Sample records for amorphous polymer solution

  1. The adsorption of surfactant at the amorphous polymer solution interface

    CERN Document Server

    Gilchrist, V A


    Adsorption of surfactants onto amorphous polymers at the solid-solution interface is of direct relevance to many industrial sectors ranging from food, pharmaceuticals, paints, paper and photographic colour films. Although it is widely accepted that surfactants play the underpinning role in these applications, little is currently understood about the interactions between surfactants and polymeric materials at the molecular level. This lack of progress is mainly due to the inability of most existing techniques in probing this type of structural information at the wet interface. Specular neutron reflection (SNR) is a recently developed technique capable of detecting structural information with resolution down to a few angstroms (A). When combined with deuterium labeling, it is possible to distinguish the surfactant from the polymeric species at the interface. The aim of this work is to explore the appropriate experimental approach that utilizes the potential of neutron reflection to unravel molecular information...

  2. Magnetoimpedance of cobalt-based amorphous ribbons/polymer composites (United States)

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


    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.

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

    DEFF Research Database (Denmark)

    Surwase, S A; Itkonen, L; Aaltonen, J;


    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......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...... 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...

  4. Cyclic behaviors of amorphous shape memory polymers. (United States)

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


    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.

  5. Lyophilization monophase solution technique for preparation of amorphous flutamide dispersions. (United States)

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


    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.

  6. Solution Processing - Rodlike Polymers (United States)


    side it necessary and identify by block number) Para-ordered Polymers High Modulus Fibers and Films Polybenzobisoxazoles Polybenzobisthiazoles 20...considerations important in solution processing are considered, with special emphasis on the dry-jet wet spinning process used to form fibers . Pertinent...Company, Summit, N.J. iii TABLE OF CONTENTS 1. INTRODUCTION ................ .......................... .. 1 2. REMARKS ON DRY-JET WET SPUN FIBER

  7. Migration of Cations and Anions in Amorphous Polymer Electrolytes

    Institute of Scientific and Technical Information of China (English)

    N.A.Stolwijk; S.H.Obeidi; M.Wiencierz


    1 Results Polymer electrolytes are used as ion conductors in batteries and fuel cells.Simple systems consist of a polymer matrix complexing an inorganic salt and are fully amorphous at the temperatures of interest.Both cations and anions are mobile and contribute to charge transport.Most studies on polymer electrolytes use the electrical conductivity to characterize the ion mobility.However,conductivity measurements cannot discriminate between cations and anions.This paper reports some recent results fr...

  8. Enhanced Physical Stability of Amorphous Drug Formulations via Dry Polymer Coating. (United States)

    Capece, Maxx; Davé, Rajesh


    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.

  9. Soft Confinement for Polymer Solutions

    CERN Document Server

    Oya, Yutaka


    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.

  10. Tandem solar cells made from amorphous silicon and polymer bulk heterojunction sub-cells. (United States)

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


    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.

  11. Amorphous stabilization and dissolution enhancement of amorphous ternary solid dispersions: combination of polymers showing drug-polymer interaction for synergistic effects. (United States)

    Prasad, Dev; Chauhan, Harsh; Atef, Eman


    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.

  12. Turbulence in dilute polymer solutions (United States)

    Liberzon, A.; Guala, M.; Lüthi, B.; Kinzelbach, W.; Tsinober, A.


    The work reported below is a comparative study of the properties of turbulence with weak mean flow in a Newtonian fluid and in a dilute polymer solution with an emphasis on the small scale phenomena. The main tool used is a three-dimensional particle tracking system allowing to measure and follow in a Lagrangian manner the field of velocities, as well as velocity derivatives, and thus vorticity, strain, and a variety of related and dynamically significant quantities. The comparison of data from the two flows allows to directly observe the influence of polymers on these quantities as well as the evolution of material elements in the presence of polymers.

  13. Amorphous metallic alloys for oxygen reduction reaction in a polymer electrolyte membrane fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Huerta, R.; Guerra-Martinez, I.; Lopez, J.S. [Inst. Politecnico Nacional, ESIQIE, Mexico City (Mexico). Lab. de Electroquimica; Pierna, A.R. [Basque Country Univ., San Sebastian (Spain). Dept. of Chemical Engineering and Environment; Solorza-Feria, O. [Inst. Politenico Nacional, Centro de Investigacion y de Estudios Avanzados, Mexico City (Mexico). Dept. de Quimica


    Direct methanol fuel cells (DMFC) and polymer electrolyte membrane fuel cells (PEMFC) represent an important, environmentally clean energy source. This has motivated extensive research on the synthesis, characterization and evaluation of novel and stable oxygen reduction electrocatalysts for the direct four-electron transfer process to water formation. Studies have shown that amorphous alloyed compounds can be used as electrode materials in electrochemical energy conversion devices. Their use in PEMFCs can optimize the electrocatalyst loading in the membrane electrode assembly (MEA). In this study, amorphous metallic PtSn, PtRu and PtRuSn alloys were synthesized by mechanical milling and used as cathodes for the oxygen reduction reaction (ORR) in sulphuric acid and in a single PEM fuel cell. Two different powder morphologies were observed before and after the chemical activation in a hydrofluoric acid (HF) solution at 25 degrees C. The kinetics of the ORR on the amorphous catalysts were investigated. The study showed that the amorphous metallic PtSn electrocatalyst was the most active of the 3 electrodes for the cathodic reaction. Fuel cell experiments were conducted at various temperatures at 30 psi for hydrogen (H{sub 2}) and at 34 psi for oxygen (O{sub 2}). MEAs made of Nafion 115 and amorphous metallic PtSn dispersed on carbon powder in a PEMFC had a power density of 156 mW per cm{sup 2} at 0.43V and 80 degrees C. 12 refs., 1 tab., 5 figs.

  14. Impact of polymers on the crystallization and phase transition kinetics of amorphous nifedipine during dissolution in aqueous media. (United States)

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


    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.

  15. Thermal transitions of the amorphous polymers in wheat straw

    DEFF Research Database (Denmark)

    Stelte, Wolfgang; Clemons, Craig; Holm, Jens K.;


    The thermal transitions of the amorphous polymers in wheat straw were investigated using dynamic mechanical thermal analysis (DMTA). The study included both natural and solvent extracted wheat straw, in moist (8–9% water content) and dry conditions, and was compared to spruce samples. Under...... these conditions two transitions arising from the glass transition of lignin and hemicelluloses have been identified. Key transitions attributed to softening of lignin were found at 53, 63 and 91 °C for moist samples of wheat straw, extracted straw and spruce, respectively. Transitions for hemicelluloses were...... determined at 2, −1 and 5 °C, respectively. Differences are likely due to different compositions of lignin and hemicelluloses from straw and spruce and structural differences between the raw materials. The high wax content in wheat straw resulted in a transition at about 40 °C which was absent in solvent...

  16. Design of bioabsorbable, amorphous polymer networks and composites

    Energy Technology Data Exchange (ETDEWEB)

    Wiggins, J.S.


    Amorphous, crosslinked, bioabsorbable polymers have been developed as an alternative to conventional linear, semi-crystalline thermoplastic bioabsorbable polymers, and as matrix resins for totally bioabsorbable composites. Bioabsorbable composites have been fabricated, consisting of poly(glycolic acid) surgical mesh embedded in polyester and polyester-urethane based matrices. Low-molecular weight precursors used in the matrices of the composites were based on D, L-lactide and [epsilon]-caprolactone polyols, which were synthesized by coordination ring-opening polymerization using glycol initiators and stannous octoate as catalyst. Polymers initiated with diols were chain extended with fumaric acid for use as unsaturated polyester prepolymers, and were crosslinked using peroxide initiation. Polyester triols synthesized from glycerol initiation were crosslinked with L-lysine diisocyanate (LDI). Networks synthesized from D, L-lactide based precursors were more rigid with higher tensile strengths and moduli, while networks synthesized from [epsilon]-caprolactone were more flexible and elastomeric. Copolymer network properties were influenced by the relative amounts of each monomer incorporated into the copolymers. A composite based on neat poly(D, L-lactide-co-[epsilon]-caprolactone) fumarate displayed a tensile strength of 37 MPa and modulus of 107 MPa; addition of 25 wt% styrene yielded tensile strength and modulus of 64 MPa and 689 MPa, respectively. A silane coupling agent was shown to dramatically improve the fiber-matrix interfacial adhesion; tensile strength of a poly(D, L-lactide-co-glycolic acid) fumarate composite was increased from 84 to 92 MPa upon fiber pretreatment. Improved adhesion was also demonstrated using SEM. DSC revealed that if the glass transitions for the matrices was maintained at [approximately]60[degrees]C, the composites were easily shaped above this temperature, yet remained rigid at biological temperatures.

  17. Free energy of binding of a small molecule to an amorphous polymer in a solvent. (United States)

    Chunsrivirot, Surasak; Trout, Bernhardt L


    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.

  18. Turbulence of Dilute Polymer Solution

    CERN Document Server

    Xi, Heng-Dong; Xu, Haitao


    In fully developed three dimensional fluid turbulence the fluctuating energy is supplied at large scales, cascades through intermediate scales, and dissipates at small scales. It is the hallmark of turbulence that for intermediate scales, in the so called inertial range, the average energy flux is constant and independent of viscosity [1-3]. One very important question is how this range is altered, when an additional agent that can also transport energy is added to the fluid. Long-chain polymers dissolved at very small concentrations in the fluid are such an agent [4,5]. Based on prior work by de Gennes and Tabor [6,7] we introduce a theory that balances the energy flux through the turbulent cascade with that of the energy flux into the elastic degrees of freedom of the dilute long-chain polymer solution. We propose a refined elastic length scale, $r_\\varepsilon$, which describes the effect of polymer elasticity on the turbulence energy cascade. Our experimental results agree excellently with this new energy ...

  19. Ultraflexible polymer solar cells using amorphous zinc-indium-tin oxide transparent electrodes. (United States)

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


    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.

  20. Airbrush Spray Coating of Amorphous Titanium Dioxide for Inverted Polymer Solar Cells

    Directory of Open Access Journals (Sweden)

    Luca La Notte


    Full Text Available One of the main topics of organic photovoltaics manufacturing is the need for simple, low cost, and large area compatible techniques. Solution-based processes are the best candidates to achieve this aim. Among these, airbrush spray coating has successfully applied to deposit both active and PEDOT layers of bulk-heterojunction solar cells. However, this technique is not yet sufficiently studied for interfacial layers (electron and hole transporting layers or optical spacers. In this paper, we show that amorphous titanium dioxide ( films, obtained with an airbrush from a solution of titanium (IV isopropoxide diluted in isopropanol, are successfully deposited on glass and PET substrates. Good surface covering results from the coalescence of droplets after optimizing the spray coating system. Simple inverted polymer solar cells are fabricated using as electron transporting layer obtaining encouraging electrical performances (% on glass/FTO and 0.7% on PET/ITO substrates.

  1. Hot Melt Extrusion and Spray Drying of Co-amorphous Indomethacin-Arginine With Polymers

    DEFF Research Database (Denmark)

    Lenz, Elisabeth; Löbmann, Korbinian; Rades, Thomas


    in a larger scale. In this study, the feasibility of hot melt extrusion for continuous manufacturing of co-amorphous drug-amino acid formulations was examined, challenging the fact that amino acids melt with degradation at high temperatures. Furthermore, the need for an addition of a polymer in this process...... was evaluated. After a polymer screening via the solvent evaporation method, co-amorphous indomethacin-arginine was prepared by a melting-solvent extrusion process without and with copovidone. The obtained products were characterized with respect to their solid-state properties, non-sink dissolution behavior......Co-amorphous drug-amino acid systems have gained growing interest as an alternative to common amorphous formulations which contain polymers as stabilizers. Several preparation methods have recently been investigated, including vibrational ball milling on a laboratory scale or spray drying...

  2. Functionalized polymers for binding to solutes in aqueous solutions (United States)

    Smith, Barbara F.; Robison, Thomas W.


    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

  3. Effects of Intercalation on the Hole Mobility of Amorphous Semiconducting Polymer Blends

    KAUST Repository

    Cates, Nichole C.


    Fullerenes have been shown to intercalate between the side chains of many crystalline and semicrystalline polymers and to affect the properties of polymer:fullerene bulk heterojunction solar cells. Here we present the first in-depth study of intercalation in an amorphous polymer. We study blends of the widely studied amorphous polymer poly(2-methoxy-5-(3studied amorphous polymer poly(,7·studied amorphous polymer poly(-dimethyloctyloxy)-p-phenylene vinylene) (MDMO-PPV) with a variety of molecules using photoluminescence measurements, scanning electron microscopy, and space-charge limited current mobility measurements. The blends with elevated hole mobilities exhibit complete photoluminescence quenching and show no phase separation in a scanning electron microscope. We conclude that intercalation occurs in MDMO-PPV:fullerene blends and is responsible for the increase in the MDMO-PPV hole mobility by several orders of magnitude when it is blended with fullerenes, despite the dilution of the hole-conducting polymer with an electron acceptor. © 2010 American Chemical Society.

  4. Solvent-mediated amorphous-to-crystalline transformation of nitrendipine in amorphous particle suspensions containing polymers

    DEFF Research Database (Denmark)

    Xia, Dengning; Wu, Jian-Xiong; Cui, Fude;


    quantitatively determined using image analysis based on polarized light microscopy. The findings from the image analysis revealed that the transformation process occurred through the dissolution of amorphous drug precipitate followed by the nucleation and growth of the crystalline phase with the amorphous....... However, a further increase in drug concentration to 100mg/ml decelerated the growth of nitrendipine crystals. Combining image analysis of polarized light micrographs together with Raman spectroscopy and XRPD provided an in-depth insight into solid state transformations in amorphous nitrendipine...

  5. Foaming behaviour of polymer-surfactant solutions

    Energy Technology Data Exchange (ETDEWEB)

    Cervantes-MartInez, Alfredo [Departamento de Investigacion en PolImeros y Materiales, Universidad de Sonora, Apartado Postal 130, 83000 Hermosillo, Sonora (Mexico); Maldonado, Amir [Departamento de Fisica, Universidad de Sonora, Apartado Postal 1626, 83000 Hermosillo, Sonora (Mexico)


    We study the effect of a non-ionic amphiphilic polymer (PEG-100 stearate also called Myrj 59) on the foaming behaviour of aqueous solutions of an anionic surfactant (sodium dodecyl sulfate or SDS). The SDS concentration was kept fixed while the Myrj 59 concentration was varied. Measurements of foamability, surface tension and electrical conductivity were carried out. The results show two opposite effects depending on the polymer concentration: foamability is higher when the Myrj 59 concentration is low; however, it decreases considerably when the polymer concentration is increased. This behaviour is due to the polymer adsorption at the air/liquid interface at lower polymer concentrations, and to the formation of a polymer-surfactant complex in the bulk at higher concentrations. The results are confirmed by surface tension and electrical conductivity measurements, which are interpreted in terms of the microstructure of the polymer-surfactant solutions. The observed behaviour is due to the amphiphilic nature of the studied polymer. The increased hydrophobicity of Myrj 59, compared to that of water-soluble polymers like PEG or PEO, increases its 'reactivity' towards SDS, i.e. the strength of its interaction with this anionic surfactant. Our results show that hydrophobically modified polymers have potential applications as additives in order to control the foaming properties of surfactant solutions.


    Institute of Scientific and Technical Information of China (English)


    The statistical counting method for the computer simulation of the thermodynamic quantities of polymer solution has been reviewed. The calculating results for a single athermal chain confirm the theory of the renormalization group. The results for the athermal solution are consistent with the scaling law of the osmotic pressure with the exponent 2.25. The results for a single chain with the segmental interaction are in a good agreement with the exact results obtained by the direct counting method. The results for the polymer solution show us that the Flory-Huggins parameter is strongly dependent on both the polymer concentration and the interaction energy between segments.

  7. Dissolution of Danazol Amorphous Solid Dispersions: Supersaturation and Phase Behavior as a Function of Drug Loading and Polymer Type. (United States)

    Jackson, Matthew J; Kestur, Umesh S; Hussain, Munir A; Taylor, Lynne S


    Amorphous solid dispersions (ASDs) are of great interest as enabling formulations because of their ability to increase the bioavailability of poorly soluble drugs. However, the dissolution of these formulations under nonsink dissolution conditions results in highly supersaturated drug solutions that can undergo different types of phase transitions. The purpose of this study was to characterize the phase behavior of solutions resulting from the dissolution of model ASDs as well as the degree of supersaturation attained. Danazol was chosen as a poorly water-soluble model drug, and three polymers were used to form the dispersions: polyvinylpyrrolidone (PVP), hydroxypropylmethyl cellulose (HPMC), and hydroxypropylmethyl cellulose acetate succinate (HPMCAS). Dissolution studies were carried out under nonsink conditions, and solution phase behavior was characterized using several orthogonal techniques. It was found that liquid-liquid phase separation (LLPS) occurred following dissolution and prior to crystallization for most of the dispersions. Using flux measurements, it was further observed that the maximum attainable supersaturation following dissolution was equivalent to the amorphous solubility. The dissolution of the ASDs led to sustained supersaturation, the duration of which varied depending on the drug loading and the type of polymer used in the formulation. The overall supersaturation profile observed thus depended on a complex interplay between dissolution rate, polymer type, drug loading, and the kinetics of crystallization.

  8. Modeling the Coupled Chemo-Thermo-Mechanical Behavior of Amorphous Polymer Networks.

    Energy Technology Data Exchange (ETDEWEB)

    Zimmerman, Jonathan A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Nguyen, Thao D. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Xiao, Rui [Sandia National Lab. (SNL-CA), Livermore, CA (United States)


    Amorphous polymers exhibit a rich landscape of time-dependent behavior including viscoelasticity, structural relaxation, and viscoplasticity. These time-dependent mechanisms can be exploited to achieve shape-memory behavior, which allows the material to store a programmed deformed shape indefinitely and to recover entirely the undeformed shape in response to specific environmental stimulus. The shape-memory performance of amorphous polymers depends on the coordination of multiple physical mechanisms, and considerable opportunities exist to tailor the polymer structure and shape-memory programming procedure to achieve the desired performance. The goal of this project was to use a combination of theoretical, numerical and experimental methods to investigate the effect of shape memory programming, thermo-mechanical properties, and physical and environmental aging on the shape memory performance. Physical and environmental aging occurs during storage and through exposure to solvents, such as water, and can significantly alter the viscoelastic behavior and shape memory behavior of amorphous polymers. This project – executed primarily by Professor Thao Nguyen and Graduate Student Rui Xiao at Johns Hopkins University in support of a DOE/NNSA Presidential Early Career Award in Science and Engineering (PECASE) – developed a theoretical framework for chemothermo- mechanical behavior of amorphous polymers to model the effects of physical aging and solvent-induced environmental factors on their thermoviscoelastic behavior.

  9. Hot Melt Extrusion and Spray Drying of Co-amorphous Indomethacin-Arginine With Polymers. (United States)

    Lenz, Elisabeth; Löbmann, Korbinian; Rades, Thomas; Knop, Klaus; Kleinebudde, Peter


    Co-amorphous drug-amino acid systems have gained growing interest as an alternative to common amorphous formulations which contain polymers as stabilizers. Several preparation methods have recently been investigated, including vibrational ball milling on a laboratory scale or spray drying in a larger scale. In this study, the feasibility of hot melt extrusion for continuous manufacturing of co-amorphous drug-amino acid formulations was examined, challenging the fact that amino acids melt with degradation at high temperatures. Furthermore, the need for an addition of a polymer in this process was evaluated. After a polymer screening via the solvent evaporation method, co-amorphous indomethacin-arginine was prepared by a melting-solvent extrusion process without and with copovidone. The obtained products were characterized with respect to their solid-state properties, non-sink dissolution behavior, and stability. Results were compared to those of spray-dried formulations with the same compositions and to spray-dried indomethacin-copovidone. Overall, stable co-amorphous systems could be prepared by extrusion without or with copovidone, which exhibited comparable molecular interaction properties to the respective spray-dried products, while phase separation was detected by differential scanning calorimetry in several cases. The formulations containing indomethacin in combination with arginine and copovidone showed enhanced dissolution behavior over the formulations with only copovidone or arginine.

  10. Amorphous/crystal and polymer/filler interphases in biocomposites from poly(butylene succinate)

    Energy Technology Data Exchange (ETDEWEB)

    Signori, Francesca [Consiglio Nazionale delle Ricerche - Istituto per i Processi Chimico-Fisici (CNR-IPCF), Via G. Moruzzi 1, I-56124 Pisa (Italy); Pelagaggi, Martina [Universita di Pisa - Dipartimento di Chimica e Chimica Industriale, Via Risorgimento 35, I-56126 Pisa (Italy); Bronco, Simona [Consiglio Nazionale delle Ricerche - Istituto per i Processi Chimico-Fisici (CNR-IPCF), Via G. Moruzzi 1, I-56124 Pisa (Italy); Righetti, Maria Cristina, E-mail: [Consiglio Nazionale delle Ricerche - Istituto per i Processi Chimico-Fisici (CNR-IPCF), Via G. Moruzzi 1, I-56124 Pisa (Italy)


    Highlights: Black-Right-Pointing-Pointer The existence of intermolecular interactions between poly(butylene succinate) and hemp fibres was proved from specific heat capacities data. Black-Right-Pointing-Pointer Different degrees of mobility of the poly(butylene succinate) amorphous segments were evidenced at the amorphous/crystal interphase. Black-Right-Pointing-Pointer Devitrification of the rigid amorphous fraction in poly(butylene succinate) was found to occur before and simultaneously with the fusion. - Abstract: Poly(butylene succinate)-hemp composites (PBS-hemp), with hemp content in the range 0-40 wt.%, were prepared in the melt and characterized. This paper focuses on the detailed analysis of the thermal behaviour of the PBS-hemp composites, investigated by differential scanning calorimetry (DSC), to enlighten the polymer/fibre interphase features. The occurrence of specific intermolecular interactions between PBS and hemp was assessed from specific heat capacity data. Different degrees of mobility of the PBS amorphous segments were found at the amorphous/crystal interphases. A broadening of the bulk glass transition was observed, and attributed to the presence of polymer segments slightly constrained. Moreover, a rigid amorphous fraction that devitrifies at temperatures higher than the bulk glass transition, partly before the melting region and partly simultaneously with the fusion, was observed and quantified, and attributed to the presence of major constraints probably occurring in geometrically restricted areas.

  11. Inhibition of surface crystallisation of amorphous indomethacin particles in physical drug-polymer mixtures. (United States)

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


    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.

  12. The still unknown azobenzene - Wavelength dependent photoanisotropy in amorphous azobenzene polymers

    DEFF Research Database (Denmark)

    Ramanujam, P.S.; Jensen, Ole Bjarlin; Tidemand-Lichtenberg, Peter


    We demonstrate a new type of anisotropy in thin films of amorphous azobenzene polymers induced between 570 and 633 nm, where the absorbance in the film is on the order of 0.05. The anisotropy has a pronounced radial contribution. This observation points to an additional mechanism for the alignment...

  13. Flow of polymer solutions through porous media


    Denys, K.F.J.


    These days leading oil and gas producing companies are investing increasing amounts of money into the development of non-fossil energy sources like wind-, solar-, biomass energy and forestry. On the other hand these companies are persisting in developing techniques to make energy recovery more efficient intending to stretch the life span of fossil resources. One of the more mature techniques to improve recovery efficiency is polymer flooding. Herein polymer solutions are injected in injector ...

  14. Solution growth of microcrystalline silicon on amorphous substrates

    Energy Technology Data Exchange (ETDEWEB)

    Heimburger, Robert


    This work deals with low-temperature solution growth of micro-crystalline silicon on glass. The task is motivated by the application in low-cost solar cells. As glass is an amorphous material, conventional epitaxy is not applicable. Therefore, growth is conducted in a two-step process. The first step aims at the spatial arrangement of silicon seed crystals on conductive coated glass substrates, which is realized by means of vapor-liquid-solid processing using indium as the solvent. Seed crystals are afterwards enlarged by applying a specially developed steady-state solution growth apparatus. This laboratory prototype mainly consists of a vertical stack of a silicon feeding source and the solvent (indium). The growth substrate can be dipped into the solution from the top. The system can be heated to a temperature below the softening point of the utilized glass substrate. A temperature gradient between feeding source and growth substrate promotes both, supersaturation and material transport by solvent convection. This setup offers advantages over conventional liquid phase epitaxy at low temperatures in terms of achievable layer thickness and required growth times. The need for convective solute transport to gain the desired thickness of at least 50 {mu}m is emphasized by equilibrium calculations in the binary system indium-silicon. Material transport and supersaturation conditions inside the utilized solution growth crucible are analyzed. It results that the solute can be transported from the lower feeding source to the growth substrate by applying an appropriate heating regime. These findings are interpreted by means of a hydrodynamic analysis of fluid flow and supporting FEM simulation. To ensure thermodynamic stability of all materials involved during steady-state solution growth, the ternary phase equilibrium between molybdenum, indium and silicon at 600 C was considered. Based on the obtained results, the use of molybdenum disilicide as conductive coating

  15. Photodeposition of amorphous polydiacetylene films from monomer solutions onto transparent substrates (United States)

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


    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.

  16. Effect of polymers and media type on extending the dissolution of amorphous pioglitazone and inhibiting the recrystallization from a supersaturated state. (United States)

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


    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.

  17. Downstream processing of polymer-based amorphous solid dispersions to generate tablet formulations. (United States)

    Démuth, B; Nagy, Z K; Balogh, A; Vigh, T; Marosi, G; Verreck, G; Van Assche, I; Brewster, M E


    Application of amorphous solid dispersions (ASDs) is considered one of the most promising approaches to increase the dissolution rate and extent of bioavailability of poorly water soluble drugs. Such intervention is often required for new drug candidates in that enablement, bioavailability is not sufficient to generate a useful product. Importantly, tableting of ASDs is often complicated by a number of pharmaceutical and technological challenges including poor flowability and compressibility of the powders, compression-induced phase changes or phase separation and slow disintegration due to the formation of a gelling polymer network (GPN). The design principles of an ASD-based system include its ability to generate supersaturated systems of the drug of interest during dissolution. These metastable solutions can be prone to precipitation and crystallization reducing the biopharmaceutical performance of the dosage form. The main aim of the research in this area is to maintain the supersaturated state and optimally enhance bioavailability, meaning that crystallization should be delayed or inhibited during dissolution, as well as in solid phase (e.g., during manufacturing and storage). Based on the expanding use of ASD technology as well as their downstream processing, there is an acute need to summarize the results achieved to this point to better understand progress and future risks. The aim of this review is to focus on the conversion of ASDs into tablets highlighting results from various viewpoints.

  18. A Polymer "Pollution Solution" Classroom Activity. (United States)

    Helser, Terry L.


    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)

  19. Brownian particles in supramolecular polymer solutions

    NARCIS (Netherlands)

    Gucht, van der J.; Besseling, N.A.M.; Knoben, W.; Bouteiller, L.; Cohen Stuart, M.A.


    The Brownian motion of colloidal particles embedded in solutions of hydrogen-bonded supramolecular polymers has been studied using dynamic light scattering. At short times, the motion of the probe particles is diffusive with a diffusion coefficient equal to that in pure solvent. At intermediate time

  20. Extensional properties of mobile polymer solutions (United States)

    Tirel, Christophe; Renoult, Marie-Charlotte; Dumouchel, Christophe; Crumeyrolle, Olivier; Lisiecki, Denis; Mutabazi, Innocent


    A deep understanding of the influence of viscoelasticity on the dynamics of liquid flows remains a challenge in the non-Newtonian fluid mechanics field. Previous work has revealed that the addition of minute amount (2.5 part per million) of high molecular weight polymer to water, forming a viscoelastic solution with strong extensional properties, modifies the fission process during droplet snap off with spectacular effects: inhibition of the singularity observed in the reference Newtonian case and formation of a long-lived (milli-second) filament. The measurement of the extensional properties for such mobile polymer solutions is one of the most pressing problem. Here, a global measurement technique, based on the multi-scale analysis of the capillary instability of a free falling jet of a mobile polymer solution, is introduced. The method of analysis allows the characterisation of the jet breakup mechanism from which the relaxation time of the polymer solution can be extracted. One of the advantages of the technique is the simple experiment it requires.

  1. Role of amorphous and aggregate phases on field-induced exciton dissociation in a conjugated polymer (United States)

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


    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.

  2. Light-emitting nanocomposites and novel amorphous polymers for optical applications (United States)

    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

  3. Fourier transform Raman spectroscopic study of the interaction of water vapor with amorphous polymers. (United States)

    Taylor, L S; Langkilde, F W; Zografi, G


    Water associated with amorphous polymers is known to affect their chemical and physical properties. The purpose of this study was to investigate the nature of water-polymer interactions for some polymers of pharmaceutical interest. Using Raman spectroscopy, polymer-water hydrogen bond interactions were probed for two molecular weight grades of poly(vinylpyrrolidone), namely PVP K90 and PVP K12, and also for poly(vinylacetate) and poly(vinyl pyrrolidone-co-vinyl acetate). Water vapor absorption isotherms were obtained for the polymers, and the effect of the absorbed water on the glass transition temperature was determined. A knowledge of the water content and physical state of the polymer was used to aid interpretation of Raman spectral changes. The strength of the hydrogen bond formed with water was found to depend on the chemistry of the polymer, with the pyrrolidone group interacting more strongly than the acetate group. However, minor differences were also observed between the degree of interaction of water and polymer for PVP K12 and PVP K90 at some water contents. This result is attributed to differences in the structural relaxation changes accompanying plasticization by water for the two molecular weight grades. Using principal components analysis of the spectral data, it was also possible to differentiate between samples in the rubbery state and samples in the glassy state. In conclusion, water sorbed into polymers causes changes in the polymer Raman spectra not only because of hydrogen bonding, but also as a result of the plasticizing effect of water on polymer mobility.

  4. Role of Chain Morphology and Stiffness in Thermal Conductivity of Amorphous Polymers. (United States)

    Zhang, Teng; Luo, Tengfei


    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.

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

    DEFF Research Database (Denmark)

    Knopp, Matthias Manne; Chourak, Nabil; Khan, Fauzan;


    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...... relevant in vitro doses, in order to rationally assess the performance of amorphous solid dispersions and avoid confusion in early in vivo studies....

  6. Formation, Structure and Properties of Amorphous Carbon Char from Polymer Materials in Extreme Atmospheric Reentry Environments (United States)

    Lawson, John W.


    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.

  7. The Soft-Confined Method for Creating Molecular Models of Amorphous Polymer Surfaces

    KAUST Repository

    Liu, Hongyi


    The goal of this work was to use molecular dynamics (MD) simulations to build amorphous surface layers of polypropylene (PP) and cellulose and to inspect their physical and interfacial properties. A new method to produce molecular models for these surfaces was developed, which involved the use of a "soft" confining layer comprised of a xenon crystal. This method compacts the polymers into a density distribution and a degree of molecular surface roughness that corresponds well to experimental values. In addition, calculated properties such as density, cohesive energy density, coefficient of thermal expansion, and the surface energy agree with experimental values and thus validate the use of soft confining layers. The method can be applied to polymers with a linear backbone such as PP as well as those whose backbones contain rings, such as cellulose. The developed PP and cellulose surfaces were characterized by their interactions with water. It was found that a water nanodroplet spreads on the amorphous cellulose surfaces, but there was no significant change in the dimension of the droplet on the PP surface; the resulting MD water contact angles on PP and amorphous cellulose surfaces were determined to be 106 and 33°, respectively. © 2012 American Chemical Society.

  8. Spin coating of an evaporating polymer solution

    KAUST Repository

    Münch, Andreas


    We consider a mathematical model of spin coating of a single polymer blended in a solvent. The model describes the one-dimensional development of a thin layer of the mixture as the layer thins due to flow created by a balance of viscous forces and centrifugal forces and evaporation of the solvent. In the model both the diffusivity of the solvent in the polymer and the viscosity of the mixture are very rapidly varying functions of the solvent mass fraction. Guided by numerical solutions an asymptotic analysis reveals a number of different possible behaviours of the thinning layer dependent on the nondimensional parameters describing the system. The main practical interest is in controlling the appearance and development of a "skin" on the polymer where the solvent concentration reduces rapidly on the outer surface leaving the bulk of the layer still with high concentrations of solvent. In practice, a fast and uniform drying of the film is required. The critical parameters controlling this behaviour are found to be the ratio of the diffusion to advection time scales ε, the ratio of the evaporation to advection time scales δ and the ratio of the diffusivity of the pure polymer and the initial mixture exp(-1/γ). In particular, our analysis shows that for very small evaporation with δ

  9. Numerical solution of the polymer system

    Energy Technology Data Exchange (ETDEWEB)

    Haugse, V.; Karlsen, K.H.; Lie, K.-A.; Natvig, J.R.


    The paper describes the application of front tracking to the polymer system, an example of a nonstrictly hyperbolic system. Front tracking computes piecewise constant approximations based on approximate Remain solutions and exact tracking of waves. It is well known that the front tracking method may introduce a blow-up of the initial total variation for initial data along the curve where the two eigenvalues of the hyperbolic system are identical. It is demonstrated by numerical examples that the method converges to the correct solution after a finite time that decreases with the discretization parameter. For multidimensional problems, front tracking is combined with dimensional splitting and numerical experiments indicate that large splitting steps can be used without loss of accuracy. Typical CFL numbers are in the range of 10 to 20 and comparisons with the Riemann free, high-resolution method confirm the high efficiency of front tracking. The polymer system, coupled with an elliptic pressure equation, models two-phase, tree-component polymer flooding in an oil reservoir. Two examples are presented where this model is solved by a sequential time stepping procedure. Because of the approximate Riemann solver, the method is non-conservative and CFL members must be chosen only moderately larger than unity to avoid substantial material balance errors generated in near-well regions after water breakthrough. Moreover, it is demonstrated that dimensional splitting may introduce severe grid orientation effects for unstable displacements that are accentuated for decreasing discretization parameters. 9 figs., 2 tabs., 26 refs.

  10. Polymer solution phase separation: Microgravity simulation (United States)

    Cerny, Lawrence C.; Sutter, James K.


    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.

  11. Irreversible adsorption from concentrated polymer solutions (United States)

    Auvray, Loïc; Cruz, Margerida; Auroy, Philippe


    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.

  12. Constant force extensional rheometry of polymer solutions

    DEFF Research Database (Denmark)

    Szabo, Peter; McKinley, Gareth H.; Clasen, Christian


    We revisit the rapid stretching of a liquid filament under the action of a constant imposed tensile force, a problem which was first considered by Matta and Tytus [J. Non-Newton. Fluid Mech. 35 (1990) 215–229]. A liquid bridge formed from a viscous Newtonian fluid or from a dilute polymer solution...... is first established between two cylindrical disks. The upper disk is held fixed and may be connected to a force transducer while the lower cylinder falls due to gravity. By varying the mass of the falling cylinder and measuring its resulting acceleration, the viscoelastic nature of the elongating fluid...

  13. A bifunctional amorphous polymer exhibiting equal linear and circular photoinduced birefringences. (United States)

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


    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.

  14. 10.5% efficient polymer and amorphous silicon hybrid tandem photovoltaic cell (United States)

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


    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 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.

  15. 10.5% efficient polymer and amorphous silicon hybrid tandem photovoltaic cell. (United States)

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


    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 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.

  16. Corrosion resistance of amorphous and crystalline Pd40Ni40P20 alloys in aqueous solutions

    DEFF Research Database (Denmark)

    Wu, Y.F.; Chiang, Wen-Chi; Chu, J.;


    The corrosion behaviors of amorphous and crystalline Pd40Ni40P20 alloys in various aqueous solutions are reported in this paper. The corrosion resistance of crystalline (annealed) Pd40Ni40P20 is better than that of amorphous Pd40Ni40P20 in various corrosive solutions, due to crystalline Pd40Ni40P20...... and mainly consists of inert Pd5P2, NI3P, Ni2Pd2P and noble Pd phases. These inert and noble properties result in a higher corrosion resistance in crystalline Pd40Ni40P20....

  17. On the Mass Fractal Character of Si-Based Structural Networks in Amorphous Polymer Derived Ceramics (United States)

    Sen, Sabyasachi; Widgeon, Scarlett


    The intermediate-range packing of SiNxC4−x (0 ≤ x ≤ 4) tetrahedra in polysilycarbodiimide and polysilazane-derived amorphous SiCN ceramics is investigated using 29Si spin-lattice relaxation nuclear magnetic resonance (SLR NMR) spectroscopy. The SiCN network in the polysilylcarbodiimide-derived ceramic consists predominantly of SiN4 tetrahedra that are characterized by a 3-dimensional spatial distribution signifying compact packing of such units to form amorphous Si3N4 clusters. On the other hand, the SiCN network of the polysilazane-derived ceramic is characterized by mixed bonded SiNxC4−x tetrahedra that are inefficiently packed with a mass fractal dimension of Df ~2.5 that is significantly lower than the embedding Euclidean dimension (D = 3). This result unequivocally confirms the hypothesis that the presence of dissimilar atoms, namely, 4-coordinated C and 3-coordinated N, in the nearest neighbor environment of Si along with some exclusion in connectivity between SiCxN4−x tetrahedra with widely different N:C ratios and the absence of bonding between C and N result in steric hindrance to an efficient packing of these structural units. It is noted that similar inefficiencies in packing are observed in polymer-derived amorphous SiOC ceramics as well as in proteins and binary hard sphere systems.

  18. On the Mass Fractal Character of Si-Based Structural Networks in Amorphous Polymer Derived Ceramics

    Directory of Open Access Journals (Sweden)

    Sabyasachi Sen


    Full Text Available The intermediate-range packing of SiNxC4−x (0 ≤ x ≤ 4 tetrahedra in polysilycarbodiimide and polysilazane-derived amorphous SiCN ceramics is investigated using 29Si spin-lattice relaxation nuclear magnetic resonance (SLR NMR spectroscopy. The SiCN network in the polysilylcarbodiimide-derived ceramic consists predominantly of SiN4 tetrahedra that are characterized by a 3-dimensional spatial distribution signifying compact packing of such units to form amorphous Si3N4 clusters. On the other hand, the SiCN network of the polysilazane-derived ceramic is characterized by mixed bonded SiNxC4−x tetrahedra that are inefficiently packed with a mass fractal dimension of Df ~2.5 that is significantly lower than the embedding Euclidean dimension (D = 3. This result unequivocally confirms the hypothesis that the presence of dissimilar atoms, namely, 4-coordinated C and 3-coordinated N, in the nearest neighbor environment of Si along with some exclusion in connectivity between SiCxN4−x tetrahedra with widely different N:C ratios and the absence of bonding between C and N result in steric hindrance to an efficient packing of these structural units. It is noted that similar inefficiencies in packing are observed in polymer-derived amorphous SiOC ceramics as well as in proteins and binary hard sphere systems.

  19. Stationary solutions of equations of incompressible viscoelastic polymer liquid (United States)

    Bambaeva, N. V.; Blokhin, A. M.


    The equations describing flows of an incompressible viscoelastic polymer liquid are studied. Stationary solutions similar to the Poiseuille and Couette solutions for the system of the Navier-Stokes equations are constructed. Stationary discontinuous solutions of the polymer liquid equation are also considered.

  20. Effects of the Terminal Structure, Purity, and Molecular Weight of an Amorphous Conjugated Polymer on Its Photovoltaic Characteristics. (United States)

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


    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.

  1. Optimising Drug Solubilisation in Amorphous Polymer Dispersions: Rational Selection of Hot-melt Extrusion Processing Parameters. (United States)

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


    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.

  2. Flow-induced phase separation in polymer solutions

    NARCIS (Netherlands)

    Moel, K. de; Flikkema, E.; Szleifer, I.; Brinke, G. ten


    A correct description of phase behaviour in polymer solutions requires a coupling between configurational statistics and thermodynamics. The effect of flow-induced chain deformation on the polymer-solvent interaction energy depends on the concentration and on the polymer architecture. It will be dem

  3. Modeling of Dilute Polymer Solutions in Confined Space

    DEFF Research Database (Denmark)

    Wang, Yanwei


    by simple mathematical analyses. When the CABS method is applied to compute the equilibrium distribution (the equilibrium partition coefficient, Ko) of polymers between a dilute macroscopic solution phase and a solution confined by inert impenetrable boundaries, a sphere-like universal partitioning feature...... of polymers in SEC, one may reach a conclusion that SEC fractionates polymers based on the steric exclusion radius, Rs . The CABS method is further applied to determine the depletion profiles of dilute polymer solutions confined to a slit or near an inert wall. We show that the entire spatial density......This thesis deals with modeling of a polymer chain subject to spatial confinement. The properties of confined macromolecules are both of fundamental interest in polymer physics and of practical importance in a variety of applications including chromatographic separation of polymers, and the use...

  4. Performance of dielectric nanocomposites: matrix-free, hairy nanoparticle assemblies and amorphous polymer-nanoparticle blends. (United States)

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


    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

  5. Dehydration and crystallization of amorphous calcium carbonate in solution and in air. (United States)

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


    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.

  6. Clozapine-carboxylic acid plasticized co-amorphous dispersions: Preparation, characterization and solution stability evaluation

    Directory of Open Access Journals (Sweden)

    Ali Ahmed Mahmoud Abdelhaleem


    Full Text Available This study addressed the possibility of forming of co-amorphous systems between clozapine (CZ and various carboxylic acid plasticizers (CAPs. The aim was to improve the solubility and oral bioavailability of clozapine. Co-amorphous dispersions were prepared using modified solvent evaporation methodology at drug/plasticizer stoichiometric ratios of 1:1, 1:1.5 and 1:2. Solid state characterization was performed using differential scanning calorimetry, X-ray diffraction and infra red spectroscopy. Highly soluble homogeneous co-amorphous dispersions were formed between clozapine and CAPs via hydrogen bonding. The co-amorphous dispersions formed with tartaric acid (1:2 showed the highest dissolution percentage (> 95 % in 20 minutes compared to pure crystalline CZ (56 %. Highly stable solutions were obtained from co-amorphous CZ-citric and CZ-tartaric acid at 1:1.5 molar ratio. The prepared dispersions suggest the possibility of peroral or sublingual administration of highly soluble clozapine at a reduced dose with the great chance to bypass the first pass metabolism.

  7. Effect of polymer type and drug dose on the in vitro and in vivo behavior of amorphous solid dispersions. (United States)

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


    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.

  8. Optical properties of plasma deposited amorphous carbon nitride films on polymer substrates

    Energy Technology Data Exchange (ETDEWEB)

    Mohamed, S.H., E-mail: [Physics Department, Faculty of Science, Sohag University, 82524 Sohag (Egypt); El-Hossary, F.M. [Physics Department, Faculty of Science, Sohag University, 82524 Sohag (Egypt); Gamal, G.A.; Kahlid, M.M. [Physics Department, Faculty of Science, South Valley University, 83523 Qena (Egypt)


    Amorphous carbon nitride thin films were deposited on polymer substrates using radio frequency (rf) plasma in a mixture of nitrogen (N{sub 2}) and acetylene (C{sub 2}H{sub 2}) gasses. The samples were prepared at different rf plasma power (350, 400, 450, 500, and 550 W), at constant plasma exposure time of 10 min, and constant N{sub 2}/C{sub 2}H{sub 2} ratio of 50%. The crystal structure and surface morphology of the prepared samples were examined using X-ray diffraction and atomic force microscopy analysis, respectively. The absence of the carbon nitride diffraction peaks confirms the amorphous nature of these films. The root mean square roughness of the films increased from 3.77 to 25.22 nm as the power increased from 350 to 550 W. The thickness and the deposition rate were found to increase with increasing plasma power. Over the whole studied wavelength range, from 200 to 2500 nm, the transmittance decreased with increasing plasma power. A shift in the onset of absorption towards higher wavelengths with increasing plasma power, indicating a decrease in the optical band gap, has been observed. The refractive index values were found to decrease while the extinction coefficient increased with increasing plasma power.


