficient is poorly predicted when the pore diameter is estimated as the distance between adjacent crosslinker molecules. On the other hand, our results prove that the pore sizes obtained from the pore model by fitting partitioning data of swollen gels are overestimated.

  12. Size-exclusion partitioning of neutral solutes in crosslinked polymer networks: a Monte Carlo simulation study.

    PubMed

    Quesada-Pérez, Manuel; Adroher-Benítez, Irene; Maroto-Centeno, José Alberto

    2014-05-28

    In this work, the size-exclusion partitioning of neutral solutes in crosslinked polymer networks has been studied through Monte Carlo simulations. Two models that provide user-friendly expressions to predict the partition coefficient have been tested over a wide range of volume fractions: Ogston's model (especially devised for fibrous media) and the pore model. The effects of crosslinking and bond stiffness have also been analyzed. Our results suggest that the fiber model can acceptably account for size-exclusion effects in crosslinked gels. Its predictions are good for large solutes if the fiber diameter is assumed to be the effective monomer diameter. For solutes sizes comparable to the monomer dimensions, a smaller fiber diameter must be used. Regarding the pore model, the partition coefficient is poorly predicted when the pore diameter is estimated as the distance between adjacent crosslinker molecules. On the other hand, our results prove that the pore sizes obtained from the pore model by fitting partitioning data of swollen gels are overestimated.

  13. Electrophoretic mobility of linear and star-branched DNA in semidilute polymer solutions.

    PubMed

    Saha, Sourav; Heuer, Daniel M; Archer, Lynden A

    2006-08-01

    Electrophoresis of large linear T2 (162 kbp) and 3-arm star-branched (N(Arm) = 48.5 kbp) DNA in linear polyacrylamide (LPA) solutions above the overlap concentration c* has been investigated using a fluorescence visualization technique that allows both the conformation and mobility mu of the DNA to be determined. LPA solutions of moderate polydispersity index (PI approximately 1.7-2.1) and variable polymer molecular weight Mw (0.59-2.05 MDa) are used as the sieving media. In unentangled semidilute solutions (c* < c < c(e)), we find that the conformational dynamics of linear and star-branched DNA in electric fields are strikingly different; the former migrating in predominantly U- or I-shaped conformations, depending on electric field strength E, and the latter migrating in a squid-like profile with the star-arms outstretched in the direction opposite to E and dragging the branch point through the sieving medium. Despite these visual differences, mu for linear and star-branched DNA of comparable size are found to be nearly identical in semidilute, unentangled LPA solutions. For LPA concentrations above the entanglement threshold (c > c(e)), the conformation of migrating linear and star-shaped DNA manifest only subtle changes from their unentangled solution features, but mu for the stars decreases strongly with increasing LPA concentration and molecular weight, while mu for linear DNA becomes nearly independent of c and Mw. These findings are discussed in the context of current theories for electrophoresis of large polyelectrolytes. PMID:16850503

  14. Electrophoretic mobility of linear and star-branched DNA in semidilute polymer solutions.

    PubMed

    Saha, Sourav; Heuer, Daniel M; Archer, Lynden A

    2006-08-01

    Electrophoresis of large linear T2 (162 kbp) and 3-arm star-branched (N(Arm) = 48.5 kbp) DNA in linear polyacrylamide (LPA) solutions above the overlap concentration c* has been investigated using a fluorescence visualization technique that allows both the conformation and mobility mu of the DNA to be determined. LPA solutions of moderate polydispersity index (PI approximately 1.7-2.1) and variable polymer molecular weight Mw (0.59-2.05 MDa) are used as the sieving media. In unentangled semidilute solutions (c* < c < c(e)), we find that the conformational dynamics of linear and star-branched DNA in electric fields are strikingly different; the former migrating in predominantly U- or I-shaped conformations, depending on electric field strength E, and the latter migrating in a squid-like profile with the star-arms outstretched in the direction opposite to E and dragging the branch point through the sieving medium. Despite these visual differences, mu for linear and star-branched DNA of comparable size are found to be nearly identical in semidilute, unentangled LPA solutions. For LPA concentrations above the entanglement threshold (c > c(e)), the conformation of migrating linear and star-shaped DNA manifest only subtle changes from their unentangled solution features, but mu for the stars decreases strongly with increasing LPA concentration and molecular weight, while mu for linear DNA becomes nearly independent of c and Mw. These findings are discussed in the context of current theories for electrophoresis of large polyelectrolytes.

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

    PubMed

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

    2016-02-01

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

  16. Dynamical properties of semidilute solutions of hydrogen-bonded supramolecular polymers

    NASA Astrophysics Data System (ADS)

    Buhler, Eric; Candau, Sauveur-Jean; Kolomiets, Elena; Lehn, Jean-Marie

    2007-12-01

    The dynamical properties of semidilute solutions of supramolecular polymers formed from molecular recognition directed association between monomers bearing complementary hydrogen bonding groups were investigated by rheological and dynamic light scattering experiments. The steady-state flow curves showed a shear banding type instability, namely the occurrence of a stress plateau σp above a critical shear rate γ˙c . The values of σp and γ˙c were found to be of the same order of magnitude as those of the elastic plateau modulus and the inverse stress relaxation time, respectively. The above features are in agreement with the theoretical predictions based on the reptation model. Dynamic light scattering experiments showed the presence in the autocorrelation function of the concentration fluctuations of a slow viscoelastic relaxation process that is likely to be of Rouse type.

  17. Investigating the particle to fibre transition threshold during electrohydrodynamic atomization of a polymer solution.

    PubMed

    Husain, O; Lau, W; Edirisinghe, M; Parhizkar, M

    2016-08-01

    Electrohydrodynamic atomization (EHDA) is a key research area for producing micro and nano-sized structures. This process can be categorized into two main operating regimes: electrospraying for particle generation and electrospinning for fibre production. Producing particles/fibres of the desired size or morphology depends on two main factors; properties of the polymeric solution used and the processing conditions including flow rate, applied voltage and collection distance. In this work the particle-fibre transition region was analyzed by changing the polymer concentration of PLGA poly (lactic-co-glycolic acid) in acetone between 2 and 25wt%. Subsequently the processing conditions were adjusted to study the optimum transition parameters. Additionally the EHDA configuration was also modified by adding a metallic plate to observe the deposition area. The diameter and the distance of the plate from the capillary tip were adjusted to investigate variations in particle and fibre morphologies as well. It was found that complete transition from particles to fibres occurs at 20wt% indicating concentration to be the dominant criterion. Low flow rates yielded fibres without beads. However the applied voltage and distance between the tip of the nozzle jetting the polymer solution and collector (working distance) did not yield definitive results. Reducing the collector distance and increasing applied voltages produces smooth as well as beaded fibres. Addition of a metal plate reduces particle size by ~1μm; the fibre size increases especially with increasing plate diameter while bead density and size reduces when the disc is fixed closer to the capillary tip. Additionally, the deposition area is reduced by 70% and 57% with the addition of metal plates of 30mm and 60mm, respectively. The results indicate that a metal plate can be utilized further to tune the particle/fibre size and morphology and this also significantly increases the yield of EHDA process which is currently a

  18. Threshold-like complexation of conjugated polymers with small molecule acceptors in solution within the neighbor-effect model.

    PubMed

    Sosorev, Andrey Yu; Parashchuk, Olga D; Zapunidi, Sergey A; Kashtanov, Grigoriy S; Golovnin, Ilya V; Kommanaboyina, Srikanth; Perepichka, Igor F; Paraschuk, Dmitry Yu

    2016-02-14

    In some donor-acceptor blends based on conjugated polymers, a pronounced charge-transfer complex (CTC) forms in the electronic ground state. In contrast to small-molecule donor-acceptor blends, the CTC concentration in polymer:acceptor solution can increase with the acceptor content in a threshold-like way. This threshold-like behavior was earlier attributed to the neighbor effect (NE) in the polymer complexation, i.e., next CTCs are preferentially formed near the existing ones; however, the NE origin is unknown. To address the factors affecting the NE, we record the optical absorption data for blends of the most studied conjugated polymers, poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and poly(3-hexylthiophene) (P3HT), with electron acceptors of fluorene series, 1,8-dinitro-9,10-antraquinone (), and 7,7,8,8-tetracyanoquinodimethane () in different solvents, and then analyze the data within the NE model. We have found that the NE depends on the polymer and acceptor molecular skeletons and solvent, while it does not depend on the acceptor electron affinity and polymer concentration. We conclude that the NE operates within a single macromolecule and stems from planarization of the polymer chain involved in the CTC with an acceptor molecule; as a result, the probability of further complexation with the next acceptor molecules at the adjacent repeat units increases. The steric and electronic microscopic mechanisms of NE are discussed.

  19. Simple framework for understanding the universality of the maximum drag reduction asymptote in turbulent flow of polymer solutions.

    PubMed

    Li, Chang-Feng; Sureshkumar, Radhakrishna; Khomami, Bamin

    2015-10-01

    Self-consistent direct numerical simulations of turbulent channel flows of dilute polymer solutions exhibiting friction drag reduction (DR) show that an effective Deborah number defined as the ratio of polymer relaxation time to the time scale of fluctuations in the vorticity in the mean flow direction remains O(1) from the onset of DR to the maximum drag reduction (MDR) asymptote. However, the ratio of the convective time scale associated with streamwise vorticity fluctuations to the vortex rotation time decreases with increasing DR, and the maximum drag reduction asymptote is achieved when these two time scales become nearly equal. Based on these observations, a simple framework is proposed that adequately describes the influence of polymer additives on the extent of DR from the onset of DR to MDR as well as the universality of the MDR in wall-bounded turbulent flows with polymer additives. PMID:26565339

  20. Controlling the drying and film formation processes of polymer solution droplets with addition of small amount of surfactants.

    PubMed

    Kajiya, Tadashi; Kobayashi, Wataru; Okuzono, Tohru; Doi, Masao

    2009-11-26

    We studied how the addition of surfactants alters the drying and film formation processes of polymer solution droplets with contact lines strongly fixed by bank structures. We found that even if the amount of surfactant is quite small, it drastically changes the final profile of the polymer film from a ringlike profile to a flat profile. This property is observed commonly, irrespective of the polymer concentration, droplet volume, and type of solvent. We conjecture that the inhomogeneous distribution of the surfactant caused by the outward capillary flow induces the Marangoni flow directed toward the center of the droplet, which suppresses the outward flow. The present phenomenon implies an effective method for controlling the profile of the polymer film in inkjet printing technologies.

  1. Simple framework for understanding the universality of the maximum drag reduction asymptote in turbulent flow of polymer solutions.

    PubMed

    Li, Chang-Feng; Sureshkumar, Radhakrishna; Khomami, Bamin

    2015-10-01

    Self-consistent direct numerical simulations of turbulent channel flows of dilute polymer solutions exhibiting friction drag reduction (DR) show that an effective Deborah number defined as the ratio of polymer relaxation time to the time scale of fluctuations in the vorticity in the mean flow direction remains O(1) from the onset of DR to the maximum drag reduction (MDR) asymptote. However, the ratio of the convective time scale associated with streamwise vorticity fluctuations to the vortex rotation time decreases with increasing DR, and the maximum drag reduction asymptote is achieved when these two time scales become nearly equal. Based on these observations, a simple framework is proposed that adequately describes the influence of polymer additives on the extent of DR from the onset of DR to MDR as well as the universality of the MDR in wall-bounded turbulent flows with polymer additives.

  2. The derivation and moments solution of approximate transport equations for the implantation of ions into amorphous targets

    NASA Astrophysics Data System (ADS)

    Ashworth, D. G.; Bowyer, M. D. J.; Oven, R.

    1995-06-01

    Commencing with the LSS integro-differential equation, an approximate transport equation is derived from which the moments of the range distribution may be obtained. The resulting equation set is known as the Kent Range ALgorithm (KRAL). The method for numerical solution of these equations, when written as a set of coupled second order ordinary differential equations (ODEs) of the initial value type, is then outlined. Solution is achieved by recasting the equation set in the form of first order ODEs designed for iterative solution. The technique used is an iterative refinement (or residual correction) procedure and the set of first order ODEs is called the Kent Optimised Range ALgorithm (KORAL). Finally, the first three moments from KORAL, first and second order PRAL codes and the full transport equation code KUBBIC-91 are compared with Monte Carlo data obtained from a TRIM code modified to treat targets of infinite extent. Comparisons are performed using consistent nuclear and electronic energy loss models.

  3. Chain Confinement in Electrospun Nanocomposites: using Thermal Analysis to Investigate Polymer-Filler Interactions

    SciTech Connect

    Q Ma; B Mao; P Cebe

    2011-12-31

    We investigate the interaction of the polymer matrix and filler in electrospun nanofibers using advanced thermal analysis methods. In particular, we study the ability of silicon dioxide nanoparticles to affect the phase structure of poly(ethylene terephthalate), PET. SiO{sub 2} nanoparticles (either unmodified or modified with silane) ranging from 0 to 2.0 wt% in PET were electrospun from hexafluoro-2-propanol solutions. The morphologies of both the electrospun (ES) nanofibers and the SiO{sub 2} powders were observed by scanning and transmission electron microscopy, while the amorphous or crystalline nature of the fibers was determined by real-time wide-angle X-ray scattering. The fractions of the crystal, mobile amorphous, and rigid amorphous phases of the non-woven, nanofibrous composite mats were quantified by using heat capacity measurements. The amount of the immobilized polymer layer, the rigid amorphous fraction, was obtained from the specific reversing heat capacity for both as-spun amorphous fibers and isothermally crystallized fibers. Existence of the rigid amorphous phase in the absence of crystallinity was verified in nanocomposite fibers, and two origins for confinement of the rigid amorphous fraction are proposed. Thermal analysis of electrospun fibers, including quasi-isothermal methods, provides new insights to quantitatively characterize the polymer matrix phase structure and thermal transitions, such as devitrification of the rigid amorphous fraction.

  4. Facile Routes To Improve Performance of Solution-Processed Amorphous Metal Oxide Thin Film Transistors by Water Vapor Annealing.

    PubMed

    Park, Won-Tae; Son, Inyoung; Park, Hyun-Woo; Chung, Kwun-Bum; Xu, Yong; Lee, Taegweon; Noh, Yong-Young

    2015-06-24

    Here, we report on a simple and high-rate oxidization method for producing solution-based compound mixtures of indium zinc oxide (IZO) and indium gallium zinc oxide (IGZO) metal-oxide semiconductors (MOS) for thin-film transistor (TFT) applications. One of the issues for solution-based MOS fabrication is how to sufficiently oxidize the precursor in order to achieve high performance. As the oxidation rate of solution processing is lower than vacuum-based deposition such as sputtering, devices using solution-processed MOS exhibit relatively poorer performance. Therefore, we propose a method to prepare the metal-oxide precursor upon exposure to saturated water vapor in a closed volume for increasing the oxidization efficiency without requiring additional oxidizing agent. We found that the hydroxide rate of the MOS film exposed to water vapor is lower than when unexposed (≤18%). Hence, we successfully fabricated oxide TFTs with high electron mobility (27.9 cm(2)/V·s) and established a rapid process (annealing at 400 °C for 5 min) that is much shorter than the conventional as-deposited long-duration annealing (at 400 °C for 1 h) whose corresponding mobility is even lower (19.2 cm(2)/V·s). PMID:26043206

  5. Piling-to-buckling transition in the drying process of polymer solution drop on substrate having a large contact angle

    NASA Astrophysics Data System (ADS)

    Kajiya, Tadashi; Nishitani, Eisuke; Yamaue, Tatsuya; Doi, Masao

    2006-01-01

    We studied the drying process of polymer solution drops placed on a substrate having a large contact angle with the drop. The drying process takes place in three stages. First, the droplet evaporates keeping the contact line fixed. Second, the droplet shrinks uniformly with receding contact line. Finally the contact line is pinned again, and the droplet starts to be deformed. The shape of the final polymer deposit changes from concave dot, to flat dot, and then to concave dot again with the increase of the initial polymer concentration. This shape change is caused by the gradual transition from the solute piling mechanism proposed by Deegan to the crust buckling mechanism proposed by de Gennes and Pauchard.

  6. Preparation of a unique microporous structure via two step phase separation in the course of drying a ternary polymer solution.

    PubMed

    Kim, Jae-Kyung; Taki, Kentaro; Ohshima, Masahiro

    2007-11-20

    A unique porous polymeric film was prepared by drying a ternary polymer solution: a polystyrene (PS), polyethylene glycol (PEG), and toluene solution. Highly ordered micropores, ranging from 5 to 12 mum in diameter, were formed on the film surface, and the rim of each micropore was surrounded by a ring of PEG. The effects of the weight ratio of the polymer blend and molecular weight of the polymer (PEG) on the porous structure were investigated. Based on in situ visual observation and light scattering measurements, the formation mechanism of the porous structure was speculated to be a two step phase separation: the phase separation into PEG-rich and PEG-poor (i.e., PS-rich) phases occurred first at the surface area of the ternary solutions, where polymers were condensed due to solvent evaporation. The PEG-rich phase became droplets and had an ordered structure on the surface. The PEG-poor phase became a matrix where PS and solvent coexisted as a single phase solution. Secondary phase separation then followed in the PEG droplets, which was induced by further solvent evaporation, and formed into solvent-rich and PEG-rich domains within the droplets. Solvent evaporation and secondary phase separation created a cavity structure in each PEG droplet structured on the film surface.

  7. Solution assembly behaviors of 3-hexylthiophene polymer based rod-coil graft copolymer

    NASA Astrophysics Data System (ADS)

    Kim, Youngkwon; Kim, Jin-Sung; Kim, Hyeong Jun; Kim, Bumjoon

    Solution assembly of conjugated polymer based block copolymers (BCPs) is an attractive approach for achieving conducting nanowires (NWs) with nanometer-scale cross-sectional dimensions. In particular, conjugated block offers one-dimensional self-growth of crystalline NWs, and secondary block gives rise to stable dispersion of NWs and additional tuning parameter for the structures of NWs. Herein, we developed a series of poly(3-hexylthiophene)-graft-poly(2-vinylpyridine) (P3HT-g-P2VP) rod-coil copolymers with systematically controlled crystallinity by modifying both grafting density and molecular weight (Mn) of coil block, and their solution assembly behaviors were carefully examined. As increasing the volume fraction and grafting density of the secondary blocks, melting temperatures, crystallization temperatures, and the crystallinity were gradually decreased by hindering rod-rod interaction between P3HT backbones, resulting in the formation of short NWs. Furthermore, the length of NMs was relatively shorter for the densely grafted copolymer despite same volume fraction of secondary block. These results suggested that controlling Mn and the number of branched coil block was critical to regulate the crystalline properties and new approach for determining the NWs growth.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  9. Influence of Processing Conditions and Material Properties on Electrohydrodynamic Direct Patterning of a Polymer Solution

    NASA Astrophysics Data System (ADS)

    Jang, Shin; Kim, Yeongjun; Oh, Je Hoon

    2016-04-01

    An electrohydrodynamic (EHD) patterning method was utilized to obtain high-resolution line patterns in a low electric field regime without an additional mechanical drawing process. Molecular weight and weight percent of a polymer were selected as key parameters to reduce the voltage. EHD patterning was performed using polyethylene oxide (PEO) solutions. The threshold voltages (V th) to initiate jet ejection are almost the same for all solutions. A method verified in this study, reducing the driving voltage (V d) just after the initiation of the jet at the threshold voltage, can make a very thin, continuous jet, while increasing molecular weight and weight percent were enabled to further reduce the input voltage. As the voltage reduction ratio (V d/ V th) is decreased, the jet behaves like a solid rather than a liquid due to its fast solidification. The line width of the resultant line pattern could be tuned from 50 nm to 10 μm depending on the substrate moving speed. Contour maps were also developed that show the pattern mode variation as a function of the voltage reduction ratio and key parameters. The results show that well-defined PEO line and grid patterns can be fabricated via the proposed EHD direct patterning under appropriate conditions.