    Institute of Scientific and Technical Information of China (English)

    Yun-fei Yan; Hai-yang Yang; Wen-yong Liu; Ping-ping Zhu; Ping-sheng He


    The tetrahedral borate ion can crosslink with polymer guar gum in aqueous solutions. If the concentration of guar gum is less than 0.045 g/dL, the intramolecular interaction between guar gum and borate ion increases due to the formation of crosslinks. As a result, the polymer chains of guar gum in solution shrink in size and the reduced viscosity of polymer solution decreases accordingly. On the other hand, if the concentration of guar gum is greater than 0.045 g/dL, the intermolecular interaction becomes apparent due to the same reason. The polymer chains, therefore, associate together and the reduced viscosity of polymer solution increases considerably. According to this technique, the critical concentration c*,presented by de-Gennes[1], is determined successfully.

  10. Porous polymers: enabling solutions for energy applications. (United States)

    Thomas, Arne; Kuhn, Pierre; Weber, Jens; Titirici, Maria-Magdalena; Antonietti, Markus


    A new generation of porous polymers was made for various energy-related applications, e.g., as fuel cell membranes, as electrode materials for batteries, for gas storage, partly from renewable resources. This review intends to catch this emerging field by reporting on a variety of different approaches to make high performing polymers porous. This includes template techniques, polymers with inherent microporosity, polymer frameworks by ionothermal polymerization, and the polymerization of carbon from appropriate precursors and by hydrothermal polymerization. In this process, we try to not only identify the current status of the field, but also point to open question and tasks to identify the potentially relevant progress.


    Institute of Scientific and Technical Information of China (English)

    Rong-shi Cheng; Yu-fang Shao; Ming-zhu Liu; Rong-qing Lu


    Careful measurements of the dilute solution viscosities of polyethylene glycol and polyvinyl alcohol in water were carried out. The reduced viscosities of both polymer solutions plot upward curves at extremely dilute concentration levels similar to the phenomena observed for many polymer solutions in the early 1950's. Upon observation of the changes of the flow times of pure water in and the wall surface wettability of the viscometer after measuring solution viscosity, a view was formed that the observed viscosity abnormality at extremely dilute concentration regions is solely due to the effect of adsorption of polymer chains onto the wall surface of viscometer. A theory of adsorption effect based on the Langmuir isotherms was proposed and a mathematical analysis for data treatment was performed. The theory could adequately describe the existing viscosity data. It seems necessary to correct the viscosity result of dilute polymer solutions measured by glass capillary viscometer by taking into account the effect of adsorption in all cases.

  12. Direct Uniaxial Alignment of a Donor-Acceptor Semiconducting Polymer Using Single-Step Solution Shearing. (United States)

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


    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

  13. Pressure-volume-temperature and excess molar volume prediction of amorphous and crystallizable polymer blends by equation of state

    Institute of Scientific and Technical Information of China (English)

    Fakhri Yousefi; Hajir Karimi; Maryam Gomar


    In this work the statistical mechanical equation of state was developed for volumetric properties of crystal ine and amorphous polymer blends. The Ihm–Song–Mason equations of state (ISMEOS) based on temperature and density at melting point (Tm andρm) as scaling constants were developed for crystalline polymers such as poly(propylene glycol)+poly(ethylene glycol)-200 (PPG+PEG-200), poly(ethylene glycol) methyl ether-300 (PEGME-350)+PEG-200 and PEGME-350+PEG-600. Furthermore, for amorphous polymer blends con-taining poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)+polystyrene (PS) and PS+poly(vinylmethylether) (PVME), the density and surface tension at glass transition (ρg andγg) were used for estimation of second Virial coefficient. The calculation of second Virial coefficients (B2), effective van der Waals co-volume (b) and correction factor (α) was required for judgment about applicability of this model. The obtained results by ISMEOS for crys-talline and amorphous polymer blends were in good agreement with the experimental data with absolute aver-age deviations of 0.84%and 1.04%, respectively.

  14. Investigation of Phase Mixing in Amorphous Solid Dispersions of AMG 517 in HPMC-AS Using DSC, Solid-State NMR, and Solution Calorimetry. (United States)

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


    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.

  15. Investigation and correlation of drug polymer miscibility and molecular interactions by various approaches for the preparation of amorphous solid dispersions. (United States)

    Meng, Fan; Trivino, Anne; Prasad, Dev; Chauhan, Harsh


    Curcumin (CUR) was used as a poorly soluble drug whereas polyvinyl pyrrolidone K90 (PVP), Eudragit EPO (EPO), hydroxypropyl methylcellulose E5 (HPMC) and polyethylene glycol 8000 (PEG) were used as hydrophilic polymers. CUR polymer miscibility was evaluated by solubility parameter, melting point depression and glass transition temperature (Tg) measurements. Molecular interactions between CUR and polymers were determined by Fourier-transform infrared spectroscopy (FTIR) and Raman. Amorphous solid dispersions were prepared with CUR-polymer ratio of 70:30 (w/w) by solvent evaporation technique and were evaluated for dissolution enhancement using USP II method. Physical states of solid dispersions were characterized by X-ray diffraction (XRD) whereas thermal behaviors were investigated using modulated differential scanning calorimetry (MDSC). CUR-EPO system showed good miscibility through all the approaches, whereas immiscibility was found in other CUR-polymer systems. CUR-EPO and CUR-HPMC systems showed significant molecular interactions whereas CUR-PVP and CUR-PEG showed no molecular interactions. All solid dispersions showed significant dissolution enhancement with CUR-EPO showing highest dissolution rate during first 1h whereas CUR-HPMC was effective in maintaining high CUR concentrations for 6h. The study highlights the importance of investigating and correlating drug polymer miscibility and molecular interactions by various approaches for successful formulation of amorphous solid dispersions.

  16. Adsorption of Cr(VI) from synthetic solutions and electroplating wastewaters on amorphous aluminium oxide. (United States)

    Alvarez-Ayuso, E; García-Sánchez, A; Querol, X


    The adsorption behaviour of amorphous aluminium oxide was studied with respect to Cr(VI) in order to consider its application to purify electroplating wastewaters. A batch method was employed using Cr(VI) concentrations ranged from 10 to 200mg/l. The Langmuir model was found to describe the adsorption process well, offering a maximum adsorption capacity of 78.1mg/g. The effect of ionic strength (0-0.1M KNO(3)), pH (3-9) and competitive solutes (molar ratio [Cr(VI)]/[SO(4)(2-)]=1 and 100) on the retention process was evaluated. Cr(VI) adsorption on amorphous aluminium oxide appeared to be dependent on ionic strength with a more pronounced effect in acid conditions. Conversely, adsorption was not affected by pH in acid medium, but decreased when pH sifted to alkaline values. The presence of SO(4)(2-) greatly reduced Cr(VI) removal across the entire pH range when both solutes were present in similar concentrations. Amorphous aluminium oxide also showed a high adsorption capacity when used in the purification of Cr(VI) electroplating wastewaters. The adsorbent doses required to attain more than 90% of Cr(VI) removal varied between 1 and 5 g/l depending on Cr(VI) concentration in wastewaters.

  17. Polymer fullerene solution phase behaviour and film formation pathways. (United States)

    Dattani, Rajeev; Cabral, João T


    We report the phase behaviour of polymer/fullerene/solvent ternary mixtures and its consequence for the morphology of the resulting composite thin films. We focus particularly on solutions of polystyrene (PS), C60 fullerene and toluene, which are examined by static and dynamic light scattering, and films obtained from various solution ages and thermal annealing conditions, using atomic force and light microscopy. Unexpectedly, the solution phase behaviour below the polymer overlap concentration, c*, is found to be described by a simple excluded volume argument (occupied by the polymer chains) and the neat C60/solvent miscibility. Scaling consistent with full exclusion is found when the miscibility of the fullerene in the solvent is much lower than that of the polymer, giving way to partial exclusion with more soluble fullerenes (phenyl-C61-butyric acid methyl ester, PCBM) and a less asymmetric solvent (chlorobenzene), employed in photovoltaic devices. Spun cast and drop cast films were prepared from PS/C60/toluene solutions across the phase diagram to yield an identical PS/C60 composition and film thickness, resulting in qualitatively different morphologies in agreement with our measured solution phase boundaries. Our findings are relevant to the solution processing of polymer/fullerene composites (including organic photovoltaic devices), which generally require effective solubilisation of fullerene derivatives and polymer pairs in this concentration range, and the design of well-defined thin film morphologies.

  18. Nanostructure investigation of polymer solutions, polymer gels, and polymer thin films (United States)

    Lee, Wonjoo

    This thesis discusses two systems. One is structured hydrogels which are hydrogel systems based on crosslinked poly((2-dimethylamino)ethyl methacrylate) (PDMAEMA) containing micelles which form nanoscale pores within the PDMAEMA hydrogel. The other is nanoporous block copolymer thin films where solvent selectivity is exploited to create nanopores in PS-b-P4VP thin films. Both of these are multicomponent polymer systems which have nanoscale porous structures. 1. Small angle neutron scattering of micellization of anionic surfactants in water, polymer solutions and hydrogels. Nanoporous materials have been broadly investigated due to the potential for a wide range of applications, including nano-reactors, low-K materials, and membranes. Among those, molecularly imprinted polymers (MIP) have attracted a large amount of interest because these materials resemble the "lock and key" paradigm of enzymes. MIPs are created by crosslinking either polymers or monomers in the presence of template molecules, usually in water. Initially, functional groups on the polymer or the monomer are bound either covalently or noncovalently to the template, and crosslinking results in a highly crosslinked hydrogel. The MIPs containing templates are immersed in a solvent (usually water), and the large difference in the osmotic pressure between the hydrogel and solvent removes the template molecules from the MIP, leaving pores in the polymer network containing functionalized groups. A broad range of different templates have been used ranging from molecules to nanoscale structures inclucing stereoisomers, virus, and micelles. When micelles are used as templates, the size and shape before and after crosslinking is an important variable as micelles are thermodynamic objects whose structure depends on the surfactant concentration of the solution, temperature, electrolyte concentration and polymer concentration. In our research, the first goal is to understand the micellization of anionic

  19. Surface dynamics of amorphous polymers used for high-voltage insulators. (United States)

    Shemella, Philip T; Laino, Teodoro; Fritz, Oliver; Curioni, Alessandro


    Amorphous siloxane polymers are the backbone of high-voltage insulation materials. The natural hydrophobicity of their surface is a necessary property for avoiding leakage currents and dielectric breakdown. As these surfaces are exposed to the environment, electrical discharges or strong mechanical impact can temporarily destroy their water-repellent properties. After such events, however, a self-healing process sets in and restores the original hydrophobicity within some hours. In the present study, we investigate possible mechanisms of this restoration process. Using large-scale, all-atom molecular dynamics simulations, we show that molecules on the material surface have augmented motion that allows them to rearrange with a net polarization. The overall surface region has a net orientation that contributes to hydrophobicity, and charged groups that are placed at the surface migrate inward, away from the vacuum interface and into the bulk-like region. Our simulations provide insight into the mechanisms for hydrophobic self-recovery that repair material strength and functionality and suggest material compositions for future high-voltage insulators.

  20. Dispersive Non-Geminate Recombination in an Amorphous Polymer:Fullerene Blend (United States)

    Kurpiers, Jona; Neher, Dieter


    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.

  1. Mechanism of sulfide effect on viscosity of HPAM polymer solution

    Institute of Scientific and Technical Information of China (English)

    康万利; 周阳; 王志伟; 孟令伟; 刘述忍; 白宝君


    The effect of sulfide on HPAM solution viscosity was studied using BROOKFIELD DV-II viscometer,and the interaction mechanism was discussed.The HPAM solution viscosity was investigated through fully reducing sulfide by the addition of hydrogen peroxide oxidation,and the mechanism of increasing polymer viscosity was investigated.The experimental results also show that there is a critical concentration of 15 mg/L.Below it,the loss rate of HPAM solution viscosity increases more rapidly,but becomes slowly above the critical concentration.A theoretical guidance for oilfields to prepare polymer solution using sewage-water by eliminating sulfide,and it is also importance to prepare polymer solution using sewage-water and save fresh water.

  2. Entrainment Reduction and Additional Dissipation in Dilute Polymer Solutions (United States)

    Holzner, Markus; Lüthi, Beat; Liberzon, Alexander; Guala, Michele; Kinzelbach, Wolfgang

    We present a comparative experimental study of a turbulent flow developing in clear water and dilute polymer solutions (25 and 50 wppm polyethylene oxide). The flow is forced by a planar grid that oscillates vertically in a square container of initially still fluid. The two-component velocity fields are measured in a vertical plane passing through the center of the tank by using time resolved Particle Image Velocimetry (PIV).We obtain a lower entrainment rate for polymer solutions as compared to clear water. Extending arguments based on similarity and fractal theory to the case of dilute polymer solutions, we derive a relation between the entrainment rate and the fraction of input energy dissipated by the polymers.

  3. Phase Equilibria for Complex Polymer Solutions

    DEFF Research Database (Denmark)

    Lindvig, Thomas; Hestkjær, L. L.; Hansen, A. F.


    Many commercially important mixtures contain complex polymers, e.g. paints and coatings. If a good thermodynamic description can be given of these systems it is possible to develop paints, which possess a certain set of properties and at the same time meet some basic requirement as, e.g. regarding...

  4. Controlling molecular ordering in solution-state conjugated polymers. (United States)

    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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Curro, John G.; Frischknecht, Amalie Lucile


    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.

  6. Low-temperature solution-processed amorphous indium tin oxide field-effect transistors. (United States)

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


    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) 0.2 cm(2) V(-1) s(-1), which is encouraging for processing on plastic substrates.

  7. Versatile solution for growing thin films of conducting polymers. (United States)

    D'Arcy, Julio M; Tran, Henry D; Tung, Vincent C; Tucker-Schwartz, Alexander K; Wong, Rain P; Yang, Yang; Kaner, Richard B


    The method employed for depositing nanostructures of conducting polymers dictates potential uses in a variety of applications such as organic solar cells, light-emitting diodes, electrochromics, and sensors. A simple and scalable film fabrication technique that allows reproducible control of thickness, and morphological homogeneity at the nanoscale, is an attractive option for industrial applications. Here we demonstrate that under the proper conditions of volume, doping, and polymer concentration, films consisting of monolayers of conducting polymer nanofibers such as polyaniline, polythiophene, and poly(3-hexylthiophene) can be produced in a matter of seconds. A thermodynamically driven solution-based process leads to the growth of transparent thin films of interfacially adsorbed nanofibers. High quality transparent thin films are deposited at ambient conditions on virtually any substrate. This inexpensive process uses solutions that are recyclable and affords a new technique in the field of conducting polymers for coating large substrate areas.

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

    DEFF Research Database (Denmark)

    Priemel, Petra A; Laitinen, Riikka; Barthold, Sarah;


    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...... 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...

  9. Segment Orientation and Optical Birefringence of Amorphous Polymers Under Tensile Deformation: Novel Computational Method applied to Different Glassy Polycarbonates (United States)

    Natarajan, Upendra; Sulatha, M. S.


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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. Submicron flow of polymer solutions: slippage reduction due to confinement. (United States)

    Cuenca, Amandine; Bodiguel, Hugues


    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.

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

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


    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

  13. Synthesis and Solution Properties of Hydrophobic Associating Polymers

    Institute of Scientific and Technical Information of China (English)

    任鲲; 姜桂元; 徐春明; 林梅钦


    Acrylamide/2-acrylamido alkane sulfonic acid hydrophobic associating copolymers were synthesized by micellar copolymerization. Effects of hydrophobe content, polymer concentration, salinity and surfactant on rheological behavior of copolymers were investigated and the conformation of polymers in solution was studied by means of environmental scanning electronic microscopy and dynamic light scattering. The experimental results showed that in the dilute regime the hydrophobic parts could interact intramolecularly, while in the regime where the polymer concentration was higher than the critical association concentration, intermolecular hydrophobic association became predominant. Within the limit of the solubility, the critical association concentration of the polymer decreased with the increase of the salinity. The experimental results of the solution conformation indicated the presence of the three-dimensional network structure in deionized water and the size of the mesh in the network varied with the polymer concentration. In NaG1 solution, above the critical association concentration, an increase in polymer concentration enhanced the intermolecular association and also enlarged the hydrodynamic radius. It would result in the imorovement of the thickening power of polvmers.

  14. Ideal solution behaviour of glassy Cu–Ti, Zr, Hf alloys and properties of amorphous copper

    Energy Technology Data Exchange (ETDEWEB)

    Ristić, R. [Department of Physics, University of Osijek, Trg Ljudevita Gaja 6, HR-3100 Osijek (Croatia); Cooper, J.R. [Department of Physics, Cavendish Laboratory, J.J. Thomson Avenue, CB3 0HE Cambridge (United Kingdom); Zadro, K.; Pajić, D. [Department of Physics, Faculty of Science, Bijenička cesta 32, HR-10002 Zagreb (Croatia); Ivkov, J. [Institute of Physics, Bijenička cesta 46, HR-10002 Zagreb (Croatia); Babić, E. [Department of Physics, Faculty of Science, Bijenička cesta 32, HR-10002 Zagreb (Croatia)


    Highlights: • Ideal solution behaviour (ISB) is established in all Cu–Ti, Zr, Hf glassy alloys. • ISB enables reliable estimates for various properties of amorphous Cu. • ISB also impacts glass forming ability in these and probably other similar alloys. - Abstract: A comprehensive study of selected properties of amorphous (a) Cu–TE alloys (TE = Ti, Zr and Hf) has been performed. Data for average atomic volumes of a-Cu–Hf, Ti alloys combined with literature data show that ideal solution behaviour (Vegard’s law) extends over the whole glass forming range (GFR) in all a-Cu–TE alloys. This enables one to obtain an insight into some properties and probable atomic arrangements for both, a-TEs (Ristić et al., 2010) and a-Cu by extrapolation of the data for alloys. Indeed the atomic volumes and other properties studied for all a-Cu–TE alloys extrapolate to the same values for a-Cu. Depending on the property, these values are either close to those of crystalline (c) Cu, or are close to those for liquid (L) Cu. In particular, the electronic transport properties of a-Cu seem close to those of L-Cu, whereas the static properties, such as the density of states, and Young’s modulus, converge to those of c-Cu. The possible impact of these results on our understanding of a-Cu–TE alloys, including glass forming ability, is discussed.

  15. Solid solution or amorphous phase formation in TiZr-based ternary to quinternary multi-principal-element films

    Directory of Open Access Journals (Sweden)

    Mariana Braic


    The deposited films exhibited only solid solution (fcc, bcc or hcp or amorphous phases, no intermetallic components being detected. It was found that the hcp structure was stabilized by the presence of Hf or Y, bcc by Nb or Al and fcc by Cu. For the investigated films, the atomic size difference, mixing enthalpy, mixing entropy, Gibbs free energy of mixing and the electronegativity difference for solid solution and amorphous phases were calculated based on Miedema׳s approach of the regular solution model. It was shown that the atomic size difference and the ratio between the Gibbs free energies of mixing of the solid solution and amorphous phases were the most significant parameters controlling the film crystallinity.

  16. Dynamic dilution exponent in monodisperse entangled polymer solutions

    DEFF Research Database (Denmark)

    Shahid, T.; Huang, Qian; Oosterlinck, F.;


    We study and model the linear viscoelastic properties of several entangled semi-dilute and concentrated solutions of linear chains of different molar masses and at different concentrations dissolved in their oligomers. We discuss the dilution effect of the oligomers on the entangled long chains...... of the long chain extremities. Then we discuss the influence of the polymer concentration on the terminal relaxation time of the solutions and how this can be modelled by the enhanced contour length fluctuation process (CR-CLF). We point out that this larger dilution effect is not only a function...... of concentration but also depends on the molar mass of the chains. While the proposed approach successfully explains the viscoelastic properties of a large number of semi-dilute solutions of polymers in their own oligomers, important discrepancies are found for semi-dilute entangled polymers in small...

  17. A lattice Boltzmann method for dilute polymer solutions. (United States)

    Singh, Shiwani; Subramanian, Ganesh; Ansumali, Santosh


    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).

  18. On turbulent entrainment and dissipation in dilute polymer solutions (United States)

    Liberzon, A.; Holzner, M.; Lüthi, B.; Guala, M.; Kinzelbach, W.


    We present a comparative experimental study of a turbulent flow developing in clear water and dilute polymer solutions (25 and 50 wppm polyethylene oxide). The flow is forced by a planar grid that oscillates vertically with stroke S and frequency f in a square container of initially still fluid. Two-component velocity fields are measured in a vertical plane passing through the center of the tank by using time resolved particle image velocimetry. After the forcing is initiated, a turbulent layer develops that is separated from the initially irrotational fluid by a sharp interface, the so-called turbulent/nonturbulent interface (TNTI). The turbulent region grows in time through entrainment of surrounding fluid until the fluid in the whole container is in turbulent motion. From the comparison of the experiments in clear water and polymer solutions we conclude: (i) Polymer additives modify the large scale shape of the TNTI. (ii) Both, in water and in the polymer solution the mean depth of the turbulent layer, H(t ), follows the theoretical prediction for Newtonian fluids H(t )∝√Kt , where K ∝S2f is the "grid action." (iii) We find a larger grid action for dilute polymer solutions than for water. As a consequence, the turbulent kinetic energy of the flow increases and the rate of energy input becomes higher. (iv) The entrainment rate β =ve/vrms (where ve=dH/dt is the interface propagation velocity and vrms is the root mean square of the vertical velocity) is lower for polymers (βp≈0.7) than for water (βw≈0.8). The measured values for β are in good agreement with similarity arguments, from which we estimate that in our experiment about 28% of the input energy is dissipated by polymers.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    Highlights: • Economical method for crack-free amorphous yttria layer deposition by dip coating. • Simpler process for planar yttria film as a diffusion barrier and nucleation layer. • Easy control over the film properties with better characteristics. • Easy control over the thickness of the deposited films. • A feasible process that can be easily adopted by HTSCC industries. - Abstract: 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 Y{sub 2}O{sub 3} 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 μm{sup 2} area. After Y{sub 2}O{sub 3} deposition, MgO was deposited using ion-beam assisted deposition (IBAD), then LaMnO{sub 3} (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/Y{sub 2}O{sub 3} and GdBCO/LMO/MgO/Y{sub 2}O{sub 3} stack films have good out-of-plane and in-plane textures with strong c-axis alignment. The critical current (Ic) of GdBCO/LMO/MgO/Y{sub 2}O{sub 3} 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.

  20. Numerical Simulation and Experimental Investigation of the Viscoelastic Heating Mechanism in Ultrasonic Plasticizing of Amorphous Polymers for Micro Injection Molding

    Directory of Open Access Journals (Sweden)

    Bingyan Jiang


    Full Text Available Ultrasonic plasticizing of polymers for micro-injection molding has been proposed and studied for its unique potential in materials and energy-saving. In our previous work, we have demonstrated the characteristics of the interfacial friction heating mechanism in ultrasonic plasticizing of polymer granulates. In this paper, the other important heating mechanism in ultrasonic plasticizing, i.e., viscoelastic heating for amorphous polymer, was studied by both theoretical modeling and experimentation. The influence mechanism of several parameters, such as the initial temperature of the polymer, the ultrasonic frequency, and the ultrasonic amplitude, was investigated. The results from both numerical simulation and experimentation indicate that the heat generation rate of viscoelastic heating can be significantly influenced by the initial temperature of polymer. The glass transition temperature was found to be a significant shifting point in viscoelastic heating. The heat generation rate is relatively low at the beginning and can have a steep increase after reaching glass transition temperature. In comparison with the ultrasonic frequency, the ultrasonic amplitude has much greater influence on the heat generation rate. In light of the quantitative difference in the viscoelastic heating rate, the limitation of the numerical simulation was discussed in the aspect of the assumptions and the applied mathematical models.

  1. Enhancement of flagellated bacterial motility in polymer solutions (United States)

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


    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).

  2. Predicting morphologies of solution processed polymer: Fullerene blends

    NARCIS (Netherlands)

    Kouijzer, S.; Michels, J.J.; Berg, M. van den; Gevaerts, V.S.; Turbiez, M.; Wienk, M.M.; Janssen, R.A.J.


    The performance of solution processed polymer:fullerene thin film photovoltaic cells is largely determined by the nanoscopic and mesoscopic morphology of these blends that is formed during the drying of the layer. Although blend morphologies have been studied in detail using a variety of microscopic


    Institute of Scientific and Technical Information of China (English)

    Attila R.Imre


    In this paper we would like to give a brief review about the extensibility of the liquid-liquid locus into the negative pressure region. Negative pressure states are hardly explored; most researchers believe that the pressure scale ends at p = 0.We would like to show that this is not true, thep = 0 point is not a special point for liquids, it can be "easily" crossed. We are going to give a few example, where the extension of liquid-liquid locus for polymer blends and solutions below p = 0 gives us some interesting results, like the merging of UCST and LCST branches in weakly interacting polymer solutions or the reason why most UCST blends exhibit pressure induced immiscibility. Also, we will see what happens with the immiscibility island of aqueous polymer solutions when - reaching the critical molar mass - it "disappears".

  4. A Comprehensive study of the Effects of Chain Morphology on the Transport Properties of Amorphous Polymer Films (United States)

    Mendels, Dan; Tessler, Nir


    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.

  5. Cake Filtration in Viscoelastic Polymer Solutions (United States)

    Surý, Alexander; Machač, Ivan


    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.

  6. Nanoscale Infrared, Thermal, and Mechanical Characterization of Telaprevir-Polymer Miscibility in Amorphous Solid Dispersions Prepared by Solvent Evaporation. (United States)

    Li, Na; Taylor, Lynne S


    Miscibility is of great interest for pharmaceutical systems, in particular, for amorphous solid dispersions, as phase separation can lead to a higher tendency to crystallize, resulting in a loss in solubility, decreased dissolution rate, and compromised bioavailability. The purpose of this study was to investigate the miscibility behavior of a model poorly water-soluble drug, telaprevir (TPV), with three different polymers using atomic force microscopy-based infrared, thermal, and mechanical analysis. Standard atomic force microscopy (AFM) imaging together with nanoscale infrared spectroscopy (AFM-IR), nanoscale thermal analysis (nanoTA), and Lorentz contact resonance (LCR) measurements were used to evaluate the miscibility behavior of TPV with three polymers, hydroxypropyl methylcellulose (HPMC), HPMC acetate succinate (HPMCAS), and poly(vinylpyrrolidone-co-vinyl acetate) (PVPVA), at different drug to polymer ratios. Phase separation was observed with HPMC and PVPVA at drug loadings above 10%. For HPMCAS, a smaller miscibility gap was observed, with phase separation being observed at drug loadings higher than ∼30-40%. The domain size of phase-separated regions varied from below 50 nm to a few hundred nanometers. Localized infrared spectra, nano-TA measurements, images from AFM-based IR, and LCR measurements showed clear contrast between the continuous and discrete domains for these phase-separated systems, whereby the discrete domains were drug-rich. Fluorescence microscopy provided additional evidence for phase separation. These methods appear to be promising to evaluate miscibility in drug-polymer systems with similar Tgs and submicron domain sizes. Furthermore, such findings are of obvious importance in the context of contributing to a mechanistic understanding of amorphous solid dispersion phase behavior.

  7. Nonequilibrium thermodynamics of dilute polymer solutions in flow. (United States)

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


    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.


    DEFF Research Database (Denmark)

    Beyer, Andreas; Grohganz, Holger; Löbmann, Korbinian;


    Co-amorphisation represents a promising approach to increase the physical stability and dissolution rate of amorphous active pharmaceutical ingredients (APIs) as an alternative to polymer glass solutions. For amorphous and co-amorphous systems, it is reported that the preparation method and the b...

  9. Viscosity solutions for a polymer crystal growth model

    CERN Document Server

    Cardaliaguet, Pierre; Monteillet, Aurélien


    We prove existence of a solution for a polymer crystal growth model describing the movement of a front $(\\Gamma(t))$ evolving with a nonlocal velocity. In this model the nonlocal velocity is linked to the solution of a heat equation with source $\\delta_\\Gamma$. The proof relies on new regularity results for the eikonal equation, in which the velocity is positive but merely measurable in time and with H\\"{o}lder bounds in space. From this result, we deduce \\textit{a priori} regularity for the front. On the other hand, under this regularity assumption, we prove bounds and regularity estimates for the solution of the heat equation.

  10. Chain conformation-dependent thermal conductivity of amorphous polymer blends: the impact of inter- and intra-chain interactions. (United States)

    Wei, Xingfei; Zhang, Teng; Luo, Tengfei


    Polymers with high thermal conductivities are of great interest for both scientific research and industrial applications. In this study, model amorphous polymer blends are studied using molecular dynamics simulations. We have examined the effects of inter- and intra-chain interactions on the molecular-level conformations of the blends, which in turn impact their thermal conductivity. It is found that the thermal conductivity of polymer blends is strongly related to the molecular conformation, especially the spatial extent of the molecular chains indicated by their radius of gyration. Tuning the intra-chain van der Waals (vdW) interaction leads to different molecular structures of the minor component in the binary blend, but the thermal conductivity is not changed. However, increasing the inter-chain vdW interactions between the major and the minor components will increase the thermal conductivity of the blend, which is due to the conformation change in the major component that leads to enhanced thermal transport along the chain backbone through the intra-chain bonding interactions. The fundamental structure-property relationship from this study may provide useful guidance for designing and synthesizing polymer blends with desirable thermal conductivity.

  11. Glass solution formation in water - In situ amorphization of naproxen and ibuprofen with Eudragit® E PO

    DEFF Research Database (Denmark)

    Doreth, Maria; Löbmann, Korbinian; Grohganz, Holger;


    a glass solution with Eudragit® E when immersed into water. In XRPD, reflections of the respective drugs decreased or disappeared completely. All samples showed a single glass transition temperature in the DSC, suggesting the formation of single phase amorphous systems. Ionic interactions between drug...

  12. Modeling the Rheology of Polymer Melts and Solutions (United States)

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


    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.

  13. The Dynamics of Nanoparticles in Polymer Solutions and Melts (United States)

    Mukhopadhyay, Ashis; Alam, Sharmine; Kohli, Indermeet


    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.

  14. Dynamic contact angles in oil-aqueous polymer solutions. (United States)

    Al-Shareef, Amer; Neogi, P; Bai, Baojun


    Polymer flooding is an important process in enhanced oil recovery. The displacement front is unstable when low viscosity brine displaces the heavy crude oil in the reservoir. Water-soluble polymers are added to the brine to increase its viscosity which stabilizes the displacement process. To analyze the displacement process at the micro-level, we have investigated the dynamic contact angles in silicone oil-polymer (polyethylene oxide) solution and for the first time. The dynamic contact angle is the apparent contact angle at the three-phase contact line which governs the capillary pressure, and thus is important for the displacement process. The data show no obvious signs of either shear thinning or elastic behavior, although for some systems with highest elastic effects some unexplained effects on dynamic contact angles are observed that correlate with elastic effects. Overall, dynamic contact angles are explained well using existing models for two Newtonian fluids, when the zero shear viscosity is used for the polymer solution.

  15. Linear topology in amorphous metal oxide electrochromic networks obtained via low-temperature solution processing (United States)

    Llordés, Anna; Wang, Yang; Fernandez-Martinez, Alejandro; Xiao, Penghao; Lee, Tom; Poulain, Agnieszka; Zandi, Omid; Saez Cabezas, Camila A.; Henkelman, Graeme; Milliron, Delia J.


    Amorphous transition metal oxides are recognized as leading candidates for electrochromic window coatings that can dynamically modulate solar irradiation and improve building energy efficiency. However, their thin films are normally prepared by energy-intensive sputtering techniques or high-temperature solution methods, which increase manufacturing cost and complexity. Here, we report on a room-temperature solution process to fabricate electrochromic films of niobium oxide glass (NbOx) and `nanocrystal-in-glass’ composites (that is, tin-doped indium oxide (ITO) nanocrystals embedded in NbOx glass) via acid-catalysed condensation of polyniobate clusters. A combination of X-ray scattering and spectroscopic characterization with complementary simulations reveals that this strategy leads to a unique one-dimensional chain-like NbOx structure, which significantly enhances the electrochromic performance, compared to a typical three-dimensional NbOx network obtained from conventional high-temperature thermal processing. In addition, we show how self-assembled ITO-in-NbOx composite films can be successfully integrated into high-performance flexible electrochromic devices.

  16. Instability and morphology of polymer solutions coating a fiber

    CERN Document Server

    Boulogne, François; Giorgiutti-Dauphiné, Frédérique


    We report an experimental study on the dynamics of a thin film of polymer solution coating a vertical fiber. The liquid film has first a constant thickness and then undergoes the Rayleigh-Plateau instability which leads to the formation of sequences of drops, separated by a thin film, moving down at a constant velocity. Different polymer solutions are used, i.e. xanthan solutions and polyacrylamide (PAAm) solutions. These solutions both exhibit shear-rate dependence of the viscosity, but for PAAm solutions, there are strong normal stresses in addition of the shear-thinning effect. We characterize experimentally and separately the effects of these two non-Newtonian properties on the flow on the fiber. Thus, in the flat film observed before the emergence of the drops, only shear-thinning effect plays a role and tends to thin the film compared to the Newtonian case. The effect of the non-Newtonian rheology on the Rayleigh-Plateau instability is then investigated through the measurements of the growth rate and th...

  17. Self-bonding in an amorphous polymer below the glass transition

    DEFF Research Database (Denmark)

    Boiko, Yuri M.; Bach, Anders; Lyngaae-Jørgensen, Jørgen


    Films of amorphous polystyrene (PS) with a weight-average molecular weight (Mw) of 225 × 103 g/mol were bonded in a T-peel test geometry, and the fracture energy (G) of a PS/PS interface was measured at the ambient temperature as a function of the healing time (th) and healing temperature (Th). G...

  18. Measurement of cloud point temperature in polymer solutions. (United States)

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


    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.

  19. Viscosity solutions for a polymer crystal growth model


    Cardaliaguet, Pierre; Ley, Olivier; Monteillet, Aurélien


    International audience; We prove existence of a solution for a polymer crystal growth model describing the movement of a front $(\\Gamma(t))$ evolving with a nonlocal velocity. In this model the nonlocal velocity is linked to the solution of a heat equation with source $\\delta_\\Gamma$. The proof relies on new regularity results for the eikonal equation, in which the velocity is positive but merely measurable in time and with H\\"{o}lder bounds in space. From this result, we deduce \\textit{a pri...

  20. Structure of polymer layers adsorbed from concentrated solutions (United States)

    Auvray, Loïc; Auroy, Philippe; Cruz, Margarida


    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

  1. Influence of polymer molecular weight on in vitro dissolution behavior and in vivo performance of celecoxib:PVP amorphous solid dispersions. (United States)

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


    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.

  2. Theoretical Considerations in Developing Amorphous Solid Dispersions

    DEFF Research Database (Denmark)

    Laitinen, Riikka; Priemel, Petra Alexandra; Surwase, Sachin;


    Before pursuing the laborious route of amorphous solid dispersion formulation and development, which is the topic of many of the subsequent chapters in this book, the formulation scientist would benefit from a priori knowledge whether the amorphous route is a viable one for a given drug and how...... to their glass-forming ability and glass stability. In the main parts of this chapter, we review theoretical approaches to determine amorphous drug polymer miscibility and crystalline drug polymer solubility, as a prerequisite to develop amorphous solid dispersions (glass solutions)....... much solubility improvement, and hence increase in bioavailability, can be expected, and what forms of solid dispersion have been developed in the past. In this chapter, we therefore initially define the various forms of solid dispersions, and then go on to discuss properties of pure drugs with respect...

  3. Sequentially solution-processed, nanostructured polymer photovoltaics using selective solvents

    KAUST Repository

    Kim, Do Hwan


    We demonstrate high-performance sequentially solution-processed organic photovoltaics (OPVs) with a power conversion efficiency (PCE) of 5% for blend films using a donor polymer based on the isoindigo-bithiophene repeat unit (PII2T-C10C8) and a fullerene derivative [6,6]-phenyl-C[71]-butyric acid methyl ester (PC71BM). This has been accomplished by systematically controlling the swelling and intermixing processes of the layer with various processing solvents during deposition of the fullerene. We find that among the solvents used for fullerene deposition that primarily swell but do not re-dissolve the polymer underlayer, there were significant microstructural differences between chloro and o-dichlorobenzene solvents (CB and ODCB, respectively). Specifically, we show that the polymer crystallite orientation distribution in films where ODCB was used to cast the fullerene is broad. This indicates that out-of-plane charge transport through a tortuous transport network is relatively efficient due to a large density of inter-grain connections. In contrast, using CB results in primarily edge-on oriented polymer crystallites, which leads to diminished out-of-plane charge transport. We correlate these microstructural differences with photocurrent measurements, which clearly show that casting the fullerene out of ODCB leads to significantly enhanced power conversion efficiencies. Thus, we believe that tuning the processing solvents used to cast the electron acceptor in sequentially-processed devices is a viable way to controllably tune the blend film microstructure. © 2014 The Royal Society of Chemistry.

  4. Amorphous TiO2-coated reduced graphene oxide hybrid nanostructures for polymer composites with low dielectric loss (United States)

    Tong, Wangshu; Zhang, Yihe; Yu, Li; Lv, Fengzhu; Liu, Leipeng; Zhang, Qian; An, Qi


    Nanocomposite of poly(vinylidene fluoride-co-hexafluoropropylene) incorporated with titanium dioxide-modified reduced graphene oxide sheets (rGO-TiO2/PVDF-HFP) was prepared by in situ assembling TiO2 on graphene oxide (GO), and its dielectric properties were carefully characterized. The GO layers were completely coated with amorphous TiO2. The dielectric permittivity increased stably as rGO-TiO2 content increased, and the loss was low at low frequencies. TiO2 inter-layer acted as an inter-particle barrier to prevent direct contact of rGO, which provided a new simple way for tuning the dielectric properties of polymer composites with low dielectric loss by controlling the structure of fillers.

  5. Hot melt extrusion for amorphous solid dispersions: temperature and moisture activated drug-polymer interactions for enhanced stability. (United States)

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


    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.

  6. Predicting morphologies of solution processed polymer:fullerene blends. (United States)

    Kouijzer, Sandra; Michels, Jasper J; van den Berg, Mauricio; Gevaerts, Veronique S; Turbiez, Mathieu; Wienk, Martijn M; Janssen, René A J


    The performance of solution processed polymer:fullerene thin film photovoltaic cells is largely determined by the nanoscopic and mesoscopic morphology of these blends that is formed during the drying of the layer. Although blend morphologies have been studied in detail using a variety of microscopic, spectroscopic, and scattering techniques and a large degree of control has been obtained, the current understanding of the processes involved is limited. Hence, predicting the optimized processing conditions and the corresponding device performance remains a challenge. We present an experimental and modeling study on blends of a small band gap diketopyrrolopyrrole-quinquethiophene alternating copolymer (PDPP5T) and [6,6]-phenyl-C71-butyric acid methyl ester ([70]PCBM) cast from chloroform solution. The model uses the homogeneous Flory-Huggins free energy of the multicomponent blend and accounts for interfacial interactions between (locally) separated phases, based on physical properties of the polymer, fullerene, and solvent. We show that the spinodal liquid-liquid demixing that occurs during drying is responsible for the observed morphologies. The model predicts an increasing feature size and decreasing fullerene concentration in the polymer matrix with increasing drying time in accordance with experimental observations and device performance. The results represent a first step toward a predictive model for morphology formation.

  7. High-performance solution-processed amorphous zinc-indium-tin oxide thin-film transistors. (United States)

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


    Films of the high-performance solution-processed amorphous oxide semiconductor a-ZnIn(4)Sn(4)O(15), grown from 2-methoxyethanol/ethanolamine solutions, were used to fabricate thin-film transistors (TFTs) in combination with an organic self-assembled nanodielectric as the gate insulator. This structurally dense-packed semiconductor composition with minimal Zn(2+) incorporation strongly suppresses transistor off-currents without significant mobility degradation, and affords field-effect electron mobilities of approximately 90 cm(2) V(-1) s(-1) (104 cm(2) V(-1) s(-1) maximum obtained for patterned ZITO films), with I(on)/I(off) ratio approximately 10(5), a subthreshhold swing of approximately 0.2 V/dec, and operating voltage <2 V for patterned devices with W/L = 50. The microstructural and electronic properties of ZITO semiconductor film compositions in the range Zn(9-2x)In(x)Sn(x)O(9+1.5x) (x = 1-4) and ZnIn(8-x)Sn(x)O(13+0.5x) (x = 1-7) were systematically investigated to elucidate those factors which yield optimum mobility, I(on)/I(off), and threshold voltage parameters. It is shown that structural relaxation and densification by In(3+) and Sn(4+) mixing is effective in reducing carrier trap sites and in creating carrier-generating oxygen vacancies. In contrast to the above results for TFTs fabricated with the organic self-assembled nanodielectric, ZnIn(4)Sn(4)O(15) TFTs fabricated with SiO(2) gate insulators exhibit electron mobilities of only approximately 11 cm(2) V(-1) s(-1) with I(on)/I(off) ratios approximately 10(5), and a subthreshhold swing of approximately 9.5 V/dec.

  8. Solution-processed small molecule-polymer blend organic thin-film transistors with hole mobility greater than 5 cm 2/Vs

    KAUST Repository

    Smith, Jeremy N.


    Using phase-separated organic semiconducting blends containing a small molecule, as the hole transporting material, and a conjugated amorphous polymer, as the binder material, we demonstrate solution-processed organic thin-film transistors with superior performance characteristics that include; hole mobility >5 cm 2/Vs, current on/off ratio ≥10 6 and narrow transistor parameter spread. These exceptional characteristics are attributed to the electronic properties of the binder polymer and the advantageous nanomorphology of the blend film. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Solid solution or amorphous phase formation in TiZr-based ternary to quinternary multi-principal-element films

    Institute of Scientific and Technical Information of China (English)

    Mariana Braic; Viorel Braic; Alina Vladescu; Catalin N. Zoita; Mihai Balaceanu


    TiZr-based multicomponent metallic films composed of 3-5 constituents with almost equal atomic concentrations were prepared by co-sputtering of pure metallic targets in an Ar atmosphere. X-ray diffraction was employed to determine phase composition, crystalline structure, lattice parameters, texture and crystallite size of the deposited films. The deposited films exhibited only solid solution (fcc, bcc or hcp) or amorphous phases, no intermetallic components being detected. It was found that the hcp structure was stabilized by the presence of Hf or Y, bcc by Nb or Al and fcc by Cu. For the investigated films, the atomic size difference, mixing enthalpy, mixing entropy, Gibbs free energy of mixing and the electronegativity difference for solid solution and amorphous phases were calculated based on Miedema's approach of the regular solution model. It was shown that the atomic size difference and the ratio between the Gibbs free energies of mixing of the solid solution and amorphous phases were the most significant parameters controlling the film crystallinity.

  10. Tuning the critical solution temperature of polymers by copolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, Bernhard; Chudoba, Richard; Dzubiella, Joachim, E-mail: [Institut für Weiche Materie und Funktionale Materialien, Helmholtz-Zentrum Berlin, 14109 Berlin (Germany); Institut für Physik, Humboldt-Universität zu Berlin, 12489 Berlin (Germany); Heyda, Jan [Department of Physical Chemistry, University of Chemistry and Technology, Prague, 166 28 Praha 6 (Czech Republic)


    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. Adsorption of catechol from aqueous solution by aminated hypercrosslinked polymers

    Institute of Scientific and Technical Information of China (English)

    SUN Yue; LI Xiao-tao; XU Chao; CHEN Jin-long; LI Ai-min; ZHANG Quan-xing


    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.

  12. Microstructure of Sheared Entangled Solutions of Semiflexible Polymers

    Directory of Open Access Journals (Sweden)

    Marc Lämmel


    Full Text Available We study the influence of finite shear deformations on the microstructure and rheology of solutions of entangled semiflexible polymers theoretically and by numerical simulations and experiments with filamentous actin. Based on the tube model of semiflexible polymers, we predict that large finite shear deformations strongly affect the average tube width and curvature, thereby exciting considerable restoring stresses. In contrast, the associated shear alignment is moderate, with little impact on the average tube parameters, and thus expected to be long-lived and detectable after cessation of shear. Similarly, topologically preserved hairpin configurations are predicted to leave a long-lived fingerprint in the shape of the distributions of tube widths and curvatures. Our numerical and experimental data support the theory.

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

    Directory of Open Access Journals (Sweden)

    Ritesh Fule


    Full Text Available 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.

  14. Hot melt extruded amorphous solid dispersion of posaconazole with improved bioavailability: investigating drug-polymer miscibility with advanced characterisation. (United States)

    Fule, Ritesh; Amin, Purnima


    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.

  15. Foaming and foam stability for mixed polymer-surfactant solutions: effects of surfactant type and polymer charge. (United States)

    Petkova, R; Tcholakova, S; Denkov, N D


    Solutions of surfactant-polymer mixtures often exhibit different foaming properties, compared to the solutions of the individual components, due to the strong tendency for formation of polymer-surfactant complexes in the bulk and on the surface of the mixed solutions. A generally shared view in the literature is that electrostatic interactions govern the formation of these complexes, for example between anionic surfactants and cationic polymers. In this study we combine foam tests with model experiments to evaluate and explain the effect of several polymer-surfactant mixtures on the foaminess and foam stability of the respective solutions. Anionic, cationic, and nonionic surfactants (SDS, C(12)TAB, and C(12)EO(23)) were studied to clarify the role of surfactant charge. Highly hydrophilic cationic and nonionic polymers (polyvinylamine and polyvinylformamide, respectivey) were chosen to eliminate the (more trivial) effect of direct hydrophobic interactions between the surfactant tails and the hydrophobic regions on the polymer chains. Our experiments showed clearly that the presence of opposite charges is not a necessary condition for boosting the foaminess and foam stability in the surfactant-polymer mixtures studied. Clear foam boosting (synergistic) effects were observed in the mixtures of cationic surfactant and cationic polymer, cationic surfactant and nonionic polymer, and anionic surfactant and nonionic polymer. The mixtures of anionic surfactant and cationic polymer showed improved foam stability, however, the foaminess was strongly reduced, as compared to the surfactant solutions without polymer. No significant synergistic or antagonistic effects were observed for the mixture of nonionic surfactant (with low critical micelle concentration) and nonionic polymer. The results from the model experiments allowed us to explain the observed trends by the different adsorption dynamics and complex formation pattern in the systems studied.

  16. Solution and Melt Rheology of Polypropylene Comb and Star Polymers (United States)

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


    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.

  17. Mechanical behavior of linear amorphous polymers: comparison between molecular dynamics and finite-element simulations. (United States)

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


    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.

  18. Microcellular Foaming of Amorphous High-Tg Polymers Using Carbon Dioxyde

    NARCIS (Netherlands)

    Krause, B.; Mettinkhof, R.; Vegt, van der N.F.A.; Wessling, M.


    The foaming of thin (~100 m) polysulfone (PSU), poly(ether sulfone) (PES), and cyclic olefin copolymer (COC) films using carbon dioxide as a physical blowing agent has been studied. Microcellular foam morphologies were obtained by saturating the polymer with carbon dioxide and heating the sample abo

  19. Development of amorphous dispersions of artemether with hydrophilic polymers via spray drying: Physicochemical and in silico studies

    Directory of Open Access Journals (Sweden)

    Jaywant N. Pawar


    Full Text Available Artemether (ARM is a poorly water soluble and poorly permeable drug effective against acute and severe falciparum malaria, hence there is a strong need to improve its solubility. The objective of the study was to enhance the solubility and dissolution rate of ARM by preparation of solid dispersions using spray-drying technique. Solid dispersions of ARM were prepared with Soluplus, Kollidon VA 64, HPMC and Eudragit EPO at weight ratios of 1:1, 1:2, 1:3 using spray drying technology, and characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry (DSC, and X-ray powder diffraction (XRD to identify the physicochemical interaction between drug and carrier, as well as effect on dissolution. The prepared solid dispersion of ARM with polymers showed reduced crystallinity as compared to neat ARM, which was confirmed by DSC and XRD. Drug/polymer interactions were studied in-silico by docking and molecular dynamics which indicated formation of van der Waals type of interactions of ARM with the polymers. Based on solubility studies, the optimum drug/Soluplus ratio was found to be 1:3. The dissolution studies of formulation SD3 showed highest drug release up to 82% compared to neat ARM giving only 20% at 60 minutes. The spray-dried products were free of crystalline ARM; possessed higher dissolution rates, and were stable over a period according to ICH guidelines. These findings suggest that an amorphous solid dispersion of ARM could be a viable option for enhancing the dissolution rate of ARM.

  20. Perovskite/polymer solar cells prepared using solution process (United States)

    Rosa, E. S.; Shobih; Nursam, N. M.; Saputri, D. G.


    We report a simple solution-based process to fabricate a perovskite/polymer tandem solar cell using inorganic CH3NH3PM3 as an absorber and organic PCBM (6,6 phenyl C61- butyric acid methyl ester) as an electron transport layer. The absorber solution was prepared by mixing the CH3NH3I (methyl ammonium iodide) with PbI2 (lead iodide) in DMF (N,N- dimethyl formamide) solvent. The absorber and electron transport layer were deposited by spin coating method. The electrical characteristics generated from the cell under 50 mW/cm2 at 25 °C comprised of an open circuit voltage of 0.31 V, a short circuit current density of 2.53 mA/cm2, and a power conversion efficiency of 0.42%.


    Institute of Scientific and Technical Information of China (English)

    ZHANG Li-juan; YUE Xiang-an


    The pore throat of porous media is modeled as a constricted channel or expanded channel. The flow of viscoelastic polymer solution in pore throat model is studied by numerical method. Relationship between pressure drop and flow rate is developed, viscoelasticity and throat size are found to be two main factors in high flow resistance. According to pore throat model, 2-D stochastic channel bundle is put forward to model porous media, which is composed of pore throat models in series - parallel connection with size and length accord to Haring - Greenkorn stochastic distribution. Percolation model of viscoelastic fluid is developed on the basis of Darcy equation and pressure drop vs. flow rate relation in 2-D stochastic channel bundle. Results indicate that the seepage ability of viscoelastic polymer solution decreases with the increase of viscoelasticity, injection rate, and heterogeneity as well as the decrease of mean pore size of porous media. The high pressure drop of viscoelastic fluid at the connection of pore to throat plays a great role in its anomalous high flow resistance through porous media.

  2. A sorption and dilation investigation of amorphous glassy polymers and physical aging (United States)

    Punsalan, David Troy

    The goal of this work was to investigate the effect of physical aging on penetrant sorption and dilation in glassy polymers. At the present time, this topic is fundamental in nature but may be relevant to previously observed declines in the productivity of polymeric gas separation membranes. Though physical aging is well known to occur in glassy polymers, it is often neglected in most contexts. However, since gas sorption and diffusion occurs on a molecular scale, reduction of unrelaxed volume due of physical aging may have a large impact on the macroscopically observed manifestations of these phenomena. In addition to experimental investigations of the effect of physical aging on the polymer-penetrant environment, various models of sorption and dilation are studied. Of the numerous models available in the literature, the theory of dual mode sorption, Sanchez-Lacombe lattice fluid equation of state and site-distribution model have previously demonstrated notable success and are applied to three polymers of varying chain flexibility: MatrimidRTM, Ultem RTM and LexanRTM (Tg = 313, 215 and 150°C respectively). Since the lattice fluid equation of state is intend for use on equilibrium media, only partial descriptions of solubility are expected. A variation of the Sanchez-Lacombe equation of state which takes into account the non-equilibrium nature of the glassy state, suitably called the Non-Equilibrium Lattice Fluid model, is also considered. In this work, the sorption and dilation data were used to study the presence of unrelaxed volume in glassy polymer materials and how it is affected by physical aging. A variety of other characterizational techniques were explored as well. Substantial changes in the sorption, dilation and CO2 partial molar volume due to physical aging were observed for bulk films of Matrimid RTM and LexanRTM, but not for Ultem RTM. Gas solubility was found to be lower in thin (ℓ = 0.1mum) MatrimidRTM films than in thick films (ℓ = 25.4mum

  3. Theoretical analysis of microscopic oil displacement mechanism by viscoelastic polymer solution

    Institute of Scientific and Technical Information of China (English)


    The microscopic oil displacement mechanism in viscoelastic polymer flooding is theoretically analyzed with mechanical method.The effects of viscoelasticity of polymer solution on such three kinds of residual oil as in pore throat,in sudden expansion pore path,and in dead end are analyzed.Results show that the critical radius of mobile residual oil for viscoelastic polymer solution is larger than that for viscous polymer solution,which makes the oil that is immobile in viscous polymer flooding displaced u...


    Directory of Open Access Journals (Sweden)

    R.A. Reis


    Full Text Available The Vrentas/Duda proposal for the diffusion of polymer-solvent systems, which is based on the free-volume theory, was employed in correlating and predicting mutual diffusion coefficients in highly concentrated polymer solutions. It has been observed that the predictive version of the model is capable of qualitatively representing the experimental data, while the use of an adjustable parameter greatly improves the performance of the model. The systems studied were poly(vinyl acetate-toluene and Neoprene-acetone, and a comparison between experimental data and calculated values from the Vrentas/Duda model is reported. A new experimental apparatus based on the sorption technique was built to provide reliable diffusivity data on the Neoprene-acetone system.

  5. Molecular Dynamics Study of Stability of Solid Solutions and Amorphous Phase in the Cu-Al System

    Institute of Scientific and Technical Information of China (English)

    YANG Bin; LAI Wen-Sheng


    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 bcc 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).

  6. Microscopic theory of light-induced deformation in amorphous side-chain azobenzene polymers. (United States)

    Toshchevikov, V; Saphiannikova, M; Heinrich, G


    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.

  7. Method of solution preparation of polyolefin class polymers for electrospinning processing included (United States)

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


    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.

  8. Phosphorylcholine substituted polyolefins: New syntheses, solution assemblies, and polymer vesicles (United States)

    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

  9. Improvement of small-area, amorphous-silicon thin-film photovoltaics on polymer substrate

    Energy Technology Data Exchange (ETDEWEB)

    Weber, M.F. (Minnesota Mining and Mfg. Co., St. Paul, MN (USA). Applied Technologies Lab.)


    This report describes a contract to produce, using roll-to-roll deposition on polyamide substrate, a small-area amorphous-silicon p-i-n photovoltaic (PV) cell with an energy conversion efficiency of 10% under air mass 1.5 insolation. Three improvements were attempted to achieve this goal: (1) zinc oxide, a transparent conducting oxide, was used as a top contact; the zinc oxide conductivity was improved to 8--9 ohms/square sheet resistance with less than 8% average optical absorption. (2) The red light response was improved with dielectric enhanced metal reflecting electrodes, which increased the short-circuit current density by more than 1 mA/Cm{sup 2}; a three-layer dielectric mirror coating was also designed that can increase the current density by another 1 mA/cm{sup 2}. (3) Improving the fill factor of the n-i-p (reverse structured) devices was also achieved in a multichamber deposition system. The overall energy conversion efficiency of the PV cell was 8.36%. Major obstacles to higher efficiencies are (1) controlling the thin-film defects that cause electrical shunts in devices fabricated on enhanced reflection electrodes, and (2) controlling impurities and introducing dopant profiles near the p/i interface in a continuous web deposition system.

  10. Low-density, polymer foams as structural models for phase-separation in polymer solutions

    Energy Technology Data Exchange (ETDEWEB)

    Beaucage, G. [Univ. of Cincinnati, OH (United States); Lagasse, R.R.; Aubert, J.H. [Sandia National Labs., Albuquerque, NM (United States)] [and others


    Low density polymer foams are produced through nano-scale phase separation of 5 to 15% solutions yielding gels. The gels are solvent exchanged and dried by supercritical extraction. We have found that the morphology of the phase separated gel, the intermediate solvent exchanged gels and the final foams are essentially identical over a wide range of size. Through the combination of several scattering techniques covering many decades of size we can distinguish structural levels in these low-density foams. The combined scattering data spans sizes ranging from 10{mu}m to 1{Angstrom}. A recently developed global fitting approach can describe the multiple levels of structure observed in these complex materials. Several morphological classes of foams are observed. A perplexing feature in the scattering patterns from all of the foams is a 3-dimensional structure with a radius of gyration from 40 to 100{Angstrom}. By variation of the polymer molecular-weight, scattering data supports a model describing this nano-scale structure as partially isolated, collapsed polymer coils. This model indicates that collapsed base structural unit in these morphologies.

  11. Performance of SuSi: a method for generating atomistic models of amorphous polymers based on a random search of energy minima. (United States)

    Curcó, David; Alemán, Carlos


    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.

  12. Solvent-shift strategy to identify suitable polymers to inhibit humidity-induced solid-state crystallization of lacidipine amorphous solid dispersions. (United States)

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


    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.


    Institute of Scientific and Technical Information of China (English)

    SHI Lianghe; ZHANG Xinsheng; SI Yuandong; YE Meiling; LI Dingcai


    Solution properties of ladder-like polymer polyphenylsilsesquioxane (PPS) were studied by measurement of intrinsic viscosity, small angle laser light scattering and gel permeation chromatography. It was found that PPS can be modeled with a wormlike continuous cylinder rather than a wormlike coil. A plot of (M2/[η])1/3 vs. M1/2 was employed in obtaining the persistence length (2λ)-1 and effective hydrodynamic diameter. When MW≤5 × 105, Mark-Houwink equation is adequate in describing the relationship between MW and [η] with α about unity. This implies that PPS chain is semi-stiff. For GPC experiments, it was shown that universal calibration can be applied in PPS. When molecular weights of PPS are sufficiently high, their molecular weight distributions are often very broad.

  14. Flow induced/ refined solution crystallization of a semiconducting polymer (United States)

    Nguyen, Ngoc A.

    Organic photovoltaics, a new generation of solar cells, has gained scientific and economic interests due to the ability of solution-processing and potentially low-cost power production. Though, the low power conversion efficiency of organic/ plastic solar cells is one of the most pertinent challenges that has appealed to research communities from many different fields including materials science and engineering, electrical engineering, chemical engineering, physics and chemistry. This thesis focuses on investigating and controlling the morphology of a semi-conducting, semi-crystalline polymer formed under shear-flow. Molecular structures and processing techniques are critical factors that significantly affect the morphology formation in the plastic solar cells, thus influencing device performance. In this study, flow-induced solution crystallization of poly (3-hexylthiophene) (P3HT) in a poor solvent, 2-ethylnapthalene (2-EN) was utilized to make a paint-like, structural liquid. The polymer crystals observed in this structured paint are micrometers long, nanometers in cross section and have a structure similar to that formed under quiescent conditions. There is pi-pi stacking order along the fibril axis, while polymer chain folding occurs along the fibril width and the order of the side-chain stacking is along fibril height. It was revealed that shear-flow not only induces P3HT crystallization from solution, but also refines and perfects the P3HT crystals. Thus, a general strategy to refine the semiconducting polymer crystals from solution under shear-flow has been developed and employed by simply tuning the processing (shearing) conditions with respect to the dissolution temperature of P3HT in 2-EN. The experimental results demonstrated that shear removes defects and allows more perfect crystals to be formed. There is no glass transition temperature observed in the crystals formed using the flow-induced crystallization indicating a significantly different

  15. Engineering solutions for polymer composites solar water heaters production (United States)

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


    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.

  16. Solution and Diffusion Behavior of Pure Gases and Gas Mixtures in Glassy Polymer Membranes

    Institute of Scientific and Technical Information of China (English)

    庄震万; 卫伟; 时钧


    A general model for the solution and diffusion behavior in pure gas-polymer membrane systems and gas mixture-polymer membrane systems has been developed. Proved by experiments on different glassy and rubbery polymer membranes at various temperatures and pressures, this model can achieve the prediction of permeation behavior of pure gases and gas mixtures in polymer membranes only using the model parameters obtained from experiments on pure gases. The calculated results are in good agreement with experimental.

  17. Artificial Neural Network Model to Estimate the Viscosity of Polymer Solutions for Enhanced Oil Recovery

    Directory of Open Access Journals (Sweden)

    Pan-Sang Kang


    Full Text Available Polymer flooding is now considered a technically- and commercially-proven method for enhanced oil recovery (EOR. The viscosity of the injected polymer solution is the key property for successful polymer flooding. Given that the viscosity of a polymer solution has a non-linear relationship with various influential parameters (molecular weight, degree of hydrolysis, polymer concentration, cation concentration of polymer solution, shear rate, temperature and that measurement of viscosity based on these parameters is a time-consuming process, the range of solution samples and the measurement conditions need to be limited and precise. Viscosity estimation of the polymer solution is effective for these purposes. An artificial neural network (ANN was applied to the viscosity estimation of FlopaamTM 3330S, FlopaamTM 3630S and AN-125 solutions, three commonly-used EOR polymers. The viscosities measured and estimated by ANN and the Carreau model using Lee’s correlation, the only method for estimating the viscosity of an EOR polymer solution in unmeasured conditions, were compared. Estimation accuracy was evaluated by the average absolute relative deviation, which has been widely used for accuracy evaluation of the results of ANN models. In all conditions, the accuracy of the ANN model is higher than that of the Carreau model using Lee’s correlation.

  18. Vapor-liquid equilibria of polymer solutions determined by molecular mechanics

    DEFF Research Database (Denmark)

    Jonsdottir, Svava Osk; Rasmussen, Kjeld; Rasmussen, Peter;


    A method of calculating interaction parameters used in phaseequilibrium calculations has been extended for predicting solventactivities of polymer solutions. A pair of interaction parameters aredetermined by calculating interaction energies between all pairs ofmolecules in the solution of interest...

  19. Linear polymer aqueous solutions in soft lubrication:From boundary to mixed lubrication

    Institute of Scientific and Technical Information of China (English)

    LIU; ShuHai; TAN; GuiBin; WANG; DeGuo


    In order to better understand linear polymer aqueous solutions in soft lubrication from boundary to mixed lubrication,poly(ethylene glycol) and sodium hyaluronateare used as model polymers were investigated by using UMT-2 tribometer with the ball-on-disk mode. The relationship between the master Stribeck curves of the polymer aqueous solutions and the influence factors were investigated. Experimental results indicated that soft lubrication is determined by lubricant rheological properties and surface-lubricant interactions, e.g., wetting behavior of polymer aqueous solution on tribological surfaces.

  20. Growth and Structure of Zirconium Hydrous Polymers in Aqueous Solutions (United States)

    Singhal; Toth; Beaucage; Lin; Peterson


    Zirconium oxychloride solutions prepared at different pH were heated at elevated temperatures for various aging periods to gain an understanding of the growth mechanism and structure of zirconium hydrous polymers. Small angle X-ray scattering (SAXS) measurements were made on these solutions. It was observed that shape of clusters at the earlier stages of growth is close to a rod rather than a sheet as suggested earlier. The scattering data indicate that a rod-shaped primary particle is formed at pH 1.2, and on an increase in the pH, the primary particles become more branched. On aging more than 1250 min at 92°C, these primary particles form large aggregates while retaining the primary particle structure. These aggregates, which are mass fractal in nature, restructure while growing in size and eventually transform into dense particles. Scattering data in this study were not enough to determine a specific kinetic growth model of the aggregates because the scattering intensity at low q constantly changes with time during the restructuring process. Copyright 1997 Academic Press. Copyright 1997Academic Press

  1. Growth and structure of zirconium hydrous polymers in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Singhal, A. [Oak Ridge National Lab., TN (United States)]|[Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Toth, L.M.; Lin, J.S. [Oak Ridge National Lab., TN (United States); Beaucage, G. [Univ. of Cincinnati, OH (United States). Dept. of Materials Science and Engineering; Peterson, J. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry


    Zirconium oxychloride solutions prepared at different pH were heated at elevated temperatures for various aging periods to gain an understanding of the growth mechanism and structure of zirconium hydrous polymers. Small angle X-ray scattering (SAXS) measurements were made on these solutions. It was observed that shape of clusters at the earlier stages of growth is close to a rod rather than a sheet as suggested earlier. The scattering data indicate that a rod-shaped primary particle is formed at pH 1.2, and on an increase in the pH, the primary particles become more branched. On aging more than 1,250 min at 92 C, these primary particles form large aggregates while retaining the primary particle structure. These aggregates, which are mass fractal in nature, restructure while growing in size and eventually transform into dense particles. Scattering data in this study were not enough to determine a specific kinetic growth model of the aggregates because the scattering intensity at low q constantly changes with time during the restructuring process.

  2. Electrostatics of polymer translocation events in electrolyte solutions. (United States)

    Buyukdagli, Sahin; Ala-Nissila, T


    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.

  3. CO2 switchable dual responsive polymers as draw solutes for forward osmosis desalination. (United States)

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


    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.

  4. The missing link between the extensional dynamics of polymer melts and solutions

    DEFF Research Database (Denmark)

    Rasmussen, Henrik K.; Huang, Qian


    Based on extensional viscosities measured on narrow molecular weight distributed (NMMD) polystyrenes and polystyrene oligomer dilutions thereof, we discuss the relation between the flow physics of polymer solutions and melts. A polymer solution is here characterized as a dilution where the diluen...

  5. 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. (United States)

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


    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.

  6. Understanding API-polymer proximities in amorphous stabilized composite drug products using fluorine-carbon 2D HETCOR solid-state NMR. (United States)

    Abraham, Anuji; Crull, George


    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.

  7. The Construction and Validation of All-Atom Bulk-Phase Models of Amorphous Polymers Using the TIGER2/TIGER3 Empirical Sampling Method. (United States)

    Li, Xianfeng; Murthy, Sanjeeva; Latour, Robert A


    A new empirical sampling method termed "temperature intervals with global exchange of replicas and reduced radii" (TIGER3) is presented and demonstrated to efficiently equilibrate entangled long-chain molecular systems such as amorphous polymers. The TIGER3 algorithm is a replica exchange method in which simulations are run in parallel over a range of temperature levels at and above a designated baseline temperature. The replicas sampled at temperature levels above the baseline are run through a series of cycles with each cycle containing four stages - heating, sampling, quenching, and temperature level reassignment. The method allows chain segments to pass through one another at elevated temperature levels during the sampling stage by reducing the van der Waals radii of the atoms, thus eliminating chain entanglement problems. Atomic radii are then returned to their regular values and re-equilibrated at elevated temperature prior to quenching to the baseline temperature. Following quenching, replicas are compared using a Metropolis Monte Carlo exchange process for the construction of an approximate Boltzmann-weighted ensemble of states and then reassigned to the elevated temperature levels for additional sampling. Further system equilibration is performed by periodic implementation of the previously developed TIGER2 algorithm between cycles of TIGER3, which applies thermal cycling without radii reduction. When coupled with a coarse-grained modeling approach, the combined TIGER2/TIGER3 algorithm yields fast equilibration of bulk-phase models of amorphous polymer, even for polymers with complex, highly branched structures. The developed method was tested by modeling the polyethylene melt. The calculated properties of chain conformation and chain segment packing agreed well with published data. The method was also applied to generate equilibrated structural models of three increasingly complex amorphous polymer systems: poly(methyl methacrylate), poly

  8. Structure and interaction in the polymer-dependent reentrant phase behavior of a charged nanoparticle solution. (United States)

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


    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.

  9. High performance solution-deposited amorphous indium gallium zinc oxide thin film transistors by oxygen plasma treatment

    KAUST Repository

    Nayak, Pradipta K.


    Solution-deposited amorphous indium gallium zinc oxide (a-IGZO) thin film transistors(TFTs) with high performance were fabricated using O2-plasma treatment of the films prior to high temperature annealing. The O2-plasma treatment resulted in a decrease in oxygen vacancy and residual hydrocarbon concentration in the a-IGZO films, as well as an improvement in the dielectric/channel interfacial roughness. As a result, the TFTs with O2-plasma treated a-IGZO channel layers showed three times higher linear field-effect mobility compared to the untreated a-IGZO over a range of processing temperatures. The O2-plasma treatment effectively reduces the required processing temperature of solution-deposited a-IGZO films to achieve the required performance.

  10. Elasticity and Extensibility Determine Printability and Spinnability of Polymer Solutions (United States)

    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.

  11. Side Chain Engineering in Solution-Processable Conjugated Polymers

    KAUST Repository

    Mei, Jianguo


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

  12. Cohesional Entanglement of Amorphous Polymer in Glass State as Probed by Equilibrium Swelling in a "Non-Solvent"

    Institute of Scientific and Technical Information of China (English)

    YU,Yan-Sheng(于燕生); QIAN,Ren-Yuan(钱人元)


    The equilibrium swelling of the system Polystyrene (PS) (M=1.7× 105, monodisperse)/diethyl ether at30 ℃ and35 ℃ has been studied in detail in quiescent state for a time span over 150d. Arguments are given to show that the swellingg process in a "non-solvent" is a network swelling rather than a phase separation process. It is different from the cloud point curve (CPC)experiment studied in literature, where the experiment starts from a one-phase solution, so that the cohesional entanglement present in the solid polymer is disrupted by dissolution. The cohesional entanglement structure of the solid polymer, on the contrary, is retained in the concentrated phase on swelling, at least in the initial stage. The course of swelling as presented by the curve Vs(t) was found to proceed in three stages, where Vs is the volume of the concentratd phase. In the first and third stages of Vs(t), the curve goes up smoothly, while in the second stage the curve Vs( t ) shows large up and down jumps,indicating probably a readjustment in the network structure.Some results on a monodisperse PS sample of M = 5.8 × 105and a polydisperse sample of M = 2.0 × 105 are also given. The values of Vs observed at swelling equilibrium are not in accord with the expected cloud point temperature. The cloud point curve represents a phase separation process occurring in local regions (space limited to um) and in time scale of the order of mimute, while the process Vs( t ) occurred in the whole space of the concentrated phase, in time scale of days. For quantitative characterization of the network present in the concentrated phase, a precise value of the polymer- solvent interaction parameter χ is needed.

  13. Aspects récents de la thermodynamique des solutions de polymères Recent Aspects of the Thermodynamics of Polymer Solutions

    Directory of Open Access Journals (Sweden)

    Dayantis J.


    Full Text Available On examine dans cet article différentes approches de la thermodynamique des solutions de polymères placées dans leur contexte historique. On rappelle d'abord le modèle du réseau de Flory-Huggins et on en souligne les déficiences. On traite ensuite brièvement de la mécanique statistique des solutions de polymères introduite par Prigogine en 1957 et on montre qu'elle constitue un progrès qualitatif par rapport à la théorie du réseau, mais qu'elle ne prévoit cependant pas de manière quantitative les propriétés de ces solutions. On montre ensuite que le concept de volume libre, qui permet un traitement simplifié de certaines quantités, permet également d'expliquer tout naturellement l'existence d'une deuxième température de séparation en phase lorsque l'on élève la température, propriété qui différencie les solutions de polymères des mélanges de liquidés simples. Enfin, dans une dernière partie, on mentionne brièvement les travaux récents de l'École de Paris, qui traite les solutions de polymères par analogie avec les transitions magnétiques. This article examines différent approaches ta the thermodynamics of polymer solutions set in their historical context. First of all, the Flory-Huggins network model is described and ifs deficiencies are pointed out. Then attention is briefly drawn to the statistical mechanics of polymer solutions as introduced by Prigogine in 1957, and this mechanics is shown to be a qualitative advance compared with the network theory, but it nonetheless does not quantitatively predict the properties of such solutions. It is then shown that the concept of free volume, enabling some quantifies to be treated in a simplified way, also serves to provide a quite natural explanation for the existence of a second phase separation temperature when the temperature is raised, i. e. a property that differentiates polymer solutions from simple liquid mixtures. In the final part, brief mention is made

  14. Variation of persistence length with concentration in a hydrogen bonding polymer solution (United States)

    Sukumaran, S.; Beaucage, G.


    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.

  15. Preparation of CdTe nanocrystal-polymer composite microspheres in aqueous solution by dispersing method

    Institute of Scientific and Technical Information of China (English)

    LI Minjie; WANG Chunlei; HAN Kun; YANG Bai


    Highly fluorescent CdTe nanocrystals were synthesized in aqueous solution, and then processible CdTe nanocrystal-polymer composites were fabricated by coating the aqueous nanocrystals with copolymers of styrene and octadecyl-p-vinyl-benzyldimethylammonium chloride (SOV- DAC) directly. A dichloromethane solution of CdTe nano- crystal-polymer composites was dispersed in the aqueous solution of poly (vinyl alcohol) (PVA) generating highly fluorescent microspheres. Experimental parameters such as the concentration of nanocrystal-polymer composites, the concentration of PVA, and stirring speed which had important effect on the preparation of the microspheres were investigated in detail with fluorescent microscope characterization.

  16. Toward a Mesoscale Model for the Dynamics of Polymer Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Miller, G H; Trebotich, D


    To model entire microfluidic systems containing solvated polymers we argue that it is necessary to have a numerical stability constraint governed only by the advective CFL condition. Advancements in the treatment of Kramers bead-rod polymer models are presented to enable tightly-coupled fluid-particle algorithms in the context of system-level modeling.

  17. Coil size oscillatory packing in polymer solutions near a surface

    NARCIS (Netherlands)

    Gucht, van der J.; Besseling, N.A.M.; Male, van J.; Cohen Stuart, M.A.


    The theory developed by Scheutjens and Fleer to describe polymer adsorption and depletion is used to calculate the density profile of nonadsorbing polymers near a surface. The theory predicts damped oscillations in the segment density profile with a wavelength of about the coil size. As a consequenc

  18. Simple solution-processed titanium oxide electron transport layer for efficient inverted polymer solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Liang [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Shen, Wenfei [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Institute of Hybrid Materials, Laboratory of New Fiber Materials and Modern Textile—The Growing Base for State Key Laboratory, Qingdao University, Qingdao 266071 (China); Chen, Weichao [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Bao, Xichang, E-mail: [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Wang, Ning; Dou, Xiaowei; Han, Liangliang; Wen, Shuguang [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China)


    Titanium oxide (TiO{sub X}) is an effective electron transport layer (ETL) in polymer solar cells (PSCs). We report efficient inverted PSCs with a simple solution-processed amorphous TiO{sub X} (s-TiO{sub X}) film as an ETL. The s-TiO{sub X} film with high light transmittance was prepared by spin-coating titanium (IV) isopropoxide isopropanol solution on indium tin oxide coated glass in inert and then placed in air under room temperature for 60 min. The introduction of s-TiO{sub X} ETL greatly improved the short circuit current density of the devices. PSCs based on poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester and poly(4,8-bis-alkyloxy-benzo[1,2-b:4,5-b′]dithiophene-alt-alkylcarbonyl -thieno[3,4-b]thiophene):[6,6]-phenyl- C71-butyric acid methyl ester using s-TiO{sub X} film as ETL shows high power conversion efficiency of 4.29% and 6.7% under the illumination of AM 1.5G, 100 mW/cm{sup 2}, which shows enhancements compared to the conventional PSCs with poly(styrenesulfonate)-doped poly(ethylenedioxythiophene) as anode buffer layer. In addition, the device exhibits good stability in a humid ambient atmosphere without capsulation. The results indicate that the annealing-free, simple solution processed s-TiO{sub X} film is an efficient ETL for high-performance PSCs. - Highlights: • High quality s-TiO{sub X} films were prepared by a simple, solution method without thermal treatment. • The s-TiO{sub X} films with high transmittance are very smooth. • The organic photovoltaic performance with s-TiO{sub X} film improved greatly and exhibited good stability. • The annealing-free, simple prepared s-TiO{sub X} film will be much compatible with flexible substrates.


    Institute of Scientific and Technical Information of China (English)

    Xiao-ming Chen; Hai-yang Yang; Xian You; Ping-ping Zhu; Ping-sheng Hea


    The reduced viscosity of polymer guar gum solutions containing a certain concentration of sodium dodecyl benzene sulfonate (SDBS) was measured. It has been found that the Huggins coefficient kH of polymer solutions is verysensitive to the concentration of the surfactant, cSDBS, in solutions. If cSDBS is lower than CMC, the critical micelle concentration of SDBS, kH increases rapidly with cSDBS. On the other hand, if cSDBS is larger than CMC, kH decreases rapidly with cSDBS. Comparatively, the intrinsic viscosity of polymer solution does not show a notable change with cSDBS. The experimental results indicate that the interchain association of polymer guar gum in solution is greatly associated with SDBS interacted with polymer chains through hydrogen bonds. However, the effect of SDBS upon the intrachain association of polymer guar gum solution is negligible, presumably due to the fact that guar gum is a slightly stiffened random-coil chain polymer.

  20. Sub-100 °C solution processed amorphous titania nanowire thin films for high-performance perovskite solar cells (United States)

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


    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.

  1. Sorption of Ochratoxin A from aqueous solutions using beta-cyclodextrin-polyurethane polymer (United States)

    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. Crystallization and Corrosion Resistance in Different Aqueous Solutions of Zr50.7Ni28Cu9Al12.3 Amorphous Alloy and Its Crystallization Counterparts (United States)

    Ge, Wenjuan; Li, Boyu; Axinte, Eugen; Zhang, Zitang; Shang, Caiyun; Wang, Yan


    The Zr50.7Ni28Cu9Al12.3 amorphous alloy and its crystallization counterparts have been prepared using a melt spinning technique and proper annealing treatment. The as-annealed products at 768 K are amorphous composites consisting of a main amorphous phase and a few ZrO2 nanocrystals. The corrosion behaviors have been investigated in 0.5-M NaCl, 1-M HCl, and 0.5-M H2SO4 solutions. The results show that amorphous composites present the enhanced corrosion resistance in Cl- containing solutions due to the formation of compact passive films, which are promoted by an appropriate quantity of ZrO2 nanocrystals. Nevertheless, the relaxed samples possess good corrosion resistance in H2SO4 solution, which is attributed to the existence of Zr(Al, Ni)-rich protective film induced by the depletion of Cu. In addition, corrosion resistance of the tested alloys is relatively superior in H2SO4 solution, especially for pitting corrosion resistance, and inferior in HCl solution.


    Institute of Scientific and Technical Information of China (English)

    Yan Pan; Rong-shi Cheng


    The concentration dependence of the reduced viscosity of dilute polymer solution is interpreted in the light of a new concept of the self-association of polymer chains in dilute solution. The apparent self-association constant is defined as the molar association constant divided by the molar mass of individual polymer chain and is numerically interconvertible with the Huggins coefficient. The molar association constant is directly proportional to the effective hydrodynamic volume of the polymer chain in solution and is irrespective of the chain architecture. The effective hydrodynamic volume accounts for the non-spherical conformation of a short polymer chain in solution and is a product of a shape factor and hydrodynamic volume. The observed enhancement of Huggins coefficient for short chain and branched polymer is satisfactorily interpreted by the concept of self-association. The concept of self-association allows us to predict the existence of a boundary concentration Cs (dynamic contact concentration) which divides the dilute polymer solution into two regions.

  4. Effect of added polymer in free jets of a dilute polymer solution (United States)

    Renoult, Marie-Charlotte; Charpentier, Jean-Baptiste; Crumeyrolle, Olivier; Mutabazi, Innocent


    The instability of a free viscoelastic jet is experimentally investigated by extruding an aqueous solution containing five parts per million of Poly(ethylene oxide) into air from a sixty micrometers orifice at relative low speeds. A method of image analysis was developed to quantify the effect of the added polymer on the morphology and the stability of the jet breakup. Three main representations were considered: the area versus perimeter relation for all liquid objects detected on the images, i.e. jets and jet fragments, the equivalent diameter distribution of jet fragments and the standard deviation curve of jets profiles. The former two provide information on the morphology of jet fragments: distinction of two classes, products and residues, and existence of coalescence. The latter gives information on the jet breakup stability: measurement of the growth rate and initial amplitude of the jet instability and detection of beads-on-a-string structures in the jet interface deformation. Experimental results will be presented and compared to theory.


    Institute of Scientific and Technical Information of China (English)

    Hui-dan Liu; Takahiro Sato


    The polyelectrolyte complex formed from the polyanion and polycation was studied by turbidimetry,static and electrophoretic light scattering,and elementary analysis.Sodium salts of polyacrylate (PA) and heparin (Hep) were chosen as the polyanion,and hydrochloric salts of poly(vinyl amine) (PVA) and chitosan (Chts) as the polycation.Although these vinyl polymers and polysaccharides have remarkably different backbone chemical structures and linear charge densities,all the four combinations PA-PVA,PA-Chts,Hep-PVA,and Hep-Chts provide almost stoichiometric polyelectrolyte complexes which are slightly charged owing to the adsorption of the excess polyelectrolyte component onto the neutral complex.The charges stabilize the complex colloids in aqueous solution of a non-stoichiometric mixture,and the aggregation number of the complex colloids increases with approaching to the stoichiometric mixing ratio.The mixing ratio dependence of the aggregation number for the four complexes is explained by the model proposed in the previous study.

  6. Tribocorrosion Behavior of Fe-Based Amorphous Composite Coating Reinforced by Al2O3 in 3.5% NaCl Solution (United States)

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


    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.

  7. Tribocorrosion Behavior of Fe-Based Amorphous Composite Coating Reinforced by Al2O3 in 3.5% NaCl Solution (United States)

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


    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.

  8. Elastic Energy Transfer in Turbulence of Dilute Polymer Solution (United States)

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


    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.

  9. Exact Solution of the Cluster Size Distribution for Multi-polymer Coagulation Process

    Institute of Scientific and Technical Information of China (English)

    KE Jian-Hong; LIN Zhen-Quan; WANG Xiang-Hong


    We propose a simple irreversible multi-polymer coagulation model in which m polymers consist of multiple components bond spontaneously to form a larger cluster. We solve the generalized Smoluchowski rate equation with constant reaction rates to obtain the exact solution of the cluster size distribution. The results indicate that the evolution behaviour of the system depends crucially on the polymer number m of the coagulation reaction. The cluster concentrations decay as t~m/(m~l) ; anc; tne typical size S(t) of the m-polymer coagulation system grows as t /'m~1'. On the other hand, the cluster size distribution may approach unusual scaling form in some cases.

  10. Impact of sodium polyacrylate on the amorphous calcium carbonate formation from supersaturated solution. (United States)

    Liu, J; Pancera, S; Boyko, V; Gummel, J; Nayuk, R; Huber, K


    A detailed in situ scattering study has been carried out on the formation of amorphous calcium carbonate (ACC) particles modulated by the presence of small amounts of sodium polyacrylate chains. The work is aiming at an insight into the modulation of ACC formation by means of two polyacrylate samples differing in their molecular weight by a factor of 50. The ACC formation process was initiated by an in situ generation of CO(3)(2-) ions via hydrolysis of 10 mM dimethylcarbonate in the presence of 10 mM CaCl(2). Analysis of the formation process by means of time-resolved small-angle X-ray and light scattering in the absence of any additives provided evidence for a monomer addition mechanism for the growth of ACC particles. ACC formation under these conditions sets in after a lag-period of some 350 s. In the presence of sodium polyacrylate chains, calcium polyacrylate aggregates are formed during the lag-period, succeeded by a modulated ACC growth in a second step. The presence of anionic polyacrylate chains changed the shape of the growing particles toward loose and less homogeneous entities. In the case of low amounts (1.5-7.5 mg/L) of the long chain additive with 97 kDa, the size of the aggregates is comparable to the size of the successively formed hybrid particles. No variation of the lag-period has been observed in this case. Use of the short chain additive with 2 kDa enabled increase of the additive concentration up to 100 mg/L and resulted in a significant increase of the lag-period. This fact, together with the finding that the resulting hybrid particles remained stable in the latter case, identified short chain sodium polyacrylates as more efficient modulators than long chain polyacrylates.

  11. Application of the van der Waals equation of state to polymers .4. Correlation and prediction of lower critical solution temperatures for polymer solutions

    DEFF Research Database (Denmark)

    Goncalves, Ana Saraiva; Kontogeorgis, Georgios; Harismiadis, Vassilis I.


    The van der Waals equation of state is used for the correlation and the prediction of the lower critical solution behavior or mixtures including a solvent and a polymer. The equation of state parameters for the polymer are estimated from experimental volumetric data at low pressures. The equation...... of state parameters for the solvent are estimated via the classical Soave method, i.e. using the critical properties and a generalized equation for the energy parameter. When extended to mixtures, the van der Waals one-fluid mixing rules along with the Berthelot combining rule for the molecular cross...... energy parameter are used. The arithmetic mean combining rule is used for the cross co-volume parameter. The deviations from the Berthelot combining rule are taken into account via a simple expression which has been previously obtained from vapor-liquid equilibrium data of athermal polymer solutions...

  12. Study on the sound absorption mechanism in gradient water-soluble polymer solution

    Institute of Scientific and Technical Information of China (English)

    WANG Yuansheng; YANG Xue; ZHU Jinhua; YAO Shuren


    Attention was paid to the study on the sound absorption mechanism of watersoluble polymer during dissolving. A specially designed water-soluble polymer coating was synthesized in our lab. The sound attenuation property was measured in sound tube. The results showed that the sound attenuation of the gradient polymer solution was larger than that of the uniform. Depending on the experimental result and the theory of sound wave propagation in layered medium, a mechanism of gradient water-soluble polymer solution was developed. This mechanism can be described as follows: a water-soluble polymer coating formed a concentration gradient layer when it was dissolved in water. This gradient layer led to multiple reflection and absorption of sound. Finally the sound energy was transferred into heat.

  13. On the origin of Gaussian network theory in the thermo/chemo-responsive shape memory effect of amorphous polymers undergoing photo-elastic transition (United States)

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


    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.

  14. Sonochemical precipitation of amorphous uranium phosphates from trialkyl phosphate solutions and their thermal conversion to UP2O7. (United States)

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


    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.

  15. Hybrid light emitting diodes based on solution processed polymers, colloidal quantum dots, and colloidal metal nanoparticles (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Budkov, Yu. A., E-mail: [G. A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Laboratory of NMR Spectroscopy and Numerical Investigations of Liquids, Ivanovo (Russian Federation); Department of Applied Mathematics, National Research University Higher School of Economics, Moscow (Russian Federation); Kolesnikov, A. L. [Institut für Nichtklassische Chemie e.V., Universitat Leipzig, Leipzig (Germany); Kiselev, M. G. [G. A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Laboratory of NMR Spectroscopy and Numerical Investigations of Liquids, Ivanovo (Russian Federation)


    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.

  17. Large velocity fluctuations in small-Reynolds-number pipe flow of polymer solutions

    NARCIS (Netherlands)

    Bonn, D.; Ingremeau, F.; Amarouchene, Y.; Kellay, H.


    The flow of polymer solutions is examined in a flow geometry where a jet is used to inject the viscoelastic solution into a cylindrical tube. We show that this geometry allows for the generation of a "turbulentlike" flow at very low Reynolds numbers with a fluctuation level which can be as high as 3

  18. Investigation of the in-solution relaxation of polymer optical fibre Bragg gratings

    DEFF Research Database (Denmark)

    Fasano, Andrea; Woyessa, Getinet; Janting, Jakob


    We investigate the response of PMMA microstructured polymer optical fibre Bragg gratings whenimmersed in methanol/water solutions. Overall we observe a permanent blue-shift in Bragg gratingwavelength after solvent evaporation. The main contribution in the resonance wavelength shift probably...... arisesfrom a permanent change in the size of the fibre, as already reported for high-temperature annealing ofpolymer optical fibres. As a consequence of the solution concentration dependence of the glass transitiontemperature of polymers, different methanol/water solutions lead to various degrees of frozen...