  10. Electronic Structure of Low-Temperature Solution-Processed Amorphous Metal Oxide Semiconductors for Thin-Film Transistor Applications

    PubMed Central

    Socratous, Josephine; Banger, Kulbinder K; Vaynzof, Yana; Sadhanala, Aditya; Brown, Adam D; Sepe, Alessandro; Steiner, Ullrich; Sirringhaus, Henning

    2015-01-01

    The electronic structure of low temperature, solution-processed indium–zinc oxide thin-film transistors is complex and remains insufficiently understood. As commonly observed, high device performance with mobility >1 cm2 V−1 s−1 is achievable after annealing in air above typically 250 °C but performance decreases rapidly when annealing temperatures ≤200 °C are used. Here, the electronic structure of low temperature, solution-processed oxide thin films as a function of annealing temperature and environment using a combination of X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and photothermal deflection spectroscopy is investigated. The drop-off in performance at temperatures ≤200 °C to incomplete conversion of metal hydroxide species into the fully coordinated oxide is attributed. The effect of an additional vacuum annealing step, which is beneficial if performed for short times at low temperatures, but leads to catastrophic device failure if performed at too high temperatures or for too long is also investigated. Evidence is found that during vacuum annealing, the workfunction increases and a large concentration of sub-bandgap defect states (re)appears. These results demonstrate that good devices can only be achieved in low temperature, solution-processed oxides if a significant concentration of acceptor states below the conduction band minimum is compensated or passivated by shallow hydrogen and oxygen vacancy-induced donor levels. PMID:26190964

  11. Effect of divalent ions on electroosmotic transport in a sodium chloride aqueous solution confined in an amorphous silica nanochannel

    NASA Astrophysics Data System (ADS)

    Conlisk, A. T.; Zambrano, Harvey; Cevheri, Necmettin; Yoda, Minami; Computational Micro-; Nanofluidics Lab Team; The Fluids, Optical; Interfacial Diagnostics Lab Team

    2012-11-01

    A critical enabling technology for the next generation of nanoscale devices, such as nanoscale ``lab on a chip'' systems, is controlling electroosmotic flow (EOF) in nanochannels. In this work, we control EOF in an aqueous sodium chloride (NaCl) solution confined in a silica nanochannel by systematically adding different amounts of divalent ions. Multivalent ions have a different affinity for the silica surface and different hydration characteristics in comparison to monovalent ions. Therefore by adding Mg++ and Ca++ to the sodium chloride solution, the electroosmotic velocity and the structure of the electrical double layer will be modified. The effects of adding Mg++ and Ca++ will be compared using non-equilibrium molecular dynamics simulations of the EOF at different electric fields of a NaCl solution in a silica nanochannel with different fractions of Ca++ and Mg++ ions. In general, the wall zeta-potential magnitude, and hence the EOF velocity, decreases as the Ca++ or Mg++ concentration increases. The system responds linearly with electric field. We will compare the computational results with the experimental data of Cevheri and Yoda (2012). This work is supported by Army Research Office (ARO) grant number W911NF1010290.

  12. Separation and quantification of viral double-stranded RNA fragments by capillary electrophoresis in hydroxyethylcellulose polymer solutions.

    PubMed

    Shambaugh, C L; Bodmer, J L; Hsu, D; Ranucci, C S

    2004-10-01

    Capillary electrophoresis (CE) is an analytical technique widely utilized to resolve complex mixtures of nucleic acids. CE uses a variety of polymers in solution that act as a molecular sieve to separate nucleic acid fragments according to size. It has been shown previously that purified dsDNA can be resolved efficiently by solutions of hydroxyethylcellulose (HEC) polymer, providing a rapid and high resolution method of separation. We have applied this separation technique to viral double-stranded (ds) RNA segments derived from rotavirus process samples. HEC polymers of various molecular masses and concentrations were identified and compared for their ability to separate dsRNA based on the extent of expected polymer network formation. The HEC polymer exhibiting the most desirable separation characteristics was then used for subsequent optimization of various method parameters, such as, injection time, electric field strength, dye concentration and capillary equilibration. The optimized method was then applied to the quantification of genome concentration based on a representative segment of the rotavirus genome. This study demonstrated that purified viral dsRNA material of known concentration could be used to generate an external standard curve relating concentration to peak area. This standard curve was used to determine the concentration of unknown samples by interpolation. This novel RNA quantification assay is likely to be applicable to other types of virus, including those containing dsDNA.

  13. Electrostatic free energy of weakly charged macromolecules in solution and intermacromolecular complexes consisting of oppositely charged polymers.

    PubMed

    Biesheuvel, P Maarten; Cohen Stuart, Martien A

    2004-03-30

    When oppositely charged polyelectrolytes are mixed in water, attraction between oppositely charged groups may lead to the formation of polyelectrolyte complexes (associative phase separation, complex coacervation, interpolymer complexes). Theory is presented to describe the electrostatic free energy change when ionizable (annealed) (macro-)molecules form a macroscopic polyelectrolyte complex. The electrostatic free energy includes an electric term as well as a chemical term that is related to the dissociation of the ionic groups in the polymer. An example calculation for complexation of polyacid with polybase uses a cylindrical diffuse double layer model for free polymer in solution and electroneutrality within the complex and calculates the free energy of the system when the polymer is in solution or in a polyelectrolyte complex. Combined with a term for the nonelectrostatic free energy change upon complexation, a theoretical stability diagram is constructed that relates pH, salt concentration, and mixing ratio, which is in qualitative agreement with an experimental diagram obtained by Bungenberg de Jong (1949) for complex coacervation of arabic gum and gelatin. The theory furthermore explains the increased tendency toward phase separation when the polymer becomes more strongly charged and suggests that complexation of polyacid or polybase with zwitterionic polymer (e.g., protein) of the same charge sign (at the "wrong side" of the iso-electric point) may be due (in part) to an induced charge reversal of the protein.

  14. Characterization of amorphous silicon carbide and silicon carbonitride thin films synthesized by polymer-source chemical vapor deposition. Mechanical structural and metal-interface properties

    NASA Astrophysics Data System (ADS)

    Awad, Yousef

    Amorphous silicon carbide (a-SiC) and silicon carbonitride thin films have been deposited onto a variety of substrates by Polymer-Source Chemical Vapor Deposition (PS-CVD). The interfacial interaction between the a-SiC films and several substrates including silicon, SiO2, Si3N 4, Cr, Ti and refractory metal-coated silicon has been studied. The effect of thermal annealing on the structural and mechanical properties of the prepared films has been discussed in detail. The composition and bonding states are uniquely characterized with respect to the nitrogen atomic percentage introduced into the a-SiCN:H films. Capacitance-voltage (C-V) measurements were systematically used to evaluate the impurity level of the deposited a-SiC films. The chemical bonding of the films was systematically examined by means of Fourier transform infrared spectroscopy (FTIR). In addition, elastic recoil detection (ERD) and X-ray photoelectron spectroscopy (XPS) techniques were used to determine the elemental composition of the films and of their interface with substrates, while X-ray reflectivity measurements (XRR) were used to account for the film density. Spectral deconvolution was used to extract the individual components of the FTIR and XPS spectra. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were also employed to characterize the surface morphology of the films. In addition, their mechanical properties [(hardness (H) and Young's modulus (E)] were investigated by using the nanoindentation technique. The impurity levels of the a-SiC films were found to be clearly correlated with the nature of the underlying substrates. The Pt-Rh and TiN-coated Si substrates were shown to lead to the lowest impurity level (˜ 1x10 13 cm-3) in the PS-CVD grown a-SiC films, while Cr and Ti-coated Si substrates induced much higher impurity concentrations. Such high impurity levels were shown to be a consequence of a strong metallic diffusion of the metallic species (Cr or Ti). In

  15. Solution-processed low dimensional nanomaterials with self-assembled polymers for flexible photo-electronic devices (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Park, Cheolmin

    2015-09-01

    Self assembly driven by complicated but systematic hierarchical interactions offers a qualified alternative for fabricating functional micron or nanometer scale pattern structures that have been potentially useful for various organic and nanotechnological devices. Self assembled nanostructures generated from synthetic polymer systems such as controlled polymer blends, semi-crystalline polymers and block copolymers have gained a great attention not only because of the variety of nanostructures they can evolve but also because of the controllability of these structures by external stimuli. In this presentation, various novel photo-electronic materials and devices are introduced based on the solution-processed low dimensional nanomaterials such as networked carbon nanotubes (CNTs), reduced graphene oxides (rGOs) and 2 dimensional transition metal dichalcogenides (TMDs) with self assembled polymers including field effect transistor, electroluminescent device, non-volatile memory and photodetector. For instance, a nanocomposite of networked CNTs and a fluorescent polymer turned out an efficient field induced electroluminescent layer under alternating current (AC) as a potential candidate for next generation displays and lightings. Furthermore, scalable and simple strategies employed for fabricating rGO as well as TMD nanohybrid films allowed for high performance and mechanically flexible non-volatile resistive polymer memory devices and broad band photo-detectors, respectively.

  16. A simple experiment to determine the activation energy of the viscous flow of polymer solutions using a glass capillary viscometer

    NASA Astrophysics Data System (ADS)

    Rohindra, D. R.; Lata, R. A.; Coll, R. K.

    2012-09-01

    A simple viscometry experiment undertaken by an undergraduate polymer class as a research project is described. Viscosity is a measure of a fluid's resistance to flow and is affected by several factors, such as concentration and temperature. In this experiment, the viscosities of polyvinylpyrrolidone solutions (a polymeric material) of different concentrations were prepared in water and measured at various temperatures. The solution viscosity was found to increase gradually with increasing concentration up to ∼5 mass%, with a dramatic increase after this. The calculated viscosity of water at different temperatures was comparable to reported values. The activation energy of viscous flow (Ea) of the different solutions was calculated and followed a similar trend as that for the viscosities of solutions of various concentrations. This experiment allowed students to better understand and explain the behaviour of macromolecules with respect to changing concentration and temperature. Furthermore, students correlated the viscosity and Ea results to understand how an increase in the concentration of a polymer solution resulted in increased entanglement of the polymer chains, consequently leading to an increase in viscosity and an increase in the activation energy of viscous flow. This experiment is safe, low cost, simple and requires only readily available apparatus.

  17. Effect of plasticizer on surface of free films prepared from aqueous solutions of salts of cationic polymers with different plasticizers

    NASA Astrophysics Data System (ADS)

    Bajdik, János; Fehér, Máté; Pintye-Hódi, Klára

    2007-06-01

    Acquisition of a more detailed understanding of all technological processes is currently a relevant tendency in pharmaceutical technology and hence in industry. A knowledge of film formation from dispersion of polymers is very important during the coating of solid dosage forms. This process and the structure of the film can be influenced by different additives. In the present study, taste-masking films were prepared from aqueous citric acid solutions of a cationic polymer (Eudragit ® E PO) with various hydrophilic plasticizers (glycerol, propylene glycol and different poly(ethylene glycols)). The mechanical properties, film thickness, wetting properties and surface free energy of the free films were studied. The aim was to evaluate the properties of surface of free films to predict the arrangement of macromolecules in films formed from aqueous solutions of salts of cationic polymers. A high molecular weight of the plasticizer decreased the work of deformation. The surface free energy and the polarity were highest for the film without plasticizer; the hydrophilic additives decreased these parameters. The direction of the change in polarity (a hydrophilic component caused a decrease in the polarity) was unexpected. It can be explained by the change in orientation of the macromolecules, a hydrophobic surface being formed. Examination of the mechanical properties and film thickness can furnish additional results towards a knowledge of film formation by this not frequently applied type of polymer from aqueous solution.

  18. Determine the permeability of an amorphous mixture of polydimethylsiloxane and dealuminated zeolite ZSM-5 to various ethanol-water solutions using molecular simulations.

    EPA Science Inventory

    An amorphous mixture of PDMS and multi-cellular fragments of ZSM-5 is brought together to approximate the properties of a mixed matrix membrane of PDMS with ZSM-5. The permeability coefficient of the amorphous mixture for pure water is the product of the diffusion coefficient of...

  19. Miscibility of poly(lactic acid) and poly(ethylene oxide) solvent polymer blends and nanofibers made by solution blow spinning

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The miscibility of blends of poly(lactic acid) (PLA) and poly(ethylene oxide) (PEO) was studied in polymer solutions by dilute solution viscometry and in solution blow spun nanofibers by microscopy (SEM, TEM) and by thermal and spectral analysis. Three blends of PLA and PEO were solution blended in...

  20. Development of Novel Method for Rapid Extract of Radionuclides from Solution Using Polymer Ligand Film

    NASA Astrophysics Data System (ADS)

    Rim, Jung H.

    Accurate and fast determination of the activity of radionuclides in a sample is critical for nuclear forensics and emergency response. Radioanalytical techniques are well established for radionuclides measurement, however, they are slow and labor intensive, requiring extensive radiochemical separations and purification prior to analysis. With these limitations of current methods, there is great interest for a new technique to rapidly process samples. This dissertation describes a new analyte extraction medium called Polymer Ligand Film (PLF) developed to rapidly extract radionuclides. Polymer Ligand Film is a polymer medium with ligands incorporated in its matrix that selectively and rapidly extract analytes from a solution. The main focus of the new technique is to shorten and simplify the procedure necessary to chemically isolate radionuclides for determination by alpha spectrometry or beta counting. Five different ligands were tested for plutonium extraction: bis(2-ethylhexyl) methanediphosphonic acid (H2DEH[MDP]), di(2-ethyl hexyl) phosphoric acid (HDEHP), trialkyl methylammonium chloride (Aliquat-336), 4,4'(5')-di-t-butylcyclohexano 18-crown-6 (DtBuCH18C6), and 2-ethylhexyl 2-ethylhexylphosphonic acid (HEH[EHP]). The ligands that were effective for plutonium extraction further studied for uranium extraction. The plutonium recovery by PLFs has shown dependency on nitric acid concentration and ligand to total mass ratio. H2DEH[MDP] PLFs performed best with 1:10 and 1:20 ratio PLFs. 50.44% and 47.61% of plutonium were extracted on the surface of PLFs with 1M nitric acid for 1:10 and 1:20 PLF, respectively. HDEHP PLF provided the best combination of alpha spectroscopy resolution and plutonium recovery with 1:5 PLF when used with 0.1M nitric acid. The overall analyte recovery was lower than electrodeposited samples, which typically has recovery above 80%. However, PLF is designed to be a rapid field deployable screening technique and consistency is more important

  1. ``Living polymers'' in organic solvents : stress relaxation in bicopper tetracarboxylate/tert-butyl cyclohexane solutions

    NASA Astrophysics Data System (ADS)

    Terech, P.; Maldivi, P.; Dammer, C.

    1994-10-01

    Viscoelastic solutions of a bicopper tetracarboxylate complex in tert-butylcyclohexane have been studied by dynamic rheology in a wide range of concentrations (0.5-1.5 % volume fraction). The zero shear viscosity, the elastic modulus, the terminal stress relaxation time and the height of the high-frequency dip, in a Cole-Cole representation of the complex elastic modulus, follow scaling laws. The related exponents are discussed in the context of the physics of “living polymers” : a term used to describe worm-like species undergoing scission/recombination reactions competing mainly with the reptation motions of the chains. The current system, made up of molecular threads (17.5 Å diameter) of Cu2(O2C-CH(C2H5)C4H9)4 in the apolar solvent, is representative of a “living polymer” where, instead of mechanisms involving transient star polymeric crosslinks, a reversible scission mechanism prevails. The dynamics in the high-frequency range evolves from a regime where reptation is the dominant relaxation mechanism to a cross-over regime where “breathing” fluctuations and Rouse motions become important. Large modifications of the stress relaxation function occur for more concentrated systems. The binary system is the first example of a “living polymer” in an organic solvent and exhibits elastic moduli (G ≈ ca. 120 Pa à φ = 1 %) which are at least 20 times larger than those found for the aqueous “living polymer” systems. Les solutions viscoélastiques d'un tétracarboxylate binucléaire de cuivre dans le tert-butylcyclohexane sont étudiées par rhéologie en mode dynamique dans une gamme étendue de concentrations (0,5 %-15,5 %). La viscosité à gradient nul, le module élastique, le temps terminal de relaxation et la hauteur du puits à haute fréquence, dans une représentation Cole-Cole du module élastique complexe, suivent des lois d'échelles. Les exposants correspondants sont discutés dans le contexte de la physique des “polymères vivants

  2. Efficient inverted polymer solar cells using low-temperature zinc oxide interlayer processed from aqueous solution

    NASA Astrophysics Data System (ADS)

    Chen, Dazheng; Zhang, Chunfu; Heng, Ting; Wei, Wei; Wang, Zhizhe; Han, Genquan; Feng, Qian; Hao, Yue; Zhang, Jincheng

    2015-04-01

    In this work, an aqueous solution method that entails processing at low temperatures is utilized to deposit a ZnO interlayer in poly(3-hexylthiophene-2,5-diyl):[6,6]-phenyl C61 butyric acid methyl ester-based inverted polymer solar cells (PSCs). The effect of ZnO annealing temperature from 50 to 150 °C on PSC performance is systemically studied and it is found that the transition point is approximately 80 °C. When the ZnO annealing temperature is higher than 80 °C, PSCs show similar current density-voltage (J-V) characteristics and achieve a power conversion efficiency higher than 3.5%. Transmittance spectrum, PL spectrum, and surface morphology studies show that an annealing temperature above 80 °C is sufficient for ZnO to achieve a relatively good quality, and that a higher temperature only slightly improves ZnO quality, which is confirmed from statistical results. Furthermore, flexible PSCs based on PET substrates show a comparable power conversion efficiency and good flexibility.

  3. Exploring the Loading Capacity of Generation Six to Eight Dendronized Polymers in Aqueous Solution.

    PubMed

    Maltar-Strmečki, Nadica; Yu, Hao; Messmer, Daniel; Zhang, Baozhong; Schlüter, A Dieter; Hinderberger, Dariush

    2016-09-01

    Aspects of size, structural (im)perfection, inner density, and guest molecule loading capacity of dendronized polymers (DPs) of high generation (6≤g≤8) in aqueous solution are studied using electron paramagnetic resonance spectroscopy on amphiphilic, spin-labeled guest molecules. The results show that the interior of the charged DPs is strongly polar, especially in comparison to their lower generation (1-4) analogues. This is a direct sign that large amounts of water penetrate the DP surface, reflecting the structural (im)perfections of these high-generation DPs and much lower segmental densities than theoretically achievable. Images obtained with atomic force microscopy reveal that the high-generation DPs do not aggregate and give further insights into the structural imperfections. Electron paramagnetic resonance spectroscopic data further show that despite their structural imperfections, these DPs can bind and release large numbers of amphiphilic molecules. It is concluded that attention should be paid to their synthesis, for which a protocol needs to be developed that avoids the relatively large amount of defects generated in the direct conversion of a generation g=4 DP to a generation g=6 DP, which had to be used here. PMID:27273228

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

    PubMed

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

    2014-12-19

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

  5. Solution processable 2-(trityloxy)ethyl and tert-butyl group containing amorphous molecular glasses of pyranylidene derivatives with light-emitting and amplified spontaneous emission properties

    NASA Astrophysics Data System (ADS)

    Zarins, Elmars; Vembris, Aivars; Misina, Elina; Narels, Martins; Grzibovskis, Raitis; Kokars, Valdis

    2015-11-01

    Small organic molecules with incorporated 4H-pyran-4-ylidene (pyranylidene) fragment as the π-conjugation system which bonds the electron acceptor fragment (A) with electron donor part (D) in the molecule - also well known as derivatives of 4-(dicyano-methylene)-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran (DCM) laser dye-have attracted considerable attention of scientists as potential new generation materials for organic photonics and molecular electronics due to their low-cost fabrication possibility, flexibility and low-weight. Six glassy derivatives of 4H-pyran-4-ylidene (pyranylidene) with attached bulky 2-(trityloxy)ethyl and tert-butyl groups are described in this report. Almost all of the synthesized compounds form good optical quality transparent amorphous films from volatile organic solvents and could be obtained in good yields up to 75%. Their light emission in solution and thin solid films is in the range of 600-700 nm, they are thermally stable and show glass transition in the range of 108-158 °C. The amplified spontaneous emission threshold values of the neat films of the glassy pyranylidene derivatives vary from 155 to 450 μJ/cm2 and their HOMO and LUMO energy levels are between of those of tris(8-hydroxy quinolinato) aluminum (Alq3). The photoluminescence quantum yields of the glassy compounds are in the range from 1% to about 7.7% and their electroluminescence properties have been investigated. Therefore, glassy pyranylidene derivatives could be a very potential low-cost solution processable materials for Alq3 hosted light-amplification and light-emitting application studies.