  19. Elastic turbulence in a shell model of polymer solution

    CERN Document Server

    Ray, Samriddhi Sankar


    We show that, at low inertia and large elasticity, shell models of viscoelastic fluids develop a chaotic behaviour with properties similar to those of elastic turbulence. The low dimensionality of shell models allows us to explore a wide range both in polymer concentration and in Weissenberg number. Our results demonstrate that the physical mechanisms at the origin of elastic turbulence do not rely on the boundary conditions or on the geometry of the mean flow.

  20. Solution electrospinning of particle-polymer composite fibres

    DEFF Research Database (Denmark)

    Christiansen, Lasse; Fojan, Peter


    Electrospinning is a fast, simple way to produce nano/microfibers, resulting in porous mats with a high surface to volume ratio. Another material with high surface to volume ratio is aerogel. A drawback of aerogels is its inherent mechanical weakness. To counteract this, aerogels can be embedded......-supporting abilities of these fibres are discussed. It is concluded that selfsupporting polymer/aerogel composites can be made by electrospinning....

  1. SANS structural characterization of fullerenol-derived star polymers in solutions

    CERN Document Server

    Jeng, U S; Wang, L Y; Chiang, L Y; Ho, D L; Han, C C


    We have studied the chain conformations of fullerenol-derived star polymers in two organic solvents using small-angle neutron scattering (SANS). The SANS results indicate that the six poly(urethane-ether) arms, chemically bonded on the fullerenol of the C sub 6 sub 0 -based star polymer, have a Gaussian chain conformation in toluene. However, these arms exhibit a pronounced excluded-volume effect in dimethylformamide solutions. We use a scattering model, with the polydispersity of the polymer taken into account, and a fractal model to extract the radius of gyration R sub g values and the persistence lengths of the C sub 6 sub 0 -star polymers in these two organic solutions. (orig.)

  2. Ultrafast photogeneration of charged polarons on conjugated polymer chains in dilute solution (United States)

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


    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.

  3. Impact of soft annealing on the performance of solution-processed amorphous zinc tin oxide thin-film transistors. (United States)

    Nayak, Pradipta K; Hedhili, Mohamed N; Cha, Dongkyu; Alshareef, H N


    It is demonstrated that soft annealing duration strongly affects the performance of solution-processed amorphous zinc tin oxide thin-film transistors. Prolonged soft annealing times are found to induce two important changes in the device: (i) a decrease in zinc tin oxide film thickness, and (ii) an increase in oxygen vacancy concentration. The devices prepared without soft annealing exhibited inferior transistor performances, in comparison to devices in which the active channel layer (zinc tin oxide) was subjected to soft annealing. The highest saturation field-effect mobility-5.6 cm(2) V(-1) s(-1) with a drain-to-source on-off current ratio (Ion/Ioff) of 2 × 10(8)-was achieved in the case of devices with 10-min soft-annealed zinc tin oxide thin films as the channel layer. The findings of this work identify soft annealing as a critical parameter for the processing of chemically derived thin-film transistors, and it correlates device performance to the changes in material structure induced by soft annealing.

  4. Impact of soft annealing on the performance of solution-processed amorphous zinc tin oxide thin-film transistors

    KAUST Repository

    Nayak, Pradipta K.


    It is demonstrated that soft annealing duration strongly affects the performance of solution-processed amorphous zinc tin oxide thin-film transistors. Prolonged soft annealing times are found to induce two important changes in the device: (i) a decrease in zinc tin oxide film thickness, and (ii) an increase in oxygen vacancy concentration. The devices prepared without soft annealing exhibited inferior transistor performances, in comparison to devices in which the active channel layer (zinc tin oxide) was subjected to soft annealing. The highest saturation field-effect mobility - 5.6 cm2 V-1 s-1 with a drain-to-source on-off current ratio (Ion/Ioff) of 2 × 108 - was achieved in the case of devices with 10-min soft-annealed zinc tin oxide thin films as the channel layer. The findings of this work identify soft annealing as a critical parameter for the processing of chemically derived thin-film transistors, and it correlates device performance to the changes in material structure induced by soft annealing. © 2013 American Chemical Society.

  5. Visualizing phase transition behavior of dilute stimuli responsive polymer solutions via Mueller matrix polarimetry. (United States)

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


    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.

  6. Phase diagrams of binary crystalline-crystalline polymer blends. (United States)

    Matkar, Rushikesh A; Kyu, Thein


    A thermodynamically self-consistent theory has been developed to establish binary phase diagrams for two-crystalline polymer blends by taking into consideration all interactions including amorphous-amorphous, crystal-amorphous, amorphous-crystal, and crystal-crystal interactions. The present theory basically involves combination of the Flory-Huggins free energy for amorphous-amorphous isotropic mixing and the Landau free energy of polymer solidification (e.g., crystallization) of the crystalline constituents. The self-consistent solution via minimization of the free energy of the mixture affords determination of eutectic, peritectic, and azeotrope phase diagrams involving various coexistence regions such as liquid-liquid, liquid-solid, and solid-solid coexistence regions bound by liquidus and solidus lines. To validate the present theory, the predicted eutectic phase diagrams have been compared with the reported experimental binary phase diagrams of blends such as polyethylene fractions as well as polycaprolactone/trioxane mixtures.

  7. A modified coaxial electrospinning for preparing fibers from a high concentration polymer solution

    Directory of Open Access Journals (Sweden)


    Full Text Available A new process technology modified from conventional coaxial electrospinning process has been developed to prepare polymer fibers from a high concentration solution. This process involves a pure solvent concentrically surrounding polymer fluid in the spinneret. The concentric spinneret was constructed simply by inserting a metal needle through a high elastic silica gel tube. Two syringe pumps were used to drive the core polymer solution and the sheath solvent. Using polyvinylpyrrolidone (PVP as the polymer model, which normally has an electrospinnable concentration of 10% w/v in ethanol, it was possible to electrospin 35% w/v of PVP in the same solvent, when pure N, N-dimethylacetamide (DMAc was used as sheath fluid. The resultant fibers have a smooth surface morphology and good structural uniformity. The diameter of the fibers was 2.0±0.25 µm when the DMAc-to-polymer-solution flow rate ratio was set as 0.1. The process technology reported here opens a new window to tune the polymer fibers obtained by the electrospinning, and is useful for improving productivity of the electrospinning process.

  8. Interactions between ring polymers in dilute solution studied by Monte Carlo simulation (United States)

    Suzuki, Jiro; Takano, Atsushi; Matsushita, Yushu


    The second virial coefficient, A2, for trivial-ring polymers in dilute condition was estimated from a Metropolis Monte Carlo (MC) simulation, and the temperature dependence of A2 has been discussed with their Flory's scaling exponent, ν, in Rg ∝ Nν, where Rg is radius of gyration of a polymer molecule. A limited but not too small number of polymer molecules were employed in the simulation, and the A2 values at various temperatures were calculated from the molecular density fluctuation in the solution. In the simulation, the topology of ring polymers was kept, since chain crossing was prohibited. The excluded volume effects can be screened by the attractive force between segments, which depends on the temperature, Tα, defined in the Metropolis MC method. Linear and trivial-ring polymers have the ν value of 1/2 at Tα = 10.605 and 10.504. At Tα = 10.504, the excluded volume effects are screened by the attractive force generated between segments in a ring polymer, but the A2 value for ring polymers is positive. Thus, the temperature at A2 = 0 for a ring polymer is lower than that at ν = 1/2, and this fact can be explained with the following two reasons. (a) Rg value for a ring polymer is much smaller than that for a linear polymer at the same temperature and molecular weight, where interpenetration of a ring polymer chain into neighboring chains is apparently less than a linear chain. (b) The conformation of trivial rings can be statistically described as a closed random walk at ν = 1/2, but their topologies are kept, being produced topological constraints, which strongly relate not only to the long-distance interaction between segments in a molecule but also the inter-molecular interaction.

  9. Refining stability and dissolution rate of amorphous drug formulations

    DEFF Research Database (Denmark)

    Grohganz, Holger; Priemel, Petra A; Löbmann, Korbinian;


    amorphous counterpart is often seen as a potential solution to increase the solubility. However, amorphous systems are physically unstable. Therefore, pharmaceutical formulations scientists need to find ways to stabilise amorphous forms. Areas covered: The use of polymer-based solid dispersions is the most......Introduction: Poor aqueous solubility of active pharmaceutical ingredients (APIs) is one of the main challenges in the development of new small molecular drugs. Additionally, the proportion of poorly soluble drugs among new chemical entities is increasing. The transfer of a crystalline drug to its...... established technique for the stabilisation of amorphous forms, and this review will initially focus on new developments in this field. Additionally, newly discovered formulation approaches will be investigated, including approaches based on the physical restriction of crystallisation and crystal growth...

  10. Spectroscopic and calorimetric investigation of short and intermediate-range structures and energetics of amorphous SiCO, SiCN, and SiBCN polymer-derived ceramics (United States)

    Widgeon, Scarlett J.

    Polymer-derived ceramics (PDCs) are a new class of amorphous ceramics in the Si-B-C-N system that are synthesized by the pyrolysis of silicon-based organic polymers. PDCs are lightweight and are resistant to creep, crystallization, and oxidation at temperatures near 1800 K making them ideal for a variety of high temperature applications. In spite of being X-ray amorphous, these materials display structural heterogeneity at the nanometer length scale. Their structure and resulting properties can be drastically altered by the utilization of preceramic polymers with differing chemistry and architectures. Fundamental understanding of the atomic structure is critical in deciphering the structure-property relationships and ultimately in controlling their properties for specific engineering applications. The short-range atomic structure has been extensively investigated using a variety of techniques, however, the structures at length scales beyond next-nearest neighbors remained highly controversial. Here we report the results of a spectroscopic and calorimetric study of short and intermediate -range structure and energetic of SiOC and SiBCN PDCs derived from a wide variety of precursors. SiOC PDCs with different carbon contents were synthesized from polysiloxane precurors and their structures were studied using high-resolution 13C and 29Si nuclear magnetic resonance (NMR) spectroscopy. The results suggest that these PDCs consists of a continuous mass fractal backbone of corner-shared SiC xO4-x tetrahedral units with "voids" occupied by sp 2-hybridized graphitic carbon. The oxygen-rich SiCxO 4-x units are located at the interior of this backbone with a mass fractal dimension of ~ 2.5, while the carbon-rich units occupy the two-dimensional interface between the backbone and the free carbon nanodomains. Such fractal topology is expected to give rise to unusual mechanical and transport properties characteristic of fractal percolation networks. For example, elastic moduli and

  11. Influence of Salts on Electrospinning of Aqueous and Nonaqueous Polymer Solutions

    Directory of Open Access Journals (Sweden)

    Fatma Yalcinkaya


    Full Text Available A roller electrospinning system was used to produce nanofibres by using different solution systems. Although the process of electrospinning has been known for over half a century, knowledge about spinning behaviour is still lacking. In this work, we investigated the effects of salt for two solution systems on spinning performance, fibre diameter, and web structure. Polyurethane (PU and polyethylene oxide (PEO were used as polymer, and tetraethylammonium bromide and lithium chloride were used as salt. Both polymer and salt concentrations had a noteworthy influence on the spinning performance, morphology, and diameter of the nanofibres. Results indicated that adding salt increased the spinnability of PU. Salt created complex bonding with dimethylformamide solvent and PU polymer. Salt added to PEO solution decreased the spinning performance of fibres while creating thin nanofibres, as explained by the leaky dielectric model.

  12. Sorption of ochratoxin A from aqueous solutions using β-cyclodextrin-polyurethane polymer. (United States)

    Appell, Michael; Jackson, Michael A


    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.

  13. Comparison of viscous fingering patterns in polymer and newtonian solutions (United States)

    Kawaguchi, Masami; Makino, Kyoko; Kato, Tadaya


    Viscous fingering patterns of aqueous glycerol and hydroxypropyl methyl cellulose (HPMC) solutions pushed by air in the Hele-Shaw cell were observed as a function of isopropyl alcohol. An increase in isopropyl alcohol led to a decrease in surface tension as well as an increase in viscosity of the respective solutions. For the glycerol solutions, namely Newtonian fluids, only the tip splitting pattern was observed, where the fingers were indeed narrower and the number of the fingers increased with increasing isopropyl alcohol content. These morphological changes in the patterns for the glycerol solutions were in agreement with the computer simulations based on the diffusion limited aggregation model. The finger tip velocity is proportional to the ratio of the injection pressure to viscosity according to Darcy's law prediction. In contrast, for HPMC solutions, which show shear-thinning, highly branched pattern only appeared when the injection pressure was changed. When isopropyl alcohol was added to HPMC solutions, a morphological transition from highly branched pattern to tip splitting one was observed. The transition in the pattern would be related to changes in both elastic properties and surface tension. The finger tip velocity of HPMC solutions is scaled with 1.5 power of the ratio of injection pressure to viscosity.

  14. The influence of the amorphous polymer on conductivity, morphologies and thermal properties of polyether-based blends with addition of inorganic salt (United States)

    Chan, C. H.; Sim, L. H.; Kammer, H. W.; Tan, W.


    Thermodynamic control of the dispersion of lithium (Li) salt in different phases of semicrystalline/amorphous polymer blends is elucidated in this study. Solid polymer electrolytes of poly(ethylene oxide) (PEO), epoxidized natural rubber (ENR), random copolymer of poly(acrylate) (PAc) and as well as polymer blends of PEO with ENR and PAc doped with various concentrations of Li salt were studied. The salt concentrations (CLi) of solid polymer electrolytes vary between CLi = 0.02 and 0.15. The influence of the ENR or PAc on the properties of PEO after addition of Li salt is discussed. Blends of PEO/ENR and PEO/PAc are immiscible by elucidation of the glass transition temperature (Tg) as well as the morphological analyses. PEO, ENR and PAc possess oxygen in their respective chemical structures, which may be able to coordinate with the Li salt added. Non uniformity of Li salt concentration in different phases of the blends is highlighted for both systems. The conductivity of PEO/ENR and PEO/PAc blends doped with Li salt is primarily governed by PEO. The results for Tg suggest that higher solubility of Li salt in PEO as compared to ENR in the former case and restricted ion transport in the glassy PAc (with Tg≈30°C after addition of Li salt in the latter system. These may be the attributing factors for the enhancement of conductivity of the doped-PEO/ENR blends as compared to that of the doped-PEO/PAc blends. This suggests that PEO exhibits greater extent of complexation with LiClO4 as compared to that of the ENR and PAc as supported by Fourier-transform infra-red (FTIR) studies.

  15. Bridging the Gap between Polymer Melts and Solutions in Extensional Rheology

    DEFF Research Database (Denmark)

    Huang, Qian; Hengeller, Ludovica; Alvarez, Nicolas J.


    Since its inception, the tube model of polymer dynamics has undergone several modifications to account for observed experimental trends. One trend that has yet to be captured by a modified version of the tube model is the observed experimental difference between concentrated polymer solutions...... per chain and are diluted in the same solvent (oligomeric styrene). We show that the difference in nonlinear rheological behavior between polystyrene melts reported by Bach et al.1 and polystyrene solutions reported by Bhattacharjee et al.2 and Sridhar et al.3 can be bridged by changing...... the polystyrene concentration. The results presented represent a unique benchmark for all future modifications to the tube model....

  16. All solution processed tandem polymer solar cells based on thermocleavable materials

    DEFF Research Database (Denmark)

    Hagemann, Ole; Bjerring, Morten; Nielsen, Niels Chr.


    Multilayer tandem polymer solar cells were prepared by solution processing using thermocleavable polymer materials that allow for conversion to an insoluble state through a short thermal treatment. The problems associated with solubility during application of subsequent layers in the stack were...... efficiently solved. Devices comprised a transparent front cathode based on solution processed zinc oxide nanoparticles, a large band gap active layer based on a bulk heterojunction between zinc oxide and poly(3-carboxydithiophene) (P3CT) followed by a layer of PEDOT:PSS processed from water. The second cell...

  17. CISM Course on Fluid Mechanics of Surfactant and Polymer Solutions

    CERN Document Server

    Ivanov, Ivan


    Colloidal systems and dispersions are of great importance in oil recovery, waist water treatment, coating, food and beverage industry, pharmaceutical industry, medicine, environmental protection etc. Colloidal systems and dispersions are always multi-component and multiphase systems. In these systems at least one dimension is in a range of colloidal forces action: colloidal dispersions/emulsions are examples of three dimensional colloidal systems, while thin liquid films are examples of one dimensional colloidal systems. The contribution presented in this issue deals with flow, distribution and redistribution, coating and deposition of surfactant and polymer molecules in colloidal systems. The book presents reviews of recent advances and trends by well-know scientists and engineers in this area.

  18. On turbulent kinetic energy production and dissipation in dilute polymer solutions (United States)

    Liberzon, A.; Guala, M.; Kinzelbach, W.; Tsinober, A.


    Drag reduction by dilute polymer solutions is the most recognized phenomenon in wall-bounded turbulent flows, which is associated with large scales (e.g., velocity scales) in spite of a consensus that polymers act mainly on much smaller scales of velocity derivatives. We demonstrate that drag reduction is only one sort of polymers' effect on a turbulent flow and show how turbulent velocity and velocity derivatives are altered in the presence of dilute polymers, irrespective of drag reduction phenomena. This is an experimental study on the interaction of dilute polymers with a complex three-dimensional turbulent flow with small mean velocity gradients. Lagrangian data (e.g., velocities and velocity gradients) of flow tracers were obtained by using three-dimensional particle tracking velocimetry in an observational volume in the turbulent bulk region, far from the boundaries. The focus is on aspects related to the turbulent kinetic energy (TKE) production, -⟨uiuj⟩Sij (ui is the fluctuating velocity, ⟨uiuj⟩ is the Reynolds stress tensor, and Sij is the mean rate-of-strain tensor), such as an anisotropy of Reynolds stresses and the alignment of the velocity vector field with respect to the eigenframe of Sij, among others. We base our study on the comparison of turbulent quantities in flows of water and of dilute polymer solution, forced in two distinct ways: frictional forcing by smooth rotating disks and inertial forcing by disks with baffles. The comparison of the results from the water and from the dilute polymer solution flows allows a critical examination of the influence of polymers on the TKE production, viscous dissipation, and the related turbulent properties. We conclude with (i) quantification of the direct effect of polymers on the small scales of velocity derivatives, (ii) evidence of an additional dissipation mechanism by the polymers, which is the main reason for the strong inhibition of the viscous dissipation, 2νs2, in a turbulent bulk, (iii


    Institute of Scientific and Technical Information of China (English)


    The rheological behavior of polyvinyl acetate (PVAc) in N,N'-dimethylformamide (DMF), methyl ethyl ketone (MEK), 1,2-dichloroethane (DCE), tetrahydrofuran (THF) and toluene (TOL), polystyrene (PS) in DMF, MEK, DCE, THF and cyclohexane (CYH), and random ethylene-vinyl acetate (EVA) copolymer in DCE, TOL, CYH with and without surfactant of Span80 and in the DCE/CYH solvent mixtures with surfactant of Span80 was examined at high dilution. It was shown that the extent and type of the upsweep or downsweep (anomalous rheological behavior) of the reduced viscosity-concentration curves of these different polymers at high dilution are markedly dependent on the dielectric constant of the solvent and the polarity of the polymer used. The experimental results indicated that the anomalous rheological behavior of EVA copolymer, widely used as a flow improver, is related to its efficiency in reducing viscosity and depressing pour point of crude oil and waxy solvents.

  20. Modeling lower critical solution temperature behavior of associating polymer brushes with classical density functional theory. (United States)

    Gong, Kai; Marshall, Bennett D; Chapman, Walter G


    We study the lower critical solution temperature (LCST) behavior of associating polymer brushes (i.e., poly(N-isopropylacrylamide)) using classical density functional theory. Without using any empirical or temperature-dependent parameters, we find the phase transition of polymer brushes from extended to collapsed structure with increasing temperature, indicating the LCST behavior of polymer brushes. The LCST behavior of associating polymer brushes is attributed to the interplay of hydrogen bonding interactions and Lennard-Jones attractions in the system. The effect of grafting density and molecular weight on the phase behavior of associating polymer brushes has been also investigated. We find no LCST behavior at low grafting density or molecular weight. Moreover, increasing grafting density decreases the LCST and swelling ratio of polymer brushes. Similarly, increasing molecular weight decreases the LCST but increases the swelling ratio. At very high grafting density, a partial collapsed structure appears near the LCST. Qualitatively consistent with experiments, our results provide insight into the molecular mechanism of LCST behavior of associating polymer brushes.

  1. Use of pH-sensitive polymer hydrogels in lead removal from aqueous solution. (United States)

    Ramírez, Elizabeth; Burillo, S Guillermina; Barrera-Díaz, C; Roa, Gabriela; Bilyeu, Bryan


    Three gamma crosslinked polymeric hydrogels were synthesized and evaluated as lead ion sorbents. A crosslinked poly(acrylic acid) hydrogel was compared with two 4-vinylpiridine-grafted poly(acrylic acid) hydrogels (26.74 and 48.1% 4-vinylpiridine). The retention properties for Pb(II) from aqueous solutions of these three polymers were investigated by batch equilibrium procedure. The effects of pH, contact time and Pb(II) concentration were evaluated. The optimal pH range for all polymers was 4-6. The lightly grafted polymer (PAAc-g-4VP at 26.74%) exhibited a Pb(II) removal close to 80% at 5h and above 90% at 24h. The maximum Pb(II) removal was 117.9mg g(-1) of polymer and followed the Freundlich adsorption model. XPS characterization indicates that the carboxyl groups are involved in the Pb(II) removal.

  2. Quasi-elastic neutron scattering study on water and polymer dynamics in thermo/pressure sensitive polymer solutions. (United States)

    Osaka, Noboru; Shibayama, Mitsuhiro; Kikuchi, Tatsuya; Yamamuro, Osamu


    Dynamics of water and poly(N-isopropylacrylamide) (PNIPA) in concentrated aqueous solutions, where the majority of water molecules are attached to polymer chains, has been investigated with use of incoherent quasi-elastic neutron scattering (QENS) and dynamic light scattering (DLS) measurements as functions of temperature, T, and hydrostatic pressure, P. It was observed by QENS that the self-diffusion coefficient, D(water), of water in PNIPA/H(2)O solutions increased by P at temperatures below the lower critical solution temperature (LCST) of PNIPA aqueous solutions. However, above the LCST, D(water) decreased by P, as is often reported in non-hydrogen bonding solutions. In isobaric heating runs, therefore, the jump in D(water) at LCST decreased with increasing pressure. On the other hand, the mean-square displacement, , of the local vibrational motion of PNIPA in PNIPA/D(2)O solutions, where the incoherent scattering signal of PNIPA was predominantly observed, was reduced due to the aggregation behavior of PNIPA by pressurizing, which was also confirmed by using DLS. The jump in at the LCST became gradual by pressurizing, which was consistent with the changes of the dynamics of water obtained in PNIPA/H(2)O solutions.

  3. Flow-enhanced solution printing of all-polymer solar cells. (United States)

    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


    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.

  4. The relevance of molecular weight in the design of amorphous biodegradable polymers with optimized shape memory effect. (United States)

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


    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.

  5. Experimental observations and dissipative particle dynamic simulations on microstructures of pH-sensitive polymer containing amorphous solid dispersions. (United States)

    Sun, Mengchi; Li, Bingyu; Li, Yanchun; Liu, Yangdan; Liu, Qi; Jiang, Hailun; He, Zhonggui; Zhao, Yongshan; Sun, Jin


    Amorphous solid dispersion (ASD) technique is an effective strategy to increase the dissolution rate of poorly soluble drugs. However, it is inherently unstable, and the molecular basis for achieving kinetic stability is not well understood. In this study, lacidipine-Eudragit_E_100 solid dispersions with 20% drug loading were prepared using the solvent evaporation. Dissolution tested showed that ASD had a significantly high rate, which was dependent on the pH of the medium. Based on time-dependent measurement of supersaturation and particle size, inhibition of crystal growth by Eudragit_E_100 differed at pH 1.2 and 6.8 to a great extent. Dissipative particle dynamic (DPD) simulation revealed that at pH 1.2, the swollen microstructures of the particles were associated with rapid drug release. At pH 6.8, a compacted microstructure of small amorphous particle-aggregated large particles was associated with slow dissolution. The DPD simulation provides insight into the structural basis for experimental observations, and thus is a useful tool to investigate the microstructures of ASD.

  6. Prediction of Solution Properties of Flexible-Chain Polymers: A Computer Simulation Undergraduate Experiment (United States)

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


    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…

  7. All-solution processed polymer light-emitting diodes with air stable metal-oxide electrodes

    NARCIS (Netherlands)

    Bruyn, P. de; Moet, D.J.D.; Blom, P.W.M.


    We present an all-solution processed polymer light-emitting diode (PLED) using spincoated zinc oxide (ZnO) and vanadium pentoxide (V2O5) as electron and hole injecting contact, respectively. We compare the performance of these devices to the standard PLED design using PEDOT:PSS as anode and Ba/Al as

  8. Liquid-liquid equilibria for binary and ternary polymer solutions with PC-SAFT

    DEFF Research Database (Denmark)

    Lindvig, Thomas; Michelsen, Michael Locht; Kontogeorgis, Georgios


    Two algorithms for evaluating liquid-liquid equilibria (LLE) for binary and ternary polymer solutions are presented. The binary algorithm provides the temperature versus concentration cloud-point curve at fixed pressure, whereas the ternary algorithm provides component 1 versus component 2...

  9. Tension, rigidity and preferential curvature of interfaces between coexisting polymer solutions

    NARCIS (Netherlands)

    Tromp, R.H.; Blokhuis, E.M.


    The properties of the interface in a phase-separated solution of polymers with different degrees of polymerization and Kuhn segment lengths are calculated. The starting point is the planar interface, the profile of which is calculated in the so-called “blob model”, which incorporates the solvent in

  10. Flow of Viscoelastic Polymer Solutions through Filter Screens (United States)

    Machač, Ivan; Surý, Alexander; Šiška, Bedřich


    In this contribution, the measurements are presented of the pressure drop in the creeping flow of viscoelastic solution of polyacrylamides through metal wire screens, differing in wire diameter, aperture dimension, and type of weaving. In this flow, a strong elastic pressure drop excess manifest itself. Analysing the extensive set of experimental data, it was verified that for engineering estimation of the pressure drop excess, a simple form of the corrective Deborah number function can be used.

  11. Effect of stretching-induced changes in hydrodynamic screening on coil-stretch hysteresis of unentangled polymer solutions (United States)

    Prabhakar, Ranganathan; Sasmal, Chandi; Nguyen, Duc At; Sridhar, Tam; Prakash, J. Ravi


    Extensional rheometry and Brownian dynamics simulations of flexible polymer solutions confirm predictions based on blob concepts that coil-stretch hysteresis in extensional flows increases with concentration, reaching a maximum at the critical overlap concentration c* before progressively vanishing in the semidilute regime. These observations demonstrate that chain stretching strengthens intermolecular hydrodynamic screening in dilute solutions, but weakens it in semidilute solutions. Flow can thus strongly modify the concentration dependence of viscoelastic properties of polymer solutions.

  12. Skin formation and bubble growth during drying process of polymer solution. (United States)

    Arai, S; Doi, M


    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.

  13. Phase behavior and second osmotic virial coefficient for competitive polymer solvation in mixed solvent solutions. (United States)

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


    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.

  14. Effect of some anionic polymers on pH of triethanolamine aqueous solutions. (United States)

    Musiał, Witold; Kubis, Aleksander


    One of the suggested approaches in the management and prophylaxis of acne involves binding of free fatty acids in the form of soap with alcoholamines. Due to a possible irritating effect of alcoholamines associated with a relatively high pH of their aqueous solutions, complexation of alcoholamines with acid polymers is advocated. Triethanolamine is one of the best recognized alcoholamines. It was conventionally neutralized with Carbopols, Eudragits, alginic acid and pectin. During neutralization of polymer dispersions with triethanolamine, variations in the course of the neutralization curve have been observed among individual macromolecular compounds. The pH of 0.1 mol/l triethanolamine solution reaches 10.51, while following a complete neutralization with anionic polymers, such as Carbopols, Eudragits, alginic acid and pectin, pH ranges from 3.88 for systems neutralized with alginic acid to 8.50 for the system neutralized with Eudragit S-100. Complexation of triethanolamine with anionic polymers decreases its pH, and it is possible to find such pH range in which pH of the preparation containing the polymer and triethanolamine will correspond to the physiological pH of the skin.

  15. Current applications of foams formed from mixed surfactant-polymer solutions. (United States)

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


    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.

  16. Drug-excipient behavior in polymeric amorphous solid dispersions.


    Surikutchi Bhanu Teja; Shashank Pralhad Patil; Ganesh Shete; Sarsvatkumar Patel; Arvind Kumar Bansal


    Amorphous drug delivery systems are increasingly utilized to enhance aqueous solubility and oral bioavailability. However, they lack physical and/or chemical stability. One of the most common ways of stabilizing an amorphous form is by formulating it as an amorphous solid dispersion. This review focuses on polymeric amorphous solid dispersions wherein polymers are used as excipients to stabilize the amorphous form. A brief introduction to the basic concepts of amorphous systems such as glass ...

  17. Drug excipient behavior in polymeric amorphous solid dispersions


    Bhanu Teja Surikutchi; Shashank Pralhad Patil; Ganesh Shete; Sarsvatkumar Patel; Arvind Kumar Bansal


    Amorphous drug delivery system is being increasingly utilized for enhancing aqueous solubility and oral bioavailability. However it suffers from lack of physical/chemical stability. One of the most common ways of stabilizing an amorphous form is by formulating it as amorphous solid dispersion. This review focuses on the polymeric amorphous solid dispersion wherein polymers are used as excipients to stabilize the amorphous form. We present a brief introduction of basic concepts of amorphous sy...

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

    Directory of Open Access Journals (Sweden)

    Mhd Radzi Bin Abas


    Full Text Available 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.

  19. Removal of parabens from aqueous solution using β-cyclodextrin cross-linked polymer. (United States)

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


    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.

  20. An investigation into the role of polymeric carriers on crystal growth within amorphous solid dispersion systems. (United States)

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


    Using phase diagrams derived from Flory-Huggins theory, we defined the thermodynamic state of amorphous felodipine within three different polymeric carriers. Variation in the solubility and miscibility of felodipine within different polymeric materials (using F-H theory) has been identified and used to select the most suitable polymeric carriers for the production of amorphous drug-polymer solid dispersions. With this information, amorphous felodipine solid dispersions were manufactured using three different polymeric materials (HPMCAS-HF, Soluplus, and PVPK15) at predefined drug loadings, and the crystal growth rates of felodipine from these solid dispersions were investigated. Crystallization of amorphous felodipine was studied using Raman spectral imaging and polarized light microscopy. Using this data, we examined the correlation among several characteristics of solid dispersions to the crystal growth rate of felodipine. An exponential relationship was found to exist between drug loading and crystal growth rate. Moreover, crystal growth within all selected amorphous drug-polymer solid dispersion systems were viscosity dependent (η(-ξ)). The exponent, ξ, was estimated to be 1.36 at a temperature of 80 °C. Values of ξ exceeding 1 may indicate strong viscosity dependent crystal growth in the amorphous drug-polymer solid dispersion systems. We argue that the elevated exponent value (ξ > 1) is a result of drug-polymer mixing which leads to a less fragile amorphous drug-polymer solid dispersion system. All systems investigated displayed an upper critical solution temperature, and the solid-liquid boundary was always higher than the spinodal decomposition curve. Furthermore, for PVP-FD amorphous dispersions at drug loadings exceeding 0.6 volume ratio, the mechanism of phase separation within the metastable zone was found to be driven by nucleation and growth rather than liquid-liquid separation.

  1. A solution state diode using semiconductor polymer nanorods with nanogap electrodes. (United States)

    Mutlu, Senol; Sonmez, Bedri Gurkan


    A solution state polymer diode, which uses regioregular poly(3-hexylthiophene-2,5-diyl) (P3HT):dichlorobenzene solution as the semiconductor between highly doped p-type silicon and aluminum electrodes has been built. Electrodes separated by a 40 nm gap enable intra-chain charge carrier transfer through the lengths of single polymer chains. This prevents chain to chain hopping and chain entanglements, increasing carrier mobility. The degradation with time and hysteresis effects of the diodes are measured. An optimal P3HT solution concentration of 6 mg ml(-1) is found. A current density of at least 300 mA cm(-2) is achieved, indicating at least a six-fold improvement in carrier mobility compared to previously fabricated solid state P3HT diodes.

  2. Diffusion in Evaporating Polymer Solutions: A Model in the Dissipative Formalism of Nonequilibrium Thermodynamics

    CERN Document Server

    Es-haghi, Siamak Shams


    In this paper, diffusion in polymer solutions undergoing evaporation of solvent is modeled as a coupled heat and mass transfer problem with moving boundary condition within the framework of nonequilibrium thermodynamics. The proposed governing equations derived from the fundamental equation of classical thermodynamics using the local equilibrium hypothesis display more complex connection between heat and non-convective mass fluxes than what has been presented in the previous research works. Numerical computations, performed using an explicit finite difference scheme, indicate that the model is able to capture the effect of thermal diffusion in polymer solutions. This effect manifests itself as an increase in local concentration of solvent near warm substrates during solution casting process.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  4. Preparation of Laminin-apatite-polymer Composites Using Metastable Calcium Phosphate Solutions

    Institute of Scientific and Technical Information of China (English)


    A synthetic polymer with a laminin-apatite composite layer on its surface would be useful as a percutaneous device. The preparation of such a composite was attempted in the present study using poly ( ethylene terephthalate ) (PET) and polyethylene ( PE ) as the synthetic polymer. PET and PE plates and those pretreated with an oxygen plasma were alternately dipped in calcium and phosphate ion solutions, and then immersed in a metastable ealcium phosphate solution supplemented with laminin ( LCP solution ). The PET and PE plates pretreated with an oxygen plasma formed a uniform and continuous layer of a laminin- apatite composite on their surfaces. In contrast, the PET and PE plates that had not been pretreated with an oxygen plasma did not form a continuous layer of a laminin-apatite composite on their surfaces. The hydrophilic functional groups on the PET and PE surfaces introduced by the plasma treatment were responsible for the successful laminin-apatite composite coating.

  5. Displacement of polymer solution on residual oil trapped in dead ends

    Institute of Scientific and Technical Information of China (English)

    张立娟; 岳湘安


    For waterflooding reservoir,oil trapped in pore’s dead ends is hardly flushed out,and usually becomes one typical type of residual oil.The microscopic displacement characteristics of polymer solution with varied viscoelastic property were studied by numerical and experimental method.According to main pore structure characteristics and rheological property of polymer solution through porous media,displacement models for residual oil trapped in dead ends were proposed,and upper-convected Maxwell rheological model was used as polymer solution’s constitutive equation.The flow and stress field was given and displacement characteristic was quantified by introducing a parameter of micro swept coefficient.The calculated and experimental results show that micro swept coefficient rises with the increase of viscoelasticity;for greater viscoelasticity of polymer solution,vortices in the dead end have greater swept volume and displacing force on oil,and consequently entraining the swept oil in time.In addition,micro swept coefficient in dead end is function of the inclination angle(θ) between pore and dead end.The smaller of θ and 180-θ,the flow field of viscoelastic fluid is developed in dead ends more deeply,resulting in more contact with oil and larger swept coefficient.

  6. Interaction Mechanisms between Air Bubble and Molybdenite Surface: Impact of Solution Salinity and Polymer Adsorption. (United States)

    Xie, Lei; Wang, Jingyi; Yuan, Duowei; Shi, Chen; Cui, Xin; Zhang, Hao; Liu, Qi; Liu, Qingxia; Zeng, Hongbo


    The surface characteristics of molybdenite (MoS2) such as wettability and surface interactions have attracted much research interest in a wide range of engineering applications, such as froth flotation. In this work, a bubble probe atomic force microscope (AFM) technique was employed to directly measure the interaction forces between an air bubble and molybdenite mineral surface before/after polymer (i.e., guar gum) adsorption treatment. The AFM imaging showed that the polymer coverage on the surface of molybdenite could achieve ∼5.6, ∼44.5, and ∼100% after conditioning in 1, 5, and 10 ppm polymer solution, respectively, which coincided with the polymer coverage results based on contact angle measurements. The electrolyte concentration and surface treatment by polymer adsorption were found to significantly affect bubble-mineral interaction and attachment. The experimental force results on bubble-molybdenite (without polymer treatment) agreed well with the calculations using a theoretical model based on the Reynolds lubrication theory and augmented Young-Laplace equation including the effect of disjoining pressure. The overall surface repulsion was enhanced when the NaCl concentration decreased from 100 to 1 mM, which inhibited the bubble-molybdenite attachment. After conditioning the molybdenite surface in 1 ppm polymer solution, it was more difficult for air bubbles to attach to the molybdenite surface due to the weakened hydrophobic interaction with a shorter decay length. Increasing the polymer concentration to 5 ppm effectively inhibited bubble attachment on mineral surface, which was mainly due to the much reduced hydrophobic interaction as well as the additional steric repulsion between the extended polymer chains and bubble surface. The results provide quantitative information on the interaction mechanism between air bubbles and molybdenite mineral surfaces on the nanoscale, with useful implications for the development of effective polymer depressants


    Institute of Scientific and Technical Information of China (English)

    YIN Hong-jun; FU Chun-quan; LV Yan-ping


    With the consideration of the visco-elasticity,the adsorption effect and the variation of rheological parameters, a seepage flow model of visco-elastic polymer solutions was established. The model was numerically treated with the finite difference method. Then curves of Bottom Hole Pressure (BHP) and formation pressure were drawn. The influences of the relaxation time, the injection rate, the permeability reduction co efficient, the consistency coefficient and the power-law exponent of the injected fluid on pressure performance were analyzed. This study shows that it is necessary to consider the visco-elasticity of non-Newtonian fluid in analyzing of pressure performance in the polymer flooding.

  8. Solution-processed cathode interfacial layer materials for high-efficiency polymer solar cells

    Directory of Open Access Journals (Sweden)

    Biao Xiao


    Full Text Available Polymer solar cells (PSCs are a new type of renewable energy source currently being extensively investigated due to perceived advantages; such as being lightweight, low-cost and because of the unlimited materials resource. The power conversion efficiency of state-of-the-art PSCs has increased dramatically in the past few years, obtained mainly through the development of new electron donor polymers, acceptors, and novel device structures through the use of various electrode interfacial materials. In this short review, recent progress in solution-processed cathode interfacial layers that could significantly improve device performances is summarized and highlighted.

  9. Emerging trends in the stabilization of amorphous drugs

    DEFF Research Database (Denmark)

    Laitinen, Riikka; Löbmann, Korbinian; Strachan, Clare J.;


    water-soluble drugs can be increased by the formation of stabilized amorphous forms. Currently, formulation as solid polymer dispersions is the preferred method to enhance drug dissolution and to stabilize the amorphous form of a drug. The purpose of this review is to highlight emerging alternative...... methods to amorphous polymer dispersions for stabilizing the amorphous form of drugs. First, an overview of the properties and stabilization mechanisms of amorphous forms is provided. Subsequently, formulation approaches such as the preparation of co-amorphous small-molecule mixtures and the use...... of mesoporous silicon and silica-based carriers are presented as potential means to increase the stability of amorphous pharmaceuticals....

  10. Dynamics of single semiflexible polymers in dilute solution (United States)

    Nikoubashman, Arash; Milchev, Andrey; Binder, Kurt


    We study the dynamics of a single semiflexible chain in solution using computer simulations, where we systematically investigate the effect of excluded volume, chain stiffness, and hydrodynamic interactions. We achieve excellent agreement with previous theoretical considerations, but find that the crossover from the time τb, up to which free ballistic motion of the monomers describes the chain dynamics, to the times W-1 or τ0, where anomalous monomer diffusion described by Rouse-type and Zimm-type models sets in, requires two decades of time. While in the limit of fully flexible chains the visibility of the anomalous diffusion behavior is thus rather restricted, the t3/4 power law predicted for stiff chains without hydrodynamic interactions is verified. Including hydrodynamics, evidence for the predicted [tln (t ) ] 3 /4 behavior is obtained. Similar good agreement with previous theoretical predictions is found for the decay of the bond autocorrelation functions and the end-to-end vector correlation. Finally, several predictions on the variation of characteristic relaxation times with persistence length describing the chain stiffness are tested.

  11. Biodegradable Polycaprolactone as Ion Solvating Polymer for Solution-Processed Light-Emitting Electrochemical Cells (United States)

    Jürgensen, Nils; Zimmermann, Johannes; Morfa, Anthony John; Hernandez-Sosa, Gerardo


    In this work, we demonstrate the use of the biodegradable polymer polycaprolactone (PCL) as the ion solvating polymer in solution-processed light-emitting electrochemical cells (LEC). We show that the inclusion of PCL in the active layer yields higher ionic conductivities and thus contributes to a rapid formation of the dynamic p-i-n junction and reduction of operating voltages. PCL shows no phase separation with the emitter polymer and reduces film roughness. The devices show light-emission at voltages as low as 3.2 V and lifetimes on the order of 30 h operating above 150 cd m‑2 with turn-on times <20 s and current and luminous efficacies of 3.2 Cd A‑1 and 1.5 lm W‑1 respectively.

  12. Henry constants in polymer solutions with the van der Waals equation of state

    DEFF Research Database (Denmark)

    Bithas, Sotiris; Kalospiros, Nikolaos; Kontogeorgis, Georgios


    The simple der Waals equation of state, as extended to polymer systems, is applied to the correlation and prediction of Henry constants in polymer solutions comprising five polymers and many nonpolar and polar solvents, including supercritical gases. The correlation achieved with one adjustable...... parameter is satisfactory, with typical errors within the experimental uncertainty and comparable to those with the more complex Perturbed Hard Chain Theory-based equations of state with the same number of adjustable parameters. A predictive scheme for calculating Henry constants is also presented, which...... is a corresponding-states correlation for a dimensionless Henry constant defined based on the van der Waals equation of state. Satisfactory results-often close to the ones from the one-parameter correlation-are obtained for all systems investigated in this work. Compared with literature models that have been applied...

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

    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


    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. Polymer solutions in co-rotating Taylor-Couette flow without vorticity (United States)

    Zell, A.; Wagner, C.


    We present experimental results of the flow of dilute and semi-dilute polymer solutions in co-rotating Taylor-Couette cylinders. The experimental set-up consists of a modified Mars II rheometer (Thermo Scientific) with two drive units that are mounted opposite each other. The rotational velocities of the inner and outer cylinders are chosen in a way such that the angular velocity has a 1/r profile and the flow is free of vorticity, but the direction of elongation is not constant, but rotates with the flow. Our particle image velocimetry (PIV) measurements show that for polymer solutions without shear thinning the flow is indeed free of vorticity and is equal to a stagnation point flow at a given position and a given instant in time. In contrast, torque measurements reveal that the stresses are identical to the stresses that are present in a plane shear flow. Thus, we find that for polymer solutions a flow with vorticity and a constant direction of elongation is equal to a flow without vorticity in which the direction of elongation is rotating. Finally, we show that for shear thinning solutions the flow velocity becomes non-monotonic through the gap and resembles a pluglike profile which is known from the Poiseuille flow.

  15. The effect of heat developed during high strain rate deformation on the constitutive modeling of amorphous polymers (United States)

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


    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.

  16. Gate-induced superconductivity in a solution-processed organic polymer film. (United States)

    Schön, J H; Dodabalapur, A; Bao, Z; Kloc, C; Schenker, O; Batlogg, B


    The electrical and optical properties of conjugated polymers have received considerable attention in the context of potentially low-cost replacements for conventional metals and inorganic semiconductors. Charge transport in these organic materials has been characterized in both the doped-metallic and the semiconducting state, but superconductivity has not hitherto been observed in these polymers. Here we report a distinct metal-insulator transition and metallic levels of conductivity in a polymer field-effect transistor. The active material is solution-cast regioregular poly(3-hexylthiophene), which forms relatively well ordered films owing to self-organization, and which yields a high charge carrier mobility (0.05-0.1 cm2 V(-1) s(-1)) at room temperature. At temperatures below approximately 2.35 K with sheet carrier densities exceeding 2.5 x 10(14) cm(-2), the polythiophene film becomes superconducting. The appearance of superconductivity seems to be closely related to the self-assembly properties of the polymer, as the introduction of additional disorder is found to suppress superconductivity. Our findings therefore demonstrate the feasibility of tuning the electrical properties of conjugated polymers over the largest range possible-from insulating to superconducting.

  17. Polymer dynamics in semidilute solution during electrospinning: A simple model and experimental observations (United States)

    Greenfeld, Israel; Arinstein, Arkadii; Fezzaa, Kamel; Rafailovich, Miriam H.; Zussman, Eyal


    Electrospun polymer nanofibers demonstrate outstanding mechanical and thermodynamic properties as compared to macroscopic-scale structures. Our previous work has demonstrated that these features are attributed to nanofiber microstructure [Nat. Nanotechnol.1748-338710.1038/nnano.2006.172 2, 59 (2007)]. It is clear that this microstructure is formed during the electrospinning process, characterized by a high stretching rate and rapid evaporation. Thus, when studying microstructure formation, its fast evolution must be taken into account. This study focuses on the dynamics of a highly entangled semidilute polymer solution under extreme longitudinal acceleration. The theoretical modeling predicts substantial longitudinal stretching and transversal contraction of the polymer network caused by the jet hydrodynamic forces, transforming the network to an almost fully stretched state. This prediction was verified by x-ray phase-contrast imaging of electrospinning jets of poly(ethylene oxide) and poly(methyl methacrylate) semidilute solutions, which revealed a noticeable increase in polymer concentration at the jet center, within less than 1 mm from the jet start. Thus, the proposed mechanism is applicable to the initial stage of the microstructure formation.

  18. Coarse-graining polymer solutions: A critical appraisal of single- and multi-site models (United States)

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


    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.

  19. Polymer-Controlled Growth of CuO Nanodiscs in the Mild Aqueous Solution

    Institute of Scientific and Technical Information of China (English)

    PENG Yin; LIU Zhengyin; YANG Zihui


    CuO nanodiscs have been synthesized on a large scale by a facile solution-based method using polymers as crystal growth modifiers. X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and high resolu-tion transmission electron microscopy (HRTEM) were carded out to characterize the structures and morphologies of the obtained products. The effects of reaction temperature, concentrations of polyacrylamide (PAM) and reac-tants on the morphology and size of the product were studied. The results revealed that the CuO nanodisc had sin-gle-crystal monoclinic structures, and grew along (002) and (110) planes. Experimental conditions had all influence on the shape and size of the final products, but polymer PAM played the key role in formation of the CuO nanodisc.A possible growth mechanism of the CuO nanostructures based on typical polymer-crystal interactions in a mild aqueous solution was given. Polymer-directed crystal growth may provide promising routes to rational synthesis of various ordered inorganic and inorganic-organic hybrid materials with complex forms and structural specialization.

  20. Correlation between thermal diffusion and solvent self-diffusion in semidilute and concentrated polymer solutions. (United States)

    Rauch, J; Hartung, M; Privalov, A F; Köhler, W


    We have performed measurements of thermal diffusion coefficients DT and solvent self-diffusion coefficients Dss in semidilute to concentrated polymer solutions. Solutes of different glass transition temperatures and solvents of different solvent qualities have been used. The investigated systems are in detail: poly(dimethyl-siloxane) in toluene, tristyrene in toluene, polystyrene in toluene, polystyrene in tetrahydrofuran, polystyrene in benzene, and polystyrene in cyclohexane. The thermal diffusion data are compared to our data and literature data for solvent self-diffusion coefficients. In all systems the concentration dependence of DT closely parallels the one of Dss which may be viewed as a local probe for friction on a length scale of the size of one polymer segment. This identifies local friction as the dominating parameter determining the concentration dependence of DT. Solvent quality, in contrast, has no influence on DT.

  1. Polymer Conformation near the Critical Demixing Point of a Binary Solution (United States)

    He, Lilin; Cheng, Gang; Melnichenko, Yuri


    We have used Contrast Matching Small Angle Neutron Scattering (CMSANS) to probe directly the conformation change of polyethylene glycerol (PEO) chains in the critical demixing region of Acetonitrile-d3 in (D2O + H2O) at concentration of the components corresponding to zero-average contrast condition. The d-PEO and h-PEO were mixed to match the scattering length density (SLD) of the critical liquid solution, which allowed us to extract single-chain dimension of polymer molecules in the aggregates near the critical point of the solvent. A non-monotonic variation of Rg was detected as temperature approached the critical temperature of phase demixing of acetonitrile- water solution, which was attributed to the interaction asymmetry of the solvent molecules with polymers predicted by Brochard and de Gennes two decades ago. To our best knowledge, this is the first direct experimental evidence supporting this prediction.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jeffrey, F.


    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Minelli, Matteo; Doghieri, Ferruccio [Dipartimento di Ingegneria Civile, Chimica, Ambientale e dei Materiali (DICAM), Centro Interdipartimentale per la Ricerca Industriale - Meccanica Avanzata e Materiali (CIRI-MAM), Alma Mater Studiorum - Università di Bologna, via Terracini 28 - (Italy)


    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.

  4. Trehalose amorphization and recrystallization. (United States)

    Sussich, Fabiana; Cesàro, Attilio


    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.

  5. Radiation chemical studies on thermosensitive N-isopropylacrylamide and its polymer in aqueous solutions. (United States)

    Acharya, Anjali; Mohan, Hari; Sabharwal, S


    The pulse radiolysis technique has been employed to determine the initiation and propagation rates of different transient species involved in the polymerization of N-isopropylacrylamide (NIPA) in aqueous solutions. Polymerization by anionic mechanism has been observed to be faster than by the free-radical mechanism. The kinetic, spectroscopic and redox properties of the transient species formed upon reaction of primary radiolytic species of water radiolysis with NIPA have been evaluated. The one-electron oxidation potential for the formation of a radical cation is quite high (>2 V), but the one-electron reduction potential is low (in the range of -0.3 to -0.7 V). The radical anion of NIPA is able to undergo an electron-transfer reaction with MV(2+), and has a pK(a) value of 3.2. The tert-butyl alcohol radical was also able to initiate polymerization. Gamma radiation-induced polymerization studies showed that the reaction of H(.)/(.)OH/e(aq)(-)/tert-butyl alcohol radicals with NIPA results in a nearly equal yield of the gel fraction. The hydrogel is observed to have very little swelling below pH 3 and above pH 10. The linear polymer of NIPA formed by irradiating dilute aqueous solution is found to be a thermosensitive polymer with lower a critical solution temperature (LCST) of ~33 degrees C. The diameters of polymer molecules were 290 and 20 nm at temperature below and above LCST, respectively.

  6. Theory of DNA electrophoresis in physical gels and entangled polymer solutions (United States)

    Duke, Thomas; Viovy, Jean Louis


    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.

  7. Solution-based single molecule imaging of surface-immobilized conjugated polymers. (United States)

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


    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.

  8. Concurrent solution-like decoloration rate and high mechanical strength from polymer-dispersed photochromic organogel. (United States)

    Long, Shijun; Bi, Shuguang; Liao, Yonggui; Xue, Zhigang; Xie, Xiaolin


    To achieve a fast photochromic response in solid matrix, photochromic molecules/segments have been either dispersed into elastomers via physical doping or linked to glassy polymers by soft units through covalent bonding. However, the former is lack of high mechanical strength and the latter owes the drawback of time-consumption of synthesis. Here, we propose a facile strategy of co-solvent evaporation to prepare polymer-dispersed photochromic organogel where both high mechanical strength of the glassy polymer matrix and solution-like fast photochromism of the photochromic molecule within organogel can be retained concurrently. Glassy PVA matrix and dispersed organogel of 1,3:2,4-di-O-benzylidene-d-sorbitol/poly(propylene glycol) (DBS/PPG) provide high mechanical strength and sufficient free volume for intramolecular rotation of photochromic spiropyran (SP), respectively. Interestingly, these thin films behave a solution-like decoloration the decay rate of which is 65-70 fold faster than that in the SP-directly doped PVA film and only slightly slower than those in their corresponding PPG solutions.

  9. Impact of Polymer Conformation on the Crystal Growth Inhibition of a Poorly Water-Soluble Drug in Aqueous Solution


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


    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 a...

  10. The effect of injection molding conditions on the near-surface rubber morphology, surface chemistry, and adhesion performance of semi-crystalline and amorphous polymers (United States)

    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


    Institute of Scientific and Technical Information of China (English)

    YAN Xin; WANG Dehua; QIAN Baogong


    An intermolecular 13C{1H} NOE of CCl4 in the solutions of polystyrene and polybutadiene and their copolymers was observed. The results show that the defined polymer-CCl4 interaction variable has a linear relation with the polymer composition and the difference of solubility parameters and exponentially depends on the reciprocal of temperature.

  12. Solution-processable MoOx nanocrystals enable highly efficient reflective and semitransparent polymer solar cells

    KAUST Repository

    Jagadamma, Lethy Krishnan


    Solution-manufacturing of organic solar cells with best-in-class power conversion efficiency (PCE) will require all layers to be solution-coated without compromising solar cell performance. To date, the hole transporting layer (HTL) deposited on top of the organic bulk heterojunction layer in the inverted architecture is most commonly an ultrathin (<10 nm) metal oxide layer prepared by vacuum-deposition. Here, we show that an alcohol-based nanocrystalline MoOx suspension with carefully controlled nanocrystal (NC) size can yield state of the art reflective and semitransparent solar cells. Using NCs smaller than the target HTL thickness (∼10 nm) can yield compact, pinhole-free films which result in highly efficient polymer:fullerene bulk heterojunction (BHJ) solar cells with PCE=9.5%. The solution processed HTL is shown to achieve performance parity with vacuum-evaporated HTLs for several polymer:fullerene combinations and is even shown to work as hole injection layer in polymer light emitting diodes (PLED). We also demonstrate that larger MoOx NCs (30–50 nm) successfully composite MoOx with Ag nanowires (NW) to form a highly conducting, transparent top anode with exceptional contact properties. This yields state-of-the-art semitransparent polymer: fullerene solar cells with PCE of 6.5% and overall transmission >30%. The remarkable performance of reflective and semitransparent OPVs is due to the uncommonly high fill factors achieved using a carefully designed strategy for implementation of MoOx nanocrystals as HTL materials. © 2016 Elsevier Ltd

  13. Continuum theory of critical phenomena in polymer solutions: Formalism and mean field approximation (United States)

    Goldstein, Raymond E.; Cherayil, Binny J.


    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.

  14. Application of X-ray microtomography for the characterisation of hollow polymer-stabilised spray dried amorphous dispersion particles. (United States)

    Gamble, John F; Terada, Masako; Holzner, Christian; Lavery, Leah; Nicholson, Sarah J; Timmins, Peter; Tobyn, Mike


    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.

  15. Entanglements in Marginal Solutions: A Means of Tuning Pre-Aggregation of Conjugated Polymers with Positive Implications for Charge Transport

    KAUST Repository

    Hu, Hanlin


    The solution-processing of conjugated polymers, just like commodity polymers, is subject to solvent and molecular weight-dependent solubility, interactions and chain entanglements within the polymer, all of which can influence the crystallization and microstructure development in semi-crystalline polymers and consequently affect charge transport and optoelectronic properties. Disentanglement of polymer chains in marginal solvents was reported to work via ultrasonication, facilitating the formation of photophysically ordered polymer aggregates. In this contribution, we explore how a wide range of technologically relevant solvents and formulations commonly used in organic electronics influence chain entanglement and the aggregation behaviour of P3HT using a combination of rheological and spectrophotometric measurements. The specific viscosity of the solution offers an excellent indication of the degree of entanglements in the solution, which is found to be related to the solubility of P3HT in a given solvent. Moreover, deliberately disentangling the solution in the presence of solvophobic driving forces, leads consistently to formation of photophysically visible aggregates which is indicative of local and perhaps long range order in the solute. We show for a broad range of solvents and molecular weights that disentanglement ultimately leads to significant ordering of the polymer in the solid state and a commensurate increase in charge transport properties. In doing so we demonstrate a remarkable ability to tune the microstructure which has important implications for transport properties. We discuss its potential implications in the context of organic photovoltaics.

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

    KAUST Repository

    Zhao, Kui


    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 dielectric surface with solution-state disentanglement and pre-aggregation of P3HT in a theta solvent, leading to a very significant enhancement of the field effect carrier mobility. The pre-aggregation 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 pre-aggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of pre-aggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to un-aggregated polymer chains. Additional investigations reveal the combined pre-aggregation 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 pre-aggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

  17. Solution-Processed p-Dopant as Interlayer in Polymer Solar Cells. (United States)

    Guillain, F; Endres, J; Bourgeois, L; Kahn, A; Vignau, L; Wantz, G


    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.

  18. Thermally cross-linkable hole transport polymers for solution-based organic light-emitting diodes. (United States)

    Cha, Seung Ji; Cho, Se-Na; Lee, Woo-Hyung; Chung, Ha-Seul; Kang, In-Nam; Suh, Min Chul


    Two thermally cross-linkable hole transport polymers that contain phenoxazine and triphenylamine moieties, X-P1 and X-P2, are developed for use in solution-processed multi-stack organic light-emitting diodes (OLEDs). Both X-P1 and X-P2 exhibit satisfactory cross-linking and optoelectronic properties. The highest occupied molecular orbital (HOMO) levels of X-P1 and X-P2 are -5.24 and -5.16 eV, respectively. Solution-processed super yellow polymer devices (ITO/X-P1 or X-P2/PDY-132/LiF/Al) with X-P1 or X-P2 hole transport layers of various thicknesses are fabricated with the aim of optimizing the device characteristics. The fabricated multi-stack yellow devices containing the newly synthesized hole transport polymers exhibit satisfactory currents and power efficiencies. The optimized X-P2 device exhibits a device efficiency that is dramatically improved by more than 66% over that of a reference device without an HTL.

  19. Shear Rheology of Suspensions of Porous Zeolite Particles in Concentrated Polymer Solutions (United States)

    Olanrewaju, Kayode O.; Breedveld, Victor


    We present experimental data on the shear rheology of Ultem (polyetherimide)/NMP(l-methyl-2-pyrrolidinone) solutions with and without suspended surface-modified porous/nonporous zeolite (ZSM-5) particles. We found that the porous zeolite suspensions have relative viscosities that significantly exceed the Krieger-Dougherty predictions for hard sphere suspensions. The major origin of this discrepancy is the selective absorption of NMP solvent into the zeolite pores, which raises both the polymer concentration and the particle volume fraction, thus enhancing both the viscosity of the continuous phase Ultem/NMP polymer solution and the particle contribution to the suspension viscosity. Other factors, such as zeolite non-sphericity and specific interactions with Ultem polymer, contribute to the suspension viscosity to a lesser extent. We propose a predictive model for the viscosity of porous zeolite suspensions by incorporating an absorption parameter, α, into the Krieger-Dougherty model. We also propose independent approaches to determine α. The first one is indirect and based on zeolite density/porosity data, assuming that all pores will be filled with solvent. The other method is based on our experimental data, by comparing the viscosity data of porous versus non-porous zeolite suspensions. The different approaches are compared.

  20. Polymer-clay nanocomposites obtained by solution polymerization of vinyl benzyl triammonium chloride in the presence of advanced functionalized clay

    Indian Academy of Sciences (India)

    Raluca Ianchis; Dan Donescu; Ludmila Otilia Cinteza; Violeta Purcar; Cristina Lavinia Nistor; Critian Petcu; Cristian Andi Nicolae; Raluca Gabor; Silviu Preda


    Polymer-clay nanocomposites were synthesized by solution polymerization method using advanced functionalized clay and vinyl benzyl trimethyl ammonium chloride as monomer. First stage consisted in the silylation of a commercial organo-modified clay-Cl 20A using alkoxysilanes with different chain lengths. In the second step, the synthesis and characterization of polymer-nanocomposites were followed. To evaluate the clay functionalization process as well as the final polymer-clay products, thermogravimetric,X-ray diffraction, dynamic light scattering, Fourier transform infrared spectroscopy and three test liquid contact angles analyses were used. The loss of ammonium ions from commercial clay, the grafting degree, the lengths and the nature of alkyl chain influence the dispersion of the advanced modified clay into the polymer solution and, furthermore, the properties of the final polymer-clay nanocomposite film.

  1. Deviations from a simple Debye relaxation in aqueous solutions of differently flexible polyions induced by polymer concentration. (United States)

    Cametti, C; Sennato, S; Truzzolillo, D


    The electrical conductivity of aqueous solutions of differently flexible polymers has been measured in the frequency range from 1 MHz to 2 GHz. This note evidences how the shape parameter alpha of the conductivity relaxation associated with the orientational polarization of the aqueous phase depends on the polymer concentration and, moreover, reflects the different concentration regimes of the polymer solution (dilute, semidilute entangled and nonentangled, and concentrated regimes). The relevance of this dependence, as far as the microscopic environment of water molecules is concerned, is briefly discussed.

  2. Interpolymer reactions of nonionic polymers with polyacrylic acid in aqueous solutions

    Directory of Open Access Journals (Sweden)

    E. Shaikhutdinov


    Full Text Available Results of fundamental investigations in the intermacromolecular reactions and interpolymer complexes to be performed by authors with co-workes within last 20 years have been intergrated and summarized in the present review. The raw of fundamental regularities in the effect of factors of different nature (pH, ionic strength, temperature, hydrophilic-hydrophobic balance of macrochain, etc. on the complexation of nonionic polymers with polycarboxylic acids in aqueous solutions has been revealed. Critical pH upon complexation (pHcrit. has been used for evaluation of the complexing ability of the polymers. It was shown tha tdepending on pHcrit. all systems can be divided into 2 groups, namely, weak complexing and strongly complexing. The existence of two critical pH upon complexation responsible for formation typical interpolymer complexes and hydrophilic associations has been demonstrated by the method of luminescence spectroscopy.

  3. A Solution-Doped Polymer Semiconductor:Insulator Blend for Thermoelectrics

    KAUST Repository

    Kiefer, David


    Poly(ethylene oxide) is demonstrated to be a suitable matrix polymer for the solution-doped conjugated polymer poly(3-hexylthiophene). The polarity of the insulator combined with carefully chosen processing conditions permits the fabrication of tens of micrometer-thick films that feature a fine distribution of the F4TCNQ dopant:semiconductor complex. Changes in electrical conductivity from 0.1 to 0.3 S cm−1 and Seebeck coefficient from 100 to 60 μV K−1 upon addition of the insulator correlate with an increase in doping efficiency from 20% to 40% for heavily doped ternary blends. An invariant bulk thermal conductivity of about 0.3 W m−1 K−1 gives rise to a thermoelectric Figure of merit ZT ∼ 10−4 that remains unaltered for an insulator content of more than 60 wt%. Free-standing, mechanically robust tapes illustrate the versatility of the developed dopant:semiconductor:insulator ternary blends.

  4. N-doped P25 TiO2-amorphous Al2O3 composites: one-step solution combustion preparation and enhanced visible-light photocatalytic activity. (United States)

    Li, Fa-tang; Zhao, Ye; Hao, Ying-juan; Wang, Xiao-jing; Liu, Rui-hong; Zhao, Di-shun; Chen, Dai-mei


    Nitrogen-doped Degussa P25 TiO2-amorphous Al2O3 composites were prepared via facile solution combustion. The composites were characterised using X-ray diffraction, high-resolution transmission microscopy, scanning electron microscopy, nitrogen adsorption-desorption measurements, X-ray photoelectron spectroscopy, UV-vis light-diffusion reflectance spectrometry (DRS), zeta-potential measurements, and photoluminescence spectroscopy. The DRS results showed that TiO2 and amorphous Al2O3 exhibited absorption in the UV region. However, the Al2O3/TiO2 composite exhibited visible-light absorption, which was attributed to N-doping during high-temperature combustion and to alterations in the electronic structure of Ti species induced by the addition of Al. The optimal molar ratio of TiO2 to Al2O3 was 1.5:1, and this composite exhibited a large specific surface area of 152 m2/g, surface positive charges, and enhanced photocatalytic activity. These characteristics enhanced the degradation rate of anionic methylene orange, which was 43.6 times greater than that of pure P25 TiO2. The high visible-light photocatalytic activity was attributed to synthetic effects between amorphous Al2O3 and TiO2, low recombination efficiency of photo-excited electrons and holes, N-doping, and a large specific surface area. Experiments that involved radical scavengers indicated that OH and O2- were the main reactive species. A potential photocatalytic mechanism was also proposed.

  5. Removal of Chloroform from Hydrochloride Acid Solution Using Fine Powder of Polymer as Adsorbent

    Institute of Scientific and Technical Information of China (English)

    LU,Yingzhou; QUE,Yong; LI,Chunxi; MENG,Hong; WANG,Zihao


    In order to choose a suitable adsorbent for the removal of chloroform from its hydrochloric acid solution,the adsorptive ability of some polymer adsorbents was investigated in terms of their adsorption curves in water and 20% hydrochloric acid solutions at 298.15 K,and compared with that of active carbon (AC) and solid paraffin (SP).The adsorbents studied include the fine powders of chlorinated rubber (CR),polypropylene (PP),chlorinated polypropylene (CPP) and polyvinylchloride (PVC).The results showed that the adsorption behavior followed the Langmuir equation and the adsorption ability of these adsorbents followed the order AC > PVC > CR > PP > CPP> SP.This order is basically in line with the decrease of chloro-content of the adsorbents from PVC to SP.The adsorptivity of PVC and CR was nearly equivalent to that of AC with their saturated adsorption being about 1.4 g-CHCl3 (g-absorbent) -1.For all adsorbents studied,the adsorption capacity always decreases with the increase of hydrochloric acid concentration.It is showed that the commercial polymer powder of PVC or CR can be used as an efficient absorbent for the removal of chloroform from its aqueous solution for its low cost,good adsorption ability and ease of thermal desorption for recycling.

  6. Effect of solution processed and thermally evaporated interlayers on the performance of backgrated polymer solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Jayawardena, K.D.G.I.; Amarasinghe, K.M.P.; Nismy, N.A. [Advanced Technology Institute, Department of Electronic Engineering, University of Surrey, Guildford GU2 7XH (United Kingdom); Mills, C.A. [Advanced Technology Institute, Department of Electronic Engineering, University of Surrey, Guildford GU2 7XH (United Kingdom); Advanced Coatings Group, Surface Engineering Department, Tata Steel Research Development and Technology, Swinden Technology Centre, Rotherham, S60 3AR (United Kingdom); Silva, S.R.P., E-mail: [Advanced Technology Institute, Department of Electronic Engineering, University of Surrey, Guildford GU2 7XH (United Kingdom)


    Polymer solar cells are fast gaining momentum as a potential solution towards low cost sustainable energy generation. However, the performance of architectures is known to be limited by the thin film nature of the active layer which, although required due to low charge carrier mobilities, limits the optical coupling to the active layer. The formation of periodic backgratings has been proposed as a solution to this problem. Here, we investigate the effect of solution processed and thermally evaporated interlayers on the performance of backgrated polymer solar cells. Analysis of device performance under standard conditions indicates higher power conversion efficiencies with the incorporation of the evaporated interlayer (5.7%) over a sol–gel processed interlayer (4.9%). This is driven by a more conformal coating as evidenced through two orders of magnitude higher electron mobilities (10{sup −5} versus 10{sup −7} cm{sup 2} V{sup −1} s{sup −1}) as well as the balanced electron and hole transport observed for the former architecture. It is believed that these results will catalyse further development of such device engineering concepts for improved optical coupling in thin film photovoltaics. - Highlights: • Effect of interlayers on backgrated photovoltaic devices is tested. • Evaporated interlayers lead to better device performance. • Better charge extraction is observed for evaporated interlayers.

  7. Mannitol influence on the separation of DNA fragments by capillary electrophoresis in entangled polymer solutions. (United States)

    Han, F; Xue, J; Lin, B


    A new kind of sieving matrix is presented in this paper to allow satisfactory separation of DNA fragments in a relatively low viscous solution. When a certain amount of mannitol was added to cellulose solution not concentrated enough to separate PGEM-3Zf(+)/HaeIII standards well, a polymer solution with low viscosity but with very good separation effects was obtained. The separation result of this sieving buffer was comparable with those using highly concentrated cellulose solutions. The sieving ability of solutions with different cellulose concentrations and different amounts of mannitol has been investigated. It was proved that 0.5% was the minimum hydroxypropylmethylcellulose (HPMC) concentration that could be used to separate DNA fragments satisfactorily. HPMC solutions with a concentration of less than 0.5% could not separate the standard DNA fragments even in the presence of mannitol. It was found that 6% was the optimized mannitol concentration because either more or less mannitol will lead a decrease of resolution. The principle of the positive influence of mannitol has also been discussed.

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

    DEFF Research Database (Denmark)

    Knopp, Matthias Manne; Nguyen, Julia Hoang; Becker, Christian;


    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...... 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...

  9. Synthesis and Rheological Properties of an Associative Star Polymer in Aqueous Solutions

    DEFF Research Database (Denmark)

    Hietala, Sami; Mononen, Pekka; Strandman, Satu


    synthesised by atom transfer radical. polymerization (ATRP) was found to fonn hydrogels at room temperature at polymer concentrations. Cp, over 22 gIL due to the interpolymer drophobic association of the PS blocks. Increasing Cp leads to stronger elastic networks at room temperature that show a gel......-to-solution transition with increasing temperature. Increase of ionic strength decreases the moduli compared with the pure hydrogel but did not affect the gel-sol transition temperature significantly. Small-angle X-ray experiments showed two distinct scattering correlation peaks for samples above the gelling Cp, which...

  10. Amorphous Silk Fibroin Membranes for Separation of CO2 (United States)

    Aberg, Christopher M.; Patel, Anand K.; Gil, Eun Seok; Spontak, Richard J.; Hagg, May-Britt


    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.

  11. Thermoresponsive Polymers with Lower Critical Solution Temperature- or Upper Critical Solution Temperature-Type Phase Behaviour Do Not Induce Toxicity to Human Endothelial Cells. (United States)

    Ji, Yuejia; Zhu, Mengxiang; Gong, Yu; Tang, Haoyu; Li, Juan; Cao, Yi


    Thermoresponsive polymers have gained extensive attention as biomedical materials especially for targeted drug delivery systems. We have recently developed water-soluble polypeptide-based thermoresponsive polymers that exhibit lower critical solution temperature (LCST)- or upper critical solution temperature (UCST)-type phase behaviours. In this study, the toxicity of these polymers to human umbilical vein endothelial cells (HUVECs) was investigated to assess the safety and biocompatibility. Up to 100 μg/ml, thermoresponsive polymers did not induce cytotoxicity to HUVECs, showing as unaltered mitochondrial viability assessed as cell counting kit-8 (CCK-8) assay and membrane integrity assessed as lactate dehydrogenase (LDH) assay. Inflammatory response, assessed as the release of chemokine-soluble monocyte chemotactic protein 1 (sMCP-1) and interleukin-8 (IL-8) as well as cytokine IL-6, was not significantly affected by the polymers. In addition, 1 μM thapsigargin (TG), an endoplasmic reticulum (ER) stress inducer, significantly decreased mitochondrial viability, but did not affect membrane integrity or inflammatory response. The presence of thermoresponsive polymers with LCST-type phase behaviour did not further affect the effects of TG. In conclusion, the thermoresponsive polymers used in this study are not toxic to endothelial cells and therefore could be further considered as safe materials for biomedical applications.

  12. Amorphous nanophotonics

    CERN Document Server

    Scharf, Toralf


    This book represents the first comprehensive overview over amorphous nano-optical and nano-photonic systems. Nanophotonics is a burgeoning branch of optics that enables many applications by steering the mould of light on length scales smaller than the wavelength with devoted nanostructures. Amorphous nanophotonics exploits self-organization mechanisms based on bottom-up approaches to fabricate nanooptical systems. The resulting structures presented in the book are characterized by a deterministic unit cell with tailored geometries; but their spatial arrangement is not controlled. Instead of periodic, the structures appear either amorphous or random. The aim of this book is to discuss all aspects related to observable effects in amorphous nanophotonic material and aspects related to their design, fabrication, characterization and integration into applications. The book has an interdisciplinary nature with contributions from scientists in physics, chemistry and materials sciences and sheds light on the topic fr...

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

    Directory of Open Access Journals (Sweden)

    D.A. Zimnyakov


    Full Text Available 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.

  14. Reduction in Friction and Wear of Alumina Surfaces as Assisted with Surface-Adsorbing Polymers in Aqueous Solutions

    DEFF Research Database (Denmark)

    Røn, Troels; Lee, Seunghwan


    electrostatic attraction and form a protective layer. For example, polyacrylic acid (PAA) showed a reduction in coefficient of friction by ca. 28% and wear rate by 50% at a concentration of 10 mg/mL in PBS solution compared to polymer-free buffer solution. This effect was comparable to reported lubricating...

  15. Fabrication of conductive polymer nanofibers through SWNT supramolecular functionalization and aqueous solution processing. (United States)

    Naeem, Fahim; Prestayko, Rachel; Saem, Sokunthearath; Nowicki, Lauren; Imit, Mokhtar; Adronov, Alex; Moran-Mirabal, Jose M


    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

  16. Fabrication of conductive polymer nanofibers through SWNT supramolecular functionalization and aqueous solution processing (United States)

    Naeem, Fahim; Prestayko, Rachel; Saem, Sokunthearath; Nowicki, Lauren; Imit, Mokhtar; Adronov, Alex; Moran-Mirabal, Jose M.


    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

  17. Solution-processed parallel tandem polymer solar cells using silver nanowires as intermediate electrode. (United States)

    Guo, Fei; Kubis, Peter; Li, Ning; Przybilla, Thomas; Matt, Gebhard; Stubhan, Tobias; Ameri, Tayebeh; Butz, Benjamin; Spiecker, Erdmann; Forberich, Karen; Brabec, Christoph J


    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.

  18. Chemical solution deposition of YBCO thin film by different polymer additives

    Energy Technology Data Exchange (ETDEWEB)

    Wang, W.T.; Li, G.; Pu, M.H.; Sun, R.P.; Zhou, H.M.; Zhang, Y. [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu 610031 (China); Zhang, H. [Department of Physics, Peking University, Beijing 100871 (China); Yang, Y. [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu 610031 (China); Cheng, C.H. [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu 610031 (China); School of Materials Science and Engineering, University of New South Wale, Sydney, 2052 NSW (Australia); Zhao, Y. [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu 610031 (China); School of Materials Science and Engineering, University of New South Wale, Sydney, 2052 NSW (Australia)], E-mail:


    A polymer-assisted chemical solution deposition approach has been proposed for the preparation of YBCO thin film. Different additives like PVB (polyvinyl butyral), PEG (polyethylene glycol) and PVP (polyvinylpyrrolidone) have been used to adjust the final viscosity of the precursor solution and thus the film formation. In this fluorine-free approach, YBCO has been deposited on single crystal substrates with metal acetates being starting materials. Biaxially textured YBCO thin films have been obtained. However, different additives lead to different microstructure. Dense, smooth and crack-free YBCO film prepared with PVB as additive yields sharp superconducting transition around T{sub c} = 90 K as well as high J{sub c} (0 T, 77 K) over 3 MA/cm{sup 2}.

  19. Chemical solution deposition of YBCO thin film by different polymer additives (United States)

    Wang, W. T.; Li, G.; Pu, M. H.; Sun, R. P.; Zhou, H. M.; Zhang, Y.; Zhang, H.; Yang, Y.; Cheng, C. H.; Zhao, Y.


    A polymer-assisted chemical solution deposition approach has been proposed for the preparation of YBCO thin film. Different additives like PVB (polyvinyl butyral), PEG (polyethylene glycol) and PVP (polyvinylpyrrolidone) have been used to adjust the final viscosity of the precursor solution and thus the film formation. In this fluorine-free approach, YBCO has been deposited on single crystal substrates with metal acetates being starting materials. Biaxially textured YBCO thin films have been obtained. However, different additives lead to different microstructure. Dense, smooth and crack-free YBCO film prepared with PVB as additive yields sharp superconducting transition around Tc = 90 K as well as high Jc (0 T, 77 K) over 3 MA/cm 2.

  20. Study of diffusion in polymer solutions and networks by fluorescence correlation spectroscopy (United States)

    Chehreghanianzabi, Yasaman

    Diffusion in polymer solutions and networks is a topic of vast importance in many fields related to medical devices, tissue engineering, and drug delivery. Understanding diffusion in such environments is also essential for describing molecular transport through biological systems such as cells and tissues. Fluorescence correlation spectroscopy (FCS) is single molecule spectroscopic technique that measures the fluctuations of fluorescent probes in a defined confocal volume and correlates them in time to give information on diffusion times, concentrations, and interactions as well as indirectly, on macromolecular structure or conformation. In the first project we used diffusivity data obtained by FCS to develop a novel homogenization theory model to accurately predict solute diffusivity in polymer solutions. We focused on a setting where diffusivity was hindered by obstruction only. By choosing experimental conditions that satisfied the model assumptions, we were able to validate the homogenization theory model. While testing diffusivity in various polymer solutions, we also observed an unexpected phenomenon--a dramatic decrease in diffusivity of small fluorophores in dilute solutions of polyethylene glycol (PEG), which led to the second project. Here, we determined that the rapid drop was due to a complexation between the PEG and the fluorophore. We also determined that this complexation was highly specific and could be attributed to hydrogel bonding between the ether oxygen of PEG and the carboxylic hydrogen of the fluorophore. We then transitioned to a more complex hydrogel network environment, namely fluorophore diffusivity in various alginate hydrogels--varied by concentration and modifications with a cell adhesive ligand. Importantly, we were able to determine that while the fluorophore diffusivity was hindered due to electrostatic interactions, it was the same irrespective of the alginate concentration or modifications. The last part of this thesis was focused

  1. The corrosion effect of ozonated seawater solution on titanium in polymer generated crevice environments

    Energy Technology Data Exchange (ETDEWEB)

    Leveillee, S.Y.


    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.

  2. Hydrodynamic effects on phase separation morphologies in evaporating thin films of polymer solutions (United States)

    Zoumpouli, Garyfalia A.; Yiantsios, Stergios G.


    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

  3. Viscoelastic rheological property of different types of polymer solutions for enhanced oil recovery

    Institute of Scientific and Technical Information of China (English)

    孟令伟; 康万利; 周阳; 王志伟; 刘述忍; 白宝君


    The capability of hydrophobic association polymer(HAPAM) to displace oil is different from that of hydrolyzed polyacrylamide(HPAM) because they have different rheological properties.The viscoelasticity of five polymers was measured using Physica MCR301 rheometer and was compared.The five polymers include three HAPAMs with relative molecular mass of 1 248×104(TypeⅠ),750×104(TypeⅡ),and 571×104(Type Ⅲ) separately and two HPAMs with relative molecular mass of 1 200×104 and 3 800×104 respectively.The experiment results indicate that the viscoelasticity of HAPAM is better than that of HPAM.The storage modulus G’ and the loss modulus G″ for HAPAM solutions are also larger than those for HPAM.Comparing the rheological curves of different HAPAM types,it is found that the viscosity of typeⅡ and type Ⅲ is almost same at different shear rates while the viscosity of type I is the lower than that of Types Ⅱ and Ⅲ.The storage modulus G’ and the loss modulus G″ for three types of HAPAM were measured in low oscillation frequency range,and the results show that G’ is greater than G″ for all three different types of HAPAM,but their loss modulus is almost same,and the G’ is in the order of type Ⅱ>type Ⅲ>type I.In addition,the G’ and G″ increase with aging time for all three HAPAM solutions were stayed at different days.The viscoelasticity of type Ⅰ reaches the highest value when aging time is 9 d at 45 ℃,but it is 7 d for type Ⅱ and type Ⅲ.The different viscoelasticity properties can be attributed to self-organization supermolecule networks which is formed by hydrophobic association of HAPAM molecular and molecular chain entanglement.


    Directory of Open Access Journals (Sweden)

    A. G. Savvina


    Full Text Available The widespread use of aromatic acids (benzoic acid, salicylic as preservatives necessitates their qualitative and quantitative determination in food. Effective and common way to separation and concentration of aromatic acids liquid extraction. Biphasic system of water-soluble polymers based on (poly-N-vinyl pyrrolidone, and poly-N-vinylcaprolactam satisfy the requirements of the extraction system. When sorption concentration improved definition of the metrological characteristics, comply with the requirements for sensitivity and selectivity definition appears possible, use of inexpensive and readily available analytical equipment. When studying the adsorption of benzoic acid used as a sorbent crosslinked polymer based on N-vinyl pyrrolidone, obtained by radical polymerisation of a functional monomer and crosslinker. In the extraction of benzoic acid to maximize the allocation of water and the organic phase of the polymer used salt solutions with concentrations close to saturation. Regardless of the nature of the anion salt is used as salting-out agent, aromatic acids sorption increases with the size of the cations. In the experiment the maximum recovery rate (80% benzoic acid obtained in the PVP (0.2 weight%. Ammonium sulphate. The dependence stepepni benzoic acid extraction from time sorption sorbent mass and the pH of the aqueous phase. To establish equilibrium in the system, for 20 minutes. The dependence of the degree of extraction of the acid pH indicates that the acid is extracted into the molecular form. The maximum adsorption is reached at pH 3,5, with its efficiency decreases symbatically reduce the amount of undissociated acid molecules in solution.

  5. Recent Advances in Characterization of Lignin Polymer by Solution-State Nuclear Magnetic Resonance (NMR Methodology

    Directory of Open Access Journals (Sweden)

    Run-Cang Sun


    Full Text Available The demand for efficient utilization of biomass induces a detailed analysis of the fundamental chemical structures of biomass, especially the complex structures of lignin polymers, which have long been recognized for their negative impact on biorefinery. Traditionally, it has been attempted to reveal the complicated and heterogeneous structure of lignin by a series of chemical analyses, such as thioacidolysis (TA, nitrobenzene oxidation (NBO, and derivatization followed by reductive cleavage (DFRC. Recent advances in nuclear magnetic resonance (NMR technology undoubtedly have made solution-state NMR become the most widely used technique in structural characterization of lignin due to its versatility in illustrating structural features and structural transformations of lignin polymers. As one of the most promising diagnostic tools, NMR provides unambiguous evidence for specific structures as well as quantitative structural information. The recent advances in two-dimensional solution-state NMR techniques for structural analysis of lignin in isolated and whole cell wall states (in situ, as well as their applications are reviewed.


    Institute of Scientific and Technical Information of China (English)

    Jun-fang Li; Yi-jie Lu; Guang-zhao Zhang; Wei Li; Chi Wu


    Dust-free semidilute and concentrated polystyrene (PS) solutions in different solvents were prepared by slow evaporation and in situ anionic polymerization, which removes the effects of troublesome artifacts such as dust contamination and concentration gradient. The dynamics was reexamined by a combination of static and dynamic laser light scattering. In benzene and toluene (good solvents for PS), only one fast diffusive mode of polymer chains can be observed when the concentration (c) is up to 20%, which is attributed to thermally agitated fluctuation of "blobs" or chain segments.Static and dynamic correlation lengths (ξS and ξD) are scaled with c as ξSS(or ξD)~c-0.72±0.02. In cyclohexane, whose quality decreases with temperature in the range 32-50℃, an additional slow mode of polymer chains can be observed. Such a slow mode is viewed more obviously at a large scattering angle even in a concentrated solution with high chain entanglement. The present study indicates that the slow mode is due to the solvent quality.

  7. Pore scale mixing and macroscopic solute dispersion regimes in polymer flows inside 2D model networks

    CERN Document Server

    D'Angelo, M V; Allain, C; Hulin, J P; Angelo, Maria Veronica D'; Auradou, Harold; Allain, Catherine; Hulin, Jean-Pierre


    A change of solute dispersion regime with the flow velocity has been studied both at the macroscopic and pore scales in a transparent array of capillary channels using an optical technique allowing for simultaneous local and global concentration mappings. Two solutions of different polymer concentrations (500 and 1000 ppm) have been used at different P\\'eclet numbers. At the macroscopic scale, the displacement front displays a diffusive spreading: for $Pe \\leq 10$, the dispersivity $l\\_d$ is constant with $Pe$ and increases with the polymer concentration; for $Pe > 10$, $l\\_d$ increases as $Pe^{1.35}$ and is similar for the two concentrations. At the local scale, a time lag between the saturations of channels parallel and perpendicular to the mean flow has been observed and studied as a function of the flow rate. These local measurements suggest that the change of dispersion regime is related to variations of the degree of mixing at the junctions. For $Pe \\leq 10$, complete mixing leads to pure geometrical di...

  8. Visualization of TCE recovery mechanisms using surfactant-polymer solutions in a two-dimensional heterogeneous sand model. (United States)

    Robert, Thomas; Martel, Richard; Conrad, Stephen H; Lefebvre, René; Gabriel, Uta


    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.

  9. Polymer fractionation

    Energy Technology Data Exchange (ETDEWEB)

    Hadermann, A. F.


    Soluble polymers are fractionated according to molecular weight by cryogenically comminuting the polymer and introducing the polymer particles, while still in the active state induced by cryogenic grinding, into a liquid having a solvent power selected to produce a coacervate fraction containing high molecular weight polymer species and a dilute polymer solution containing lower molecular weight polymer species. The coacervate may be physically separated from the solution and finds use in the production of antimisting jet fuels and the like.

  10. Controlling solution-phase polymer aggregation with molecular weight and solvent additives to optimize polymer-fullerene bulk heterojunction solar cells

    KAUST Repository

    Bartelt, Jonathan A.


    The bulk heterojunction (BHJ) solar cell performance of many polymers depends on the polymer molecular weight (M n) and the solvent additive(s) used for solution processing. However, the mechanism that causes these dependencies is not well understood. This work determines how M n and solvent additives affect the performance of BHJ solar cells made with the polymer poly(di(2-ethylhexyloxy)benzo[1,2-b:4,5-b\\']dithiophene-co- octylthieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD). Low M n PBDTTPD devices have exceedingly large fullerene-rich domains, which cause extensive charge-carrier recombination. Increasing the M n of PBDTTPD decreases the size of these domains and significantly improves device performance. PBDTTPD aggregation in solution affects the size of the fullerene-rich domains and this effect is linked to the dependency of PBDTTPD solubility on M n. Due to its poor solubility high M n PBDTTPD quickly forms a fibrillar polymer network during spin-casting and this network acts as a template that prevents large-scale phase separation. Furthermore, processing low M n PBDTTPD devices with a solvent additive improves device performance by inducing polymer aggregation in solution and preventing large fullerene-rich domains from forming. These findings highlight that polymer aggregation in solution plays a significant role in determining the morphology and performance of BHJ solar cells. The performance of poly(di(2-ethylhexyloxy) benzo[1,2-b:4,5-b\\']dithiophene-co-octylthieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) bulk heterojunction solar cells strongly depends on the polymer molecular weight, and processing these bulk heterojunctions with a solvent additive preferentially improves the performance of low molecular weight devices. It is demonstrated that polymer aggregation in solution significantly impacts the thin-film bulk heterojunction morphology and is vital for high device performance. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Interaction of derived polymers from pyrrole with biocompatible solutions; Interaccion de polimeros derivados de pirrol con soluciones biocompatibles

    Energy Technology Data Exchange (ETDEWEB)

    Lopez G, O. G.