  6. Self-aligned, full solution process polymer field-effect transistor on flexible substrates

    PubMed Central

    Yan, Yan; Huang, Long-Biao; Zhou, Ye; Han, Su-Ting; Zhou, Li; Zhuang, Jiaqing; Xu, Zong-Xiang; Roy, V. A. L.

    2015-01-01

    Conventional techniques to form selective surface energy regions on rigid inorganic substrates are not suitable for polymer interfaces due to sensitive and soft limitation of intrinsic polymer properties. Therefore, there is a strong demand for finding a novel and compatible method for polymeric surface energy modification. Here, by employing the confined photo-catalytic oxidation method, we successfully demonstrate full polymer filed-effect transistors fabricated through four-step spin-coating process on a flexible polymer substrate. The approach shows negligible etching effect on polymeric film. Even more, the insulating property of polymeric dielectric is not affected by the method, which is vital for polymer electronics. Finally, the self-aligned full polymer field-effect transistors on the flexible polymeric substrate are fabricated, showing good electrical properties and mechanical flexibility under bending tests. PMID:26497412

  7. Amorphic complexity

    NASA Astrophysics Data System (ADS)

    Fuhrmann, G.; Gröger, M.; Jäger, T.

    2016-02-01

    We introduce amorphic complexity as a new topological invariant that measures the complexity of dynamical systems in the regime of zero entropy. Its main purpose is to detect the very onset of disorder in the asymptotic behaviour. For instance, it gives positive value to Denjoy examples on the circle and Sturmian subshifts, while being zero for all isometries and Morse-Smale systems. After discussing basic properties and examples, we show that amorphic complexity and the underlying asymptotic separation numbers can be used to distinguish almost automorphic minimal systems from equicontinuous ones. For symbolic systems, amorphic complexity equals the box dimension of the associated Besicovitch space. In this context, we concentrate on regular Toeplitz flows and give a detailed description of the relation to the scaling behaviour of the densities of the p-skeletons. Finally, we take a look at strange non-chaotic attractors appearing in so-called pinched skew product systems. Continuous-time systems, more general group actions and the application to cut and project quasicrystals will be treated in subsequent work.

  8. Self-Assembly of Telechelic Tyrosine End-Capped PEO and Poly(alanine) Polymers in Aqueous Solution.

    PubMed

    Kirkham, Steven; Castelletto, Valeria; Hamley, Ian William; Reza, Mehedi; Ruokolainen, Janne; Hermida-Merino, Daniel; Bilalis, Panayiotis; Iatrou, Hermis

    2016-03-14

    The self-assembly in aqueous solution of three novel telechelic conjugates comprising a central hydrophilic polymer and short (trimeric or pentameric) tyrosine end-caps has been investigated. Two of the conjugates have a central poly(oxyethylene) (polyethylene oxide, PEO) central block with different molar masses. The other conjugate has a central poly(L-alanine) (PAla) sequence in a purely amino-acid based conjugate. All three conjugates self-assemble into β-sheet based fibrillar structures, although the fibrillar morphology revealed by cryogenic-TEM is distinct for the three polymers--in particular the Tyr5-PEO6k-Tyr5 forms a population of short straight fibrils in contrast to the more diffuse fibril aggregates observed for Tyr5-PEO2k-Tyr5 and Tyr3-PAla-Tyr3. Hydrogel formation was not observed for these samples (in contrast to prior work on related systems) up to quite high concentrations, showing that it is possible to prepare solutions of peptide-polymer-peptide conjugates with hydrophobic end-caps without conformational constraints associated with hydrogelation. The Tyr5-PEO6k-Tyr5 shows significant PEO crystallization upon drying in contrast to the Tyr5-PEO2k-Tyr5 conjugate. Our findings point to the remarkable ability of short hydrophobic peptide end groups to modulate the self-assembly properties of polymers in solution in model peptide-capped "associative polymers". Retention of fluidity at high conjugate concentration may be valuable in potential future applications of these conjugates as bioresponsive or biocompatible materials, for example exploiting the enzyme-responsiveness of the tyrosine end-groups. PMID:26867986

  9. Activation energy for mobility of dyes and proteins in polymer solutions: from diffusion of single particles to macroscale flow.

    PubMed

    Sozański, Krzysztof; Wiśniewska, Agnieszka; Kalwarczyk, Tomasz; Hołyst, Robert

    2013-11-27

    We measure the activation energy Ea for the diffusion of molecular probes (dyes and proteins of radii from 0.52 to 6.9 nm) and for macroscopic flow in a model complex liquid-aqueous solutions of polyethylene glycol. We cover a broad range of polymer molecular weights, concentrations, and temperatures. Fluorescence correlation spectroscopy and rheometry experiments reveal a relationship between the excess of the activation energy in polymer solutions over the one in pure solvent ΔEa and simple parameters describing the structure of the system: probe radius, polymer hydrodynamic radius, and correlation length. ΔEa varies by more than an order of magnitude in the investigated systems (in the range of ca. 1-15 kJ/mol) and for probes significantly larger than the polymer hydrodynamic radius approaches the value measured for macroscopic flow. We develop an explicit formula describing the smooth transition of ΔEa from the diffusion of molecular probes to macroscopic flow. This formula is a reference for the quantitative analysis of specific interactions of moving nano-objects with their environment as well as active transport. For instance, the power developed by a molecular motor moving at constant velocity u is proportional to u2exp(Ea/RT).

  10. Binary Mutual Diffusion Coefficients of Polymer/Solvent Systems Using Compressible Regular Solutions Theory and Free Volume Theory

    NASA Astrophysics Data System (ADS)

    Farajnezhad, Arsalan; Asef Afshar, Orang; Asgarpour Khansary, Milad; Shirazian, Saeed

    2016-07-01

    The free volume theory has found practical application for prediction of diffusional behavior of polymer/solvent systems. In this paper, reviewing free volume theory, binary mutual diffusion coefficients in some polymer/solvent systems have been systematically presented through chemical thermodynamic modeling in terms of both activity coefficients and fugacity coefficients models. Here chemical thermodynamic model of compressible regular solution (CRS) was used for evaluation of diffusion coefficients calculations as the pure component properties would be required only. Four binary polymeric solutions of cyclohexane/polyisobutylene, n-pentane/polyisobutylene, toluene/polyisobutylene and chloroform/polyisobutylene were considered. The agreement between calculated data and the experimentally collected data was desirable and no considerable error propagation in approximating mutual diffusion coefficients has been observed.

  11. Polymer-induced phase separation and crystallization in immunoglobulin G solutions.

    PubMed

    Li, Jianguo; Rajagopalan, Raj; Jiang, Jianwen

    2008-05-28

    We study the effects of the size of polymer additives and ionic strength on the phase behavior of a nonglobular protein-immunoglobulin G (IgG)-by using a simple four-site model to mimic the shape of IgG. The interaction potential between the protein molecules consists of a Derjaguin-Landau-Verwey-Overbeek-type colloidal potential and an Asakura-Oosawa depletion potential arising from the addition of polymer. Liquid-liquid equilibria and fluid-solid equilibria are calculated by using the Gibbs ensemble Monte Carlo technique and the Gibbs-Duhem integration (GDI) method, respectively. Absolute Helmholtz energy is also calculated to get an initial coexisting point as required by GDI. The results reveal a nonmonotonic dependence of the critical polymer concentration rho(PEG) (*) (i.e., the minimum polymer concentration needed to induce liquid-liquid phase separation) on the polymer-to-protein size ratio q (equivalently, the range of the polymer-induced depletion interaction potential). We have developed a simple equation for estimating the minimum amount of polymer needed to induce the liquid-liquid phase separation and show that rho(PEG) (*) approximately [q(1+q)(3)]. The results also show that the liquid-liquid phase separation is metastable for low-molecular weight polymers (q=0.2) but stable at large molecular weights (q=1.0), thereby indicating that small sizes of polymer are required for protein crystallization. The simulation results provide practical guidelines for the selection of polymer size and ionic strength for protein phase separation and crystallization.

  12. Solution-Processed 8-Hydroquinolatolithium as Effective Cathode Interlayer for High-Performance Polymer Solar Cells.

    PubMed

    Liu, Wenqing; Liang, Tao; Chen, Qi; Yu, Zhikai; Zhang, Yingying; Liu, Yujing; Fu, Weifei; Tang, Feng; Chen, Liwei; Chen, Hongzheng

    2016-04-13

    Solution-processed 8-hydroxyquinolinatolithium (s-Liq) was successfully applied as an efficient cathode interlayer in bulk heterojunction polymer solar cells (PSCs), giving rise to enhancement in device performance. The ultraviolet photoelectron spectra results revealed that the presence of s-Liq could lower work function of Al cathode, allowing for the ohmic contacts with the fullerene acceptor for better electron extraction and also a larger work function difference between the two electrodes, which leads to an increase in open-circuit voltage (V(oc)). Scanning Kelvin probe microscopy study on the surface potential of active layers suggested that an interfacial dipole was formed in the s-Liq interlayer between the active layer and the Al cathode, which enhanced the intrinsic built-in potential in the device for better charge transportation and extraction. Consequently, the V(oc), fill factor, and current density of the device can be improved by the introduction of s-Liq interlayer, leading to a power conversion efficiency (PCE) improvement. With PTB7 (or PTB7-Th) as the donor and PC71BM as the acceptor, the s-Liq-based PSC devices exhibited a PCE of 8.37% (or 9.04%), much higher than those of devices with the evaporated Liq (7.62%) or commonly used PFN (8.14%) as the cathode interlayer. Moreover, the s-Liq-based devices showed good stability, maintaining 75% (in N2) and 45% (in air) of the initial PCE after 7 days, respectively. These results suggest the great potential of s-Liq as cathode interlayer material for high-performance solar cells application.

  13. Solution-Processed 8-Hydroquinolatolithium as Effective Cathode Interlayer for High-Performance Polymer Solar Cells.

    PubMed

    Liu, Wenqing; Liang, Tao; Chen, Qi; Yu, Zhikai; Zhang, Yingying; Liu, Yujing; Fu, Weifei; Tang, Feng; Chen, Liwei; Chen, Hongzheng

    2016-04-13

    Solution-processed 8-hydroxyquinolinatolithium (s-Liq) was successfully applied as an efficient cathode interlayer in bulk heterojunction polymer solar cells (PSCs), giving rise to enhancement in device performance. The ultraviolet photoelectron spectra results revealed that the presence of s-Liq could lower work function of Al cathode, allowing for the ohmic contacts with the fullerene acceptor for better electron extraction and also a larger work function difference between the two electrodes, which leads to an increase in open-circuit voltage (V(oc)). Scanning Kelvin probe microscopy study on the surface potential of active layers suggested that an interfacial dipole was formed in the s-Liq interlayer between the active layer and the Al cathode, which enhanced the intrinsic built-in potential in the device for better charge transportation and extraction. Consequently, the V(oc), fill factor, and current density of the device can be improved by the introduction of s-Liq interlayer, leading to a power conversion efficiency (PCE) improvement. With PTB7 (or PTB7-Th) as the donor and PC71BM as the acceptor, the s-Liq-based PSC devices exhibited a PCE of 8.37% (or 9.04%), much higher than those of devices with the evaporated Liq (7.62%) or commonly used PFN (8.14%) as the cathode interlayer. Moreover, the s-Liq-based devices showed good stability, maintaining 75% (in N2) and 45% (in air) of the initial PCE after 7 days, respectively. These results suggest the great potential of s-Liq as cathode interlayer material for high-performance solar cells application. PMID:27015527

  14. A unifying model for elongational flow of polymer melts and solutions based on the interchain tube pressure concept

    NASA Astrophysics Data System (ADS)

    Wagner, Manfred Hermann; Rolón-Garrido, Víctor Hugo

    2015-04-01

    An extended interchain tube pressure model for polymer melts and concentrated solutions is presented, based on the idea that the pressures exerted by a polymer chain on the walls of an anisotropic confinement are anisotropic (M. Doi and S. F. Edwards, The Theory of Polymer Dynamics, Oxford University Press, New York, 1986). In a tube model with variable tube diameter, chain stretch and tube diameter reduction are related, and at deformation rates larger than the inverse Rouse time τR, the chain is stretched and its confining tube becomes increasingly anisotropic. Tube diameter reduction leads to an interchain pressure in the lateral direction of the tube, which is proportional to the 3rd power of stretch (G. Marrucci and G. Ianniruberto. Macromolecules 37, 3934-3942, 2004). In the extended interchain tube pressure (EIP) model, it is assumed that chain stretch is balanced by interchain tube pressure in the lateral direction, and by a spring force in the longitudinal direction of the tube, which is linear in stretch. The scaling relations established for the relaxation modulus of concentrated solutions of polystyrene in oligomeric styrene (M. H. Wagner, Rheol. Acta 53, 765-777, 2014, M. H. Wagner, J. Non-Newtonian Fluid Mech. http://dx.doi.org/10.1016/j.jnnfm.2014.09.017, 2014) are applied to the solutions of polystyrene (PS) in diethyl phthalate (DEP) investigated by Bhattacharjee et al. (P. K. Bhattacharjee et al., Macromolecules 35, 10131-10148, 2002) and Acharya et al. (M. V. Acharya et al. AIP Conference Proceedings 1027, 391-393, 2008). The scaling relies on the difference ΔTg between the glass-transition temperatures of the melt and the glass-transition temperatures of the solutions. ΔTg can be inferred from the reported zero-shear viscosities, and the BSW spectra of the solutions are obtained from the BSW spectrum of the reference melt with good accuracy. Predictions of the EIP model are compared to the steady-state elongational viscosity data of PS

  15. Evaluating the effects of plasticizer interactions with HPMC on the tack-behavior of polymer film-forming coating solutions.

    PubMed

    Saringat, Haji Baie; Sheikh, Khalid Ahmad; Khan, Gul Majid

    2004-07-01

    Tack is a concept that is widely used to describe the forces or energies involved in the separation of two parallel surfaces initially in contact through an intervening thin liquid film. The tackiness may cause tablets to stick with each other or to the walls of the coating apparatus. In this study, the HPMC coating solutions were evaluated for their tackiness and the effects of interactions between the polymer and plasticizers on the tack behavior of HPMC film-forming coating solutions were investigated, using type TA-XT2 texture analyzer. It was found that experimental factors such as the contact time, rate of separation and volume of the film-forming test solution could effectively influence the magnitude of tack behavior. Moreover, up to certain levels, the addition of plasticizers such as PEG 400 & 1000 and of triacetin caused a reduction in the tack value of the polymer solutions. It was concluded that in general, the tackiness depended upon the molecular weight and/or type and concentration of a plasticizer. The efficiency of plasticizers used to reduce the tackiness of HPMC solutions ranked as PEG1000 > triacetin > PEG400. PMID:16414595

  16. Evaluating the effects of plasticizer interactions with HPMC on the tack-behavior of polymer film-forming coating solutions.

    PubMed

    Saringat, Haji Baie; Sheikh, Khalid Ahmad; Khan, Gul Majid

    2004-07-01

    Tack is a concept that is widely used to describe the forces or energies involved in the separation of two parallel surfaces initially in contact through an intervening thin liquid film. The tackiness may cause tablets to stick with each other or to the walls of the coating apparatus. In this study, the HPMC coating solutions were evaluated for their tackiness and the effects of interactions between the polymer and plasticizers on the tack behavior of HPMC film-forming coating solutions were investigated, using type TA-XT2 texture analyzer. It was found that experimental factors such as the contact time, rate of separation and volume of the film-forming test solution could effectively influence the magnitude of tack behavior. Moreover, up to certain levels, the addition of plasticizers such as PEG 400 & 1000 and of triacetin caused a reduction in the tack value of the polymer solutions. It was concluded that in general, the tackiness depended upon the molecular weight and/or type and concentration of a plasticizer. The efficiency of plasticizers used to reduce the tackiness of HPMC solutions ranked as PEG1000 > triacetin > PEG400.

  17. Determination of the interaction parameter and topological scaling features of symmetric star polymers in dilute solution.

    PubMed

    Rai, Durgesh K; Beaucage, Gregory; Ratkanthwar, Kedar; Beaucage, Peter; Ramachandran, Ramnath; Hadjichristidis, Nikos

    2015-07-01

    Star polymers provide model architectures to understand the dynamic and rheological effects of chain confinement for a range of complex topological structures like branched polymers, colloids, and micelles. It is important to describe the structure of such macromolecular topologies using small-angle neutron and x-ray scattering to facilitate understanding of their structure-property relationships. Modeling of scattering from linear, Gaussian polymers, such as in the melt, has applied the random phase approximation using the Debye polymer scattering function. The Flory-Huggins interaction parameter can be obtained using neutron scattering by this method. Gaussian scaling no longer applies for more complicated chain topologies or when chains are in good solvents. For symmetric star polymers, chain scaling can differ from ν=0.5(d(f)=2) due to excluded volume, steric interaction between arms, and enhanced density due to branching. Further, correlation between arms in a symmetric star leads to an interference term in the scattering function first described by Benoit for Gaussian chains. In this work, a scattering function is derived which accounts for interarm correlations in symmetric star polymers as well as the polymer-solvent interaction parameter for chains of arbitrary scaling dimension using a hybrid Unified scattering function. The approach is demonstrated for linear, four-arm and eight-arm polyisoprene stars in deuterated p-xylene.

  18. Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host–guest complexation

    PubMed Central

    Wang, Jie; Qiu, Zhiqiang; Wang, Yiming; Li, Li; Pham, Duc-Truc; Prud’homme, Robert K

    2016-01-01

    Summary The employment of cyclodextrin host–guest complexation to construct supramolecular assemblies with an emphasis on polymer networks is reviewed. The main driving force for this supramolecular assembly is host–guest complexation between cyclodextrin hosts and guest groups either of which may be discrete molecular species or substituents on a polymer backbone. The effects of such complexation on properties at the molecular and macroscopic levels are discussed. It is shown that cyclodextrin complexation may be used to design functional polymer materials with tailorable properties, especially for photo-, pH-, thermo- and redox-responsiveness and self-healing. PMID:26877808

  19. Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host-guest complexation.

    PubMed

    Wang, Jie; Qiu, Zhiqiang; Wang, Yiming; Li, Li; Guo, Xuhong; Pham, Duc-Truc; Lincoln, Stephen F; Prud'homme, Robert K

    2016-01-01

    The employment of cyclodextrin host-guest complexation to construct supramolecular assemblies with an emphasis on polymer networks is reviewed. The main driving force for this supramolecular assembly is host-guest complexation between cyclodextrin hosts and guest groups either of which may be discrete molecular species or substituents on a polymer backbone. The effects of such complexation on properties at the molecular and macroscopic levels are discussed. It is shown that cyclodextrin complexation may be used to design functional polymer materials with tailorable properties, especially for photo-, pH-, thermo- and redox-responsiveness and self-healing. PMID:26877808

  20. Scaling of dynamics in 2d semi-dilute polymer solutions

    NASA Astrophysics Data System (ADS)

    Cicuta, P.; Hopkinson, I.

    2004-10-01

    We consider the dynamics of thermal concentration fluctuations in polymer Langmuir monolayers, probed with surface light scattering. We present data on the proteins β-lactoglobulin and β-casein and on the synthetic polymers Poly(vinyl acetate) and Poly(4-hydroxystyrene). We show that for all these systems, in the semi-dilute concentration regime, there is a power law dependency of both the elastic and viscous components of the dilational modulus on the concentration. We find that for all the systems considered, the viscosity scales with a power that is double that of the elasticity. A simple explanation for this universal dynamical behavior in semidilute polymer monolayers is suggested.