    This work presents a study about the synthesis by plasma, the electric properties and superficial interaction of polymers derived from pyrrole doped with Iodine with potential use as bio material. Poly-pyrrole is a semiconductor and biocompatible polymer with potential application in the development of artificial muscles and implants where the electric interaction between cells and material is an important variable. The syntheses were made at 13.5 MHz in a glass tubular reactor of 1500 cm{sup 3} with electrodes of 6.5 cm diameter and stainless steel flanges. An electrode was connected to the RF terminal of the power supply that is combined with a matching coupling resistance. The monomer and dopant used in this work were pyrrole and Iodine respectively, in closed containers. They were vaporized and injected separately into the reactor at room temperature and 0.1 mbar. The vapors of the reagents mixed freely in the reactor. The synthesis time was 240 min at 40, 60, 80 and 100 W. The polymers were obtained as thin films adhered to the reactor walls. The films were washed and swollen with distilled water and removed from the reactor walls with a small spatula. The polymers were irradiated with gamma rays at 18 and 22 KGy. Due to the fact that the doses are cumulative, the final dose applied was 40 KGy. The polymers characterization was carried out by Fourier Transform Infrared Spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy, contact angle, electrical conductivity and X-ray diffraction. The analyses indicates that the polymers have very similar structure in almost the entire power range, showing C-O, C=C, C-H, O-H, N-H bonds with a predominantly amorphous structure. The TGA analyses showed that the material has 4 or 5 loses of material. The first one starts after that 115 C except for the material irradiated at 40 KGy, this one begins in 87 C, the second one is in the interval of 196 and 295 C, the third one between 311 and 500 C, and the

  12. Solvent-dependent self-assembly and ordering in slow-drying semi-crystalline conjugated polymer solutions

    KAUST Repository

    Zhao, Kui


    The mechanistic understanding of the intrinsic molecular self-assembly of conjugated polymers is of immense importance to controlling the microstructure development in organic semiconducting thin films, with meaningful impact on charge transport and optoelectronic properties. Yet, to date the vast majority of studies have focused on the fast solution process itself, with studies of slower intrinsic molecular self-assembly in formulations lagging behind. Here we have investigated molecular self-assembly during spontaneous organization and uncovered how changes in formulation influence the microstructure, morphology and transport properties of conjugated polymer thin films. Our results suggest that the polymer-solvent interaction is the key factor for the molecular self-assembly and changes in macroscopic charge transport, which is in contrast with most solution processes, such as spin-coating and blade coating, where solvent drying kinetics dominates the aggregation and crystallization processes. Energetically favourable interactions between the polymer and its solvent are shown to cause chain expansion, resulting in a large hydrodynamic volume and few chain entanglements in solution. This provides molecular freedom for self-assembly and is shown to greatly enhance the local and long range order of the polymer, intra-chain backbone planarity and crystallite size. These improvements, in turn, are shown to endow the conjugated polymer with high carrier transport, as demonstrated by organic thin film transistors.

  13. Inclusion of mPRISM potential for polymer-induced protein interactions enables modeling of second osmotic virial coefficients in aqueous polymer-salt solutions. (United States)

    Herhut, Marcel; Brandenbusch, Christoph; Sadowski, Gabriele


    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.

  14. Investigation into Degradation Property of Methyl Orange Solution by Fe-based Amorphous Powder%铁基非晶粉末对甲基橙溶液降解性能的影响

    Institute of Scientific and Technical Information of China (English)

    袁亚东; 彭程; 李维火; 方斌


    对铁基非晶粉末(Fe73.5Si13.5B9Nb3Cu1)进行等温退火和球磨处理,获得球磨的非晶粉末和球磨的退火非晶粉末。分析铁粉和3种非晶粉末对甲基橙溶液的降解率,研究铁基非晶粉末降解甲基橙溶液的能力,考察温度、溶液初始pH值、粉末投加量对铁基非晶粉末降解甲基橙溶液的影响。结果表明:与铁粉、球磨的非晶粉末和球磨的退火非晶粉末相比,铁基非晶粉末对甲基橙溶液的降解效果更好,质量浓度为10 mg/L的甲基橙溶液的降解率在23 h内可达97%;温度升高、甲基橙溶液初始pH值降低均有利于提高铁基非晶粉末对甲基橙溶液的降解率;粉末投加量对铁基非晶粉末降解甲基橙溶液有较大影响,本实验最佳铁基非晶粉末投加量为0.30 g(4.29 mg/mL),当粉末投加量增加为0.70 g(10 mg/mL)时,降解率下降。%Ball-milled amorphous powder and ball-milled annealed amorphous powder were obtained from Fe73.5Si13.5B9Nb3Cu1 amorphous powder, which were treated by isothermal anneal and ball milling. Comparing the degradation rates of iron powder and the 3 kinds of amorphous powder to methyl orange solution, the degradation property of methyl orange solution by Fe-based amorphous powder (Fe73.5Si13.5B9Nb3Cu1) was studied, and the effects of reaction temperature, initial pH value of methyl orange solution and powder dosage on methyl orange solution by Fe-based amorphous powder were also investigated. The results indicate that the Fe-based amorphous powder performs better on the degradation of methyl orange solution compared with iron powder, ball-milled amorphous powder and ball-milled annealed amorphous powder, which can degrade 10 mg/L methyl orange solution near 97% within 23 h; higher temperature and lower pH value of methyl orange solution lead to the increase of degradation efficiency of methyl orange solution. The amount of Fe-based amorphous powder has a significant influence on

  15. A novel polymer inclusion membrane applied in chromium (VI) separation from aqueous solutions. (United States)

    Gherasim, Cristina-Veronica; Bourceanu, Gelu; Olariu, Romeo-Iulian; Arsene, Cecilia


    In the present work, we analyze the transport properties of a novel polymer inclusion membrane (PIM) containing a poly-vinyl chloride (PVC) polymer matrix and the organic anion exchanger Aliquat 336 as a specific carrier, without addition of plasticizers. The study was specifically focused on the transport properties of Cr(VI) in conditions simulating industrial wastewaters. We analyzed the impact of several parameters on the Cr(VI) transport process such as: the carrier content of the PIM, the pH, and the phases' composition. We concluded that efficient transport processes occur through a PIM containing 40% Aliquat 336/60% PVC (w/w). The process is very fast and efficient for solutions of initial Cr(VI) concentration smaller than 10(-3)mol/L, in which nearly all of Cr(VI) is removed within 3h. The performed experiments prove that Cr(VI) transport through the membrane is a facilitated counter-transport process. The obtained results sustain that this novel non-plasticized membrane possesses enhanced transport properties towards other liquid membranes and plasticized PIMs previously reported as used for Cr(VI) transport. Additionally, it possesses an excellent reliability and a high selectivity for Cr(VI) from mixtures with other metal ions and anions existing in the real industrial effluents. The PIM characterization highlights the plasticizing role of the carrier Aliquat 336.

  16. Mimicking conjugated polymer thin-film photophysics with a well-defined triblock copolymer in solution. (United States)

    Brazard, Johanna; Ono, Robert J; Bielawski, Christopher W; Barbara, Paul F; Vanden Bout, David A


    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.

  17. Removal of anionic azo dyes from aqueous solution by functional ionic liquid cross-linked polymer

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Hejun [Key Laboratory of Colloid and Interface Chemistry, Shandong University, Ministry of Education, Jinan 250100 (China); Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, China West Normal University, Nanchong 637000 (China); Kan, Taotao [CNOOC Energy Technology and Services-oilfield Technology Services Co., Tanggu, Tianjin 300452 (China); Zhao, Siyuan; Qian, Yixia; Cheng, Xiyuan; Wu, Wenli [School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China); Wang, Xiaodong [Shandong Provincial Analysis and Test Center, Jinan 250100 (China); Zheng, Liqiang, E-mail: [Key Laboratory of Colloid and Interface Chemistry, Shandong University, Ministry of Education, Jinan 250100 (China)


    Highlights: • Equilibrium, kinetic and thermodynamic of adsorption of dyes onto PDVB-IL was investigated. • PDVB-IL has a high adsorption capacity to treat dyes solution. • Higher adsorption capacity is due to the functional groups of PDVB-IL. • Molecular structure of dyes influences the adsorption capacity. -- Abstract: 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.

  18. Size-exclusion partitioning of neutral solutes in crosslinked polymer networks: A Monte Carlo simulation study

    Energy Technology Data Exchange (ETDEWEB)

    Quesada-Pérez, Manuel; Maroto-Centeno, José Alberto [Departamento de Física, Escuela Politécnica Superior de Linares, Universidad de Jaén, 23700 Linares, Jaén (Spain); Adroher-Benítez, Irene [Grupo de Física de Fluidos y Biocoloides, Departamento de Física Aplicada, Facultad de Ciencias, Universidad de Granada, 18071 Granada (Spain)


    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.

  19. Tuning the Microcavity of Organic Light Emitting Diodes by Solution Processable Polymer-Nanoparticle Composite Layers. (United States)

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


    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.

  20. A simple derivation of the critical condition for the ultrasonic atomization of polymer solutions. (United States)

    Kim, Hyungsu; Lee, Jaegeun; Won, You-Yeon


    A simple model is proposed for the ultrasonic atomization of polymer solutions. In this model, the atomization process is approximated as an equilibrium process. It is shown that the minimum attainable droplet size is determined by two parameters, the (Rayleigh) acoustic pressure acting on the surface of the liquid, and the surface tension of the liquid. Increasing the viscosity of the liquid suppresses the formation of small-sized droplets because of increased attenuation of the sound wave and thus decreased acoustic pressure. Lowering the surface tension of the liquid (e.g., by spreading a surfactant film on the liquid surface) has the opposite effect of enhancing the formation of smaller droplets. Also, there exists a maximum limit for the droplet size, because when the produced droplet is too large, the aspiration flow is unable to carry the droplet against sedimentation. These predictions are supported by experimental observations.

  1. Modelling of solid polymer and direct methanol fuel cells: Phenomenological equations and analytical solutions (United States)

    Kauranen, P. S.


    In the solid state concept of a direct methanol fuel cell (DMFC), methanol is directly oxidized at the anode of a solid polymer electrolyte fuel cell (SPEFC). Mathematical modelling of the transport and reaction phenomena within the electrodes and the electrolyte membrane is needed in order to get a closer insight into the operation of the fuel cell. In the work, macro-homogenous porous electrode and dilute solution theories are used to derive the phenomenological equations describing the transport and reaction mechanisms in a SPEFC single cell. The equations are first derived for a conventional H2/air SPEFC, and then extended for a DMFC. The basic model is derived in a one dimensional form in which it is assumed that species transport take place only in the direction crossing the cell sandwich. In addition, two dimensional descriptions of the catalyst layer are reviewed.

  2. Viscoelasticity and nonlinear simple shear flow behavior of an entangled asymmetric exact comb polymer solution

    KAUST Repository

    Snijkers, F.


    We report upon the characterization of the steady-state shear stresses and first normal stress differences as a function of shear rate using mechanical rheometry (both with a standard cone and plate and with a cone partitioned plate) and optical rheometry (with a flow-birefringence setup) of an entangled solution of asymmetric exact combs. The combs are polybutadienes (1,4-addition) consisting of an H-skeleton with an additional off-center branch on the backbone. We chose to investigate a solution in order to obtain reliable nonlinear shear data in overlapping dynamic regions with the two different techniques. The transient measurements obtained by cone partitioned plate indicated the appearance of overshoots in both the shear stress and the first normal stress difference during start-up shear flow. Interestingly, the overshoots in the start-up normal stress difference started to occur only at rates above the inverse stretch time of the backbone, when the stretch time of the backbone was estimated in analogy with linear chains including the effects of dynamic dilution of the branches but neglecting the effects of branch point friction, in excellent agreement with the situation for linear polymers. Flow-birefringence measurements were performed in a Couette geometry, and the extracted steady-state shear and first normal stress differences were found to agree well with the mechanical data, but were limited to relatively low rates below the inverse stretch time of the backbone. Finally, the steady-state properties were found to be in good agreement with model predictions based on a nonlinear multimode tube model developed for linear polymers when the branches are treated as solvent.

  3. Threshold-like complexation of conjugated polymers with small molecule acceptors in solution within the neighbor-effect model. (United States)

    Sosorev, Andrey Yu; Parashchuk, Olga D; Zapunidi, Sergey A; Kashtanov, Grigoriy S; Golovnin, Ilya V; Kommanaboyina, Srikanth; Perepichka, Igor F; Paraschuk, Dmitry Yu


    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.

  4. One-Dimensional Modelling of Polymer Flood Performance. Analytical and Graphical Solutions Modélisation de l'efficacité du déplacement unidimensionnel par injection de polymères. Solutions analytiques et graphiques

    Directory of Open Access Journals (Sweden)

    Grattoni C. A.


    Full Text Available A graphical method for simulating linear polymer flooding is proposed. The method is based upon the analytical solution of Darcy's law and continuity equation which describe the two-phase, one-dimensional, incompressible flow of oil and polymer solution through the reservoir rock. Continuous polymer injection and polymer slug injection are considered. Several physical mechanisms determining microscopic displacement efficiency are taken into account: resistance factor, residual resistance factor, retention composed by adsorption and mechanical entrapment, and inaccessible pore volume. Other properties are not considered: mixing and dispersion, shear and thermal degradation. This analytical-graphical model closely reproduces linear laboratory oil displacement experiments. Consequently, it can be used by the Field Engineer to rapidly estimate the additional oil recoverable by a linear polymer flood. On propose dans cet article une méthode graphique de simulation de l'injection de polymères dans le cas unidimensionnel. Cette méthode est basée sur la solution analytique de la loi de Darcy et de l'équation de continuité qui décrivent l'écoulement diphasique incompressible unidimen-sionnel d'huile et d'une solution de polymères à travers la roche réservoir. On examine l'injection continue et l'injection de bouchons de polymères. On prend en compte plusieurs mécanismes physiques qui déterminent l'efficacité du déplacement microscopique : facteur de ré-sistance, facteur de résistance résiduel, rétention due à l'adsorption et au piégeage mécanique et, enfin, volume des pores inacessibles. On ne tient pas compte des autres propriétés : mélange et dispersion, dégradation mécanique et thermique. Ce modèle analytique et graphique reproduit très directement les expériences de laboratoire de déplacement d'huile en milieu unidimensionnel. II peut donc être utilisé par l'ingénieur de chantier pour une estimation rapide de l

  5. All-Solution-Processed, Ambient Method for ITO-Free, Roll-Coated Tandem Polymer Solar Cells using Solution- Processed Metal Films

    DEFF Research Database (Denmark)

    Angmo, Dechan; Dam, Henrik Friis; Andersen, Thomas Rieks;


    A solution-processed silver film is employed in the processing of top-illuminated indium-tin-oxide (ITO)-free polymer solar cells in single- and double-junction (tandem) structures. The nontransparent silver film fully covers the substrate and serves as the bottom electrode whereas a PEDOT......-effective in comparison to other reported metal films applied in polymer solar cells. Such properties result in high fill factors exceeding 50% in both single and tandem structures on large-area devices (1 cm2) and the corresponding efficiencies exceed 2%....

  6. A light review on Polymer and CO2 Flooding (With Suggestion Combination of CO2 into Polymer Solution to Superior Flooding

    Directory of Open Access Journals (Sweden)

    O. Arjmand


    Full Text Available Today carbon dioxide (CO2 is one of displacing fluids that is used in Enhanced Oil Recovery (EOR process. However the low viscosity of CO2 causes it to finger towards the production well and bypassed large amounts of oil. Because of during flooding of CO2 its mobility is very less than crude oil into reservoir that causes to leave a great amount of oil, so a reduction in CO2 mobility would be inclined to mitigate. We in this review study state that could increase CO2 viscosity with dissolving it into polymer solution, that it can delay breakthrough time of CO2 during EOR process. In addition with making of such solution can decrease oil viscosity during flooding process into reservoir simultaneously. In actual with mixing of CO2 gas at high pressure into Partial Hydrolyzed Polyacrylamide solution (HPAM as an anionic polymer can increase the viscosity of CO2 with a concentration optimum of polymer and improve the sweep efficiency of oil during EOR process using this method.

  7. Analysis of amorphous solid dispersions using 2D solid-state NMR and (1)H T(1) relaxation measurements. (United States)

    Pham, Tran N; Watson, Simon A; Edwards, Andrew J; Chavda, Manisha; Clawson, Jacalyn S; Strohmeier, Mark; Vogt, Frederick G


    Solid-state NMR (SSNMR) can provide detailed structural information about amorphous solid dispersions of pharmaceutical small molecules. In this study, the ability of SSNMR experiments based on dipolar correlation, spin diffusion, and relaxation measurements to characterize the structure of solid dispersions is explored. Observation of spin diffusion effects using the 2D (1)H-(13)C cross-polarization heteronuclear correlation (CP-HETCOR) experiment is shown to be a useful probe of association between the amorphous drug and polymer that is capable of directly proving glass solution formation. Dispersions of acetaminophen and indomethacin in different polymers are examined using this approach, as well as (1)H double-quantum correlation experiments to probe additional structural features. (1)H-(19)F CP-HETCOR serves a similar role for fluorinated drug molecules such as diflunisal in dispersions, providing a rapid means to prove the formation of a glass solution. Phase separation is detected using (13)C, (19)F, and (23)Na-detected (1)H T(1) experiments in crystalline and amorphous solid dispersions that contain small domains. (1)H T(1) measurements of amorphous nanosuspensions of trehalose and dextran illustrate the ability of SSNMR to detect domain size effects in dispersions that are not glass solutions via spin diffusion effects. Two previously unreported amorphous solid dispersions involving up to three components and containing voriconazole and telithromycin are analyzed using these experiments to demonstrate the general applicability of the approach.

  8. Effect of crystallization on corrosion behavior of Fe40Ni38B18Mo4 amorphous alloy in 3.5% sodium chloride solution

    DEFF Research Database (Denmark)

    Wu, Y.F.; Chiang, Wen-Chi; Wu, J.K.


    After the crystallization of F40Ni38B18Mo4 amorphous alloy by vacuum annealing, the corrosion resistance of its crystalline state shows inferior to its amorphous state due to the local cell action between Ni phase and (Fe, Ni, Mo)(23)B-6 phase in matrix....

  9. Determine the permeability of an amorphous mixture of polydimethylsiloxane and dealuminated zeolite ZSM-5 to various ethanol-water solutions using molecular simulations. (United States)

    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...

  10. Investigation of optical spacer layers from solution based precursors for polymer solar cells using X-ray reflectometry

    DEFF Research Database (Denmark)

    Andersen, Philip Hvidthøft Delff; Skårhøj, Jakob; Andreasen, Jens Wenzel


    Optical spacer layers based on titaniumalkoxide precursor solutions were prepared by spin-coating on top of bulk heterojunction layers based on poly-3-hexylthiophene (P3HT) and phenyl-C61-butyric acid methylester (PCBM). Models and experiment have shown that the performance of polymer solar cells...

  11. Removal of chromium(VI) from aqueous solutions by polymer inclusion membranes. (United States)

    Kozlowski, Cezary A; Walkowiak, Wladyslaw


    The transport through polymer inclusion membranes (PIMs) was found as the effective and selective method of chromium(VI) anions removal from chloride acidic aqueous solutions. The optimal PIMs content was as follows: 41 wt% of cellulose triacetate as the support, 23 wt% of tri-n-octylamine as the ionic carrier, and 36 wt% of o-nitrophenyl pentyl ether as the plasticizer. The results obtained show a linear decrease of permeability coefficient and initial flux values with source phase pH increase. Also linear decrease of initial flux in log-log scale with chromium(VI) concentration increase was observed. Value of slope of this relationship was found to be 0.96 which indicates a first order of chromium(VI) reaction with tri-n-octylamine at membrane/aqueous source interface. Transport of chromium(VI) through PIMs reduces the concentration of chromium(VI) in source aqueous phase from 1.0 to 0.0028 ppm, which is below permissible limit in drinking water in Poland. Competitive transport of chromium(VI), cadmium(II), zinc(II), and iron(III) from acidic aqueous solution across PIMs was found to be efficient for chromium(VI) (99%), and cadmium(II) (99%).

  12. Dual Function Behavior of Carbon Fiber-Reinforced Polymer in Simulated Pore Solution

    Directory of Open Access Journals (Sweden)

    Ji-Hua Zhu


    Full Text Available The mechanical and electrochemical performance of carbon fiber-reinforced polymer (CFRP were investigated regarding a novel improvement in the load-carrying capacity and durability of reinforced concrete structures by adopting CFRP as both a structural strengthener and an anode of the impressed current cathodic protection (ICCP system. The mechanical and anode performance of CFRP were investigated in an aqueous pore solution in which the electrolytes were available to the anode in a cured concrete structure. Accelerated polarization tests were designed with different test durations and various levels of applied currents in accordance with the international standard. The CFRP specimens were mechanically characterized after polarization. The measured feeding voltage and potential during the test period indicates CFRP have stable anode performance in a simulated pore solution. Two failure modes were observed through tensile testing. The tensile properties of the post-polarization CFRP specimens declined with an increased charge density. The CFRP demonstrated success as a structural strengthener and ICCP anode. We propose a mathematic model predicting the tensile strengths of CFRP with varied impressed charge densities.


    Institute of Scientific and Technical Information of China (English)

    LIU Zhong-chun; YUE Xiang-an; HOU Ji-rui; ZHANG Li-juan


    The flow performances of water, white oil and Hydrolyzing Polyacrylamide (HPAM) solution in fused quartz channels and the effect of wettability on the microscale flows have been studied respectively in this paper. The adaptability of classical fluid mechanics in channels with different sizes has been discussed. The results show that water flows in channels of 2μm diameter also have few size effects and white oil flow accord with classical fluid mechanics theory in channels of 25μm diameter too, but polymer solution appears an obvious size effect as diameters of channels decrease to 16μm. The wettability does not produce any influences on the water or white oil flows in channels of 25μm or 50μm diameter. The experimental technology of microscale flows has been first applied for studying the flow performances of pores in low permeability reservoir. This study found a base for deep investigating the percolation mechanism in low permeability reservoirs.

  14. Amorphous solid dispersions: a robust platform to address bioavailability challenges. (United States)

    Newman, Ann; Nagapudi, Karthik; Wenslow, Robert


    Amorphous solid dispersions (ASDs) are being used with increasing frequency for poorly soluble pharmaceutical compounds in development. These systems consist of an amorphous active pharmaceutical ingredient stabilized by a polymer to produce a system with improved physical and solution stability. ASDs are commonly considered as a means of improving the apparent solubility of an active pharmaceutical ingredient. This review will discuss methods of preparation and characterization of ASDs with an emphasis on understanding and predicting stability. Theoretical understanding of supersaturation and predicting in vivo performance will be stressed. Additionally, a summary of preclinical and clinical development efforts will be presented to give the reader an understanding of risks and key pitfalls when developing an ASD.

  15. Solution-phase laser processing of π-conjugated polymers: Switching between different molecular states (United States)

    Takada, K.; Tomioka, A.


    Liquid-phase laser processing, where the laser-irradiated target material is immersed in water for cooling, has been reported as a promising processing technique for thermally fragile organic materials. Although nanometer-sized particles have been reported to be obtained with the liquid-phase laser processing, the physical property did not change because quantum-mechanical size effect does not exhibit itself in the zero-radius Frenkel excitons. In the present study, we step further to use solution droplets as a target material, where organic molecules are molecularly dispersed in organic solvent and, therefore, expected to easily alter the conformation and the energy state upon laser irradiation. Small volume organic solvent is quickly evaporated upon laser irradiation, letting the bare organic molecule placed in water and rapidly cooled. To prevent the chemical decomposition of the target π-conjugated molecule, the specimen was resonantly irradiated by a ns-pulse green laser, not by a conventional UV laser. When the solid state spin-coat film made from MEH-PPV chloroform solution was used as a irradiation target immersed in water, resulting MEH-PPV particles showed similar photoluminescence (PL) like the PL of the spin-coat film and PL of the chloroform solution, including the 0→1, 0→2 vibrational transitions: this indicates that the energy levels were not modified from the spin-coat film. In comparison, when tiny droplets of MEH-PPV chloroform solution (orange color) were suspended in water, laser irradiation gave rise to yellow MEH-PPV particles which showed 550 nm and 530 nm PL (type B), blue-shifted from the spin-coat film PL 580 nm (type A), suggesting a successful phase transition of MEH-PPV polymer to type B. Further solution-phase laser processing left the type B state unchanged. The irreversible phase transition from type A to type B suggests that the type B ground state has lower energy than type A, which is consistent with the blue-shifted PL of

  16. Influence of the cooling rate and the blend ratio on the physical stability of co-amorphous naproxen/indomethacin. (United States)

    Beyer, Andreas; Grohganz, Holger; Löbmann, Korbinian; Rades, Thomas; Leopold, Claudia S


    Co-amorphization represents a promising approach to increase the physical stability and dissolution rate of amorphous active pharmaceutical ingredients (APIs) as an alternative to polymer glass solutions. For amorphous and co-amorphous systems, it is reported that the preparation method and the blend ratio play major roles with regard to the resulting physical stability. Therefore, in the present study, co-amorphous naproxen-indomethacin (NAP/IND) was prepared by melt-quenching at three different cooling rates and at ten different NAP/IND blend ratios. The samples were analyzed using XRPD and FTIR, both directly after preparation and during storage to investigate their physical stabilities. All cooling methods led to fully amorphous samples, but with significantly different physical stabilities. Samples prepared by fast cooling had a higher degree of crystallinity after 300d of storage than samples prepared by intermediate cooling and slow cooling. Intermediate cooling was subsequently used to prepare co-amorphous NAP/IND at different blend ratios. In a previous study, it was postulated that the equimolar (0.5:0.5) co-amorphous blend of NAP/IND is most stable. However, in the present study the physically most stable blend was found for a NAP/IND ratio of 0.6:0.4, which also represents the eutectic composition of the crystalline NAP/γ-IND system. This indicates that the eutectic point may be of major importance for the stability of binary co-amorphous systems. Slight deviations from the optimal naproxen molar fraction led to significant recrystallization during storage. Either naproxen or γ-indomethacin recrystallized until a naproxen molar fraction of about 0.6 in the residual co-amorphous phase was reached again. In conclusion, the physical stability of co-amorphous NAP/IND may be significantly improved, if suitable preparation conditions and the optimal phase composition are chosen.

  17. In-line monitoring of compaction properties on a rotary tablet press during tablet manufacturing of hot-melt extruded amorphous solid dispersions. (United States)

    Grymonpré, W; Verstraete, G; Van Bockstal, P J; Van Renterghem, J; Rombouts, P; De Beer, T; Remon, J P; Vervaet, C


    As the number of applications for polymers in pharmaceutical development is increasing, there is need for fundamental understanding on how such compounds behave during tableting. This research is focussed on the tableting behaviour of amorphous polymers, their solid dispersions and the impact of hot-melt extrusion on the compaction properties of these materials. Soluplus, Kollidon VA 64 and Eudragit EPO were selected as amorphous polymers since these are widely studied carriers for solid dispersions, while Celecoxib was chosen as BCS class II model drug. Neat polymers and physical mixtures (up to 35% drug load) were processed by hot-melt extrusion (HME), milled and sieved to obtain powders with comparable particle sizes as the neat polymer. A novel approach was used for in-line analysis of the compaction properties on a rotary tablet press (Modul P, GEA) using complementary sensors and software (CDAAS, GEA). By combining 'in-die' and 'out-of-die' techniques, it was possible to investigate in a comprehensive way the impact of HME on the tableting behaviour of amorphous polymers and their formulations. The formation of stable glassy solutions altered the formulations towards more fragmentary behaviour under compression which was beneficial for the tabletability. Principal component analysis (PCA) was applied to summarize the behaviour during compaction of the formulations, enabling the selection of Soluplus and Kollidon VA 64 as the most favourable polymers for compaction of glassy solutions.

  18. Solubility Advantage (and Disadvantage) of Pharmaceutical Amorphous Solid Dispersions. (United States)

    Huang, Siyuan; Mao, Chen; Williams, Robert O; Yang, Chia-Yi


    The solubility of a drug is ultimately governed by its chemical potential as it is present in the undissolved solute. For a pharmaceutical amorphous solid dispersion (ASD), its solubility depends on the state and composition of the undissolved solute when the ASD is equilibrated with water. Concerning the undissolved solute phase that can contain up to 3 components (drug, polymer, and water), we developed a complete thermodynamic model to calculate the chemical potential of a drug in the multicomponent, amorphous system. This approach enables the estimation of the true solubility advantage of ASD from calorimetric measurements and moisture sorption isotherms. Both theoretical estimation and experimental studies, using indomethacin (IMC)/Eudragit E ASD systems, show that the solubility advantage of the amorphous IMC is significantly reduced through ASD formation and water partitioning. For the ASD with 70% drug loading, the solubility of IMC is lower than its crystalline counterpart. Our results show that stabilization through the ASD formation and water sorption can be manifested by the lowering of drug solubility; they demonstrate that the core property in ASD development is the drug chemical potential, which is essentially the thermodynamic driving force and can be quantitated using the model presented in this work.

  19. Separation and quantification of viral double-stranded RNA fragments by capillary electrophoresis in hydroxyethylcellulose polymer solutions. (United States)

    Shambaugh, C L; Bodmer, J L; Hsu, D; Ranucci, C S


    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.

  20. Solution-processed low dimensional nanomaterials with self-assembled polymers for flexible photo-electronic devices (Presentation Recording) (United States)

    Park, Cheolmin


    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.

  1. Polymer electronics

    CERN Document Server

    Hsin-Fei, Meng


    Polymer semiconductor is the only semiconductor that can be processed in solution. Electronics made by these flexible materials have many advantages such as large-area solution process, low cost, and high performance. Researchers and companies are increasingly dedicating time and money in polymer electronics. This book focuses on the fundamental materials and device physics of polymer electronics. It describes polymer light-emitting diodes, polymer field-effect transistors, organic vertical transistors, polymer solar cells, and many applications based on polymer electronics. The book also disc

  2. A simple experiment to determine the activation energy of the viscous flow of polymer solutions using a glass capillary viscometer (United States)

    Rohindra, D. R.; Lata, R. A.; Coll, R. K.


    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.

  3. Orientation and Relaxation of Polymer-clay Solutions Studied by Rheology and Small-angle Neutron Scattering

    Energy Technology Data Exchange (ETDEWEB)

    Malwitz, M. M. [Louisiana State University; Butler, Paul D [ORNL; Porcar, L. [National Institute of Standards and Technology (NIST); Angelette, D. P. [Louisiana State University; Schmidt, G. [National Institute of Standards and Technology (NIST)


    The influence of shear on viscoelastic solutions of poly(ethylene oxide) (PEO) and clay [montmorillonite, i.e., Cloisite NA+ (CNA)] was investigated with rheology and small-angle neutron scattering (SANS). The steady-state viscosity and SANS were used to measure the shear-induced orientation and relaxation of the polymer and clay platelets. Anisotropic scattering patterns developed at much lower shear rates than in pure clay solutions. The scattering anisotropy saturated at low shear rates, and the CNA clay platelets aligned with the flow, with the surface normal parallel to the gradient direction. The cessation of shear led to partial and slow randomization of the CNA platelets, whereas extremely fast relaxation was observed for laponite (LRD) platelets. These PEO-CNA networklike solutions were compared with previously reported PEO-LRD networks, and the differences and similarities, with respect to the shear orientation, relaxation, and polymer-clay interactions, were examined.

  4. Application des techniques de diffusion de la lumière des rayons x et des neutrons à l'étude des systèmes colloïdaux. Deuxième partie : étude des différents systèmes : polymères en solution à l'état solide, solutions micellaires, systèmes fractals Application of Light, X-Ray and Neutron Diffusion Techniques to the Study of Colloidal Systems. Part Two: Research on Different Systems: Polymers in Solution in the Solid State, Micellar Solutions, Fractals Systems

    Directory of Open Access Journals (Sweden)

    Espinat D.


    Full Text Available Cet article fait suite à la première partie (Revue Inst. Franç. du Pétrole, vol. 45, n°6, novembre-décembre 1990 concernant l'application des techniques de diffusion de la lumière, des rayons X et des neutrons à l'étude des systèmes colloïdaux et plus précisément à la présentation théorique des trois méthodes. L'objet de cette deuxième partie est la présentation non exhaustive de quelques domaines d'applications. Nous nous attacherons tout particulièrement à présenter les potentialités des méthodes pour la caractérisation de systèmes colloïdaux ou divisés rencontrés dans de nombreuses branches d'activité de l'industrie pétrolière. Nous aborderons dans une première partie les solutions polymériques et colloïdales. En particulier nous nous attarderons sur l'importance des techniques de diffusion pour la caractérisation des polymères en solution et des solutions micellaires. Nous verrons également quelles informations la diffusion centrale peut apporter sur la macrostructure des polymères cristallisés ou amorphes à l'état solide. De nombreux systèmes présentent une structure de type fractal ; après présentation de quelques exemples, nous montrerons que les méthodes de diffusion peuvent apporter certaines informations sur ces matériaux, notamment la dimension fractale. This article is the second one (the first one was published in Revue de l'Institut Français du Pétrole No. 6, NovemberDecember 1990 concerning the application of techniques of light scattering, X rays and neutrons to the analysis of colloidal systems and more specifically to the theoretical description of the three methods. The aim of this second part is to make a nonexhaustive description of several fields of applications. A special effort is made to describe the potential of these methods for characterizing colloidal or divided systems encountered in a great many activities involving the petroleum industry. The first part of this

  5. Effect of plasticizer on surface of free films prepared from aqueous solutions of salts of cationic polymers with different plasticizers (United States)

    Bajdik, János; Fehér, Máté; Pintye-Hódi, Klára


    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.

  6. Elucidating double aggregation mechanisms in the morphology optimization of diketopyrrolopyrrole-based narrow bandgap polymer solar cells. (United States)

    Gao, Jing; Chen, Wei; Dou, Letian; Chen, Chun-Chao; Chang, Wei-Hsuan; Liu, Yongsheng; Li, Gang; Yang, Yang


    The power conversion efficiency (PCE) of a DPP-based polymer solar cell is significantly improved by using DIO or DCB as processing additives. The discovery that DCB outperforms DIO with a significantly wider solvent mixture operation window suggests different optimization mechanisms. Although both solvent mixture systems involve double aggregation processes, including a similar solution-to-film aggregation, however, two distinct solution-stage aggregations are observed: relatively amorphous polymer aggregates form in the CF-DIO solution, while more crystalline polymer aggregates form in CF-DCB solution.

  7. Investigating the particle to fibre transition threshold during electrohydrodynamic atomization of a polymer solution

    Energy Technology Data Exchange (ETDEWEB)

    Husain, O.; Lau, W.; Edirisinghe, M.; Parhizkar, M., E-mail:


    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 25 wt%. 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 20 wt% 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 ~ 1 μm; 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 30 mm and 60 mm, 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

  8. Solution processing of polymer semiconductor: Insulator blends-Tailored optical properties through liquid-liquid phase separation control

    KAUST Repository

    Hellmann, Christoph


    © 2014 Wiley Periodicals, Inc. It has been demonstrated that the 0-0 absorption transition of poly(3-hexylthiophene) (P3HT) in blends with poly(ethylene oxide) (PEO) could be rationally tuned through the control of the liquid-liquid phase separation process during solution deposition. Pronounced J-like aggregation behavior, characteristic for systems of a low exciton band width, was found for blends where the most pronounced liquid-liquid phase separation occurred in solution, leading to domains of P3HT and PEO of high phase purity. Since liquid-liquid phase separation could be readily manipulated either by the solution temperature, solute concentration, or deposition temperature, to name a few parameters, our findings promise the design from the out-set of semiconductor:insulator architectures of pre-defined properties by manipulation of the interaction parameter between the solutes as well as the respective solute:solvent system using classical polymer science principles.

  9. Development of Novel Method for Rapid Extract of Radionuclides from Solution Using Polymer Ligand Film (United States)

    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

  10. ``Living polymers'' in organic solvents : stress relaxation in bicopper tetracarboxylate/tert-butyl cyclohexane solutions (United States)

    Terech, P.; Maldivi, P.; Dammer, C.


    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

  11. Evaluation of Drug Load and Polymer by Using a 96-Well Plate Vacuum Dry System for Amorphous Solid Dispersion Drug Delivery


    Chiang, Po-Chang; Ran, Yingqing; Chou, Kang-Jye; Cui, Yong; Sambrone, Amy; Chan, Connie; Hart, Ryan


    It is well recognized that poor dissolution rate and solubility of drug candidates are key limiting factors for oral bioavailability. While numerous technologies have been developed to enhance solubility of the drug candidates, poor water solubility continuously remains a challenge for drug delivery. Among those technologies, amorphous solid dispersions (SD) have been successfully employed to enhance both dissolution rate and solubility of poorly water-soluble drugs. This research reports a h...

  12. Mechanism of dialkyl phthalates removal from aqueous solution using γ-cyclodextrin and starch based polyurethane polymer adsorbents. (United States)

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


    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.

  13. Solution-processed ultrasensitive polymer photodetectors with high external quantum efficiency and detectivity. (United States)

    Liu, Xilan; Wang, Hangxing; Yang, Tingbin; Zhang, Wei; Gong, Xiong


    Operating at room temperature, polymer photodetectors (PDs) with external quantum efficiency approximately 80%, detectivity over 10(13) Jones, linear dynamic range over 120 dB, and dark current a few decades of nA/cm(2) were demonstrated. All these performance parameters were achieved by combined treatment of active layer with solvent vapor annealing and of polymer PDs with postproduction thermal annealing. These high performance parameters demonstrated that polymer PDs is comparable to or better than inorganic counterparts.

  14. A Modified Mixing Rule for PSRK Model and Application for the Prediction of Vapor-Liquid Equilibria of Polymer Solutions

    Institute of Scientific and Technical Information of China (English)

    李敏; 王利生; J.Gmehling


    To extend the PSRK (predictive Soave-Redlich-Kwong equation of state) model to vapor-liquid equilibria of polymer solutions, a new EOS-gE mixing rule is applied in which the term ∑xiln(b/bi) in the PSRK mixing rule for the parameter a, and the combinatorial part in the original universal functional activity coefficient (UNIFAC) model are cancelled. To take into account the free volume contribution to the excess Gibbs energy in polymer solution, a quadratic mixing rule for the cross co-volume bij with an exponent equals to 1/2 is applied [bij1/2=1/2(bi1/2+bj1/2)]. The literature reported Soave-Redlich-Kwong equation of state (SRK EOS) parameters of i3 - 2- pure polymer are employed. The PSRK model with the modified mixing rule is used to predict the vapor-liquid equilibrium (VLE) of 37 solvent-polymer systems over a large range of temperature and pressure with satisfactory results.

  15. Activation energy for mobility of dyes and proteins in polymer solutions: from diffusion of single particles to macroscale flow. (United States)

    Sozański, Krzysztof; Wiśniewska, Agnieszka; Kalwarczyk, Tomasz; Hołyst, Robert


    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).

  16. Spinning process variables and polymer solution effects in the die-swell phenomenon during hollow fiber membranes formation

    Directory of Open Access Journals (Sweden)

    Pereira C.C.


    Full Text Available During hollow fiber spinning many variables are involved whose effects are still not completely clear. However, its understanding is of great interest because the control of these variables may originate membranes with the desired morphologies and physical properties. In this work, the phase inversion process induced by the immersion precipitation technique was applied to prepare hollow fibers membranes. It was verified that some of the variables involved, can promote a visco-elastic polymer solution expansion, called die-swell phenomenon, which is undesired since it may lead to low reproducibility of the permeation properties. The effects of the distance between spinneret and precipitation bath, the bore liquid composition, and the polymer solution composition were analyzed and discussed in order to avoid this phenomenon. According to the results, it was verified that the parameters investigated might promote a delay precipitation, which restrained the visco-elastic expansion.

  17. Effects of Polybenzoxazine on Shape Memory Properties of Polyurethanes with Amorphous and Crystalline Soft Segments

    Directory of Open Access Journals (Sweden)

    Senlong Gu


    Full Text Available This paper evaluates the role of minor component polybenzoxazine (PB on shape-memory properties of polyurethanes (PU with glassy and crystalline soft segments. The polymer compounds were prepared in two steps. In the first step, benzoxazine, polyurethane pre-polymer, and chain extender butanediol (BD were mixed into a solution followed by chain-extension of the pre-polymer with BD. In the second step, benzoxazine was polymerized at 180 °C for 3 h to obtain shape memory polymer compounds. The atomic force microscopy images revealed that the PB-phase formed uniform dispersions in PU. The presence of PB-phase induced shape-memory behavior in non-shape memory PU with amorphous soft segment and significantly improved the values of shape fixity, recovery ratio, and recovery stress in shape memory polyurethane with crystalline soft segment.

  18. Imprinting of Phenylalanine ethyl ester in cyclodextrin polymers in aqueous solution

    DEFF Research Database (Denmark)

    Detcheva, Anna Hr.; Yu, Donghong; Larsen, Kim Lambertsen

    During the last decades there has been a wide interest of developing molecularly imprinted polymers, which selectively can recognize small molecules. Cyclodextrins offer relatively strong binding site of a wide range of small molecules in water and molecular imprinted polymers of these have previ...

  19. Polymers and surfactants in solution and at interfaces : a model study on detergency

    NARCIS (Netherlands)

    Torn, L.H.


    This thesis deals with detergency-related adsorption phenomena of (mixtures of) polymers and surfactants. Both types of molecules play an important role in the removal and subsequent stabilization of soil from a substrate. Starting with a model detergency system consisting of polymers, surfactants,

  20. Rapid prototyping of all-solution-processed multi-lengthscale electrodes using polymer-induced thin film wrinkling (United States)

    Gabardo, Christine M.; Adams-McGavin, Robert C.; Fung, Barnabas C.; Mahoney, Eric J.; Fang, Qiyin; Soleymani, Leyla


    Three-dimensional electrodes that are controllable over multiple lengthscales are very important for use in bioanalytical systems that integrate solid-phase devices with solution-phase samples. Here we present a fabrication method based on all-solution-processing and thin film wrinkling using smart polymers that is ideal for rapid prototyping of tunable three-dimensional electrodes and is extendable to large volume manufacturing. Although all-solution-processing is an attractive alternative to vapor-based techniques for low-cost manufacturing of electrodes, it often results in films suffering from low conductivity and poor substrate adhesion. These limitations are addressed here by using a smart polymer to create a conformal layer of overlapping wrinkles on the substrate to shorten the current path and embed the conductor onto the polymer layer. The structural evolution of these wrinkled electrodes, deposited by electroless deposition onto a nanoparticle seed layer, is studied at varying deposition times to understand its effects on structural parameters such as porosity, wrinkle wavelength and height. Furthermore, the effect of structural parameters on functional properties such as electro-active surface area and surface-enhanced Raman scattering is investigated. It is found that wrinkling of electroless-deposited thin films can be used to reduce sheet resistance, increase surface area, and enhance the surface-enhanced Raman scattering signal.

  1. Using in-situ polymerization of conductive polymers to enhance the electrical properties of solution-processed carbon nanotube films and fibers. (United States)

    Allen, Ranulfo; Pan, Lijia; Fuller, Gerald G; Bao, Zhenan


    Single-walled carbon nanotubes/polymer composites typically have limited conductivity due to a low concentration of nanotubes and the insulating nature of the polymers used. Here we combined a method to align carbon nanotubes with in-situ polymerization of conductive polymer to form composite films and fibers. Use of the conducting polymer raised the conductivity of the films by 2 orders of magnitude. On the other hand, CNT fiber formation was made possible with in-situ polymerization to provide more mechanical support to the CNTs from the formed conducting polymer. The carbon nanotube/conductive polymer composite films and fibers had conductivities of 3300 and 170 S/cm, respectively. The relatively high conductivities were attributed to the polymerization process, which doped both the SWNTs and the polymer. In-situ polymerization can be a promising solution-processable method to enhance the conductivity of carbon nanotube films and fibers.

  2. Two-dimensional charge transport in self-organized, high-mobility conjugated polymers

    DEFF Research Database (Denmark)

    Sirringhaus, H.; Brown, P.J.; Friend, R.H.


    Self-organization in many solution-processed, semiconducting conjugated polymers results in complex microstructures, in which ordered microcrystalline domains are embedded in an amorphous matrix(I). This has important consequences for electrical properties of these materials: charge transport is ...

  3. A unifying model for elongational flow of polymer melts and solutions based on the interchain tube pressure concept (United States)

    Wagner, Manfred Hermann; Rolón-Garrido, Víctor Hugo


    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., 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

  4. Manipulating hybrid structures of polymer/a-Si for thin film solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Peng, Ying; He, Zhiqun, E-mail:, E-mail:; Zhang, Zhi; Liang, Chunjun [Key Laboratory of Luminescence and Optical Information, Ministry of Education, Institute of Optoelectronic Technology, Beijing Jiaotong University, Beijing 100044 (China); Diyaf, Adel; Ivaturi, Aruna; Wilson, John I. B., E-mail:, E-mail: [SUPA, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom)


    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.

  5. Manipulating hybrid structures of polymer/a-Si for thin film solar cells (United States)

    Peng, Ying; He, Zhiqun; Diyaf, Adel; Ivaturi, Aruna; Zhang, Zhi; Liang, Chunjun; Wilson, John I. B.


    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.

  6. Determination of the interaction parameter and topological scaling features of symmetric star polymers in dilute solution. (United States)

    Rai, Durgesh K; Beaucage, Gregory; Ratkanthwar, Kedar; Beaucage, Peter; Ramachandran, Ramnath; Hadjichristidis, Nikos


    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.

  7. Determination of the interaction parameter and topological scaling features of symmetric star polymers in dilute solution

    KAUST Repository

    Rai, Durgesh K.


    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(df=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.

  8. Thermoelectric Properties of Solution-Processed n-Doped Ladder-Type Conducting Polymers

    DEFF Research Database (Denmark)

    Wang, Suhao; Sun, Hengda; Ail, Ujwala;


    Ladder-type "torsion-free" conducting polymers (e.g., polybenzimidazobenzophenanthroline (BBL)) can outperform "structurally distorted" donor-acceptor polymers (e.g., P(NDI2OD-T2)), in terms of conductivity and thermoelectric power factor. The polaron delocalization length is larger in BBL than...... in P(NDI2OD-T2), resulting in a higher measured polaron mobility. Structure-function relationships are drawn, setting material-design guidelines for the next generation of conducting thermoelectric polymers....

  9. Surface segregation of fluorinated moieties on random copolymer films controlled by random-coil conformation of polymer chains in solution. (United States)

    Xue, Dongwu; Wang, Xinping; Ni, Huagang; Zhang, Wei; Xue, Gi


    The relationship between solution properties, film-forming methods, and the solid surface structures of random copolymers composed of butyl methacrylate and dodecafluorheptyl methylacrylate (DFHMA) was investigated by contact angle measurements, X-ray photoelectron spectroscopy, sum frequency generation vibrational spectroscopy, and surface tension measurements. The results, based on thermodynamic considerations, demonstrated that the random copolymer chain conformation at the solution/air interface greatly affected the surface structure of the resulting film, thereby determining the surface segregation of fluorinated moieties on films obtained by various film-forming techniques. When the fluorinated monomer content of the copolymer solution was low, entropic forces dominated the interfacial structure, with the perfluoroalkyl groups unable to migrate to the solution/air interface and thus becoming buried in a random-coil chain conformation. When employing this copolymer solution for film preparation by spin-coating, the copolymer chains in solution were likely extended due to centrifugal forces, thereby weakening the entropy effect of the polymer chains. Consequently, this resulted in the segregation of the fluorinated moieties on the film surface. For the films prepared by casting, the perfluoroalkyl groups were, similar to those in solution, incapable of segregating at the film surface and were thus buried in the random-coil chains. When the copolymers contained a high content of DFHMA, the migration of perfluoroalkyl groups at the solution/air interface was controlled by enthalpic forces, and the perfluoroalkyl groups segregated at the surface of the film regardless of the film-forming technique. The aim of the present work was to obtain an enhanced understanding of the formation mechanism of the chemical structure on the surface of the polymer film, while demonstrating that film-forming methods may be used in practice to promote the segregation of fluorinated

  10. Nature Inspired Solutions for Polymers: Will Cutinase Enzymes Make Polyesters and Polyamides Greener?

    Directory of Open Access Journals (Sweden)

    Valerio Ferrario


    Full Text Available The polymer and plastic sectors are under the urge of mitigating their environmental impact. The need for novel and more benign catalysts for polyester synthesis or targeted functionalization led, in recent years, to an increasing interest towards cutinases due to their natural ability to hydrolyze ester bonds in cutin, a natural polymer. In this review, the most recent advances in the synthesis and hydrolysis of various classes of polyesters and polyamides are discussed with a critical focus on the actual perspectives of applying enzymatic technologies for practical industrial purposes. More specifically, cutinase enzymes are compared to lipases and, in particular, to lipase B from Candida antarctica, the biocatalyst most widely employed in polymer chemistry so far. Computational and bioinformatics studies suggest that the natural role of cutinases in attacking natural polymers confer some essential features for processing also synthetic polyesters and polyamides.

  11. Reexamination of the Classical View of how Drag-Reducing Polymer Solutions Modify the Mean Velocity Profile: Baseline Results (United States)

    Farsiani, Yasaman; Baade, Jacquelyne; Elbing, Brian


    Recent numerical and experimental data have shown that the classical view of how drag-reducing polymer solutions modify the mean turbulent velocity profile is incorrect. The classical view is that the log-region is unmodified from the traditional law-of-the-wall for Newtonian fluids, though shifted outward. Thus the current study reexamines the modified velocity distribution and its dependence on flow and polymer properties. Based on previous work it is expected that the behavior will depend on the Reynolds number, Weissenberg number, ratio of solvent viscosity to the zero-shear viscosity, and the ratio between the coiled and fully extended polymer chain lengths. The long-term objective for this study includes a parametric study to assess the velocity profile sensitivity to each of these parameters. This study will be performed using a custom design water tunnel, which has a test section that is 1 m long with a 15.2 cm square cross section and a nominal speed range of 1 to 10 m/s. The current presentation focuses on baseline (non-polymeric) measurements of the velocity distribution using PIV, which will be used for comparison of the polymer modified results. Preliminary polymeric results will also be presented. This work was supported by NSF Grant 1604978.

  12. A Study of The Elongational Flow of Dilute Polymer Solutions : Estimation of The Elongational Stresses by Utilizing Pressure Drops with Orifice Flows


    福冨, 清; 長谷川, 富市; Fukutomi, Kiyoshi; Hasegawa, Tomiichi


    By assuming a uniformly converging radial flow on the upstream side of an orifice and integrating the equation of motion, an expression was derived to estimate elongational stresses for dilute polymer solutions at the orifice exit from pressure drops between the upstream and downstream of the orifice. The expression shown that the dilute polymer solutions usually give lower values of pressure drop than the solvent (water) does. An experiment was carried out to obtain the pressure drops for th...

  13. Co amorphous systems: A product development perspective. (United States)

    Chavan, Rahul B; Thipparaboina, Rajesh; Kumar, Dinesh; Shastri, Nalini R


    Solubility is one of the major problems associated with most of the new chemical entities that can be reasonably addressed by drug amorphization. However, being a high-energy form, it usually tends to re-crystallize, necessitating new formulation strategies to stabilize amorphous drugs. Polymeric amorphous solid dispersion (PASD) is one of the widely investigated strategies to stabilize amorphous drug, with major limitations like limited polymer solubility and hygroscopicity. Co amorphous system (CAM), a new entrant in amorphous arena is a promising alternative to PASD. CAMs are multi component single phase amorphous solid systems made up of two or more small molecules that may be a combination of drugs or drug and excipients. Excipients explored for CAM preparation include amino acids, carboxylic acids, nicotinamide and saccharine. Advantages offered by CAM include improved aqueous solubility and physical stability of amorphous drug, with a potential to improve therapeutic efficacy. This review attempts to address different aspects in the development of CAM as drug products. Criterion for co-former selection, various methods involved in CAM preparation, characterization tools, stability, scale up and regulatory requirements for the CAM product development are discussed.

  14. Structural study of amorphous polyaniline (United States)

    Laridjani, M.; Pouget, J. P.; MacDiarmid, A. G.; Epstein, A. J.


    Many materials, especially polymers, have a substantial volume fraction with no long range crystalline order. Through these regions are often termed amorphous, they frequently have a specific local order. We describe and use here a method, base on a non-energy dispersive X-ray diffraction technique, to obtain good quality interference functions and, by Fourier transform, radial distribution functions of the amorphous structure of polymers. We apply this approach to members of a family of electronic polymers of current interest : polyaniline emeraldine bases. We show that the local order exhibits significant differences in type I and type II materials, precipitated as salt and base respectively. These studies demonstrate the importance of sample preparation in evaluating the physical properties of polyaniline, and provide a structural origin for memory effects observed in the doping-dedoping processes. Beaucoup de matériaux, spécialement les polymères, ont une importante fraction de leur volume sans ordre cristallin à longue portée. Bien que ces régions soient souvent appelées amorphes, elles présentent fréquemment un ordre local caractéristique. Nous décrivons et utilisons dans ce papier une méthode, basée sur une technique de diffraction de rayons X non dispersive en énergie, pour obtenir des fonctions d'interférence de bonne qualité et, par transformée de Fourier, la fonction de distribution radiale des polymères amorphes. Nous appliquons cette technique à plusieurs éléments d'une même famille de polymères électroniques d'intérêt actuel : les polyanilines éméraldine bases. Nous montrons que l'ordre local présente d'appréciables différences dans les matériaux de type I et II, préparés respectivement sous forme de sel et de base. Cette étude démontre l'importance des conditions de préparation sur les propriétés physiques du polyaniline et donne une base structurale aux effets observés dans les processus de dopage-dédopage de

  15. Measurement of the equation of state and of the index of refraction of an amorphous glow discharge polymer up to 45 GPa (United States)

    Plisson, Thomas; Colin-Lalu, Pierre; Huser, Gael; Loubeyre, Paul


    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.

  16. Enhancing the efficiency of solution-processed polymer:colloidal nanocrystal hybrid photovoltaic cells using ethanedithiol treatment. (United States)

    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


    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.

  17. Thermal Processing of PVP- and HPMC-Based Amorphous Solid Dispersions. (United States)

    LaFountaine, Justin S; Prasad, Leena Kumari; Brough, Chris; Miller, Dave A; McGinity, James W; Williams, Robert O


    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.

  18. Mass and Heat Diffusion in Ternary Polymer Solutions: A Classical Irreversible Thermodynamics Approach

    CERN Document Server

    Es-haghi, S Shams


    Governing equations for evolution of concentration and temperature in three-component systems were derived in the framework of classical irreversible thermodynamics using Onsager variational principle and were presented for solvent/solvent/polymer and solvent/polymer/polymer systems. The derivation was developed from the Gibbs equation of equilibrium thermodynamics using the local equilibrium hypothesis, Onsager reciprocal relations and Prigogine theorem for systems in mechanical equilibrium. It was shown that the details of mass and heat diffusion phenomena in a ternary system are completely expressed by a 3x3 matrix whose entries are mass diffusion coefficients (4 entries), thermal diffusion coefficients (2 entries) and three entries that describe the evolution of heat in the system. The entries of the diffusion matrix are related to the elements of Onsager matrix that are bounded by some constraints to satisfy the positive definiteness of entropy production in the system. All the elements of diffusion matr...

  19. Antimicrobial Polymers in Solution and on Surfaces: Overview and Functional Principles

    Directory of Open Access Journals (Sweden)

    Felix Siedenbiedel


    Full Text Available The control of microbial infections is a very important issue in modern society. In general there are two ways to stop microbes from infecting humans or deteriorating materials—disinfection and antimicrobial surfaces. The first is usually realized by disinfectants, which are a considerable environmental pollution problem and also support the development of resistant microbial strains. Antimicrobial surfaces are usually designed by impregnation of materials with biocides that are released into the surroundings whereupon microbes are killed. Antimicrobial polymers are the up and coming new class of disinfectants, which can be used even as an alternative to antibiotics in some cases. Interestingly, antimicrobial polymers can be tethered to surfaces without losing their biological activity, which enables the design of surfaces that kill microbes without releasing biocides. The present review considers the working mechanisms of antimicrobial polymers and of contact-active antimicrobial surfaces based on examples of recent research as well as on multifunctional antimicrobial materials.

  20. Adsorption of phenolic compounds from aqueous solutions by aminated hypercrosslinked polymers

    Institute of Scientific and Technical Information of China (English)

    JIANG Zhen-mao; LI Ai-min; CAI Jian-guo; WANG Chun; ZHANG Quan-xin


    Two novel polymers (NJ- 1 and NJ-2) were synthesized by chemically modified a hypercrosslinked polymer NJ-0 with dimethylamine and trimethylamine, respectively. The comparison of the adsorption properties of the three polymers toward phenol, resorcin and phloroglucin was made. The study focused on the static equilibrium adsorption behaviors and the adsorption thermodynamics.Freundlich equation was found to fit the adsorption results well. The effect of amino groups introduced onto the surface of the resin and the structure of phenolic compounds on the adsorption were also studied. The hydrogen-bonding interaction and electrostatic interaction could happen between the amino groups and the adsorbates. The adsorption impetus increased as quantity of hydroxyl groups increased, but the adsorption capacity decreased due to the drop of the matching degree of the aperture of resins and the diameter of adsorbate molecules.

  1. Cholesterol modification of (Bio)polymers using UV-Vis traceable chemistry in aqueous solutions. (United States)

    Rasmussen, Kasper F; Smith, Anton A A; Ruiz-Sanchis, Pau; Edlund, Katrine; Zelikin, Alexander N


    Cholesterol modification of synthetic and biological polymers is achieved using of thiocholesterol (TC) and thiol-disulfide exchange. TC is reacted with Ellman's reagent to produce a mixed disulfide (TC-ER) which is activated towards thiol-disulfide exchange. TC-ER is used to obtain an inclusion complex with methyl-β-cyclodextrin, which is then employed to achieve cholesterol functionalization of a model peptide, synthetic polymers, and physical hydrogels based on poly(vinyl alcohol). It is anticipated that the established techniques will significantly broaden the use of cholesterol in bio- and nanotechnology and specifically biomedicine.

  2. Direct measurement of the intermolecular forces confining a single molecule in an entangled polymer solution. (United States)

    Robertson, Rae M; Smith, Douglas E


    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.

  3. Understanding the Tendency of Amorphous Solid Dispersions to Undergo Amorphous–Amorphous Phase Separation in the Presence of Absorbed Moisture


    Rumondor, Alfred C. F.; Wikström, Håkan; Van Eerdenbrugh, Bernard; Taylor, Lynne S.


    Formulation of an amorphous solid dispersion (ASD) is one of the methods commonly considered to increase the bioavailability of a poorly water-soluble small-molecule active pharmaceutical ingredient (API). However, many factors have to be considered in designing an API–polymer system, including any potential changes to the physical stability of the API. In this study, the tendency of ASD systems containing a poorly water-soluble API and a polymer to undergo amorphous–amorphous phase separatio...

  4. Improvement of mechanical properties of hydrogel by irradiation of polymers in aqueous solution with {kappa}-carrageenan

    Energy Technology Data Exchange (ETDEWEB)

    Makuuchi, K.; Yoshii, F. [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment; Aranilla, C.T. [Philippine Nuclear Research Institute, Diliman, Quezon (Philippines); Zhai, M. [Department of Technical Physics, Peking Univ., Beijing (China)


    Predominate radiation reaction of {kappa}-carrageenan (KC) hydrogel is the main chain scission of KC. The gel strength of KC hydrogel decreased with increasing irradiation dose. However, KC was found to enhances the radiation crosslinking of synthetic water-soluble polymer (SWSP) such as poly(ethylene oxide) (PEO) and poly(N-vinylpyrolidone) (PVP) in aqueous solution. The gel strength of SWSP hydrogel increased with increasing dose when KC was blended. Probably the radiation degraded KC radicals are recombined with radicals of PVP and PEO. The hydrogel thus prepared absorbs huge amounts of water due to the presence of strong hydrophilic -OSO{sub 3}{sup -} groups in KC. (author)

  5. Classical and recent free-volume models for polymer solutions: A comparative evaluation

    DEFF Research Database (Denmark)

    Radfarnia, H.R.; Kontogeorgis, Georgios; Ghotbi, C.


    to improve the performance of a recent model, the so-called Freed-FV First, we propose a modification of the Freed-FV model accounting for the anomalous free-volume behavior of aqueous systems (unlike the other solvents, water has a lower free-volume percentage than polymers). The results predicted...

  6. A simple relation for the concentration dependence of osmotic pressure and depletion thickness in polymer solutions

    NARCIS (Netherlands)

    Fleer, G.J.; Skvortsov, A.M.; Tuinier, R.


    We propose simple expressions II/IIo = 1 + and (omega/omega(ex))(3 alpha-1) and (delta(0)/delta)(2) = 1 + (omega/omega(ex))(2 alpha) for the osmotic pressure II and the depletion thickness 6 as a function of the polymer concentration omega. Here, IIo and delta 0 correspond to the dilute limit, and o

  7. Extensional Rheology Experiment Developed to Investigate the Rheology of Dilute Polymer Solutions in Microgravity (United States)

    Logsdon, Kirk A.


    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.

  8. 疏水缔合聚合物的合成及溶液性质研究%Synthesis and Solution Properties of Hydrophobic Associating Polymers

    Institute of Scientific and Technical Information of China (English)

    任鲲; 姜桂元; 徐春明; 林梅钦


    Acrylamide/2-acrylamido alkane sulfonic acid hydrophobic associating copolymers were synthesized by micellar copolymerization. Effects of hydrophobe content, polymer concentration, salinity and surfactant on rheological behavior of copolymers were investigated and the conformation of polymers in solution was studied by means of environmental scanning electronic microscopy and dynamic light scattering. The experimental results showed that in the dilute regime the hydrophobic parts could interact intramolecularly, while in the regime where the polymer concentration was higher than the critical association concentration, intermolecular hydrophobic association became predominant. Within the limit of the solubility, the critical association concentration of the polymer decreased with the increase of the salinity. The experimental results of the solution conformation indicated the presence of the three-dimensional network structure in deionized water and the size of the mesh in the network varied with the polymer concentration. In NaCl solution, above the critical association concentration, an increase in polymer concentration enhanced the intermolecular association and also enlarged the hydrodynamic radius. It would result in the improvement of the thickening power of polymers.

  9. Compressive cyclic ratcheting and fatigue of synthetic, soft biomedical polymers in solution. (United States)

    Miller, Andrew T; Safranski, David L; Smith, Kathryn E; Guldberg, Robert E; Gall, Ken


    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.

  10. Surface Acidity of Amorphous Aluminum Hydroxide

    Institute of Scientific and Technical Information of China (English)



    The surface acidity of synthetic amorphous Al hydroxide was determined by acid/base titration with several complementary methods including solution analyses of the reacted solutions and XRD characterization of the reacted solids. The synthetic specimen was characterized to be the amorphous material showing four broad peaks in XRD pattern. XRD analyses of reacted solids after the titration experiments showed that amorphous Al hydroxide rapidly transformed to crystalline bayerite at the alkaline condition (pH>10). The solution analyses after and during the titration experiments showed that the solubility of amorphous aluminum hydroxide, Ksp =aAl3+/a3H+,was 1010.3,The amount of consumption of added acid or base during the titration experiment was attributed to both the protonation/deprotonation of dissolved Al species and surface hydroxyl group. The surface acidity constants, surface hydroxyl density and specific surface area were estimated by FITEQL 4.0.

  11. Impact of polymer conformation on the crystal growth inhibition of a poorly water-soluble drug in aqueous solution. (United States)

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


    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.

  12. Moving through the phase diagram: morphology formation in solution cast polymer-fullerene blend films for organic solar cells. (United States)

    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


    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. Solutions for lipophilic drugs: a biodegradable polymer acting as solvent, matrix, and carrier to solve drug delivery issues. (United States)

    Asmus, Lutz R; Gurny, Robert; Möller, Michael


    The purpose of this study was to investigate the polyester hexylsubstituted poly(lactide) (hexPLA) as a possible solvent for lipophilic substances and excipient for pharmaceutical formulations. HexPLA is a biodegradable and semi-solid polymer, which allows the incorporation of active substances by simple mixing and local or systemic application to the patient through injection. The solvent behavior of hexPLA was investigated by adding the lipophilic dye Sudan III to the polymer matrix and optical monitoring of the dissolution process over time by microscopy. As a drug, the antipsychotic compound haloperidol was analyzed for its solubility in hexPLA of different molecular weights by preparing saturated solutions, and measuring the amount of incorporated drug with UV spectroscopy. The influence of the rate of solubilized to suspended drug on the burst release behavior of haloperidol from hexPLA-formulations was investigated in release tests. It is demonstrated that hexPLA dissolves both lipophilic substances, Sudan III and Haloperidol. In the molecular weight range between 2,000 g/mol and 10,000 g/mol, a lower molecular weight hexPLA resulted in a higher incorporation capacity for haloperidol. By changing from a suspension formulation of haloperidol to a solution formulation, the initial burst release established for classical PLA and PLGA systems could be minimized. HexPLA is shown to be a potent solvent and excipient for lipophilic drugs, allowing the initial burst of drug release to be modified and controlled.


    Institute of Scientific and Technical Information of China (English)

    邵雪明; 林建忠; 余钊圣


    The evolution of the coherent structures in a two-dimensional time-developing mixing layer of the FENE-P fluids is examined numerically. By the means of an appropriate filtering for the polymer stress, some characteristics of the coherent structures at high b were obtained, which Azaiez and Homsy did not address. The results indicate that adding polymer to the Newtonian fluids will cause stronger vorticity diffusion, accompanied with weaker fundamental and subharmonical perturbations and slower rotational motion of neighboring vortices during pairing. This effect decreases with the Weissenberg number, but increases with b. In addition, the time when the consecutive rollers are completely coalesced into one delays in the viscoelastic mixing layer compared with the Newtonian one of the same total viscosity.

  15. Block copolymer micelle coronas as quasi-two-dimensional dilute or semidilute polymer solutions

    DEFF Research Database (Denmark)

    Svaneborg, C.; Pedersen, J.S.


    Chain-chain interactions in a corona of polymers tethered to a spherical core under good solvent conditions are studied using Monte Carlo simulations. The total scattering function of the corona as well as different partial contributions are sampled. By combining the different contributions...... in this approach. The osmotic compressibility is extracted from the latter, and it is shown to be a universal function of surface coverage, with some deviations at high coverage due to surface curvature effects....

  16. A New Property of Conjugated Polymer PFP: Catalytic Degradation of Methylene Blue Aqueous Solution

    Institute of Scientific and Technical Information of China (English)


    A new property of conjugated polymer poly(furancarbinol-co-phenol)(PFP) was studied.The target copolymer was used as a catalyst after proper heating treatment. And dye methylene blue (MB) could be fully degraded and largely mineralized on PFP, under natural light or even in dark, in a few minutes. Furthermore, the catalytic activity could be preserved after several runs and the catalyst was readily separated. The effect of calcination temperature was also observed.

  17. Biological destruction of polymer solutions used to improve oil bed output

    Energy Technology Data Exchange (ETDEWEB)

    Gareyshina, A.Z.; Gazizov, A.Sh.; Nazmutdinov, R.Ya.; Ozhiganova, G.U.; Yaus, L.I.


    A plan is presented and the results of studying biological destruction of polyacrylamide by fresh water microflora in dynamics. It is shown that polymer destruction as a result of the vital activity of microorganisms occurs most intensively in the first 1-1.5 months. During this period, the degree of destruction of polyacrylamide reaches 70-80%, which corresponds to a decrease in the average molecular mass 4-5-fold.

  18. One-pot synthesis of ZnS/polymer composites in supercritical CO2-ethanol solution and their applications in degradation of dyes. (United States)

    Xie, Yun; Zhang, Chengliang; Miao, Shiding; Liu, Zhimin; Ding, Kunlun; Miao, Zhenjiang; An, Guimin; Yang, Zhenzhong


    A facile method to decorate the polymeric hollow spheres with ZnS nanoparticles has been presented. In this method, the precursors, Zn(Ac)(2)H(2)O and CH(3)CSNH(2), were first adsorbed by the polymer substrate in supercritical CO(2)-ethanol solution at 35 degrees C. Followed by heating the mixture at 100 degrees C for 2 h, ZnS/polymer composites were obtained. The as-produced ZnS/polymer composites were characterized by means of IR spectra, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy. It was demonstrated that crystalline ZnS nanoparticles with size of 3-5 nm were uniformly decorated on the polymer spheres under suitable conditions. The resultant ZnS/polymer composites exhibited high efficiency for degrading eosin B, methyl orange and methylene blue under UV light irradiation.

  19. Laplacian spectra of recursive treelike small-world polymer networks: analytical solutions and applications. (United States)

    Liu, Hongxiao; Zhang, Zhongzhi


    A central issue in the study of polymer physics is to understand the relation between the geometrical properties of macromolecules and various dynamics, most of which are encoded in the Laplacian spectra of a related graph describing the macrostructural structure. In this paper, we introduce a family of treelike polymer networks with a parameter, which has the same size as the Vicsek fractals modeling regular hyperbranched polymers. We study some relevant properties of the networks and show that they have an exponentially decaying degree distribution and exhibit the small-world behavior. We then study the Laplacian eigenvalues and their corresponding eigenvectors of the networks under consideration, with both quantities being determined through the recursive relations deduced from the network structure. Using the obtained recursive relations we can find all the eigenvalues and eigenvectors for the networks with any size. Finally, as some applications, we use the eigenvalues to study analytically or semi-analytically three dynamical processes occurring in the networks, including random walks, relaxation dynamics in the framework of generalized Gaussian structure, as well as the fluorescence depolarization under quasiresonant energy transfer. Moreover, we compare the results with those corresponding to Vicsek fractals, and show that the dynamics differ greatly for the two network families, which thus enables us to distinguish between them.

  20. Scaling exponent and dispersity of polymers in solution by diffusion NMR. (United States)

    Williamson, Nathan H; Röding, Magnus; Miklavcic, Stanley J; Nydén, Magnus


    Molecular mass distribution measurements by pulsed gradient spin echo nuclear magnetic resonance (PGSE NMR) spectroscopy currently require prior knowledge of scaling parameters to convert from polymer self-diffusion coefficient to molecular mass. Reversing the problem, we utilize the scaling relation as prior knowledge to uncover the scaling exponent from within the PGSE data. Thus, the scaling exponent-a measure of polymer conformation and solvent quality-and the dispersity (Mw/Mn) are obtainable from one simple PGSE experiment. The method utilizes constraints and parametric distribution models in a two-step fitting routine involving first the mass-weighted signal and second the number-weighted signal. The method is developed using lognormal and gamma distribution models and tested on experimental PGSE attenuation of the terminal methylene signal and on the sum of all methylene signals of polyethylene glycol in D2O. Scaling exponent and dispersity estimates agree with known values in the majority of instances, leading to the potential application of the method to polymers for which characterization is not possible with alternative techniques.

  1. Chelating fibers prepared with a wet spinning technique using a mixture of a viscose solution and a polymer ligand for the separation of metal ions in an aqueous solution. (United States)

    Kagaya, Shigehiro; Miyazaki, Hiroyuki; Inoue, Yoshinori; Kato, Toshifumi; Yanai, Hideyuki; Kamichatani, Waka; Kajiwara, Takehiro; Saito, Mitsuru; Tohda, Koji


    Chelating fibers containing polymer ligands such as carboxymethylated polyallylamine, carboxymethylated polyethyleneimine, and a copolymer of diallylamine hydrochloride/maleic acid were prepared with a wet spinning technique using mixtures of a viscose solution and the polymer ligands. The chelating fibers obtained effectively adsorbed various metal ions, including Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), Ti(IV), and Zn(II). The metal ions adsorbed could be readily desorbed using 0.1 or 0.5 mol L(-1) HNO(3). The chelating fiber containing carboxymethylated polyallylamine was available for the separation of some metal ions in synthetic wastewater containing a large amount of Na(2)SO(4). The wet spinning technique using a solution containing a base polymer and a polymer ligand was quite simple and effective and would be applicable for preparing various chelating fibers.

  2. Fluorescence Development of Latent Fingerprint with Conjugated Polymer Nanoparticles in Aqueous Colloidal Solution. (United States)

    Chen, Hong; Ma, Rong-Liang; Chen, Yun; Fan, Li-Juan


    Poly(p-phenylenevinylene) (PPV) nanoparticles in aqueous colloidal solution have been prepared via a modified Wessling method, with the addition of surfactant. The fluorescent colloidal solution was used as the developing solution to develop the fingerprints on different substrates. The developing process was accomplished simply by immersing the substrates into developing solution and then taking out, followed by rinsing with deionized water. The initial study about the fingerprints on the adhesive tapes showed that the developing solution is very effective in fluorescence development on both fresh and aged visible fingerprints; and such an effect was negligibly affected by treating the fingerprints with water or other organic solvents, whether before developing or after. Further study on latent fingerprints (LFPs) demonstrated that PPV nanoparticles in colloidal solution have high sensitivity in developing fingerprints to give very clearly fluorescent patterns. At least 6 months of storage of the colloidal solution did not reduce the developing effect; and each developing solution (3.6 mg/mL, 5.0 mL) can be used to develop at least 30 fingerprints without sacrificing the legibility of the pattern. The preliminary mechanism investigation suggested that selectivity achieved toward the ridge of the fingerprint is very likely due to the affinity between PPV molecules and oily secretions of the fingerprints. Digital magnification of the developed fingerprints provided more details about the fingerprint.

  3. Preparation and application of polymer inclusion membranes (PIMs) including alamine 336 for the extraction of metals from an aqueous solution: Priprava in uporaba membrane iz polimera (PIM) in alamina 336 za ločenje kovin iz vodnih raztopin:



    Polymer inclusion membranes (PIMs) present an attractive approach for the separation of metals from an aqueous solution. The present study is about the application of Alamine 336 as an ion carrier in PIMs. The separation of copper (II), cobalt (II), nickel (II) and cadmium (II) from aqueous solutions with polymer inclusion membranes was investigated. PIMs are formed by casting a solution containing a carrier (extractant), a plasticizer and a base polymer, such as cellulose tri-acetate (CTA) o...

  4. Ligase detection reaction for the analysis of point mutations using free-solution conjugate electrophoresis in a polymer microfluidic device. (United States)

    Sinville, Rondedrick; Coyne, Jennifer; Meagher, Robert J; Cheng, Yu-Wei; Barany, Francis; Barron, Annelise; Soper, Steven A


    We have developed a new method for the analysis of low abundant point mutations in genomic DNA using a combination of an allele-specific ligase detection reaction (LDR) with free-solution conjugate electrophoresis (FSCE) to generate and analyze the genetic products. FSCE eliminates the need for a polymer sieving matrix by conjugating chemically synthesized polyamide "drag-tags" onto the LDR primers. The additional drag of the charge-neutral drag-tag breaks the linear scaling of the charge-to-friction ratio of DNA and enables size-based separations of DNA in free solution using electrophoresis with no sieving matrix. We successfully demonstrate the conjugation of polyamide drag-tags onto a set of four LDR primers designed to probe the K-ras oncogene for mutations highly associated with colorectal cancer, the simultaneous generation of fluorescently labeled LDR/drag-tag conjugate (LDR-dt) products in a multiplexed, single-tube format with mutant:WT ratios as low as 1:100, respectively, and the single-base, high-resolution separation of all four LDR-dt products. Separations were conducted in free solution with no polymer network using both a commercial capillary array electrophoresis (CAE) system and a PMMA microchip replicated via hot-embossing with only a Tris-based running buffer containing additives to suppress the EOF. Typical analysis times for LDR-dt were 11 min using the CAE system and as low as 85 s for the PMMA microchips. With resolution comparable to traditional gel-based CAE, FSCE along with microchip electrophoresis decreased the separation time by more than a factor of 40.

  5. Phase Behavior of the Ternary Solution Involving Rodlike and Random Coil Polymers

    Institute of Scientific and Technical Information of China (English)


    The present paper covers the phase behavior of poly(p-benzamide)(PBA)/Nylon 6/H2SO4 and poly(p-phenylene terephthalamide) (PPTA)/Nylon 6/H2SO4 systems. The transition temperatures detected by the Depolarized Light Intensity measurements were used to construct the phase diagram in which the influence of temperature was shown. The enhanced depolarized light intensity observed in the ternary system suggests that the coil polymer chains may tend to be extended and contribute to the overall anisotropy of the liquid crystal phase.

  6. Solution-processable donor-acceptor polymers with modular electronic properties and very narrow bandgaps. (United States)

    Foster, Michael E; Zhang, Benjamin A; Murtagh, Dustin; Liu, Yi; Sfeir, Matthew Y; Wong, Bryan M; Azoulay, Jason D


    Bridgehead imine-substituted cyclopentadithiophene structural units, in combination with highly electronegative acceptors that exhibit progressively delocalized π-systems, afford donor-acceptor (DA) conjugated polymers with broad absorption profiles that span technologically relevant wavelength (λ) ranges from 0.7 electronic properties so as to achieve very narrow optical bandgaps (Eg (opt) < 0.5 eV). This strategy affords modular DA copolymers with broad- and long-wavelength light absorption in the infrared and materials with some of the narrowest bandgaps reported to date.

  7. Application of a novel 3-fluid nozzle spray drying process for the microencapsulation of therapeutic agents using incompatible drug-polymer solutions. (United States)

    Sunderland, Tara; Kelly, John G; Ramtoola, Zebunnissa


    The aim of this study was to evaluate a novel 3-fluid concentric nozzle (3-N) spray drying process for the microencapsulation of omeprazole sodium (OME) using Eudragit L100 (EL100). Feed solutions containing OME and/or EL100 in ethanol were assessed visually for OME stability. Addition of OME solution to EL100 solution resulted in precipitation of OME followed by degradation of OME reflected by a colour change from colourless to purple and brown. This was related to the low pH of 2.8 of the EL100 solution at which OME is unstable. Precipitation and progressive discoloration of the 2-fluid nozzle (2-N) feed solution was observed over the spray drying time course. In contrast, 3-N solutions of EL100 or OME in ethanol were stable over the spray drying period. Microparticles prepared using either nozzle showed similar characteristics and outer morphology however the internal morphology was different. DSC showed a homogenous matrix of drug and polymer for 2-N microparticles while 3-N microparticles had defined drug and polymer regions distributed as core and coat. The results of this study demonstrate that the novel 3-N spray drying process can allow the microencapsulation of a drug using an incompatible polymer and maintain the drug and polymer in separate regions of the microparticles.

  8. Restructuring polymers via nanoconfinement and subsequent release

    Directory of Open Access Journals (Sweden)

    Alan E. Tonelli


    Full Text Available During the past several years my students and I have been utilizing certain small-molecule hosts to create nanostructured polymers. This is accomplished by first forming noncovalently bonded inclusion complexes (ICs between these small-molecule hosts and guest polymers, followed by the careful removal of the host crystalline lattice to obtain a coalesced bulk polymer. We have repeatedly observed that such coalesced polymer samples behave distinctly from those produced from their solutions or melts. Coalesced amorphous homopolymers exhibit higher glass-transition temperatures, while crystallizable homopolymers coalesced from their ICs display higher melting and crystallization temperatures, and sometimes different crystalline polymorphs. When ICs are formed with block copolymers or with two or more different homopolymers, the resulting coalesced samples can exhibit intimate mixing between the copolymer blocks, or between entire homopolymer chains. Each of the distinct behaviors observed for polymers coalesced from their ICs is a consequence of the structural organization of the polymer–host-ICs. Polymer chains in host-IC crystals are confined to occupy narrow channels (diameter ~0.5–1.0 nm formed by the small-molecule hosts around the included guest polymers during IC crystallization. This results in the separation and high extension of the included guest polymer chains, which leads, following the careful removal of the host molecule lattice, to unique behaviors for the bulk coalesced polymer samples. Apparently, substantial degrees of the extended and unentangled natures of the IC-included chains are retained upon coalescence. In this review we summarize the behaviors and uses of coalesced polymers, and attempt to draw conclusions on the relationship between their behavior and the organization/structures/conformations of the constituent polymer chains achieved upon coalescence from their ICs.

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

    KAUST Repository

    Moreno Chaparro, Nicolas


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

  10. Hot melt extrusion based solid solution approach: Exploring polymer comparison, physicochemical characterization and in-vivo evaluation. (United States)

    Fule, Ritesh; Paithankar, Vivek; Amin, Purnima


    The objective of this study was to develop solid solution (SSL) using hot-melt extrusion as a continuous manufacturing method. Powder blends of artesunate (ARS) a water insoluble drug with either Soluplus (SOL) or Kollidon VA64 (VA64) and additives in the form of surfactants or plasticizers were extruded to manufacture extrudes. The incorporation of surfactant or plasticizers facilitates smooth extrusion processing of the drug-excipient blend which directly reduced the residence time to form extrudes and works as parameter to control flow of the drug-excipients melt inside the extruder barrel. Differential scanning calorimetry (DSC) and X-ray diffraction (TXRD) analysis revealed the existence of the drug within the extrudes in amorphous state. Scanning electron microscopy (SEM), Raman spectroscopy (RS), Raman imaging (RI) and Atomic force microscopy (AFM) analytical characterization were carry out on the SSL formulations showed a homogeneous drug distribution within the extrudes. (2)D NMR and (1)H NMR studies were undertaken to reveal the possible drug-excipient interactions. The SSL produced via continuous HME processing showed significantly faster release of ARS compared to the pure drug substance. It is observed that F1 SSL (soluplus based) have 66.44 times higher AUC(0-72) and 16.60 times higher Cmax than pure ARS. Also K1 SSL (Kollidon VA64 based) have 62.20 times higher AUC(0-72) and 13.40 times higher Cmax than pure ARS.


    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...

  12. A study of diazonium couplings with aromatic nucleophiles both in solution and on a polymer surface (United States)

    Chng, Shuyun; Parker, Emily M.; Griffiths, Jon-Paul; Moloney, Mark G.; Wu, Linda Y. L.


    Diazonium coupling is a technique finding wider application to materials and biological science, for hybridization and linking processes, and for the construction of responsive surface functionality. For this reason, detailed examination of solution and surface processes was warranted, and results of such a study are reported here. The modification of polystyrene surfaces was examined as a model, and the process compared to a solution mimic using N,N-dimethylaniline. It was confirmed that solution and solid surface reactions proceed in a similar manner in terms of the chemical functionality generated, but with lower chemical efficiency and reaction times slower for the latter, in a reaction which was pH dependent. The solution process was shown to give only the trans-azo para- coupled products. Whilst there are clear similarities between the solution and surface chemistry, the efficiency of coupling at a surface is not necessarily replicated in the chemical yield of the mimicking solution processes, but nonetheless provides an alternative to other Click-type surface modifications. It should not be assumed that such couplings occur with quantitative efficiency at the surface.

  13. Reduced Solubility of Polymer-Oriented Water for Sodium Salts, Sugars, Amino Acids, and other Solutes Normally Maintained at Low Levels in Living Cells, (United States)


    polymer was prepared often with aid of gentle heating. The polymer solution was then inserted into 1/4 inch dialysis tubing, the ends of the sac was moved to another tube filled also with non-labelled solution and the process repeated many times until after the final washing, the sacs were...tragacanth (74C-0207); and gum xantham (888-0200); corn starch (6813-0216); potato starch (65B-2060); pectin (107B-0090); alginic acid (766-818); also

  14. Removal of Chromium(VI from Aqueous Solutions Using Fe3O4 Magnetic Polymer Microspheres Functionalized with Amino Groups

    Directory of Open Access Journals (Sweden)

    Kai Wang


    Full Text Available Magnetic polymer microspheres (MPMs using glycidylmethacrylate (GMA as a functional monomer were synthesized in the presence of Fe3O4 nanoparticles via dispersion polymerization. After polymerization, the magnetic polymer microbeads were modified with ethylenediamine (EDA. The obtained ethylenediamine-functionalized magnetic microspheres (EDA-MPMs were characterized by scanning electron microscope (SEM, X-ray diffraction (XRD, vibrating-sample magnetometer (VSM and Fourier transform infrared (FT-IR spectroscopy. Then the EDA-MPMs were applied as adsorbents for the removal of Cr(VI from aqueous solution. Langmuir equation was appropriate to describe the experimental data. The maximum adsorption capacities obtained from the Langmuir model were 236.9, 242.1 and 253.2 mg/g at 298, 308 and 318 K, respectively. The Cr(VI adsorption equilibrium was established within 120 min and the adsorption kinetics was compatibly described by the pseudo-second order equation. The thermodynamic parameters (ΔG°, ΔH°, ΔS° of the sorption process revealed that the adsorption was spontaneous and was an endothermic process. The regeneration study demonstrated that the EDA-MPMs could be repeatedly utilized with no significant loss of adsorption efficiency.

  15. Biosorption Performance of Biodegradable Polymer Powders for the Removal of Gallium(III ions from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Lee Ching-Hwa


    Full Text Available Gallium (Ga is considered an important element in the semiconducting industry and as the lifespan of electronic products decrease annually Ga-containing effluent has been increasing. The present study investigated the use of biodegradable polymer powders, crab shell and chitosan, in the removal of Ga(III ions from aqueous solution. Ga(III biosorption was modeled to Lagergren-first, pseudo-second order and the Weber-Morris models. Equilibrium data was modeled to the Langmuir, Freundlich and Langmuir-Freundlich adsorption isotherms to determine the probable biosorption behavior of Ga(III with the biosorbents. The biosorbents were investigated by Fourier Transform Infrared Spectroscopy, X-ray Diffraction and Scanning Electron Microscopy/Energy Dispersive Spectra analysis.

  16. Water-compatible 'aspartame'-imprinted polymer grafted on silica surface for selective recognition in aqueous solution. (United States)

    Singh, Meenakshi; Kumar, Abhishek; Tarannum, Nazia


    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.

  17. Improved Release of Celecoxib from High Drug Loading Amorphous Solid Dispersions Formulated with Polyacrylic Acid and Cellulose Derivatives. (United States)

    Xie, Tian; Taylor, Lynne S


    Amorphous solid dispersions (ASDs) have been extensively exploited as a strategy for improving the dissolution performance of poorly water-soluble drugs. However, factors underpinning the observed dissolution profiles are not clearly understood, and the choice of polymeric carriers is largely empirical. In the current study, the dissolution performance of a high drug loading ASD containing the poorly water-soluble, anti-inflammatory agent, celecoxib, was optimized by using binary polymers combinations. Polyacrylic acid (PAA), a highly water-soluble polymer, was used to substantially increase the dissolution rate of the drug, while hydroxypropyl methyl cellulose (HPMC) or HPMC acetate succinate (HPMCAS) were added to stabilize the solid amorphous matrix against crystallization upon hydration, as well as to maintain supersaturation. Quantitative measurements of the impact of the polymers on the solution nucleation and growth rates of celecoxib revealed that, while the cellulose derivatives are effective nucleation inhibitors, it is more difficult to completely prevent crystal growth in solutions containing seed crystals, in particular at high supersaturations. Therefore, it is critical to prevent the formation of crystals in the dissolving matrix during dissolution. By using certain ratios of HPMC and PAA, both rapid release as well as crystallization inhibition could be achieved, even at high drug loadings. Utilizing combinations of polymers may therefore be useful to tailor release profiles while providing optimized crystallization inhibition.