  1. Manipulating hybrid structures of polymer/a-Si for thin film solar cells

    SciTech Connect

    Peng, Ying; He, Zhiqun E-mail: J.I.B.Wilson@hw.ac.uk; Zhang, Zhi; Liang, Chunjun; Diyaf, Adel; Ivaturi, Aruna; Wilson, John I. B. E-mail: J.I.B.Wilson@hw.ac.uk

    2014-03-10

    A series of uniform polymer/amorphous silicon hybrid structures have been fabricated by means of solution-casting for polymer and radio frequency excited plasma enhanced chemical vapour deposition for amorphous silicon (a-Si:H). Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) functioned as a photoactive donor, while the silicon layer acted as an acceptor. It is found that matching the hole mobility of the polymer to the electron mobility of amorphous silicon is critical to improve the photovoltaic performance from hybrid cells. A three-layer p-i-n structure of ITO/PEDOT:PSS(200 nm)/i-Si(450 nm)/n-Si(200 nm)/Al with a power conversion efficiency of 4.78% under a standard test condition was achieved.

  2. Development of Novel Method for Rapid Extract of Radionuclides from Solution Using Polymer Ligand Film

    NASA Astrophysics Data System (ADS)

    Rim, Jung H.

    Accurate and fast determination of the activity of radionuclides in a sample is critical for nuclear forensics and emergency response. Radioanalytical techniques are well established for radionuclides measurement, however, they are slow and labor intensive, requiring extensive radiochemical separations and purification prior to analysis. With these limitations of current methods, there is great interest for a new technique to rapidly process samples. This dissertation describes a new analyte extraction medium called Polymer Ligand Film (PLF) developed to rapidly extract radionuclides. Polymer Ligand Film is a polymer medium with ligands incorporated in its matrix that selectively and rapidly extract analytes from a solution. The main focus of the new technique is to shorten and simplify the procedure necessary to chemically isolate radionuclides for determination by alpha spectrometry or beta counting. Five different ligands were tested for plutonium extraction: bis(2-ethylhexyl) methanediphosphonic acid (H2DEH[MDP]), di(2-ethyl hexyl) phosphoric acid (HDEHP), trialkyl methylammonium chloride (Aliquat-336), 4,4'(5')-di-t-butylcyclohexano 18-crown-6 (DtBuCH18C6), and 2-ethylhexyl 2-ethylhexylphosphonic acid (HEH[EHP]). The ligands that were effective for plutonium extraction further studied for uranium extraction. The plutonium recovery by PLFs has shown dependency on nitric acid concentration and ligand to total mass ratio. H2DEH[MDP] PLFs performed best with 1:10 and 1:20 ratio PLFs. 50.44% and 47.61% of plutonium were extracted on the surface of PLFs with 1M nitric acid for 1:10 and 1:20 PLF, respectively. HDEHP PLF provided the best combination of alpha spectroscopy resolution and plutonium recovery with 1:5 PLF when used with 0.1M nitric acid. The overall analyte recovery was lower than electrodeposited samples, which typically has recovery above 80%. However, PLF is designed to be a rapid field deployable screening technique and consistency is more important

  3. Structure Elucidation of Poly-Faldaprevir: Polymer Backbone Solved Using Solid-State and Solution Nuclear Magnetic Resonance Spectroscopy.

    PubMed

    Gonnella, Nina C; Busacca, Carl A; Zhang, Li; Saha, Anjan; Wu, Jiang-Ping; Li, Guisheng; Davis, Mark; Offerdahl, Thomas; Jones, Paul-James; Herfurth, Lars; Reddig, Tim; Wagner, Klaus; Niemann, Michael; Werthmann, Ulrike; Grupe, Julia; Roos, Helmut; Reckzügel, Gaby; Ding, Andreas

    2016-06-01

    A large-scale synthesis of the hepatitis C virus drug Faldaprevir revealed precipitation of an unknown insoluble solid from methanol solutions of the drug substance. The unknown impurity was determined to be a polymer of Faldaprevir based on analytical methods that included size exclusion chromatography in combination with electrospray ionization mass spectrometry, solution nuclear magnetic resonance (NMR), matrix-assisted laser desorption ionization-time of flight, ultracentrifugation, elemental analysis, and sodium quantitation by atom absorption spectroscopy. Structure elucidation of the polymeric backbone was achieved using solid-state NMR cross-polarization/magic angle spinning (CP/MAS), cross polarization-polarization inversion, and heteronuclear correlation (HETCOR) experiments. The polymerization was found to occur at the vinyl cyclopropane via a likely free radical initiation mechanism. Full proton and carbon chemical shift assignments of the polymer were obtained using solution NMR spectroscopy. The polymer structure was corroborated with chemical synthesis of the polymer and solution NMR analysis. PMID:27238486

  4. Xanthate-Functional Temperature-Responsive Polymers: Effect on Lower Critical Solution Temperature Behavior and Affinity toward Sulfide Surfaces.

    PubMed

    Ng, Wei Sung; Forbes, Elizaveta; Franks, George V; Connal, Luke A

    2016-08-01

    Xanthate-functional polymers represent an exciting opportunity to provide temperature-responsive materials with the ability to selectively attach to specific metals, while also modifying the lower critical solution temperature (LCST) behavior. To investigate this, random copolymers of poly(N-isopropylacrylamide) (PNIPAM) with xanthate incorporations ranging from 2 to 32% were prepared via free radical polymerization. Functionalization with 2% xanthate increased the LCST by 5 °C relative to the same polymer without xanthate. With increasing xanthate composition, the transition temperature increased and the transition range broadened until a critical composition of the hydrophilic xanthate groups (≥18%) where the transition disappeared completely. The adsorption of the polymers at room temperature onto chalcopyrite (CuFeS2) surfaces increased with xanthate composition, while adsorption onto quartz (SiO2) was negligible. These findings demonstrate the affinity of these functional smart polymers toward copper iron sulfide relative to quartz surfaces, presumably due to the interactions between xanthate and specific metal centers. PMID:27434760

  5. Persistent draining crossover in DNA and other semi-flexible polymers: Evidence from hydrodynamic models and extensive measurements on DNA solutions.

    PubMed

    Mansfield, Marc L; Tsortos, Achilleas; Douglas, Jack F

    2015-09-28

    Although the scaling theory of polymer solutions has had many successes, this type of argument is deficient when applied to hydrodynamic solution properties. Since the foundation of polymer science, it has been appreciated that measurements of polymer size from diffusivity, sedimentation, and solution viscosity reflect a convolution of effects relating to polymer geometry and the strength of the hydrodynamic interactions within the polymer coil, i.e., "draining." Specifically, when polymers are expanded either by self-excluded volume interactions or inherent chain stiffness, the hydrodynamic interactions within the coil become weaker. This means there is no general relationship between static and hydrodynamic size measurements, e.g., the radius of gyration and the hydrodynamic radius. We study this problem by examining the hydrodynamic properties of duplex DNA in solution over a wide range of molecular masses both by hydrodynamic modeling using a numerical path-integration method and by comparing with extensive experimental observations. We also considered how excluded volume interactions influence the solution properties of DNA and confirm that excluded volume interactions are rather weak in duplex DNA in solution so that the simple worm-like chain model without excluded volume gives a good leading-order description of DNA for molar masses up to 10(7) or 10(8) g/mol or contour lengths between 5 μm and 50 μm. Since draining must also depend on the detailed chain monomer structure, future work aiming to characterize polymers in solution through hydrodynamic measurements will have to more carefully consider the relation between chain molecular structure and hydrodynamic solution properties. In particular, scaling theory is inadequate for quantitative polymer characterization.

  6. Impact of particle size on interaction forces between ettringite and dispersing comb-polymers in various electrolyte solutions.

    PubMed

    Ferrari, Lucia; Kaufmann, Josef; Winnefeld, Frank; Plank, Johann

    2014-04-01

    The inter-particle forces play a fundamental role for the flow properties of a particle suspension in response to shear stresses. In concrete applications, cement admixtures based on comb-polymers like polycarboxylate-ether-based superplasticizer (PCE) are used to control the rheological behavior of the fresh mixtures, as it is negatively impacted by certain early hydration products, like the mineral ettringite. In this work, dispersion forces due to PCE were measured directly at the surface of ettringite crystals in different electrolyte solutions by the means of atomic force microscopy (AFM) applying spherical and sharp silicon dioxide tips. Results show an effective repulsion between ettringite surface and AFM tips for solutions above the IEP of ettringite (pH∼12) and significant attraction in solution at lower pH. The addition of polyelectrolytes in solution provides dispersion forces exclusively between the sharp tips (radius ≈ 10 nm) and the ettringite surface, whereas the polymer layer at the ettringite surface results to be unable to disperse large colloidal probes (radius ≈ 10 μm). A simple modeling of the inter-particle forces explains that, for large particles, the steric hindrance of the studied PCE molecules is not high enough to compensate for the Van der Waals and the attractive electrostatic contributions. Therefore, in cement suspensions the impact of ettringite on rheology is probably not only related to the particle charge, but also related to the involved particle sizes. PMID:24491324

  7. Impact of particle size on interaction forces between ettringite and dispersing comb-polymers in various electrolyte solutions.

    PubMed

    Ferrari, Lucia; Kaufmann, Josef; Winnefeld, Frank; Plank, Johann

    2014-04-01

    The inter-particle forces play a fundamental role for the flow properties of a particle suspension in response to shear stresses. In concrete applications, cement admixtures based on comb-polymers like polycarboxylate-ether-based superplasticizer (PCE) are used to control the rheological behavior of the fresh mixtures, as it is negatively impacted by certain early hydration products, like the mineral ettringite. In this work, dispersion forces due to PCE were measured directly at the surface of ettringite crystals in different electrolyte solutions by the means of atomic force microscopy (AFM) applying spherical and sharp silicon dioxide tips. Results show an effective repulsion between ettringite surface and AFM tips for solutions above the IEP of ettringite (pH∼12) and significant attraction in solution at lower pH. The addition of polyelectrolytes in solution provides dispersion forces exclusively between the sharp tips (radius ≈ 10 nm) and the ettringite surface, whereas the polymer layer at the ettringite surface results to be unable to disperse large colloidal probes (radius ≈ 10 μm). A simple modeling of the inter-particle forces explains that, for large particles, the steric hindrance of the studied PCE molecules is not high enough to compensate for the Van der Waals and the attractive electrostatic contributions. Therefore, in cement suspensions the impact of ettringite on rheology is probably not only related to the particle charge, but also related to the involved particle sizes.

  8. Partitioning of mobile ions between ion exchange polymers and aqueous salt solutions: importance of counter-ion condensation.

    PubMed

    Kamcev, Jovan; Galizia, Michele; Benedetti, Francesco M; Jang, Eui-Soung; Paul, Donald R; Freeman, Benny D; Manning, Gerald S

    2016-02-17

    Equilibrium partitioning of ions between a membrane and a contiguous external solution strongly influences transport properties of polymeric membranes used for water purification and energy generation applications. This study presents a theoretical framework to quantitatively predict ion sorption from aqueous electrolytes (e.g., NaCl, MgCl2) into charged (i.e., ion exchange) polymers. The model was compared with experimental NaCl, MgCl2, and CaCl2 sorption data in commercial cation and anion exchange membranes. Ion sorption in charged polymers was modeled using a thermodynamic approach based on Donnan theory coupled with Manning's counter-ion condensation theory to describe non-ideal behavior of ions in the membrane. Ion activity coefficients in solution were calculated using the Pitzer model. The resulting model, with no adjustable parameters, provides remarkably good agreement with experimental values of membrane mobile salt concentration. The generality of the model was further demonstrated using literature data for ion sorption of various electrolytes in charged polymers, including HCl sorption in Nafion. PMID:26840776

  9. Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors

    NASA Astrophysics Data System (ADS)

    Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S.

    2016-04-01

    Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm2V‑1s‑1), on/off ratio (107), and other desirable field-effect properties that meet impactful OFET application requirements.

  10. Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors.

    PubMed

    Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S

    2016-01-01

    Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm(2)V(-1)s(-1)), on/off ratio (10(7)), and other desirable field-effect properties that meet impactful OFET application requirements. PMID:27091315

  11. Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors

    PubMed Central

    Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S.

    2016-01-01

    Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm2V−1s−1), on/off ratio (107), and other desirable field-effect properties that meet impactful OFET application requirements. PMID:27091315

  12. [Using Molecular Simulations to Understand Complex Nanoscale Dynamic Phenomena in Polymer Solutions

    NASA Technical Reports Server (NTRS)

    Smith, Grant

    2004-01-01

    The first half of the project concentrated on molecular simulation studies of the translocation of model molecules for single-stranded DNA through a nanosized pore. This has resulted in the publication, Translocation of a polymer chain across a nanopore: A Brownian dynamics simulation study, by Pu Tian and Grant D. Smith, JOURNAL OF CHEMICAL PHYSICS VOLUME 119, NUMBER 21 1 DECEMBER 2003, which is attached to this report. In this work we carried out Brownian dynamics simulation studies of the translocation of single polymer chains across a nanosized pore under the driving of an applied field (chemical potential gradient) designed to mimic an electrostatic field. The translocation process can be either dominated by the entropic barrier resulted from restricted motion of flexible polymer chains or by applied forces (or chemical gradient). We focused on the latter case in our studies. Calculation of radius of gyration of the translocating chain at the two opposite sides of the wall shows that the polymer chains are not in equilibrium during the translocation process. Despite this fact, our results show that the one-dimensional diffusion and the nucleation model provide an excellent description of the dependence of average translocation time on the chemical potential gradients, the polymer chain length and the solvent viscosity. In good agreement with experimental results and theoretical predictions, the translocation time distribution of our simple model shows strong non-Gaussian characteristics. It is observed that even for this simple tube-like pore geometry, more than one peak of translocation time distribution can be generated for proper pore diameter and applied field strengths. Both repulsive Weeks-Chandler-Anderson and attractive Lennard-Jones polymer-nanopore interaction were studied. Attraction facilitates the translocation process by shortening the total translocation time and dramatically improve the capturing of polymer chain. The width of the translocation

  13. The impact of graphene oxide particles on viscosity stabilization for diluted polymer solutions using in enhanced oil recovery at HTHP offshore reservoirs

    NASA Astrophysics Data System (ADS)

    Dung Nguyen, Ba; Kien Ngo, Trung; Bui, Truong Han; Khanh Pham, Duy; Loc Dinh, Xuan; Nguyen, Phuong Tung

    2015-03-01

    Over 60% of the original oil in a place (OOIP) is retained in a reservoir after conventional methods have been exploited. Application of enhanced oil recovery (EOR) technology gives an additional chance to get out possibly about 20% more oil from the reservoir. The use of water-soluble polymers improves the water-oil mobility ratio, therefore, the displacement efficiency increased, and leads to enhanced oil recovery. High-molecular-weight polyacrylamide group is widely and successfully used in EOR. But no commercial polymer composition can be used in conditions of high temperature and hardness brine offshore reservoirs yet. To avoid the time consumption and high expense for selection and synthesis of the appropriate-structural polymer for EOR application, we attempt to find additives to enhance the thermal stability of polymer solutions. In this paper, we report the results of improved viscosity stability of diluted polymer/seawater solutions aged at reservoir conditions for 31days by adding graphite-oxide particles (GOs). In the presence of 300 ppm of GOs, the viscosity stability of 1700 ppm acrylamide-based polymer in sea water solution increases from 92 °C to 135 °C. FESEM pictures show good distribution of GOs in polymer network, which is a result of integration of functional groups in GOs surfaces and hydrophilic polymer chains.

  14. Phase stability of a reversible supramolecular polymer solution mixed with nanospheres

    NASA Astrophysics Data System (ADS)

    Tuinier, Remco

    2011-05-01

    Theory is presented for the phase stability of mixtures containing nanospheres and non-adsorbing reversible supramolecular polymers. This was made possible by incorporating the depletion thickness and osmotic pressure of reversible supramolecular polymer chains into generalized free-volume theory, recently developed for investigating the phase behaviour of colloidal spheres mixed with interacting polymers (Fleer and Tuinier 2008 Adv. Colloid Interface Sci. 143 1-47). It follows that the fluid-fluid phase stability region where reversible supramolecular polymer chains can be mixed with nanospheres is sensitive to the energy of scission between the monomers and to the nanoparticle radius. One can then expect the fluid-fluid coexistence curves to have a strong dependence on temperature and that shifting of phase boundaries within a single experimental system should be possible by varying the temperature. The calculations reveal the width of the stability region to be rather small. This implies that phase homogeneity of product formulations containing reversible supramolecular polymers is only possible at low nanoparticle concentrations.

  15. Enhancing the efficiency of solution-processed polymer:colloidal nanocrystal hybrid photovoltaic cells using ethanedithiol treatment.

    PubMed

    Zhou, Renjia; Stalder, Romain; Xie, Dongping; Cao, Weiran; Zheng, Ying; Yang, Yixing; Plaisant, Marc; Holloway, Paul H; Schanze, Kirk S; Reynolds, John R; Xue, Jiangeng

    2013-06-25

    Advances in colloidal inorganic nanocrystal synthesis and processing have led to the demonstration of organic-inorganic hybrid photovoltaic (PV) cells using low-cost solution processes from blends of conjugated polymer and colloidal nanocrystals. However, the performance of such hybrid PV cells has been limited due to the lack of control at the complex interfaces between the organic and inorganic hybrid active materials. Here we show that the efficiency of hybrid PV devices can be significantly enhanced by engineering the polymer-nanocrystal interface with proper chemical treatment. Using two different conjugated polymers, poly(3-hexylthiophene) (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), we show that treating the polymer:nanocrystal hybrid film in an ethanedithiol-containing acetonitrile solution can increase the efficiency of the hybrid PV devices by 30-90%, and a maximum power conversion efficiency of 5.2 ± 0.3% was obtained in the PCPDTBT:CdSe devices at 0.2 sun (AM 1.5G), which was slightly reduced to 4.7 ± 0.3% at 1 sun. The ethanedithiol treatment did not result in significant changes in the morphology and UV-vis optical absorption of the hybrid thin films; however, infrared absorption, NMR, and X-ray photoelectron spectroscopies revealed the effective removal of organic ligands, especially the charged phosphonic acid ligands, from the CdSe nanorod surface after the treatment, accompanied by the possible monolayer passivation of nanorod surfaces with Cd-thiolates. We attribute the hybrid PV cell efficiency increase upon the ethanedithiol treatment to the reduction in charge and exciton recombination sites on the nanocrystal surface and the simultaneous increase in electron transport through the hybrid film.

  16. Ionic conductivity of dual-phase polymer electrolytes comprised of NBR/SBR latex films swollen with lithium salt solutions

    SciTech Connect

    Matsumoto, Morihiko; Ichino, Toshihiro; Rutt, J.S.; Nishi, Shiro . NTT Interdisciplinary Research Lab.)

    1994-08-01

    Dual-phase polymer electrolytes (DPE) with high ionic conductivity and good mechanical strength were prepared by swelling poly(acrylonitrile-co-butadiene) rubber (NBR) and poly(styrene-co-butadiene) rubber (SBR) mixed latex films with lithium salt solutions (e.g., 1M LiClO[sub 4]/[gamma]-butyrolactone). The latex films retain particle morphology in the solid state. The NBR phase (formed from fused NBR latex particles) is polar and is impregnated selectively with polar lithium salt solutions, yielding ion-conductive channels, whereas the SBR phase (formed from fused SBR latex particles) is nonpolar and is not impregnated, providing a mechanically supportive matrix. The ionic conductivity of the DPE increased dramatically with increasing content of lithium salt solution, and higher amounts of solution were imbibed with increasing content of NBR relative to SBR. Several factors which affect the ionic conductivity of this system were examined, and the highest ionic conductivity (>10[sup [minus]3] S/cm) was obtained when either an NBR/SBR 70/30 (w/w) or a 50/50 (w/w) latex film was saturated with 1M LiClO[sub 4]/[gamma]-BL solution or 1M LiClO[sub 4]/[gamma]-BL/DME solution. Ion-conductive behavior changed critically with increasing lithium salt solution uptake. At low levels of lithium salt solution uptake, evidence suggested that ionic conductivity of the absorbed lithium salt solution was strongly influenced by the presence of the NBR in the ion-conductive channel, but at higher levels, the effects of the NBR were reduced and free'' lithium salt solution was present.

  17. Direct measurement of the intermolecular forces confining a single molecule in an entangled polymer solution.

    PubMed

    Robertson, Rae M; Smith, Douglas E

    2007-09-21

    We use optical tweezers to directly measure the intermolecular forces acting on a single polymer imposed by surrounding entangled polymers (115 kbp DNA, 1 mg/ml). A tubelike confining field was measured in accord with the key assumption of reptation models. A time-dependent harmonic potential opposed transverse displacement, in accord with recent simulation findings. A tube radius of 0.8 microm was determined, close to the predicted value (0.5 microm). Three relaxation modes (approximately 0.4, 5, and 34 s) were measured following transverse displacement, consistent with predicted relaxation mechanisms.

  18. Measurement of the equation of state and of the index of refraction of an amorphous glow discharge polymer up to 45 GPa

    NASA Astrophysics Data System (ADS)

    Plisson, Thomas; Colin-Lalu, Pierre; Huser, Gael; Loubeyre, Paul

    2016-08-01

    We present an experimental determination of the ambient temperature equation of state, P ( ρ / ρ 0 , 293 K ) , up to 45 GPa, of the glow discharge polymer (GDP) used as a confining capsule for the fusible deuterium-tritium mixture in inertial confinement fusion experiments. An original method has been implemented to measure both the compression factor and the refractive index versus pressure. The data are obtained in a diamond anvil cell with two sample chambers of equal thickness containing, respectively, the GDP and a NaCl reference. This experimental equation of state is compared to numerical first principles simulations. Deviations are ascribed to the difficulty to simulate the detailed atomic structure of the polymer under moderate pressure.

  19. Calculation of amorphous silica solubilities at 25° to 300°C and apparent cation hydration numbers in aqueous salt solutions using the concept of effective density of water

    USGS Publications Warehouse

    Fournier, Robert O.; Williams, Marshall L.

    1983-01-01

    The solubility of amorphous silica in aqueous salt solutions at 25° to 300°C can be calculated using information on its solubility in pure water and a model in which the activity of water in the salt solution is defined to equal the effective density. pe, of “free” water in that solution. At temperatures of 100°C and above, pe closely equals the product of the density of the solution times the weight fraction of water in the solution. At 25°C, a correction parameter must be applied to pe that incorporates a term called the apparent cation hydration number, h. Because of the many assumptions and other uncertainties involved in determining values of h, by the model used here, the reported numbers are not necessarily real hydration numbers even though they do agree with some published values determined by activity and diffusion methods. Whether or not h is a real hydration number, it would appear to be useful in its inclusion within a more extensive activity coefficient term that describes the departure of silica solubilities in concentrated salt solutions from expected behavior according to the model presented here. Values of h can be calculated from measured amorphous silica solubilities in salt solutions at 25°C provided there is no complexing of dissolved silica with the dissolved salt, or if the degree of complexing is known. The previously postulated aqueous silica-sulfate complexing in aqueous Na2SO4 solutions is supported by results of the present effective density of water model

  20. Rate of Pu(IV) polymer formation in nitric acid solutions. A parametric study

    SciTech Connect

    Toth, L.M.; Osborne, M.M.

    1984-07-01

    The kinetics of Pu(IV) polymer formation has been examined with the intent of developing a simple mathematical equation that would predict the appearance of polymer. The fundamental polymerization rate has been found to be dependent on [Pu(IV)]{sup 1} {sup 2} and [HNO{sub 3}]{sup -6}. The activation energy for polymer formation is real temperature dependent, varying from 66.9 kJ/mol (16 kcal/mol) at 25{sup 0}C to 150.5 kJ/mol (36 kcal/mol) at 105{sup 0}C. These relationships have guided the developement of an empirical model that gives time to form 2% polymer in hours, t = [Pu/sub T/]/sup a/[HNO{sub 3}]/sup b/ Ae/sup c/T/, where a = -1.6, b = 4.6, c = 12.300 K, and A = 7.66 x 10{sup -16} h M{sup -3}; [Pu/sub T/] is the total plutonium concentration, mol/L; and [HNO{sub 3}] is the makeup nitric acid concentration, mol/L. 11 references, 26 figures, 1 table.

  1. Thin film fabricated from solution-dispersible porous hyperbranched conjugated polymer nanoparticles without surfactants

    NASA Astrophysics Data System (ADS)

    Wu, Xiaofu; Li, Haibo; Xu, Yuxiang; Xu, Bowei; Tong, Hui; Wang, Lixiang

    2014-01-01

    Porous hyperbranched conjugated polymer nanoparticles with an average particle size of 20-60 nm and a specific surface area of 225 m2 g-1 have been prepared through Suzuki polymerization in a miniemulsion, which could be stably dispersed in common organic solvents after complete removal of surfactants. Furthermore, a simple spin-coating method for the preparation of homogeneous transparent thin films of the nanoparticle has been developed. Bright blue emission of the porous nanoparticle films could be reversibly quenched by nitroaromatics with enhanced sensitivity compared to dense films of the linear conjugated polymer analogue.Porous hyperbranched conjugated polymer nanoparticles with an average particle size of 20-60 nm and a specific surface area of 225 m2 g-1 have been prepared through Suzuki polymerization in a miniemulsion, which could be stably dispersed in common organic solvents after complete removal of surfactants. Furthermore, a simple spin-coating method for the preparation of homogeneous transparent thin films of the nanoparticle has been developed. Bright blue emission of the porous nanoparticle films could be reversibly quenched by nitroaromatics with enhanced sensitivity compared to dense films of the linear conjugated polymer analogue. Electronic supplementary information (ESI) available: Synthesis, experimental details, structural characterization, morphological images, fluorescence response data etc. See DOI: 10.1039/c3nr05402k

  2. Extensional Rheology Experiment Developed to Investigate the Rheology of Dilute Polymer Solutions in Microgravity

    NASA Technical Reports Server (NTRS)

    Logsdon, Kirk A.

    2001-01-01

    A fundamental characteristic of fluid is viscosity; that is, the fluid resists forces that cause it to flow. This characteristic, or parameter, is used by manufacturers and end-users to describe the physical properties of a specific material so that they know what to expect when a material, such as a polymer, is processed through an extruder, a film blower, or a fiber-spinning apparatus. Normally, researchers will report a shear viscosity that depends on the rate of an imposed shearing flow. Although this type of characterization is sufficient for some processes, simple shearing experiments do not provide a complete picture of what a processor may expect for all materials. Extensional stretching flows are common in many polymer-processing operations such as extrusion, blow molding, and fiber spinning. Therefore, knowledge of the complete rheological (ability to flow and be deformed) properties of the polymeric fluid being processed is required to accurately predict and account for the flow behavior. In addition, if numerical simulations are ever able to serve as a priori design tools for optimizing polymer processing operations such as those described above, an accurate knowledge of the extensional viscosity of a polymer system and its variation with temperature, concentration, molecular weight, and strain rate is critical.

  3. Colloid-polymer mixtures in solution with refractive index matched acrylate colloids.

    PubMed

    Kramer, Thomas; Scholz, Stephanie; Maskos, Michael; Huber, Klaus

    2004-11-15

    Colloid-polymer (CP) mixtures extend between two limiting cases, the colloid limit with the polymer coil size small compared to the colloid radius Rcol and the protein limit with the colloidal particles much smaller in size than the radius of gyration of the polymer chains Rg. In the present work, model systems are developed for the protein limit. The colloid-solvent pairs are optimized in terms of their isorefractivity in order to facilitate the characterization of large polystyrene chains in suspensions of small colloids. The degree of isorefractivity of colloidal particles was successfully evaluated in terms of a reduced scattering intensity. Two polystyrene samples with radii of gyration of Rg = 96 nm and Rg = 78 nm, respectively, are used. The radii of the colloidal particles are close to Rcol = 12 nm, leading to size ratios of Rg/Rcol = 8 and Rg/Rcol = 6.5. Four colloid solvent systems were found to be suitable for polymer characterization by light scattering, one based on silica particles and three systems with acrylate particles. The present investigation is focused on the three acrylate systems: poly(methyl methacrylate) in ethyl benzoate (ETB) at 7 degrees C, poly(ethyl methacrylate) in toluene at 7 degrees C and poly(ethyl methacrylate) in ETB at 40 degrees C. Characterization of PS chains is for the first time performed in colloid concentrations up to 2.5% by weight. In all cases, the size and shape of the polymer chains remain unchanged. A slight mismatch of the colloid scattering or a limited colloid solubility prevented investigation of PS chains at higher colloid concentration.

  4. Compressive cyclic ratcheting and fatigue of synthetic, soft biomedical polymers in solution.

    PubMed

    Miller, Andrew T; Safranski, David L; Smith, Kathryn E; Guldberg, Robert E; Gall, Ken

    2016-02-01

    The use of soft, synthetic materials for the replacement of soft, load-bearing tissues has been largely unsuccessful due to a lack of materials with sufficient fatigue and wear properties, as well as a lack of fundamental understanding on the relationship between material structure and behavior under cyclic loads. In this study, we investigated the response of several soft, biomedical polymers to cyclic compressive stresses under aqueous conditions and utilized dynamic mechanical analysis and differential scanning calorimetry to evaluate the role of thermo-mechanical transitions on such behavior. Studied materials include: polycarbonate urethane, polydimethylsiloxane, four acrylate copolymers with systematically varied thermo-mechanical transitions, as well as bovine meniscal tissue for comparison. Materials showed compressive moduli between 2.3 and 1900MPa, with polycarbonate urethane (27.3MPa) matching closest to meniscal tissue (37.0MPa), and also demonstrated a variety of thermo-mechanical transition behaviors. Cyclic testing resulted in distinct fatigue-life curves, with failure defined as either classic fatigue fracture or a defined increased in maximum strain due to ratcheting. Our study found that polymers with sufficient dissipation mechanisms at the testing temperature, as evidenced by tan delta values, were generally tougher than those with less dissipation and exhibited ratcheting rather than fatigue fracture much like meniscal tissue. Strain recovery tests indicated that, for some toughened polymers, the residual strain following our cyclic loading protocol could be fully recovered. The similarity in ratcheting behavior, and lack of fatigue fracture, between the meniscal tissue and toughened polymers indicates that such polymers may have potential as artificial soft tissue.

  5. Lithium Ion Polymer Electrolyte Based on Pva-Pan

    NASA Astrophysics Data System (ADS)

    Genova, F. Kingslin Mary; Selvasekarapandian, S.; Rajeswari, N.; Devi, S. Siva; Karthikeyan, S.; Raja, C. Sanjeevi

    2013-07-01

    The polymer blend electrolytes based on polyvinylalcohol(PVA) and polyacrylonitrile (PAN) doped with lithium per chlorate (LiClO4) have been prepared by solution casting technique using DMF as solvent. The complex formation between blend polymer and the salt has been confirmed by Fourier transform infrared spectroscopy. The amorphous nature of the blend polymer electrolyte has been confirmed by X-ray diffraction analysis. The ionic conductivity of the prepared blend polymer electrolyte has been found by ac impedence spectroscopic analysis. The highest ionic conductivity has been found to be 5.0 X10-4 S cm -1 at room temperature for 92.5 PVA: 7.5PAN: 20 molecular wt. % of LiClO4. The effect of salt concentration on the conductivity of the blend polymer electrolyte has been discussed.

  6. Characterisation of Proton Conducting Polymer Electrolyte Based on Pan

    NASA Astrophysics Data System (ADS)

    Nithya, S.; Selvasekarapandian, S.; Rajeswari, N.; Sikkanthar, S.; Karthikeyan, S.; Sanjeeviraja, C.

    2013-07-01

    The polymer electrolytes composed of polyacrylonitrile (PAN) with various concentration of ammonium nitrare (NH4NO3) salt have been prepared by solution casting method, using DMF as solvent. The increase in amorphous nature of the polymer electrolytes has been confirmed by Xray diffraction analysis. The complex formation between polymer and dissociated salt has been confirmed by Fourier transform infrared spectroscopy. From the Ac impedance spectroscopic analysis, the ionic conductivity of 20 mol% NH4NO3 doped polymer complex has been found to be 2.742 × 10-6 S cm-1 at room temperature. The conductivity has been increased when the temperature is increased. The activation energy of 20 mol% NH4NO3 doped polymer electrolyte was calculated using Arrhenius plot and it has been found to be 0.58 eV. The dielectric permitivitty (ɛ*) and electric modulus (m*) have been discussed.

  7. Impact of polymer conformation on the crystal growth inhibition of a poorly water-soluble drug in aqueous solution.

    PubMed

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

    2015-01-01

    Poor aqueous solubility is a major hindrance to oral delivery of many emerging drugs. Supersaturated drug solutions can improve passive absorption across the gastrointestinal tract membrane as long as crystallization can be inhibited, enhancing the delivery of such poorly soluble therapeutics. Polymers can inhibit crystallization and prolong supersaturation; therefore, it is desirable to understand the attributes which render a polymer effective. In this study, the conformation of a polymer adsorbed to a crystal surface and its impact on crystal growth inhibition were investigated. The crystal growth rate of a poorly soluble pharmaceutical compound, felodipine, was measured in the presence of hydroxypropyl methylcellulose acetate succinate (HPMCAS) at two different pH conditions: pH 3 and pH 6.8. HPMCAS was found to be a less effective growth rate inhibitor at pH 3, below its pKa. It was expected that the ionization state of HPMCAS would most likely influence its conformation at the solid-liquid interface. Further investigation with atomic force microscopy (AFM) revealed significant differences in the conformation of HPMCAS adsorbed to felodipine at the two pH conditions. At pH 3, HPMCAS formed coiled globules on the surface, whereas at pH 6.8, HPMCAS adsorbed more uniformly. Thus, it appeared that the reduced effectiveness of HPMCAS at pH 3 was directly related to its conformation. The globule formation leaves many felodipine growth sites open and available for growth units to attach, rendering the polymer less effective as a growth rate inhibitor.

  8. Thermal Processing of PVP- and HPMC-Based Amorphous Solid Dispersions.

    PubMed

    LaFountaine, Justin S; Prasad, Leena Kumari; Brough, Chris; Miller, Dave A; McGinity, James W; Williams, Robert O

    2016-02-01

    Thermal processing technologies continue to gain interest in pharmaceutical manufacturing. However, the types and grades of polymers that can be utilized in common thermal processing technologies, such as hot-melt extrusion (HME), are often limited by thermal or rheological factors. The objectives of the present study were to compare and contrast two thermal processing methods, HME and KinetiSol® Dispersing (KSD), and investigate the influence of polymer type, polymer molecular weight, and drug loading on the ability to produce amorphous solid dispersions (ASDs) containing the model compound griseofulvin (GRIS). Dispersions were analyzed by a variety of imaging, solid-state, thermal, and solution-state techniques. Dispersions were prepared by both HME and KSD using polyvinylpyrrolidone (PVP) K17 or hydroxypropyl methylcellulose (HPMC) E5. Dispersions were only prepared by KSD using higher molecular weight grades of HPMC and PVP, as these could not be extruded under the conditions selected. Powder X-ray diffraction (PXRD) analysis showed that dispersions prepared by HME were amorphous at 10% and 20% drug load; however, it showed significant crystallinity at 40% drug load. PXRD analysis of KSD samples showed all formulations and drug loads to be amorphous with the exception of trace crystallinity seen in PVP K17 and PVP K30 samples at 40% drug load. These results were further supported by other analytical techniques. KSD produced amorphous dispersions at higher drug loads than could be prepared by HME, as well as with higher molecular weight polymers that were not processable by HME, due to its higher rate of shear and torque output.

  9. Variational Formulas and Cocycle solutions for Directed Polymer and Percolation Models

    NASA Astrophysics Data System (ADS)

    Georgiou, Nicos; Rassoul-Agha, Firas; Seppäläinen, Timo

    2016-09-01

    We discuss variational formulas for the law of large numbers limits of certain models of motion in a random medium: namely, the limiting time constant for last-passage percolation and the limiting free energy for directed polymers. The results are valid for models in arbitrary dimension, steps of the admissible paths can be general, the environment process is ergodic under spatial translations, and the potential accumulated along a path can depend on the environment and the next step of the path. The variational formulas come in two types: one minimizes over gradient-like cocycles, and another one maximizes over invariant measures on the space of environments and paths. Minimizing cocycles can be obtained from Busemann functions when these can be proved to exist. The results are illustrated through 1+1 dimensional exactly solvable examples, periodic examples, and polymers in weak disorder.

  10. Emission characteristics in solution-processed asymmetric white alternating current field-induced polymer electroluminescent devices

    NASA Astrophysics Data System (ADS)

    Chen, Yonghua; Xia, Yingdong; Smith, Gregory M.; Gu, Yu; Yang, Chuluo; Carroll, David L.

    2013-01-01

    In this work, the emission characteristics of a blue fluorophor poly(9, 9-dioctylfluorene) (PFO) combined with a red emitting dye: Bis(2-methyl-dibenzo[f,h]quinoxaline)(acetylacetonate)iridium (III) [Ir(MDQ)2(acac)], are examined in two different asymmetric white alternating current field-induced polymer electroluminescent (FIPEL) device structures. The first is a top-contact device in which the triplet transfer is observed resulting in the concentration-dependence of the emission similar to the standard organic light-emitting diode (OLED) structure. The second is a bottom-contact device which, however, exhibits concentration-independence of emission. Specifically, both dye emission and polymer emission are found for the concentrations as high as 10% by weight of the dye in the emitter. We attribute this to the significant different carrier injection characteristics of the two FIPEL devices. Our results suggest a simple and easy way to realize high-quality white emission.

  11. From the Solution Processing of Hydrophilic Molecules to Polymer-Phthalocyanine Hybrid Materials for Ammonia Sensing in High Humidity Atmospheres

    PubMed Central

    Gaudillat, Pierre; Jurin, Florian; Lakard, Boris; Buron, Cédric; Suisse, Jean-Moïse; Bouvet, Marcel

    2014-01-01

    We have prepared different hybrid polymer-phthalocyanine materials by solution processing, starting from two sulfonated phthalocyanines, s-CoPc and CuTsPc, and polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), poly(acrylic acid-co-acrylamide) (PAA-AM), poly(diallyldimethylammonium chloride) (PDDA) and polyaniline (PANI) as polymers. We also studied the response to ammonia (NH3) of resistors prepared from these sensing materials. The solvent casted films, prepared from s-CoPc and PVP, PEG and PAA-AM, were highly insulating and very sensitive to the relative humidity (RH) variation. The incorporation of s-CoPc in PDDA by means of layer-by-layer (LBL) technique allowed to stabilize the film, but was too insulating to be interesting. We also prepared PANI-CuTsPc hybrid films by LBL technique. It allowed a regular deposition as evidenced by the linear increase of the absorbance at 688 nm as a function of the number of bilayers. The sensitivity to ammonia (NH3) of PANi-CuTsPc resistors was very high compared to that of individual materials, giving up to 80% of current decrease when exposed to 30 ppm NH3. Contrarily to what happens with neutral polymers, in PANI, CuTsPc was stabilized by strong electrostatic interactions, leading to a stable response to NH3, whatever the relative humidity in the range 10%–70%. Thus, the synergy of PANI with ionic macrocycles used as counteranions combined with their simple aqueous solution processing opens the way to the development of new gas sensors capable of operating in real world conditions. PMID:25061841

  12. Moving through the phase diagram: morphology formation in solution cast polymer-fullerene blend films for organic solar cells.

    PubMed

    Schmidt-Hansberg, Benjamin; Sanyal, Monamie; Klein, Michael F G; Pfaff, Marina; Schnabel, Natalie; Jaiser, Stefan; Vorobiev, Alexei; Müller, Erich; Colsmann, Alexander; Scharfer, Philip; Gerthsen, Dagmar; Lemmer, Uli; Barrena, Esther; Schabel, Wilhelm

    2011-11-22

    The efficiency of organic bulk heterojunction solar cells strongly depends on the multiscale morphology of the interpenetrating polymer-fullerene network. Understanding the molecular assembly and the identification of influencing parameters is essential for a systematic optimization of such devices. Here, we investigate the molecular ordering during the drying of doctor-bladed polymer-fullerene blends on PEDOT:PSS-coated substrates simultaneously using in situ grazing incidence X-ray diffraction (GIXD) and laser reflectometry. In the process of blend crystallization, we observe the nucleation of well-aligned P3HT crystallites in edge-on orientation at the interface at the instant when P3HT solubility is crossed. A comparison of the real-time GIXD study at ternary blends with the binary phase diagrams of the drying blend film gives evidence of strong polymer-fullerene interactions that impede the crystal growth of PCBM, resulting in the aggregation of PCBM in the final drying stage. A systematic dependence of the film roughness on the drying time after crossing P3HT solubility has been shown. The highest efficiencies have been observed for slow drying at low temperatures which showed the strongest P3HT interchain π-π-ordering along the substrate surface. By adding the "unfriendly" solvent cyclohexanone to a chlorobenzene solution of P3HT:PCBM, the solubility can be crossed prior to the drying process. Such solutions exhibit randomly orientated crystalline structures in the freshly cast film which results in a large crystalline orientation distribution in the dry film that has been shown to be beneficial for solar cell performance.

  13. Amorphous fluorocarbon polymer (a-C:F) films obtained by plasma enhanced chemical vapor deposition from perfluoro-octane (C8F18) vapor I: Deposition, morphology, structural and chemical properties

    NASA Astrophysics Data System (ADS)

    Biloiu, Costel; Biloiu, Ioana Arabela; Sakai, Yosuke; Suda, Yoshiyuki; Ohta, Akitsugu

    2004-01-01

    The method of obtaining amorphous fluorocarbon polymer (a-C:F) films by plasma enhanced chemical vapor deposition in a capacitively coupled, 13.56 MHz reactor, from a new monomer, namely perfluoro-octane (C8F18) vapor, is presented. For monomer pressure ranging from 0.2 to 1 Torr and input power density from 0.15 to 0.85 W/cm3, the maximum deposition rate reached 300 nm/min, while 10% monomer dilution with argon led to a deposition rate of 200 nm/min. The film surface and bulk morphologies, chemical and structural compositions were investigated using scanning electron microscopy, x-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. It was revealed that the films have a dense and compact structure. The fluorine to carbon ratio (F/C) of the films was between 1.57 and 1.75, and the degree of cross-linking was between 55% and 58%. The relative amount of perfluoroalkyl (CF2) groups in the films was 29%. The FTIR spectra showed absorption bands corresponding to the different vibrational modes of CF, CF2, and CF3 moieties. .

  14. Conformation and diffusion behavior of ring polymers in solution: A comparison between molecular dynamics, multiparticle collision dynamics, and lattice Boltzmann simulations

    NASA Astrophysics Data System (ADS)

    Hegde, Govind A.; Chang, Jen-fang; Chen, Yeng-long; Khare, Rajesh

    2011-11-01

    We have studied the effect of chain topology on the structural properties and diffusion of polymers in a dilute solution in a good solvent. Specifically, we have used three different simulation techniques to compare the chain size and diffusion coefficient of linear and ring polymers in solution. The polymer chain is modeled using a bead-spring representation. The solvent is modeled using three different techniques: molecular dynamics (MD) simulations with a particulate solvent in which hydrodynamic interactions are accounted through the intermolecular interactions, multiparticle collision dynamics (MPCD) with a point particle solvent which has stochastic interactions with the polymer, and the lattice Boltzmann method in which the polymer chains are coupled to the lattice fluid through friction. Our results show that the three methods give quantitatively similar results for the effect of chain topology on the conformation and diffusion behavior of the polymer chain in a good solvent. The ratio of diffusivities of ring and linear polymers is observed to be close to that predicted by perturbation calculations based on the Kirkwood hydrodynamic theory.

  15. Amorphous Computing

    NASA Astrophysics Data System (ADS)

    Sussman, Gerald

    2002-03-01

    agents constructed by engineered cells, but we have few ideas for programming them effectively: How can one engineer prespecified, coherent behavior from the cooperation of immense numbers of unreliable parts that are interconnected in unknown, irregular, and time-varying ways? This is the challenge of Amorphous Computing.

  16. Analysis of the detection of organophosphate pesticides in aqueous solutions using polymer-coated single IDT sensors

    NASA Astrophysics Data System (ADS)

    McCarthy, Michael

    The single interdigital transducer (IDT) device was investigated as a micro-chemical sensor for the detection of organophosphates compounds in aqueous solutions. The compounds of interest are: parathion, parathion-methyl, and paraoxon. The polymers used as a partially-selective coating for the direct detection of these compounds are 2,2'-diallylbisphenol A- 1,1,3,3,5,5-hexamethyltrisiloxane (BPA-HMTS) and polyepichlorohydrin (PECH). BPA-HMTS is synthesized here at Marquette University. The measurement of interest for the single IDT is the change radiation resistance. The radiation resistance represents the energy stored in the propagating acoustic wave. As analyte absorbs into the polymer coating, changes in the film's properties will undergo resulting in a change in the radiation resistance i.e the acoustic wave properties. The film's properties changing include: added mass, viscoelastic properties, thickness, and dielectric properties. These properties will contribute to an overall change in the radiation resistance. A linear change in the radiation resistance is expected to occur for increasing concentrations of an organophosphate. The experimental results indicate that BPA-HMTS shows greater sensitivity towards the organophosphates than PECH. Both polymers showed greatest to lowest sensitivity to parathion, parathion-methyl, and paraoxon respectively. Thicker films tested for both polymers, 0.75μm thick, show a higher response due to a more pronounced effect of mass loading than the thinner films tested, 0.50μm. The response times for BPA-HMTS were much faster than for PECH. Both films showed fastest to slowest response time to paraoxon, parathion-methyl, and parathion respectively. The sensor is tested for reproducibility for the polymer BP-HMTS. A sensor array consisting of separately tested devices from this work as well as work done by a previous student is utilized to increase the selectivity of the three organophosphates. Radial plots are performed for

  17. Photochemical Fixation of Individual Polymer Nanoparticles on Glass Substrates in Solution at Room Temperature

    NASA Astrophysics Data System (ADS)

    Ito, Syoji; Yoshikawa, Hiroyuki; Masuhara, Hiroshi

    2004-07-01

    A new method for fixing single polymer nanoparticles onto a substrate was developed by local photopolymerization. A nanoparticle, dispersed in ethylene glycol containing monomer, crosslinker, and radical photoinitiator, was moved to the surface of a glass substrate using a focused near-infrared laser beam. Local photopolymerization around the nanoparticle was induced by additional irradiation of an ultraviolet pulsed laser beam, resulting in the generation of an acrylamide gel containing the nanoparticle on the substrate. The nanoparticles become fixed and remained after washing. The morphology of the formed polymerized gel was evaluated by atomic force microscope (AFM) observation.

  18. Adsorption properties of the nanozirconia/anionic polyacrylamide system-Effects of surfactant presence, solution pH and polymer carboxyl groups content

    NASA Astrophysics Data System (ADS)

    Wiśniewska, Małgorzata; Chibowski, Stanisław; Urban, Teresa

    2016-05-01

    The adsorption mechanism of anionic polyacrylamide (PAM) on the nanozirconia surface was examined. The effects of solution pH, carboxyl groups content in macromolecules and anionic surfactant (sodium dodecyl sulfate-SDS) addition were determined. The more probable structure of polymer adsorption layer was characterized based on the data obtained from spectrophotometry, viscosimetry and potentiometric titration methods. The adsorbed amount of polymer, size of macromolecules in the solution and surface charge density of ZrO2 particles in the absence and presence of PAM were assessed, respectively. Analysis of these results indicated that the increase of solution pH and content of carboxyl groups in the polymeric chains lead to more expanded conformations of adsorbing macromolecules. As a result, the adsorption of anionic polyacrylamide decreased. The SDS presence caused the significant increase of PAM adsorbed amount at pH 3, whereas at pH 6 and 9 the surfactant addition resulted in reduction of polymer adsorption level.

  19. Unraveling the Nanostructure and Chain Conformation of Peptide-polymer Conjugates in Solution using Small-angle X-ray Scattering

    NASA Astrophysics Data System (ADS)

    Lund, Reidar; Xu, Ting; Dong, He

    For therapeutics, polymer functionalization, often by poly(ethylene glycol), PEG (``PEGylation''), is an effective method to improve the solubility, increase the life time and protect the proteins from the immune system[1]. However it is essential that the proteins maintain their structural integrity in solution- thus the role of the polymer and their interactions with proteins needs to be understood. In this work we show how small-angle X-ray scattering (SAXS) can be used as a powerful technique to characterize the structural components of peptide-polymer conjugates in solution [2, 3]. We specifically show that by applying detailed modelling very detailed structural features can be revealed, including the PEG chain conformation. In the presentation we will provide an overview of the methodology, specifically addressing peptides that form either alpha-helical bundles [2, 3] or beta-sheet structures [4, 5] and relate their structure in solution to their crystal structure.

  20. Displacement and sweep efficiencies in a DNAPL recovery test using micellar and polymer solutions injected in a five-spot pattern.

    PubMed

    Martel, Richard; Hébert, Alain; Lefebvre, René; Gélinas, Pierre; Gabriel, Uta

    2004-11-01

    Soil washing with micellar solutions is a promising alternative for the remediation of DNAPL source zones. As with any flushing technology, the success of soil washing with micellar solutions depends in a very large part on the ability of the solution to contact the contaminant (sweep efficiency) and then on the efficiency of contaminant removal once this contact is made (displacement efficiency). We report here on a field test where a micellar solution was used to recover a DNAPL in an open five-spot pattern in which polymer solutions were also injected before and after the washing solution to improve sweep efficiency. The washing solution formulation was optimised in the laboratory prior to the test to obtain good dissolution capacity. For a high-concentration and low-volume soil flushing remediation test such as the one performed (0.8 pore volumes of actual washing solution injected), slug sizing of the washing solution is critical. It was evaluated by an analytical solution. In a five-spot pattern, the displacement efficiency of the washing solution was observed to vary in the porous medium as a function of the radial distance from the injection well because: (1) the volume of the washing solution flowing through a section of the test cell changes (maximum close to the injection well and minimal at the pumping wells); (2) the in situ velocity changes (maximum at the wells and minimum between the wells) and; (3) the contact time of the washing solution with the NAPL changes as a function of the distance from the injection well. The relative importance of the recovery mechanisms, mobilisation and dissolution, was also observed to vary in the test cell. The reduced velocity increased the contact time of the washing solution with the DNAPL enhancing its dissolution, but the decrease of the capillary number caused less mobilisation. The washing process is much more extensive around the injection well. The use of an injection-pumping pattern allowing a complete sweep

  1. Removal of anionic azo dyes from aqueous solution by functional ionic liquid cross-linked polymer.

    PubMed

    Gao, Hejun; Kan, Taotao; Zhao, Siyuan; Qian, Yixia; Cheng, Xiyuan; Wu, Wenli; Wang, Xiaodong; Zheng, Liqiang

    2013-10-15

    A novel functional ionic liquid based cross-linked polymer (PDVB-IL) was synthesized from 1-aminoethyl-3-vinylimidazolium chloride and divinylbenzene for use as an adsorbent. The physicochemical properties of PDVB-IL were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The adsorptive capacity was investigated using anionic azo dyes of orange II, sunset yellow FCF, and amaranth as adsorbates. The maximum adsorption capacity could reach 925.09, 734.62, and 547.17 mg/g for orange II, sunset yellow FCF and amaranth at 25°C, respectively, which are much better than most of the other adsorbents reported earlier. The effect of pH value was investigated in the range of 1-8. The result shows that a low pH value is found to favor the adsorption of those anionic azo dyes. The adsorption kinetics and isotherms are well fitted by a pseudo second-order model and Langmuir model, respectively. The adsorption process is found to be dominated by physisorption. The introduction of functional ionic liquid moieties into cross-linked poly(divinylbenzene) polymer constitutes a new and efficient kind of adsorbent.

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

    NASA Astrophysics Data System (ADS)

    Moreno, Nicolas; Nunes, Suzana P.; Calo, Victor M.

    2015-11-01

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

  3. Explaining the absence of high-frequency relaxation modes of polymers in dilute solutions

    NASA Astrophysics Data System (ADS)

    Saha Dalal, Indranil; Larson, Ronald

    2013-03-01

    Using multi-scale modeling, including Molecular Dynamics and Brownian dynamics (BD) simulations, we explain the long-mysterious absence of high frequency modes in the dynamics of isolated polymer chains in good solvents, reported years ago by Schrag and coworkers. The relaxation spectrum we obtain for a chain of 30 monomers at atomistic resolution is, remarkably, a single exponential while that of a chain of 100 monomers is fit by only two modes. This result is surprising in view of the many relaxation modes present in melts of such chains, but agrees perfectly with experimental observations (Peterson et al. J. Polym. Sci.: Part B 2001). We also performed BD simulations in which the explicit solvent molecules are replaced by a viscous continuum. Although the local dynamics is suppressed with the addition of bending, torsion, side groups and excluded volume interactions (as suggested in Jain and Larson, Macromolecules 2008), none of the BD simulations predict a single exponential relaxation for a short chain. Our results indicate that the chain dynamics at small length scales (down to a few Kuhn steps) is significantly different from the predictions of models based on a continuum solvent, and finally help explain the experimental results of Schrag and coworkers.

  4. SOLUTION RHEOLOGY OF HYPERBRANCHED POLYESTERS AND THEIR BLENDS WITH LINEAR POLYMERS

    EPA Science Inventory

    In this study, the rheological properties of different generations of hyperbranched polyesters in 1-methyl-2-pyrrolidinone solvent and their blends with poly(2-hydroxyethyl methacrylate) have ben investigated. All the hyperbranched polyester solutions exhibited Newtonian behavior...

  5. Unified force-level theory of multiscale transient localization and emergent elasticity in polymer solutions and melts

    NASA Astrophysics Data System (ADS)

    Dell, Zachary E.; Schweizer, Kenneth S.

    A unified, microscopic, theoretical understanding of polymer dynamics in concentrated liquids from segmental to macromolecular scales remains an open problem. We have formulated a statistical mechanical theory for this problem that explicitly accounts for intra- and inter-molecular forces at the Kuhn segment level. The theory is self-consistently closed at the level of a matrix of dynamical second moments of a tagged chain. Two distinct regimes of isotropic transient localization are predicted. In semidilute solutions, weak localization is predicted on a mesoscopic length scale between segment and chain scales which is a power law function of the invariant packing length. This is consistent with the breakdown of Rouse dynamics and the emergence of entanglements. The chain structural correlations in the dynamically arrested state are also computed. In dense melts, strong localization is predicted on a scale much smaller than the segment size which is weakly dependent on chain connectivity and signals the onset of glassy dynamics. Predictions of the dynamic plateau shear modulus are consistent with the known features of emergent rubbery and glassy elasticity. Generalizations to treat the effects of chemical crosslinking and physical bond formation in polymer gels are possible.

  6. Demonstrating the importance of polymer-conjugate conformation in solution on its therapeutic output: Diethylstilbestrol (DES)-polyacetals as prostate cancer treatment.

    PubMed

    Giménez, Vanessa; James, Craig; Armiñán, Ana; Schweins, Ralf; Paul, Alison; Vicent, María J

    2012-04-30

    The design of improved polymeric carriers to be used in the next generation of polymer therapeutics is an ongoing challenge. Biodegradable systems present potential advantages regarding safety benefit apart from the possibility to use higher molecular weight (Mw) carriers allowing PK optimization, by exploiting the enhanced permeability and retention (EPR)-mediated tumor targeting. Within this context, we previously designed pH-responsive polyacetalic systems, tert-polymers, where a drug with the adequate diol-functionality was incorporated within the polymer mainchain. The synthetic, non-steroidal estrogen, diethylstilboestrol (DES) clinically used for the treatment of advanced prostate cancer was chosen as drug. In order to improve the properties of this tert-polymer, novel polyacetalic systems as block-co-polymers, with more defined structure have been obtained. This second generation polyacetals allowed higher drug capacity than the tert-polymer, a biphasic DES release profile at acidic pH and due to its controlled amphiphilic character readily formed micelle-like structures in solution. These features result in an enhancement of conjugate therapeutic value in selected prostate cancer cell models. Exhaustive physico-chemical characterization focusing on nanoconjugate solution behavior and using advanced techniques, such as, pulsed-gradient spin-echo NMR (PGSE-NMR) and small-angle neutron scattering (SANS), has been carried out in order to demonstrate this hypothesis. Clear evidence of significantly different conformation in solution has been obtained for both polyacetals. These results demonstrate that an adequate control on molecular or supramolecular conformation in solution with polymer therapeutics is crucial in order to achieve the desired therapeutic output.

  7. High-Performance Thin Film Transistor from Solution-Processed P3HT Polymer Semiconductor Nanoparticles

    NASA Astrophysics Data System (ADS)

    Darwis, Darmawati; Elkington, Daniel; Ulum, Syahrul; Stapleton, Andrew; Bryant, Glenn; Zhou, Xiaojing; Belcher, Warwick; Dastoor, Paul

    2011-12-01

    Nanoparticulate suspensions of semiconducting polymer poly-3-hexylthiophene (P3HT) have been prepared in water through a mini-emulsion process using sodium dodecyl sulphate (SDS) as the surfactant. Using these suspensions, we have fabricated organic thin film transistors (OTFTs) in a top gate configuration. These devices operate at a low voltage and show output characteristics similar to those achieved when the P3HT film is spun from chloroform. To characterize the properties of the film made from the nanoparticle suspension, differential thermal analysis (TGA), differential scanning calorimetry (DSC), atomic force microscopy (AFM), fluorescence spectra analysis, ultraviolet/visible (UV/VIS) spectrophotometry and X-ray photoelectron spectroscopy (XPS) have been used.

  8. Shear-induced concentration fluctuations and form factor changes in polymer solution in the good-solvent regime.

    PubMed

    Morfin, I; Lindner, P; Boué, F

    2004-09-01

    Small-Angle Scattering from sheared semidilute polymer solution is reported in the good-solvent regime, at variance with former light and neutron measurements in the theta regime. First, concentration fluctuations are observed: the scattering increases noticeably along the flow at low q, but at variance with former results for the theta-solvent regime, no demixing is observed at higher shear. Here, instead, the effects follow a time-temperature superposition and saturate above a Weissenberg number around 5, like the stress which is known to present a plateau for these systems. Using the Zero Average Contrast technique, we have also measured the form factor, which displays the same saturation effect reaching a deformation ratio of the order of 2. These results agree with the Convective Constraint Release models (CCR) elaborated in order to predict the stress effects in the non-Newtonian regime (Marrucci-Ianniruberto) and their extension predicting also the scattering (Likhtman-Milner-McLeish).

  9. Water-compatible 'aspartame'-imprinted polymer grafted on silica surface for selective recognition in aqueous solution.

    PubMed

    Singh, Meenakshi; Kumar, Abhishek; Tarannum, Nazia

    2013-05-01

    Molecularly imprinted polymers selective for aspartame have been prepared using N-[2-ammonium-ethyl-piperazinium) maleimidopropane sulfonate copolymer bearing zwitterionic centres along the backbone via a surface-confined grafting procedure. Aspartame, a dipeptide, is commonly used as an artificial sweetener. Polymerisation on the surface was propagated by means of Michael addition reaction on amino-grafted silica surface. Electrostatic interactions along with complementary H-bonding and other hydrophobic interactions inducing additional synergetic effect between the template (aspartame) and the imprinted surface led to the formation of imprinted sites. The MIP was able to selectively and specifically take up aspartame from aqueous solution and certain pharmaceutical samples quantitatively. Hence, a facile, specific and selective technique using surface-grafted specific molecular contours developed for specific and selective uptake of aspartame in the presence of various interferrants, in different kinds of matrices is presented.

  10. Hierarchical Structure of Supramolecular Polymers Formed by N,N'-Di(2-ethylhexyl)urea in Solutions.

    PubMed

    Świergiel, Jolanta; Bouteiller, Laurent; Jadżyn, Jan

    2015-10-01

    Supramolecular chain polymers formed by N,N'-di(2-ethylhexyl)urea (EHU) dissolved at low concentrations (up to 0.1 mole fraction) in heptane were investigated with the use of the dielectric spectroscopy. The experimental data show an exceptional ability of the chains for the antiparallel self-aggregation due to dipole-dipole interactions, leading to an anomalous dependence of the static permittivity of EHU + heptane solutions on temperature and concentration of the urea. The primary molecular assembly into polymeric chains is therefore followed by a secondary bundling of the chains which facilitates a longitudinal translation of the chains. That peculiarity and an asymmetry of the alkyl substituent in the EHU molecule making the system a mixture of diastereoisomers of unfavorable packing of the side group, are the most probable molecular mechanisms which prevent the crystallization of EHU-the only known liquid urea derivative. PMID:26371560

  11. Polymer-assisted metal deposition (PAMD): a full-solution strategy for flexible, stretchable, compressible, and wearable metal conductors.

    PubMed

    Yu, You; Yan, Casey; Zheng, Zijian

    2014-08-20

    Metal interconnects, contacts, and electrodes are indispensable elements for most applications of flexible, stretchable, and wearable electronics. Current fabrication methods for these metal conductors are mainly based on conventional microfabrication procedures that have been migrated from Si semiconductor industries, which face significant challenges for organic-based compliant substrates. This Research News highlights a recently developed full-solution processing strategy, polymer-assisted metal deposition (PAMD), which is particularly suitable for the roll-to-roll, low-cost fabrication of high-performance compliant metal conductors (Cu, Ni, Ag, and Au) on a wide variety of organic substrates including plastics, elastomers, papers, and textiles. This paper presents i) the principles of PAMD, and how to use it for making ii) flexible, stretchable, and wearable conductive metal electrodes, iii) patterned metal interconnects, and d) 3D stretchable and compressible metal sponges. A critical perspective on this emerging strategy is also provided. PMID:24458846

  12. Fully solution-processed semitransparent organic solar cells with a silver nanowire cathode and a conducting polymer anode.

    PubMed

    Yim, Jong Hyuk; Joe, Sung-yoon; Pang, Christina; Lee, Kyung Moon; Jeong, Huiseong; Park, Ji-Yong; Ahn, Yeong Hwan; de Mello, John C; Lee, Soonil

    2014-03-25

    We report the fabrication of efficient indium-tin-oxide-free organic solar cells based on poly(3-hexylthiophene-2,5-diyl):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM). All layers of the devices from the lowermost silver nanowire cathode to the uppermost conducting polymer anode are deposited from solution and processed at plastic-compatible temperatures<200 °C. Owing to the absence of an opaque metal electrode, the devices are semitransparent with potential applications in power-generating windows and tandem-cells. The measured power conversion efficiencies (PCEs) of 2.3 and 2.0% under cathode- and anode-side illumination, respectively, match previously reported PCE values for equivalent semitransparent organic solar cells using indium tin oxide. PMID:24533638

  13. Novel low voltage and solution processable organic thin film transistors based on water dispersed polymer semiconductor nanoparticulates.

    PubMed

    Darwis, Darmawati; Elkington, Daniel; Ulum, Syahrul; Bryant, Glenn; Belcher, Warwick; Dastoor, Paul; Zhou, Xiaojing

    2013-07-01

    Two novel organic thin film transistor structures that combine a hygroscopic insulator with the use of water-dispersed polymer nanoparticles as the active layer are presented. In the first device structure, the semiconducting layer was fabricated from a nanoparticulate suspension of poly-(3-hexylthiophene) prepared through a mini-emulsion process using sodium dodecyl sulfate as the surfactant whereas a surfactant-free precipitation method has been used for the second device structure. In both cases, fully solution processable transistors have been fabricated in a top gate configuration with hygroscopic poly(4-vinylphenol) as the dielectric layer. Both device structures operate at low voltages (0 to -4V) but exhibit contrasting output characteristics. A systematic study is presented on the effect of surfactant on the synthesis of semiconducting nanoparticles, the formation of thin nanoparticulate films and, consequently, on device performance.

  14. Effect of chain architecture on the size, shape, and intrinsic viscosity of chains in polymer solutions: A molecular simulation study

    NASA Astrophysics Data System (ADS)

    Khabaz, Fardin; Khare, Rajesh

    2014-12-01

    Effect of chain architecture on the chain size, shape, and intrinsic viscosity was investigated by performing molecular dynamics simulations of polymer solutions in a good solvent. Four types of chains - linear, comb shaped, H-shaped, and star - were studied for this purpose using a model in which the solvent particles were considered explicitly. Results indicated that the chain length (N) dependence of the mean squared radius of gyration of the chains followed a power-law behavior < {R_g^2 } rangle ^{1/2} ˜ N^\\upsilon with scaling exponents of υ = 0.605, 0.642, 0.602, and 0.608, for the linear, comb shaped, H-shaped, and star shaped chains, respectively. The simulation results for the geometrical shrinking factor were higher than the prior theoretical predictions for comb shaped chains. Analysis of chain shape demonstrated that the star chains were significantly smaller and more spherical than the others, while the comb and H-shaped polymer chains showed a more cylindrical shape. It is shown that the intrinsic viscosity of the chains can be calculated by plotting the specific viscosity determined from simulations against the solution concentration. The intrinsic viscosity exhibited linear behavior with the reciprocal of the overlap concentration for all chain architectures studied. The molecular weight dependence of the intrinsic viscosity followed the Mark-Houwink relation, [η] = KMa, for all chain architectures. When comparing the calculated values of exponent a with the literature experimental values, agreement was found only for the H and star chains, and a disagreement for the linear and comb chains. The viscosity shrinking factor of the branched chains was compared with the available experimental data and the theoretical predictions and a general agreement was found.

  15. Influence of polymeric electron injection layers on the electrical properties of solution-processed multilayered polymer light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Itoh, Eiji; Kurami, Kazuhiko

    2016-02-01

    In this study, we fabricated multilayered polymer-based light-emitting diodes (pLEDs) with various solution-processed electron-injection layers (EILs), and investigated the influence of the EILs on the electrical properties of pLEDs in indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonic acid) (PEDOT:PSS)/poly[(9,9-dioctylfluorene-alt-(1,4-phenylene((4-sec-butylphenyl)amino)-1,4-phenylene))] (TFB) (HTL)/poly(9,9-dioctylfluorene-alt-1,4-benzothiadiazole) (F8BT) (EML)/EIL/Al structures. We have used the quaternized ammonium π-conjugated polyelectrolyte derivative (poly[(9,9-di(3,3‧-N,N‧-trimethylammonium)propylfluorenyl-2,7-diyl)-co-(1,4-phenylene)]diiodide salt) (PF-PDTA), a mixture of PF-PDTA and CS2CO3, and the aliphatic-amine-based polymer poly(ethylene imine) (PEI) as solution-processed EILs, and compared them with LiF as a solvent-free EIL. The EILs enhanced the electron injection and improve the pLED performance. High external quantum efficiencies of nearly 4% were obtained in the pLEDs with the combination of a multilayered structure fabricated by a transfer printing technique and EILs of a PF-PDTA:CS2CO3 mixture and PEI. On the other hand, the device with PF-PDTA exhibited lower efficiency, higher driving voltage, and larger leakage current at lower voltage. The migration of ionic charges was suggested from the abnormal dielectric behaviors, and serious damage on the electrode material occurred when both an acid hole-injection layer (PEDOT:PSS) and PF-PDTA were used. On the other hand, the pLEDs with ultrathin PEI showed high performance and stable device operation in terms of the influence of ionic charges.

  16. Enzyme-polymer composites with high biocatalytic activity and stability

    SciTech Connect

    Kim, Jungbae; Kosto, Timothy J.; Manimala, Joseph C.; Nauman, E B.; Dordick, Jonathan S.

    2004-08-22

    We have applied vacuum-spraying and electrospinning to incorporate an enzyme into a polymer matrix, creating a novel and highly active biocatalytic composite. As a unique technical approach, enzymes were co-dissolved in toluene with polymers, and the solvent was then rapidly removed by injecting the mixture into a vacuum chamber or by electrospinning. Subsequent crosslinking of the enzyme with glutaraldehyde resulted in stable entrapped enzyme within the polymeric matrices. For example, an amorphous composite of alpha-chymotrypsin and polyethylene showed no significant loss of enzymatic activity in aqueous buffer for one month. Nanofibers of alpha-chymotrypsin and polystyrene also showed no decrease in activity for more than two weeks. The normalized activity of amorphous composite in organic solvents was 3-13 times higher than that of native alpha-chymotrypsin. The activity of nanofibers was 5-7 times higher than that of amorphous composite in aqueous buffer solution. The composites of alpha-chymotrypsin and polymers demonstrate the feasibility of obtaining a wide variety of active and stable biocatalytic materials with many combinations of enzymes and polymers.

  17. Magnetic molecularly imprinted polymers synthesized by surface-initiated reversible addition-fragmentation chain transfer polymerization for the enrichment and determination of synthetic estrogens in aqueous solution.

    PubMed

    Chen, Fangfang; Zhang, Jingjing; Wang, Minjun; Kong, Jie

    2015-08-01

    Magnetic molecularly imprinted polymers have attracted significant interest because of their multifunctionality of selective recognition of target molecules and rapid magnetic response. In this contribution, magnetic molecularly imprinted polymers were synthesized via surface-initiated reversible addition addition-fragmentation chain transfer polymerization using diethylstilbestrol as the template for the enrichment of synthetic estrogens. The uniform imprinted surface layer and the magnetic property of the magnetic molecularly imprinted polymers favored a fast binding kinetics and rapid analysis of target molecules. The static and selective binding experiments demonstrated a desirable adsorption capacity and good selectivity of the magnetic molecularly imprinted polymers in comparison to magnetic non-molecularly imprinted polymers. Accordingly, a corresponding analytical method was developed in which magnetic molecularly imprinted polymers were employed as magnetic solid-phase extraction materials for the concentration and determination of four synthetic estrogens (diethylstilbestrol, hexestrol, dienestrol, and bisphenol A) in fish pond water. The recoveries of these synthetic estrogens in spiked fish pond water samples ranged from 61.2 to 99.1% with a relative standard deviation of lower than 6.3%. This study provides a versatile approach to prepare well-defined magnetic molecularly imprinted polymers sorbents for the analysis of synthetic estrogens in water solution. PMID:25989155

  18. Flow of concentrated viscoelastic polymer solutions in porous media: effect of M(W) and concentration on elastic turbulence onset in various geometries.

    PubMed

    Howe, Andrew M; Clarke, Andrew; Giernalczyk, Daniel

    2015-08-28

    Viscoelastic polymer solutions exhibit a variety of flow instabilities and in particular, in mixed shear and extensional flow, elastic turbulence. Coincident with the transition to turbulence is additional dissipation that, in porous flow, may be characterised as an increased apparent viscosity. We report elastic turbulence and apparent thickening in the flow of polymer solutions both in rock samples and in microfluidic analogues and we correlate the onset of thickening and turbulence with rheological measurements. Contrary to expectations, the characteristic relaxation time associated with the transition to turbulence is found to be independent of polymer concentration over the range studied (10c* ≲c≲ 100c*). Furthermore, this characteristic time scales with the square of molecular weight. Thus the characteristic time associated with the transition to turbulence is not the linear-viscoelastic timescale usually measured but rather scales as a dilute Rouse time despite being an entangled system.

  19. Flow of concentrated viscoelastic polymer solutions in porous media: effect of M(W) and concentration on elastic turbulence onset in various geometries.

    PubMed

    Howe, Andrew M; Clarke, Andrew; Giernalczyk, Daniel

    2015-08-28

    Viscoelastic polymer solutions exhibit a variety of flow instabilities and in particular, in mixed shear and extensional flow, elastic turbulence. Coincident with the transition to turbulence is additional dissipation that, in porous flow, may be characterised as an increased apparent viscosity. We report elastic turbulence and apparent thickening in the flow of polymer solutions both in rock samples and in microfluidic analogues and we correlate the onset of thickening and turbulence with rheological measurements. Contrary to expectations, the characteristic relaxation time associated with the transition to turbulence is found to be independent of polymer concentration over the range studied (10c* ≲c≲ 100c*). Furthermore, this characteristic time scales with the square of molecular weight. Thus the characteristic time associated with the transition to turbulence is not the linear-viscoelastic timescale usually measured but rather scales as a dilute Rouse time despite being an entangled system. PMID:26174700

  20. Contact-line recession leaving a macroscopic polymer film in the drying droplets of water-poly(N,N-dimethylacrylamide) (PDMA) solution.

    PubMed

    Kajiya, Tadashi; Monteux, Cecile; Narita, Tetsuharu; Lequeux, Francois; Doi, Masao

    2009-06-16

    We found that the drying process of the droplet of water-poly(N,N-dimethylacrylamide) (PDMA) solution on a glass substrate shows a somewhat unusual behavior. In this system, the contact line starts to recede at an early stage of drying, and as it recedes, it leaves a macroscopic polymer film behind. The resulting film has a volcano-like profile, but the peak is not located at the edge of the film but in the middle of the film. We studied the drying process changing the polymer concentration and the wetting property of the substrate. We found that the onset of the contact-line recession depends upon the initial contact angle greatly, while the receding contact angle does not depend upon the initial contact angle. We conjecture that this phenomenon is caused by the Marangoni force, which acts to bring the surface of the solution inward because of the negative dependence of the surface tension on the polymer concentration.

  1. Evaluation of polymer inclusion membranes containing crown ethers for selective cesium separation from nuclear waste solution.

    PubMed

    Mohapatra, P K; Lakshmi, D S; Bhattacharyya, A; Manchanda, V K

    2009-09-30

    Transport behaviour of (137)Cs from nitric acid feed was investigated using cellulose triacetate plasticized polymer inclusion membrane (PIM) containing several crown ether carriers viz. di-benzo-18-crown-6 (DB18C6), di-benzo-21-crown-7 (DB21C7) and di-tert-butylbenzo-18-crown-6 (DTBB18C6). The PIM was prepared from cellulose triacetate (CTA) with various crown ethers and plasticizers. DTBB18C6 and tri-n-butyl phosphate (TBP) were found to give higher transport rate for (137)Cs as compared to other carriers and plasticizers. Effect of crown ether concentration, nitric acid concentration, plasticizer and CTA concentration on the transport rate of Cs was also studied. The Cs selectivity with respect to various fission products obtained from an irradiated natural uranium target was found to be heavily dependent on the nature of the plasticizer. The present work shows that by choosing a proper plasticizer, one can get either good transport efficiency or selectivity. Though TBP plasticized membranes showed good transport efficiency, it displayed poor selectivities. On the other hand, an entirely opposite separation behaviour was observed with 2-nitrophenyloctylether (NPOE) plasticized membranes suggesting the possible application of the later membranes for the removal of bulk (137)Cs from the nuclear waste. The stability of the membrane was tested by carrying out transport runs for nearly 25 days.

  2. Pinch-off dynamics, extensional viscosity and relaxation time of dilute and ultradilute aqueous polymer solutions

    NASA Astrophysics Data System (ADS)

    Biagioli, Madeleine; Dinic, Jelena; Jimenez, Leidy Nallely; Sharma, Vivek

    Free surface flows and drop formation processes present in printing, jetting, spraying, and coating involve the development of columnar necks that undergo spontaneous surface-tension driven instability, thinning, and pinch-off. Stream-wise velocity gradients that arise within the thinning neck create and extensional flow field, which induces micro-structural changes within complex fluids that contribute elastic stresses, changing the thinning and pinch-off dynamics. In this contribution, we use dripping-onto-substrate (DoS) extensional rheometry technique for visualization and analysis of the pinch-off dynamics of dilute and ultra-dilute aqueous polyethylene oxide (PEO) solutions. Using a range of molecular weights, we study the effect of both elasticity and finite extensibility. Both effective relaxation time and the transient extensional viscosity are found to be strongly concentration-dependent even for highly dilute solutions.

  3. Short range order in amorphous polycondensates

    SciTech Connect

    Lamers, C.; Richter, D.; Schweika, W.; Batoulis, J.; Sommer, K.; Cable, J.W.; Shapiro, S.M.

    1992-12-01

    The static coherent structure factors S(Q) of the polymer glass Bisphenol-A-Polycarbonate and its chemical variation Bisphenol-A- Polyctherkctone- both in differently deuterated versions- have been measured by spin polarized neutron scattering. The method of spin polarization analysis provided an experimental separation of coherent and incoherent scattering and a reliable intensity calibration. Results are compared to structure factors calculated for model structures which were obtained by ``amorphous cell`` computer simulations. In general reasonable agreement is found between experiment and simulation; however, certain discrepancies hint at an insufficient structural relaxation in the amorphous cell method. 15 refs, 1 fig, 1 tab.

  4. A Physicochemical Approach Toward Extending Conjugation and the Ordering of Solution-Processable Semiconducting Polymers.

    PubMed

    Lee, Minjung; Jeon, Hyeonyeol; Jang, Mi; Yang, Hoichang

    2016-02-01

    Poly(3-hexylthiophene)s (P3HTs) were synthesized with a well-controlled molecular weight (Mw) and degree of regioregularity; additionally, π-conjugated P3HT structures in both solutions and films were systematically investigated. Conjugated P3HT phases in spin-cast films significantly changed from ordered nanorods, -fibrils, and -ribbons to less-ordered granules, depending on the conformation of the P3HT chains in solutions. The chain conformations could be physicochemically adjusted by modifying chain lengths (from 5 to 45 kDa), solvents, and ultrasonication. Highly extended conformations of the P3HT in ultrasound-treated solutions yielded longer degree of conjugation both the intra- and intermolecularly. When toluene was used as a marginal solvent, ultrasonicated 0.1 wt % 29 kDa P3HT solutions could be used to yield highly ordered aggregates in spin-cast films, including nanoribbons or nanosheets, with field-effect mobility (μFET) up to ∼0.1 cm(2) V(-1) s(-1) being measured for organic field-effect transistors (OFETs). However, ultrasonicated chloroform systems with good P3HT solubility (for P3HT Mw ≥ 20 kDa) yielded featureless conducting layers even at 0.4 wt % P3HT content. However, these film-based OFETs yielded μFET values up to 0.04 cm(2) V(-1) s(-1), which were much greater than 0.004 cm(2) V(-1) s(-1) for the nonultrasonicated systems. PMID:26838119

  5. Specifically increased solubility of enzymes in polyethyleneglycol solutions using polymer-bound triazine dyes.

    PubMed

    Johansson, G; Joelsson, M

    1986-10-01

    The enzymes glucose-6-phosphate dehydrogenase (EC 1.1.1.49) and 3-phosphoglycerate kinase (EC 2.7.2.3), present in an extract of Bakers' yeast, are largely kept in solution by minor amounts of polyethylene glycol-bound triazine dyes (Procion yellow HE-3G and Procion olive MX-3G) even when the solution contains such concentrations of polyethylene glycol (12.5% w/w) which normally precipitate the enzymes. The specific prevention from precipitation can be used for purification of enzyme, preferentially in dealing with crude extracts, which has been demonstrated in this work. A 3.4-fold purification of glucose-6-phosphate dehydrogenase has been achieved with good recovery (93%). Further purification has been possible by combining the recovered (enzyme-containing) supernatant liquid with a solution of dextran which generates an aqueous two-phase system. The lower, dextran-containing phase extracts part of the remaining bulk proteins leaving the target enzyme in the upper phase. The advantages of this method for enzyme purification in large scale are discussed.

  6. Air-processable silane-coupled polymers to modify a dielectric for solution-processed organic semiconductors.

    PubMed

    Jang, Mi; Yu, Young Chang; Jeon, Hyeonyeol; Youk, Ji Ho; Yang, Hoichang

    2015-03-11

    Poly(styrene-r-3-methacryloxypropyltrimethoxysilane) (PSMPTS) copolymers were synthesized by the free radical polymerization of styrene and 3-methacryloxypropyltrimethoxysilane (MPTS) for use as surface modifiers. PSMPTS copolymers were spun-cast onto a hydrophilic SiO2 layer and were then annealed at 150 °C in ambient air. The polystyrene (PS)-based copolymer, with a molecular weight of 32 700 g mol(-1) and approximately 30 MPTS coupling sites, was easily grafted onto the SiO2 surface after annealing periods longer than 1 min, yielding a physicochemically stable layer. On the untreated and polymer-treated dielectrics, spin-casting of an ultrasonicated poly(3-hexyl thiophene) (P3HT) solution yielded highly interconnected crystal nanofibrils of P3HT. The resulting organic field-effect transistors (OFETs) showed similar mobility values of 0.01-0.012 cm(2) V(-1) s(-1) for all surfaces. However, the threshold voltage (Vth) drastically decreased from +13 (for bare SiO2) to 0 V by grafting the PSMPTS copolymers to the SiO2 surface. In particular, the interfacial charge traps that affect Vth were minimized by grafting the 11 mol % MPTS-loaded copolymer to the polar dielectric surface. We believe that this ambient-air-processable silane-coupled copolymer can be used as a solution-based surface modifier for continuous, large-scale OFET fabrication. PMID:25700018

  7. Air-processable silane-coupled polymers to modify a dielectric for solution-processed organic semiconductors.

    PubMed

    Jang, Mi; Yu, Young Chang; Jeon, Hyeonyeol; Youk, Ji Ho; Yang, Hoichang

    2015-03-11

    Poly(styrene-r-3-methacryloxypropyltrimethoxysilane) (PSMPTS) copolymers were synthesized by the free radical polymerization of styrene and 3-methacryloxypropyltrimethoxysilane (MPTS) for use as surface modifiers. PSMPTS copolymers were spun-cast onto a hydrophilic SiO2 layer and were then annealed at 150 °C in ambient air. The polystyrene (PS)-based copolymer, with a molecular weight of 32 700 g mol(-1) and approximately 30 MPTS coupling sites, was easily grafted onto the SiO2 surface after annealing periods longer than 1 min, yielding a physicochemically stable layer. On the untreated and polymer-treated dielectrics, spin-casting of an ultrasonicated poly(3-hexyl thiophene) (P3HT) solution yielded highly interconnected crystal nanofibrils of P3HT. The resulting organic field-effect transistors (OFETs) showed similar mobility values of 0.01-0.012 cm(2) V(-1) s(-1) for all surfaces. However, the threshold voltage (Vth) drastically decreased from +13 (for bare SiO2) to 0 V by grafting the PSMPTS copolymers to the SiO2 surface. In particular, the interfacial charge traps that affect Vth were minimized by grafting the 11 mol % MPTS-loaded copolymer to the polar dielectric surface. We believe that this ambient-air-processable silane-coupled copolymer can be used as a solution-based surface modifier for continuous, large-scale OFET fabrication.

  8. Inorganic polymers from laterite using activation with phosphoric acid and alkaline sodium silicate solution: Mechanical and microstructural properties

    SciTech Connect

    Lassinantti Gualtieri, Magdalena

    2015-01-15

    Geopolymers from laterite, an iron-rich soil available in developing countries, have great potential as building materials. In this work, laterite from Togo (Africa) was used to prepare geopolymers using both phosphoric acid and alkaline sodium silicate solution. Microstructural properties were investigated by scanning electron microscopy, X-ray powder diffraction and mercury porosimetry, whereas thermal properties were evaluated by thermal analyses. The local environment of iron was studied by X-ray Absorption Spectroscopy (XANES region). The mechanical properties were determined. Modulus of Rupture and Young's modulus fell in the ranges 3.3–4.5 MPa and 12–33 GPa, respectively, rendering the materials good candidates for construction purposes. Heating above 900 °C results in weight-gain, presumably due to iron redox reactions. X-ray Absorption Spectroscopy data evidence changes in the chemical and structural environments of iron following thermal treatment of geopolymers. These changes indicate interaction between the geopolymer structure and iron during heating, possibly leading to redox properties. -- Highlights: •Geopolymerization of laterite is promising for fabrication of building materials. •Both phosphoric acid and alkaline sodium silicate solution can be used for activation. •Thermally activated redox properties of the inorganic polymers were observed.

  9. Roll to Roll Electric Field "Z" Alignment of Nanoparticles from Polymer Solutions for Manufacturing Multifunctional Capacitor Films.

    PubMed

    Guo, Yuanhao; Batra, Saurabh; Chen, Yuwei; Wang, Enmin; Cakmak, Miko

    2016-07-20

    A roll to roll continuous processing method is developed for vertical alignment ("Z" alignment) of barium titanate (BaTiO3) nanoparticle columns in polystyrene (PS)/toluene solutions. This is accomplished by applying an electric field to a two-layer solution film cast on a carrier: one is the top sacrificial layer contacting the electrode and the second is the polymer solution dispersed with BaTiO3 particles. Flexible Teflon coated mesh is utilized as the top electrode that allows the evaporation of solvent through the openings. The kinetics of particle alignment and chain buckling is studied by the custom-built instrument measuring the real time optical light transmission during electric field application and drying steps. The nanoparticles dispersed in the composite bottom layer form chains due to dipole-dipole interaction under an applied electric field. In relatively weak electric fields, the particle chain axis tilts away from electric field direction due to bending caused by the shrinkage of the film during drying. The use of strong electric fields leads to maintenance of alignment of particle chains parallel to the electric field direction overcoming the compression effect. At the end of the process, the surface features of the top porous electrodes are imprinted at the top of the top sacrificial layer. By removing this layer a smooth surface film is obtained. The nanocomposite films with "Z" direction alignment of BaTiO3 particles show substantially increased dielectric permittivity in the thickness direction for enhancing the performance of capacitors. PMID:27322765

  10. Roll to Roll Electric Field "Z" Alignment of Nanoparticles from Polymer Solutions for Manufacturing Multifunctional Capacitor Films.

    PubMed

    Guo, Yuanhao; Batra, Saurabh; Chen, Yuwei; Wang, Enmin; Cakmak, Miko

    2016-07-20

    A roll to roll continuous processing method is developed for vertical alignment ("Z" alignment) of barium titanate (BaTiO3) nanoparticle columns in polystyrene (PS)/toluene solutions. This is accomplished by applying an electric field to a two-layer solution film cast on a carrier: one is the top sacrificial layer contacting the electrode and the second is the polymer solution dispersed with BaTiO3 particles. Flexible Teflon coated mesh is utilized as the top electrode that allows the evaporation of solvent through the openings. The kinetics of particle alignment and chain buckling is studied by the custom-built instrument measuring the real time optical light transmission during electric field application and drying steps. The nanoparticles dispersed in the composite bottom layer form chains due to dipole-dipole interaction under an applied electric field. In relatively weak electric fields, the particle chain axis tilts away from electric field direction due to bending caused by the shrinkage of the film during drying. The use of strong electric fields leads to maintenance of alignment of particle chains parallel to the electric field direction overcoming the compression effect. At the end of the process, the surface features of the top porous electrodes are imprinted at the top of the top sacrificial layer. By removing this layer a smooth surface film is obtained. The nanocomposite films with "Z" direction alignment of BaTiO3 particles show substantially increased dielectric permittivity in the thickness direction for enhancing the performance of capacitors.

  11. Selective removal/recovery of RCRA metals from waste and process solutions using polymer filtration{trademark} technology

    SciTech Connect

    Smith, B.F.

    1997-10-01

    Resource Conservation and Recovery Act (RCRA) metals are found in a number of process and waste streams at many DOE, U.S. Department of Defense, and industrial facilities. RCRA metals consist principally of chromium, mercury, cadmium, lead, and silver. Arsenic and selenium, which form oxyanions, are also considered RCRA elements. Discharge limits for each of these metals are based on toxicity and dictated by state and federal regulations (e.g., drinking water, RCRA, etc.). RCRA metals are used in many current operations, are generated in decontamination and decommissioning (D&D) operations, and are also present in old process wastes that require treatment and stabilization. These metals can exist in solutions, as part of sludges, or as contaminants on soils or solid surfaces, as individual metals or as mixtures with other metals, mixtures with radioactive metals such as actinides (defined as mixed waste), or as mixtures with a variety of inert metals such as calcium and sodium. The authors have successfully completed a preliminary proof-of-principle evaluation of Polymer Filtration{trademark} (PF) technology for the dissolution of metallic mercury and have also shown that they can remove and concentrate RCRA metals from dilute solutions for a variety of aqueous solution types using PF technology. Another application successfully demonstrated is the dilute metal removal of americium and plutonium from process streams. This application was used to remove the total alpha contamination to below 30 pCi/L for the wastewater treatment plant at TA-50 at Los Alamos National Laboratory (LANL) and from nitric acid distillate in the acid recovery process at TA-55, the Plutonium Facility at LANL (ESP-CP TTP AL16C322). This project will develop and optimize the PF technology for specific DOE process streams containing RCRA metals and coordinate it with the needs of the commercial sector to ensure that technology transfer occurs.

  12. Solubility of crystalline organic compounds in high and low molecular weight amorphous matrices above and below the glass transition by zero enthalpy extrapolation.

    PubMed

    Amharar, Youness; Curtin, Vincent; Gallagher, Kieran H; Healy, Anne Marie

    2014-09-10

    Pharmaceutical applications which require knowledge of the solubility of a crystalline compound in an amorphous matrix are abundant in the literature. Several methods that allow the determination of such data have been reported, but so far have only been applicable to amorphous polymers above the glass transition of the resulting composites. The current work presents, for the first time, a reliable method for the determination of the solubility of crystalline pharmaceutical compounds in high and low molecular weight amorphous matrices at the glass transition and at room temperature (i.e. below the glass transition temperature), respectively. The solubilities of mannitol and indomethacin in polyvinyl pyrrolidone (PVP) K15 and PVP K25, respectively were measured at different temperatures. Mixtures of undissolved crystalline solute and saturated amorphous phase were obtained by annealing at a given temperature. The solubility at this temperature was then obtained by measuring the melting enthalpy of the crystalline phase, plotting it as a function of composition and extrapolating to zero enthalpy. This new method yielded results in accordance with the predictions reported in the literature. The method was also adapted for the measurement of the solubility of crystalline low molecular weight excipients in amorphous active pharmaceutical ingredients (APIs). The solubility of mannitol, glutaric acid and adipic acid in both indomethacin and sulfadimidine was experimentally determined and successfully compared with the difference between their respective calculated Hildebrand solubility parameters. As expected from the calculations, the dicarboxylic acids exhibited a high solubility in both amorphous indomethacin and sulfadimidine, whereas mannitol was almost insoluble in the same amorphous phases at room temperature. This work constitutes the first report of the methodology for determining an experimentally measured solubility for a low molecular weight crystalline solute

  13. Comparison of the influence of polyaspartic acid and polylysine functional groups on the adsorption at the Cr2O3-Aqueous polymer solution interface

    NASA Astrophysics Data System (ADS)

    Ostolska, Iwona; Wiśniewska, Małgorzata

    2014-08-01

    Polyamino acids are a group of synthesized polymers obtained by polymerization of a given kind of amino acid monomer. Because of high biodegradability of this class of polymers, they can be used as flocculation or stabilization agents in the environmental aspects. Therefore determination of their influence on the stability of the aqueous suspension of metal oxides is important. An influence of different functional groups of polyamino acids, their molecular weight and concentration on the adsorption at the chromium (III) oxide (Cr2O3)-aqueous solution interface was determined. Experiments were carried out for four values of solution pH varying from 3 to 10 (3, 4, 7.6 and 10, respectively). Two polymers were used: anionic polyaspartic acid (ASP) of 6800 and 27,000 as well as polylysine (LYS) of 4900 and 33,000 molecular weights. Changes of surface charge density of colloidal Cr2O3 in the presence and in the absence of macromolecular substances were determined using potentiometric titration. In these studies the influence of the concentration and molecular weight of the ionic polymers on the pHpzc value was determined. Additionally, due to the lack of appropriate literature data, potentiometric titration of the selected polymers was performed to determine pKa values.

  14. Illumination of Conjugated Polymer in Solution Alters its Conformation and Thermodynamics: The Role of Incident Light Intensity, Wavelength and Exposure Time

    NASA Astrophysics Data System (ADS)

    Morgan, Brian; Dadmun, Mark

    The importance of chain structure in conjugated polymer-based material active layers and its relation to device efficiencies in OPVs, organic field transistors, and OLEDs, has been well established. However the influence of light absorption on the conjugated polymer structure is not well understood. We have employed small angle neutron scattering to investigate structural changes occurring in solutions of poly(3-hexylthiophene-2,5-diyl) with exposure to white light. Our previous results indicate significant change in the structure of the polymer upon illumination, an effect we attribute to an alteration in the thermodynamic interactions of the polymer with the surrounding solvent. In order to further our understanding of this phenomenon, we have studied the modulation of these light/dark structural changes as a function of solvent choice, incident light intensity, illumination wavelength, and light exposure duration. Analysis of this data allows refinement and increased control of these light-initiated effects, moving our efforts closer to the development of a powerful, non-destructive, and tunable method for controlling polymer conformation in solution and novel light-responsive materials.

  15. Non-monotonic course of protein solubility in aqueous polymer-salt solutions can be modeled using the sol-mxDLVO model.

    PubMed

    Herhut, Marcel; Brandenbusch, Christoph; Sadowski, Gabriele

    2016-02-01

    Protein purification is often performed using cost-intensive chromatographic steps. To discover economic alternatives (e.g., crystallization), knowledge on protein solubility as a function of temperature, pH, and additives in solution as well as their concentration is required. State-of-the-art models for predicting protein solubility almost exclusively consider aqueous salt systems, whereas "salting-in" and "salting-out" effects induced by the presence of an additional polymer are not considered. Thus, we developed the sol-mxDLVO model. Using this newly developed model, protein solubility in the presence of one salt and one polymer, especially the non-monotonic course of protein solubility, could be predicted. Systems considered included salts (NaCl, Na-p-Ts, (NH(4))(2) SO(4)) and the polymer polyethylene glycol (MW: 2000 g/mol, 12000 g/mol) and proteins lysozyme from chicken egg white (pH 4 to 5.5) and D-xylose ketol-isomerase (pH 7) at 298.15 K. The results show that by using the sol-mxDLVO model, protein solubility in polymer-salt solutions can be modeled in good agreement with the experimental data for both proteins considered. The sol-mxDLVO model can describe the non-monotonic course of protein solubility as a function of polymer concentration and salt concentration, previously not covered by state-of-the-art models.

  16. Adsorption properties of cross-linked cellulose-epichlorohydrin polymers in aqueous solution.

    PubMed

    Udoetok, Inimfon A; Dimmick, Raquel M; Wilson, Lee D; Headley, John V

    2016-01-20

    Cellulose was cross-linked with epichlorohydrin (EP) at variable levels (CLE-0.5, CLE-2 and CLE-4), where CLE-i denotes the cellulose to EP mole ratios. The cross-linked products were characterized by TGA and FT-IR spectroscopy, pH at the point of zero charge (pHpzc), water swelling, and dye-adsorption methods employing two types of dyes [phenolphthalein (phth) and p-nitrophenol (PNP)]. The characterization methods provide evidence of cross-linking of cellulose in accordance with variations in surface area, PZC, available surface hydroxyl groups, and thermal stability when compared against pristine cellulose. The pHpzc of the sorbent materials was ∼ 6.5 indicating a negative surface charge occurs above pHpzc. The cross-linked polymers possess greater swelling properties relative to pristine cellulose. Detailed adsorption studies were carried out at pH 9 for cellulose and CLE-i with five types single component carboxylate anions [2-hexyldecanoic acid (S1), trans-4-pentylcyclohexanecarboxylic acid (S2), 2-dicyclohexylacetic acid (S3), adamantane carboxylic acid (S4), and cyclohexane carboxylic acid (S5)] at 295 K. The uptake properties of PNP with cellulose and CLE-i were also compared at pH 5 and 9, respectively. CLE-2 had the highest uptake of PNP (Qm=1.22 × 10(-1)mmol/g, pH 9) and S1 (Qm=4.27 mg/g) while cellulose and CLE-4 had the strongest binding affinity (1.43 L/mmol and 5.90 × 10(-2)L/mg), respectively. Uptake of PNP by CLE-0.5 at pH 5 (Q m=5.30 × 10(-2)mmol/g) was higher than uptake at pH 9 (Qm=3.11 × 10(-2)mmol/g). Sorption of CLE-4 with S1, S2 and S3 showed that relative uptake of the surrogates had the following order: S3>S2>S1, where S2 had the strongest binding affinity to CLE-i. CLE-2 had the highest sorption capacity towards Si in an equimolar mixture with evidence of molecular selective uptake. At pH 9, low uptake was mainly related to electrostatic repulsion between the negatively charged sorbent surface and the carboxylate head groups of Si.

  17. Adsorption properties of cross-linked cellulose-epichlorohydrin polymers in aqueous solution.

    PubMed

    Udoetok, Inimfon A; Dimmick, Raquel M; Wilson, Lee D; Headley, John V

    2016-01-20

    Cellulose was cross-linked with epichlorohydrin (EP) at variable levels (CLE-0.5, CLE-2 and CLE-4), where CLE-i denotes the cellulose to EP mole ratios. The cross-linked products were characterized by TGA and FT-IR spectroscopy, pH at the point of zero charge (pHpzc), water swelling, and dye-adsorption methods employing two types of dyes [phenolphthalein (phth) and p-nitrophenol (PNP)]. The characterization methods provide evidence of cross-linking of cellulose in accordance with variations in surface area, PZC, available surface hydroxyl groups, and thermal stability when compared against pristine cellulose. The pHpzc of the sorbent materials was ∼ 6.5 indicating a negative surface charge occurs above pHpzc. The cross-linked polymers possess greater swelling properties relative to pristine cellulose. Detailed adsorption studies were carried out at pH 9 for cellulose and CLE-i with five types single component carboxylate anions [2-hexyldecanoic acid (S1), trans-4-pentylcyclohexanecarboxylic acid (S2), 2-dicyclohexylacetic acid (S3), adamantane carboxylic acid (S4), and cyclohexane carboxylic acid (S5)] at 295 K. The uptake properties of PNP with cellulose and CLE-i were also compared at pH 5 and 9, respectively. CLE-2 had the highest uptake of PNP (Qm=1.22 × 10(-1)mmol/g, pH 9) and S1 (Qm=4.27 mg/g) while cellulose and CLE-4 had the strongest binding affinity (1.43 L/mmol and 5.90 × 10(-2)L/mg), respectively. Uptake of PNP by CLE-0.5 at pH 5 (Q m=5.30 × 10(-2)mmol/g) was higher than uptake at pH 9 (Qm=3.11 × 10(-2)mmol/g). Sorption of CLE-4 with S1, S2 and S3 showed that relative uptake of the surrogates had the following order: S3>S2>S1, where S2 had the strongest binding affinity to CLE-i. CLE-2 had the highest sorption capacity towards Si in an equimolar mixture with evidence of molecular selective uptake. At pH 9, low uptake was mainly related to electrostatic repulsion between the negatively charged sorbent surface and the carboxylate head groups of Si

  18. Polymer Chemistry

    NASA Technical Reports Server (NTRS)

    Williams, Martha; Roberson, Luke; Caraccio, Anne

    2010-01-01

    This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.

  19. Polymer Translocation Through a Nanopore from a Crosslinked Gel to Free Solution

    NASA Astrophysics Data System (ADS)

    Sean, David; de Haan, Hendrick W.; Slater, Gary W.

    2013-03-01

    We present results from a computer simulation study of DNA translocation through a nanopore in a membrane that separates a gel region from free solution. The gel is modeled by a square lattice of fixed poles such that the pore size is set by the lattice spacing. Starting with the DNA on the gel side, we examine how the gel pore size affects the dynamics of translocation. We find that due to entropic and frictional forces, the mean translocation time is affected by gel pore size. Since the spatial restrictions imposed by the gel limit the dynamics to one-dimensional motion on the cis side, variations in the width of the distribution of translocations times are also observed.

  20. Wettability alteration by novel betaines at polymer-aqueous solution interfaces

    NASA Astrophysics Data System (ADS)

    Hu, Song-Shuang; Zhang, Lei; Xu, Zhi-Cheng; Gong, Qing-Tao; Jin, Zhi-Qiang; Luo, Lan; Zhang, Lu; Zhao, Sui

    2015-11-01

    The wettability of alkyl carboxylbetaine (18C) and alkyl sulfobetaine (18S) at polytetrafluoroethylene (PTFE) and polymethylmethacrylate (PMMA) surfaces have been investigated and the different physicoc