  18. Predicting the vapor-liquid equilibrium of hydrocarbon binary mixtures and polymer solutions using predetermined pure component parameters

    Energy Technology Data Exchange (ETDEWEB)

    Ryu, Sang Kyu [Division of Chemical Engineering and Molecular Thermodynamics Laboratory, Hanyang University, Seoul 133-791 (Korea, Republic of); Bae, Young Chan, E-mail: [Division of Chemical Engineering and Molecular Thermodynamics Laboratory, Hanyang University, Seoul 133-791 (Korea, Republic of)


    Highlights: Black-Right-Pointing-Pointer We have developed a close-packed lattice model for chain-like molecules. Black-Right-Pointing-Pointer The chain length dependence determined from Monte-Carlo simulation results were used. Black-Right-Pointing-Pointer To consider the volume effect, hole theory and two mixing steps were used. Black-Right-Pointing-Pointer A lattice fluid equation of state (LF-EoS) is presented for VLE of hydrocarbon mixtures. Black-Right-Pointing-Pointer Correlation of pure polymer solutions data with use of the LF-EoS. - Abstract: In our previous work, a new close-packed lattice model was developed for multi-component system of chain fluids with taking the chain length dependence from Monte-Carlo (MC) simulation results into account. In this work, we further extend this model to describe pressure, volume and temperature (PVT) properties, such as vapor-liquid equilibrium (VLE). To consider the effect of pressure on the phase behavior, the volume change effect is taken into account by introducing holes into the incompressible lattice model with two mixing steps. The corresponding new lattice fluid equation of state (LF-EoS) is applied to predict the thermodynamic properties of pure and binary mixtures of hydrocarbons as well as pure polymer solutions. The results of the proposed model are compared to other predictive approaches based on VLE calculations using predetermined pure model parameters without further adjustment. Thermodynamic properties predicted using the method developed in this work are consistent with the experimental data.


    Institute of Scientific and Technical Information of China (English)



    We studied the temperature-dependent steady-state and time-resolved fluorescence properties of very small (1-2 nm) ZnO, CdO, and PbO amorphous nanoclusters prepared in AOT reverse micelles and imbedded in polymethyl methacrylate(PMMA) films. X-ray diffraction and electron diffraction and imaging indicate that these structures are amorphous. These amorphous oxide nanoclusters demonstrate similar structural, electronic, and optical properties. Properties of steady-state fluorescence spectra indicate the unique localization of electronic states due to the amorphous structure. ZnO and CdO show double-band fluorescence structure, which is due to the spin-orbital splitting, similar to Cu2O. Time-resolved fluorescence studies of the nanoclusters in the polymer reveal two lifetime components, as found in solution. The slow component reflects relaxation processes from band-tail states while the fast component may be related to high-lying extended states. The temperature dependence of fast fluorescence component reveals the presence of exciton hopping between anharmonic wells at temperatures higher than 200K. We correlate the barrier height between two wells formed around local atoms with the inter-atomic distance and bond ionicity.

  20. Removal of cobalt ions from aqueous solutions by polymer assisted ultrafiltration using experimental design approach. part 1: optimization of complexation conditions. (United States)

    Cojocaru, Corneliu; Zakrzewska-Trznadel, Grazyna; Jaworska, Agnieszka


    The polymer assisted ultrafiltration process combines the selectivity of the chelating agent with the filtration ability of the membrane acting in synergy. Such hybrid process (complexation-ultrafiltration) is influenced by several factors and therefore the application of experimental design for process optimization using a reduced number of experiments is of great importance. The present work deals with the investigation and optimization of cobalt ions removal from aqueous solutions by polymer enhanced ultrafiltration using experimental design and response surface methodological approach. Polyethyleneimine has been used as chelating agent for cobalt complexation and the ultrafiltration experiments were carried out in dead-end operating mode using a flat-sheet membrane made from regenerated cellulose. The aim of this part of experiments was to find optimal conditions for cobalt complexation, i.e. the influence of initial concentration of cobalt in feed solution, polymer/metal ratio and pH of feed solution, on the rejection efficiency and binding capacity of the polymer. In this respect, the central compositional design has been used for planning the experiments and for construction of second-order response surface models applicable for predictions. The analysis of variance has been employed for statistical validation of regression models. The optimum conditions for maximum rejection efficiency of 96.65% has been figured out experimentally by gradient method and was found to be as follows: [Co(2+)](0)=65 mg/L, polymer/metal ratio=5.88 and pH 6.84.

  1. Quasi-logarithmic spacing law in dewetting patterns from the drying meniscus of a polymer solution

    CERN Document Server

    Chen, Yong-Jun; Mahara, Hitoshi; Yamaguchi, Tomohiko


    We report on a periodic precipitation pattern emerged from a drying meniscus via evaporation of a polystyrene solution in a Petri dish. It appeared a quasi-logarithmic spacing relation in the pattern as a result of stick-slip motion of the contact line towards the wall. A model based on the dynamics of the evaporating meniscus is proposed.

  2. Concentrated Polymer Solutions are Different from Melts: Role of Entanglement Molecular Weight

    DEFF Research Database (Denmark)

    Huang, Qian; Mednova, Olga; Rasmussen, Henrik K.;


    We compare viscoelastic properties of several polystyrene solutions and melts with the same number of entanglements. It is demonstrated that the modulus and time can be shifted such that the linear viscoelastic properties are identical provided the number of entanglements are identical. However t...

  3. High-performance solution-processed polymer ferroelectric field-effect transistors

    NARCIS (Netherlands)

    Naber, RCG; Tanase, C; Blom, PWM; Gelinck, GH; Marsman, AW; Touwslager, FJ; Setayesh, S; De Leeuw, DM; Naber, Ronald C.G.; Gelinck, Gerwin H.; Marsman, Albert W.; Touwslager, Fred J.


    We demonstrate a rewritable, non-volatile memory device with flexible plastic active layers deposited from solution. The memory device is a ferroelectric field-effect transistor (FeFET) made with a ferroelectric fluoropolymer and a bisalkoxy-substituted poly(p-phenylene vinylene) semiconductor mater

  4. Experimental investigations and numerical simulations for an open channel flow of a weak elastic polymer solution around a T-profile

    Energy Technology Data Exchange (ETDEWEB)

    Balan, C.; Neagoe, A.; Nistoran, D. [Hydraulics and Hydraulic Machinery Department - REOROM Group, University ' ' Politehnica' ' of Bucharest, Splaiul Independentei 313, 79590, Bucharest (Romania); Legat, V. [University of Louvain-la-Neuve - Center for Systems Engineering Applied Mechanics (CESAME), Batiment Euler, Av. Georges Lemaitre 4, 1348, Louvain-la-Neuve (Belgium)


    The present paper is concerned with experimental and numerical investigations of planar complex flows of ''weak'' elastic polymer solutions (whose concentration are below the critical overlap concentration), characterised by small relaxation times ({lambda}<0.1 s) and almost constant shear viscosities for small and medium shear rates. The main aim of the study is to detect to what extent a very small amount of elasticity present in a viscous fluid can influence its behaviour in complex flows, without introducing major modifications of classical rheological tests. The samples are polymer solutions of low PIB molecular weight dissolved in highly viscous Newtonian mineral oil. The analysed motion is steady, and takes place in an open channel around a ''T'' profile. Maximum values of the characteristic parameters for the experiments, the Reynolds and Weissenberg numbers, were 45 and 0.1, respectively. The experiments show a decrease of the wake length downstream the profile for weak elastic solutions in comparison to the Newtonian solvent. Actually, the same wake length as in the Newtonian case was obtained for tested polymer solutions, but at higher Re numbers. Numerical simulations using the Giesekus model predict the same behaviour and are consistent with experiments from both qualitative and quantitative point of views. The results of research conclude that, even in small amounts, the presence of elasticity in pure viscous liquids induces quantitative changes from Newtonian flow in complex dominant elongational flows, at elongational rates for which the sudden thickening of extensional viscosity is remarkable. The study is important, since it should enable better understanding and modelling of viscoelastic flows that involve dilute polymer solutions, or fluids with similar rheology; biofluid mechanics being one area of application of this research. Corroboration of experimental flow visualization with numerical simulation is

  5. Thermophysical Properties of Irradiated Polymers (United States)

    Briskman, Boris A.


    The effect of ionising radiation on the specific heat, thermal conductivity, thermal diffusivity, and density of partially crystalline (polyethylene, polypropylene, polytetrafluoro-ethylene) and of amorphous polymers (polystyrene, poly(methyl methacrylate)) is discussed. Analytical models of the mechanism of heat conduction, and the development of anisotropic thermal conductivity in amorphous polymers, are examined. The influence of ionising radiation on the thermophysical properties of composite materials is analysed. 79 references.

  6. Evaluation of polymer inclusion membranes containing crown ethers for selective cesium separation from nuclear waste solution. (United States)

    Mohapatra, P K; Lakshmi, D S; Bhattacharyya, A; Manchanda, V K


    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.

  7. Kinetics of the electropolymerization of aminoanthraquinone from aqueous solutions and analytical applications of the polymer film

    Directory of Open Access Journals (Sweden)

    Shymaa S. Medany


    Full Text Available Poly 1-amino-9, 10-anthraquinone (PAAQ films were prepared by the electropolymerization of 1-amino-9,10-anthraquinone (AAQ on platinum substrate from aqueous media, where 5.0 × 10−3 mol L−1 AAQ and 6.0 mol L−1 H2SO4 were used. The kinetics of the electropolymerization process was investigated by determining the change of the charge consumed during the polymerization process with time at different concentrations of both monomer and electrolyte. The results have shown that the process follows first order kinetics with respect to the monomer concentration. The order of the reaction with respect to the aqueous solvent i.e. H2SO4 was found to be negative. The polymer films were successfully used as sensors for the electroanalytical determination of many hazardous compounds, e.g. phenols, and biologically important materials like dopamine. The electroanalytical determination was based on the measurements of the oxidation current peak of the material in the cyclic voltammetric measurements. The cyclic voltammograms were recorded at a scan rate of 100 mV s−1 and different analyte concentrations. A calibration curve was constructed for each analyte, from which the determination of low concentrations of catechol and hydroquinone (HQ as examples of hazardous compounds present in waste water and also for ascorbic acid and dopamine as examples of valuable biological materials can be achieved.

  8. Solution-processable graphene oxide as an efficient hole transport layer in polymer solar cells. (United States)

    Li, Shao-Sian; Tu, Kun-Hua; Lin, Chih-Cheng; Chen, Chun-Wei; Chhowalla, Manish


    The utilization of graphene oxide (GO) thin films as the hole transport and electron blocking layer in organic photovoltaics (OPVs) is demonstrated. The incorporation of GO deposited from neutral solutions between the photoactive poly(3-hexylthiophene) (P3HT):phenyl-C61-butyric acid methyl ester (PCBM) layer and the transparent and conducting indium tin oxide (ITO) leads to a decrease in recombination of electrons and holes and leakage currents. This results in a dramatic increase in the OPV efficiencies to values that are comparable to devices fabricated with PEDOT:PSS as the hole transport layer. Our results indicate that GO could be a simple solution-processable alternative to PEDOT:PSS as the effective hole transport and electron blocking layer in OPV and light-emitting diode devices.

  9. Fully Solution-Processed Inverted Polymer Solar Cells with Laminated Nanowire Electrodes

    KAUST Repository

    Gaynor, Whitney


    We demonstrate organic photovoltaic cells in which every layer is deposited by solution processing on opaque metal substrates, with efficiencies similar to those obtained in conventional device structures on transparent substrates. The device architecture is enabled by solution-processed, laminated silver nanowire films serving as the top transparent anode. The cells are based on the regioregular poly(3- hexylthiophene) and C 61 butyric acid methyl ester bulk heterojunction and reach an efficiency of 2.5% under 100 mW/cm 2 of AM 1.5G illumination. The metal substrates are adequate barriers to moisture and oxygen, in contrast to transparent plastics that have previously been used, giving rise to the possibility of roll-to-roll solutionprocessed solar cells that are packaged by lamination to glass substrates, combining the cost advantage of roll-toroll processing with the barrier properties of glass and metal foil. © 2010 American Chemical Society.

  10. Phase separation of polymer solutions. The calculation of the cloudpoint curve with a concentration and temperature-dependent free energy correction parameter

    NARCIS (Netherlands)

    Emmerik, van P.T.; Smolders, C.A.


    The free enthalpy correction parameter g in the Flory-Huggins equation for the Gibbs free enthalpy of mixing in polymer solutions is considered generally as a concentration- and temperature-independent parameter. It has been extended here with linear concentration- and temperature-dependent terms. W

  11. Phase separation in polymer solutions. II. Determination of thermodynamic parameters of poly (2,6-dimethyl-1,4-phenylene oxide) toluene mixtures

    NARCIS (Netherlands)

    Emmerik, van P.T.; Smolders, C.A.


    In liquid systems where it is possible to perform light scattering experiments at the melting points of polymer solutions without nucleation taking place because of undercooling, the thermodynamic parameters necessary to calculate the correction parameter g in the Flory-Huggins equation as modified

  12. Removal of transition metals from dilute aqueous solution by carboxylic acid group containing absorbent polymers (United States)

    A new carboxylic acid group containing resin with cation exchange capacity, 12.67 meq/g has been used to remove Cu2+, Co2+ and Ni2+ ions from dilute aqueous solution. The resin has Cu2+, Co2+ and Ni2+ removal capacity, 216 mg/g, 154 mg/g and 180 mg/g, respectively. The selectivity of the resin to ...

  13. A hybrid CMOS-imager with a solution-processable polymer as photoactive layer (United States)

    Baierl, Daniela; Pancheri, Lucio; Schmidt, Morten; Stoppa, David; Dalla Betta, Gian-Franco; Scarpa, Giuseppe; Lugli, Paolo


    The solution-processability of organic photodetectors allows a straightforward combination with other materials, including inorganic ones, without increasing cost and process complexity significantly compared with conventional crystalline semiconductors. Although the optoelectronic performance of these organic devices does not outmatch their inorganic counterparts, there are certain applications exploiting the benefit of the solution-processability. Here we demonstrate that the small pixel fill factor of present complementary metal oxide semiconductor-imagers, decreasing the light sensitivity, can be increased up to 100% by replacing silicon photodiodes with an organic photoactive layer deposited with a simple low-cost spray-coating process. By performing a full optoelectronic characterization on this first solution-processable hybrid complementary metal oxide semiconductor-imager, including the first reported observation of different noise types in organic photodiodes, we demonstrate the suitability of this novel device for imaging. Furthermore, by integrating monolithically different organic materials to the chip, we show the cost-effective portability of the hybrid concept to different wavelength regions.

  14. Inorganic polymers from laterite using activation with phosphoric acid and alkaline sodium silicate solution: Mechanical and microstructural properties

    Energy Technology Data Exchange (ETDEWEB)

    Lassinantti Gualtieri, Magdalena, E-mail: [Dipartimento di Ingegneria " Enzo Ferrari" , Università degli studi di Modena e Reggio Emilia, Via Vignolese 905/a, I-41125 Modena (Italy); Romagnoli, Marcello [Dipartimento di Ingegneria " Enzo Ferrari" , Università degli studi di Modena e Reggio Emilia, Via Vignolese 905/a, I-41125 Modena (Italy); Pollastri, Simone; Gualtieri, Alessandro F. [Dipartimento di Scienze Chimiche e Geologiche, Università degli studi di Modena e Reggio Emilia, Via S. Eufemia 19I, I-41121 Modena (Italy)


    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.

  15. [Amorphization in pharmaceutical technology]. (United States)

    Révész, Piroska; Laczkovich, Orsolya; Eros, István


    The amorphization of crystalline active ingredients may be necessary because of the polymorphism of the active substance, the poor water-solubility of the drug material, difficult processing in the crystalline form and the taking out of a patent for a new (amorphous) form. This article introduces protocols for amorphization, which use methods traditionally applied in pharmaceutical technology. The protocols involve three possible routes: solvent methods, hot-melt technologies and milling procedures. With this presentation, the authors suggest help for practising experts to find the correct amorphization method.

  16. Liquid-liquid transition in supercooled aqueous solution involving a low-temperature phase similar to low-density amorphous water

    CERN Document Server

    Woutersen, Sander; Zhao, Zuofeng; Angell, C Austen


    The striking anomalies in physical properties of supercooled water that were discovered in the 1960-70s, remain incompletely understood and so provide both a source of controversy amongst theoreticians, and a stimulus to experimentalists and simulators to find new ways of penetrating the "crystallization curtain" that effectively shields the problem from solution. Recently a new door on the problem was opened by showing that, in ideal solutions, made using ionic liquid solutes, water anomalies are not destroyed as earlier found for common salt and most molecular solutes, but instead are enhanced to the point of precipitating an apparently first order liquid-liquid transition. The evidence was a spike in apparent heat capacity during cooling that could be fully reversed during reheating before any sign of ice crystallization appeared. Here, we use decoupled-oscillator infrared spectroscopy to define the structural character of this phenomenon using similar down and upscan rates as in the calorimetric study. Th...

  17. Study of entangled network formation in concentrated solutions of polymer by 13C NMR

    Institute of Scientific and Technical Information of China (English)

    毛诗珍; 倪少儒; 杜有如; 沈联芳


    Information about the exact location of topological and cohesional entanglements at molecular level has been obtained by 13C NMR relaxation analysis. The results show that about 20% of the carbon atoms in the main chain are entangled in the 25% (by weight) solution, which is independent of the content of the 1,2-segment in polybutadiene and of the kind of solvent. However, the entanglement of the carbon atone on the end group of the side chain is very weak, they behave as slipping freely at the junctions.

  18. Selective removal/recovery of RCRA metals from waste and process solutions using polymer filtration{trademark} technology

    Energy Technology Data Exchange (ETDEWEB)

    Smith, B.F. [Los Alamos National Lab., NM (United States)


    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.

  19. Morphologies and separation characteristics of polyphenyl sulfone-based solvent resistant nanofiltration membranes: Effect of polymer concentration in casting solution and membrane pretreatment condition

    Energy Technology Data Exchange (ETDEWEB)

    Sani, Nur Aimie Abdullah; Lau, Woei Jye; Ismail, Ahmad Fauzi [Universiti Teknologi Malaysia, Skudai (Malaysia)


    The performance of polyphenylsulfone (PPSU) solvent resistant nanofiltration (SRNF)-based flat sheet membranes prepared from phase inversion method was investigated by varying the concentration of polymer in the dope solution and condition of membrane pretreatment process. The membrane properties were characterized by SEM, FTIR, AFM and contact angle goniometer, while their performance was evaluated by measuring methanol flux and rejection of different molecular weight of dyes (ranging from 269 to 1,470 g/mol) in methanol. The experimental results showed that the polymer concentration has great impact not only on the final membrane morphology but also its separation characteristics. Increasing polymer concentration from 17 to 25wt% tended to suppress finger-like structure and more pear-like pores were developed, causing methanol flux to decrease. This can be explained by the decrease in molecular weight cut off (MWCO) of the membrane prepared at high polymer concentration. With respect to the effect of membrane pretreatment conditions, the rejection of membrane was negatively affected with longer immersion period in methanol solution prior to filtration experiment. The variation in membrane rejection can be attributed to the rearrangement of the polymer chain, which results in membrane swelling and/or change of membrane surface hydrophilicity.

  20. Non-monotonic course of protein solubility in aqueous polymer-salt solutions can be modeled using the sol-mxDLVO model. (United States)

    Herhut, Marcel; Brandenbusch, Christoph; Sadowski, Gabriele


    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.

  1. Removal of uranium(VI) from aqueous solutions by CMK-3 and its polymer composite (United States)

    Liu, Yunhai; Li, Qin; Cao, Xiaohong; Wang, Youqun; Jiang, Xiaohui; Li, Min; Hua, Ming; Zhang, Zhibin


    The ability of PANI-CMK-3 composite (PANI-CMK-3) by in site polymerizing aniline onto the surface of mesoporous carbon (CMK-3) has been explored for the removal and recovery of uranium from aqueous solutions. The results of FTIR, SEM, TG/DTA and N2 adsorption-desorption demonstrated that aniline was successfully polymerized onto the inside and outside surface of CMK-3 rather than occupying the mesopore. The U(VI) sorption on PANI-CMK-3 was well fitted to the Langmuir adsorption isothermal and pseudo-second kinetics models. The monolayer maximum capacity of PANI-CMK-3 was improved from 50.12 mg g-1 of CMK-3 to 118.30 mg g-1 at 298 K due to the imine and amine groups in PANI. The thermodynamic parameters (ΔH, ΔS and ΔG) showed the U(VI) adsorption on CMK-3-PANI and CMK-3 were all endothermic and spontaneous in nature. Selective adsorption experiments (co-existing ions, Na+, Mg2+, Zn2+, Mn2+, Ni2+ and Sr2+) show that the selectivity of CMK-3 was enhanced after aniline polymerization. Moreover, the U(VI) adsorbed on the surface of PANI-CMK-3 can be eluated by 1.0 mol L-1 HCl solution with high desorption rate of 98%.

  2. Polymer Chemistry (United States)

    Williams, Martha; Roberson, Luke; Caraccio, Anne


    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.

  3. Small-angle x-ray scattering study of polymer structure: Carbosilane dendrimers in hexane solution (United States)

    Shtykova, E. V.; Feigin, L. A.; Volkov, V. V.; Malakhova, Yu. N.; Streltsov, D. R.; Buzin, A. I.; Chvalun, S. N.; Katarzhanova, E. Yu.; Ignatieva, G. M.; Muzafarov, A. M.


    The three-dimensional organization of monodisperse hyper-branched macromolecules of regular structure—carbosilane dendrimers of zero, third, and sixth generations—has been studied by small-angle X-ray scattering (SAXS) in solution. The use of modern methods of SAXS data interpretation, including ab initio modeling, has made it possible to determine the internal architecture of the dendrimers in dependence of the generation number and the number of cyclosiloxane end groups (forming the shell of dendritic macromolecules) and show dendrimers to be spherical. The structural results give grounds to consider carbosilane dendrimers promising objects for forming crystals with subsequent structural analysis and determining their structure with high resolution, as well as for designing new materials to be used in various dendrimer-based technological applications.

  4. Extensional Relaxation Times and Pinch-off Dynamics of Dilute Polymer Solutions (United States)

    Dinic, Jelena; Zhang, Yiran; Jimenez, Leidy; Sharma, Vivek


    We show that visualization and analysis of capillary-driven thinning and pinch-off dynamics of the columnar neck in an asymmetric liquid bridge created by dripping-onto-substrate can be used for characterizing the extensional rheology of complex fluids. Using a particular example of dilute, aqueous PEO solutions, we show the measurement of both the extensional relaxation time and extensional viscosity of weakly elastic, polymeric complex fluids with low shear viscosity ηsessile drop to a nozzle is detected optically, and the extensional response for viscoelastic fluids is characterized by analyzing their elastocapillary self-thinning, we refer to this technique as optically-detected elastocapillary self-thinning dripping-onto-substrate (ODES-DOS) extensional rheometry.

  5. Removal of uranium(VI) from aqueous solutions by CMK-3 and its polymer composite

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yunhai; Li, Qin; Cao, Xiaohong; Wang, Youqun [State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China Institute of Technology, Ministry of Education, Nanchang 330013 (China); Department of Chemistry, Biological and Materials Sciences, East China Institute of Technology, Fuzhou 344000 (China); Jiang, Xiaohui [Department of Chemistry, Biological and Materials Sciences, East China Institute of Technology, Fuzhou 344000 (China); Tianshan Uranium Co., Ltd., China National Nuclear Corporation, Yining 835000 (China); Li, Min; Hua, Ming [State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China Institute of Technology, Ministry of Education, Nanchang 330013 (China); Zhang, Zhibin, E-mail: [State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China Institute of Technology, Ministry of Education, Nanchang 330013 (China); Department of Chemistry, Biological and Materials Sciences, East China Institute of Technology, Fuzhou 344000 (China)


    The ability of PANI–CMK-3 composite (PANI–CMK-3) by in site polymerizing aniline onto the surface of mesoporous carbon (CMK-3) has been explored for the removal and recovery of uranium from aqueous solutions. The results of FTIR, SEM, TG/DTA and N{sub 2} adsorption–desorption demonstrated that aniline was successfully polymerized onto the inside and outside surface of CMK-3 rather than occupying the mesopore. The U(VI) sorption on PANI–CMK-3 was well fitted to the Langmuir adsorption isothermal and pseudo-second kinetics models. The monolayer maximum capacity of PANI–CMK-3 was improved from 50.12 mg g{sup −1} of CMK-3 to 118.30 mg g{sup −1} at 298 K due to the imine and amine groups in PANI. The thermodynamic parameters (ΔH, ΔS and ΔG) showed the U(VI) adsorption on CMK-3–PANI and CMK-3 were all endothermic and spontaneous in nature. Selective adsorption experiments (co-existing ions, Na{sup +}, Mg{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+} and Sr{sup 2+}) show that the selectivity of CMK-3 was enhanced after aniline polymerization. Moreover, the U(VI) adsorbed on the surface of PANI–CMK-3 can be eluated by 1.0 mol L{sup −1} HCl solution with high desorption rate of 98%.

  6. Optimization of Co2+ ions removal from water solutions via polymer enhanced ultrafiltration with application of PVA and sulfonated PVA as complexing agents. (United States)

    Uzal, Niğmet; Jaworska, Agnieszka; Miśkiewicz, Agnieszka; Zakrzewska-Trznadel, Grażyna; Cojocaru, Corneliu


    The paper presents the results of the studies of UF-complexation process applied for the removal of Co(2+) ions from water solutions. As binding agents for cobalt ions, the PVA polymer (M(w)=10,000) and its sulfonated form, synthesized in the laboratory, have been used. The method of experimental design and response surface methodology have been employed to find out the optimal conditions for the complexation process and to evaluate the interaction between the input variables, i.e., initial cobalt concentration, pH and amount of the polymer used, expressed as a polymer/Co(2+) ratio r. The data collected by the designed experiments showed that sulfonation of polymer has improved significantly the binding ability of PVA. The optimal conditions of cobalt ions complexation established by response surface model for non-sulfonated PVA polymer have been found to be as follows: the initial concentration of Co(2+)=5.70 mg L(-1), the ratio between polymer and metal ions, r=8.58 and pH=5.93. The removal efficiency of Co(2+) in these conditions was 31.81%. For sulfonated PVA polymer, the optimal conditions determined are as follows: initial concentration of [Co(2+)](0)=10 mg L(-1), r=1.2 and pH=6.5. For these conditions, a removal efficiency of 99.98% has been determined. The experiments showed that Co(2+) removal ability of sulfonated PVA was much higher than its non-sulfonated precursor. Although the polymer concentrations used in the tests with sulfonated PVA were approximately ten times lower than the non-sulfonated one, the removal efficiency of cobalt ions was significantly higher.

  7. Amino acids as co-amorphous stabilizers for poorly water soluble drugs--Part 1: preparation, stability and dissolution enhancement. (United States)

    Löbmann, Korbinian; Grohganz, Holger; Laitinen, Riikka; Strachan, Clare; Rades, Thomas


    Poor aqueous solubility of an active pharmaceutical ingredient (API) is one of the most pressing problems in pharmaceutical research and development because up to 90% of new API candidates under development are poorly water soluble. These drugs usually have a low and variable oral bioavailability, and therefore an unsatisfactory therapeutic effect. One of the most promising approaches to increase dissolution rate and solubility of these drugs is the conversion of a crystalline form of the drug into its respective amorphous form, usually by incorporation into hydrophilic polymers, forming glass solutions. However, this strategy only led to a small number of marketed products usually because of inadequate physical stability of the drug (crystallization). In this study, we investigated a fundamentally different approach to stabilize the amorphous form of drugs, namely the use of amino acids as small molecular weight excipients that form specific molecular interactions with the drug resulting in co-amorphous forms. The two poorly water soluble drugs carbamazepine and indomethacin were combined with amino acids from the binding sites of the biological receptors of these drugs. Mixtures of drug and the amino acids arginine, phenylalanine, tryptophan and tyrosine were prepared by vibrational ball milling. Solid-state characterization with X-ray powder diffraction (XRPD) and differential scanning calorimetry (DSC) revealed that the various blends could be prepared as homogeneous, single phase co-amorphous formulations indicated by the appearance of an amorphous halo in the XRPD diffractograms and a single glass transition temperature (Tg) in the DSC measurements. In addition, the Tgs of the co-amorphous mixtures were significantly increased over those of the individual drugs. The drugs remained chemically stable during the milling process and the co-amorphous formulations were generally physically stable over at least 6 months at 40 °C under dry conditions. The

  8. Study on the substrate-induced crystallisation of amorphous SiC-precursor ceramics. TIB/A; Untersuchungen zur substratinduzierten Kristallisation amorpher SiC-Precursorkeramiken

    Energy Technology Data Exchange (ETDEWEB)

    Rau, C.


    In the present thesis the crystallization behaviour of amorphous silicon-carbon materials (SiC{sub x}) was studied. The main topic of the experimental studies formed thereby the epitactical crystallization of thin silicon carbide layers on monocrystalline substrates of silicon carbides or silicon. Furthermore by thermolysis of the polymer amorphous SiC{sub x}-powder was obtained.


    Institute of Scientific and Technical Information of China (English)

    张赟; 黄筑平


    Based on the non-equilibrium thermodynamic theory, a new thermo-viscoelastic constitutive model for an incompressible material is proposed. This model can be considered as a kind of generalization of the non-Gaussian network theory in rubber elasticity to include the viscous and the thermal effects. A set of second rank tensorial internal variables was introduced, and in order to adequately describe the evolution of these internal variables, a new expression of the Helmholtz free energy was suggested. The mechanical behavior of the thermo-viscoelastic material under simple shear deformation was studied, and the "viscous dissipation induced" anisotropy due to the change of orientation distribution of molecular chains was examined. Influences of strain rate and thermal softening produced by the viscous dissipation on the shear stress were also discussed. Finally, the model predictions were compared with the experimental results performed by G'Sell et al., thus the validity of the proposed model is verified.

  10. Unusual photoanisotropic alignment in amorphous azobenzene polymers

    DEFF Research Database (Denmark)

    Ramanujam, P.S.


    560 and 630nm, where the absorption is minimal, results in a possible uniaxial hedgehog arrangement of the molecules. Experiments performed with a dye laser, which can be tuned continuously between 560 and 630nm, are described. Not only azobenzene but also another photosensitive molecule...

  11. Laser Raman and ac impedance spectroscopic studies of PVA: NH4NO3 polymer electrolyte. (United States)

    Hema, M; Selvasekarapandian, S; Hirankumar, G; Sakunthala, A; Arunkumar, D; Nithya, H


    Ion conducting polymer electrolyte PVA:NH(4)NO(3) has been prepared by solution casting technique and characterized using XRD, Raman and ac impedance spectroscopic analyses. The amorphous nature of the polymer films has been confirmed by XRD and Raman spectroscopy. An insight into the deconvoluted Raman peaks of upsilon(1) vibration of NO(3)(-) anion for the polymer electrolyte reveals the dominancy of ion aggregates at higher NH(4)NO(3) concentration. From the ac impedance studies, the highest ion conductivity at 303 K has been found to be 7.5x10(-3)Scm(-1) for 80PVA:20NH(4)NO(3). The conductivity of the polymer electrolytes has been found to depend on the degree of dissociation of the salt in the host polymer matrix. The combination of the above-mentioned analyses has proven worth while and in fact necessary in order to achieve better understanding of these complex systems.

  12. Lithium ion conducting solid polymer blend electrolyte based on bio-degradable polymers

    Indian Academy of Sciences (India)

    Natarajan Rajeswari; Subramanian Selvasekarapandian; Moni Prabu; Shunmugavel Karthikeyan; C Sanjeeviraja


    Lithium ion conducting polymer blend electrolyte films based on poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP) with different Mwt% of lithium nitrate (LiNO3) salt, using a solution cast technique, have been prepared. The polymer blend electrolyte has been characterized by XRD, FTIR, DSC and impedance analyses. The XRD study reveals the amorphous nature of the polymer electrolyte. The FTIR study confirms the complex formation between the polymer and salt. The shifts in g values of 70 PVA–30 PVP blend and 70 PVA–30 PVP with different Mwt% of LiNO3 electrolytes shown by DSC thermograms indicate an interaction between the polymer and the salt. The dependence of g and conductivity upon salt concentration has been discussed. The ion conductivity of the prepared polymer electrolyte has been found by a.c. impedance spectroscopic analysis. The PVA–PVP blend system with a composition of 70 wt% PVA: 30 wt% PVP exhibits the highest conductivity of 1.58 × 10-6 Scm-1 at room temperature. Polymer samples of 70 wt% PVA–30 wt% PVP blend with different molecular weight percentage of lithium nitrate with DMSO as solvent have been prepared and studied. High conductivity of 6.828 × 10-4 Scm-1 has been observed for the composition of 70 PVA:30 PVP:25 Mwt% of LiNO3 with low activation energy 0.2673 eV. The conductivity is found to increase with increase in temperature. The temperature dependent conductivity of the polymer electrolyte follows the Arrhenius relationship which shows hopping of ions in the polymer matrix. The relaxation parameters () and () of the complexes have been calculated by using loss tangent spectra. The mechanical properties of polymer blend electrolyte such as tensile strength, elongation and degree of swelling have been measured and the results are presented.

  13. Merging quantum dots, biomolecules, and polymers for record performance from solution-processed optoelectronics (United States)

    Sargent, Edward H.


    We apply discoveries in nanoscience towards applications relevant to health, environment, security, and connectedness. A materials fundamental to our research is the quantum dot. Each quantum dot is a particle of semiconductor only a few nanometers in diameter. These semiconductor nanoparticles confine electrons to within their characteristic wavelength. Thus, just as changing the length of a guitar string changes the frequency of sound produced, so too does changing the size of a quantum dot alter the frequency - hence energy - the electron can adopt. As a result, quantum dots are tunable matter (Fig. 2). We work with colloidal quantum dots, nanoparticles produced in, and processed from, solution. They can be coated onto nearly anything - a semiconductor substrate, a window, a wall, fabric. Compared to epitaxially-grown semiconductors used to make optical detectors, lasers, and modulators, they are cheap, safe to work with, and easy to produce. Much of our work with quantum dots involves infrared light - its measurement, production, modulation, and harnessing. While there exists an abundance of work in colloidal quantum dots active in the visible, there are fewer results in the infrared. The wavelengths between 1000 and 2000 nm are nonetheless of great practical importance: half of the sun's power reaching the earth lies in this wavelength range; 'biological windows' in which tissue is relatively transparent and does not emit background light (autofluorescence) exist in the infrared; fiber-optic networks operate at 1.3 and 1.5 um.

  14. Hydroxypropyl cellulose stabilizes amorphous solid dispersions of the poorly water soluble drug felodipine. (United States)

    Sarode, Ashish L; Malekar, Swapnil A; Cote, Catherine; Worthen, David R


    Overcoming the low oral bioavailability of many drugs due to their poor aqueous solubility is one of the major challenges in the pharmaceutical industry. The production of amorphous solid dispersions (ASDs) of these drugs using hydrophilic polymers may significantly improve their solubility. However, their storage stability and the stability of their supersaturated solutions in the gastrointestinal tract upon administration are unsolved problems. We have investigated the potential of a low viscosity grade of a cellulosic polymer, hydroxypropyl cellulose (HPC-SSL), and compared it with a commonly used vinyl polymer, polyvinylpyrrolidone vinyl acetate (PVP-VA), for stabilizing the ASDs of a poorly water soluble drug, felodipine. The ASDs were produced using hot melt mixing and stored under standard and accelerated stability conditions. The ASDs were characterized using differential scanning calorimetry, powder X-ray diffraction, and Fourier transform infrared spectroscopy. Drug dissolution and partitioning rates were evaluated using single- and biphasic dissolution studies. The ASDs displayed superior drug dissolution and partitioning as compared to the pure crystalline drug, which might be attributed to the formation of a drug-polymer molecular dispersion, amorphous conversion of the drug, and drug-polymer hydrogen bonding interactions. Late phase separation and early re-crystallization occurred at lower and higher storage temperatures, respectively, for HPC-SSL ASDs, whereas early phase separation, even at low storage temperatures, was noted for PVP-VA ASDs. Consequently, the partitioning rates for ASDs dispersed in HPC-SSL were greater than those of PVP-VA at lower and room temperature storage, whereas the performance of both of the ASDs was similar when stored at higher temperatures.

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

    Directory of Open Access Journals (Sweden)

    X.-G. Han


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

  16. Highly efficient and selective removal of trace lead from aqueous solutions by hollow mesoporous silica loaded with molecularly imprinted polymers. (United States)

    Zhang, Zulei; Zhang, Xingdi; Niu, Dechao; Li, Yongsheng; Shi, Jianlin


    A novel type of adsorbent for the selective recognition and adsorption of trace Pb(2+) from aqueous solutions has been successfully constructed simply by grafting molecularly imprinted polymers (MIPs) onto hollow mesoporous silica (HMS). Attractively, the HMS loaded with MIPs (H-MIPs) exhibits a fast adsorption kinetics, marked adsorption capacity of 40.52mg/g and extremely high selectivity toward Pb(2+) over Cu(2+), Zn(2+), Co(2+), Mn(2+) and Ni(2+), and the selectivity coefficients have been determined to be as high as 50. Moreover, such high adsorptive capability and selectivity were retained for at least 6 runs, indicating the stability and reusability of H-MIPs. Lead ion contaminants in real water samples were successfully concentrated and approximately 100% recovered using H-MIPs. Theoretical analysis shows that the adsorption process of H-MIPs follows the pseudo-second-order kinetic and Langmuir isotherm models. These demonstrate that H-MIPs are greatly potential for the rapid and highly efficient removal of trace Pb(2+) ions in complicated matrices.

  17. Forward osmosis desalination using polymer hydrogels as a draw agent: influence of draw agent, feed solution and membrane on process performance. (United States)

    Li, Dan; Zhang, Xinyi; Simon, George P; Wang, Huanting


    We have previously reported the use of hydrogel particles as the draw agent for forward osmosis desalination. In the present work, the effects of draw agent, feed concentration and membrane on the process performance were systematically examined. Our results showed that the incorporation of carbon filler particles in polymer hydrogels led to enhanced swelling ratios of the draw agents and thus higher water fluxes in the FO process. The composite polymer hydrogel particles of sizes ranging from 100 μm to 200 μm as draw agents induced greater water fluxes in FO desalination as compared with those with larger particle sizes (500-700 μm). Similar to other types of draw solutes, as the salt concentration in the feed increased, the water flux created by the polymer hydrogel draw agent decreased; the use of a cellulose triacetate forward osmosis membrane resulted in higher water flux compared with the use of a polyamide composite reverse osmosis membrane.


    NARCIS (Netherlands)



    The association of unconjugated bilirubin (UCB) with amorphous calcium phosphate was studied in vitro. To this end UCB, solubilized in different micellar bile salt solutions, was incubated with freshly prepared calcium phosphate precipitate. It was demonstrated that amorphous calcium phosphate (ACP)

  19. Analysis of water sorption isotherms of amorphous food materials by solution thermodynamics with relevance to glass transition: evaluation of plasticizing effect of water by the thermodynamic parameters. (United States)

    Shimazaki, Eriko; Tashiro, Akiko; Kumagai, Hitomi; Kumagai, Hitoshi


    Relation between the thermodynamic parameters obtained from water sorption isotherms and the degree of reduction in the glass transition temperature (Tg), accompanied by water sorption, was quantitatively studied. Two well-known glassy food materials namely, wheat gluten and maltodextrin were used as samples. The difference between the chemical potential of water in a solution and that of pure water ([Formula: see text]), the difference between the chemical potential of solid in a solution and that of a pure solid ([Formula: see text]), and the change in the integral Gibbs free energy ([Formula: see text]) were obtained by analyzing the water sorption isotherms using solution thermodynamics. The parameter [Formula: see text] correlated well with ΔTg (≡Tg - Tg0; where Tg0 is the glass transition temperature of dry material), which had been taken to be an index of plasticizing effect. This indicates that plasticizing effect of water on foods can be evaluated through the parameter [Formula: see text].

  20. A study of the distribution of polymer/surfactant coacervate between solution and foam in archetypal shampoo systems. (United States)

    Wilgus, Leigh Ann; Davis, Kathleen; Labeaud, Lauren; Gandolfi, Lisa; Lochhead, Robert Y


    The research reported here attempted to answer the question, "is the foam important in delivering coacervates from shampoos." In order to answer this question, we have measured the amount of polymer in the foam and in the liquid phases of several cationic polymer/anionic surfactant systems by gravimetry and by FTIR techniques. In all cases studied, we discovered that the concentration of solids and, especially the polymer, in the liquid phase and in the foam phase were essentially the same. We conclude that the foam is unlikely to be an important factor in the topical delivery of polymer/surfactant coacervates.

  1. Amorphous iron (II) carbonate

    DEFF Research Database (Denmark)

    Sel, Ozlem; Radha, A.V.; Dideriksen, Knud;


    exothermic than that of amorphous calcium carbonate (ACC). This suggests that enthalpy of crystallization in carbonate systems is ionic-size controlled, which may have significant implications in a wide variety of conditions, including geological sequestration of anthropogenic carbon dioxide.......Abstract The synthesis, characterization and crystallization energetics of amorphous iron (II) carbonate (AFC) are reported. AFC may form as a precursor for siderite (FeCO3). The enthalpy of crystallization (DHcrys) of AFC is similar to that of amorphous magnesium carbonate (AMC) and more...

  2. Evaluation of conductive polymers as an adsorbent for eradication of As (III from aqueous solution using inductively coupled plasma optical emission spectroscopy (ICP-OES

    Directory of Open Access Journals (Sweden)

    Muhammad Imran Din


    Full Text Available 1024x768 The main focused of this research work is the preparation of conductive polymers like polypyrrole, polyaniline and polythiophene and their application as adsorbent materials for the removal of hyper toxic metal As (III from aqueous solution. The metal ions get attached on the π-electrons at the back bone of polymer that illustrate excellent affinity for metal ions. The adsorption of As (II ions was carried out on polythiophene due to its redox properties and the stronger interaction between sulfur atoms with arsenic atoms. To attain large surface area and for maximum interaction of As (III ions with polymers, the particle size of polymers was ranged in nano scale. As the surface area increases with decrease in particle size, the active sites for metal ions also increases. These polymers were characterized by FIIR spectroscopy and SEM analysis. Adsorption isothermal data was examined by two parameters (Langmuir, Freundlich, and Dubinin-Radushkevich and three parameters Redlich-Petrson, Sips and Toth models. Experimental results showed that based on standard deviation (SD and Chi square test (χ2 the experimental data was best explained by Freundlich and Toth isotherm. Thermodynamics parameters such as free energy change (ΔG0, enthalpy change (ΔH0 and entropy change (ΔS0 have been calculated respectively, which revealed the spontaneous, endothermic and feasible nature of adsorption process.   Normal 0 false false false EN-US X-NONE X-NONE

  3. Heat-induced solution mixing in thermo-responsive polymer-coated microchannels for the fluorometric determination of polyamines in saliva. (United States)

    Saitoh, Tohru; Suzuki, Norio; Furuse, Takehiro; Hiraide, Masataka


    We developed a simple and easy method for solution mixing based on the heat-induced regulation of capillary action in thermo-responsive polymer-coated microchannels. The channels having two T-junctions were fabricated on a glass plate by a sand-blast technique and then coated with a poly(N-isopropylacrylamide) film. The polymer-coating was performed by the modification with allyltrimethoxysilane and the subsequent radical polymerization of N-isopropylacrylamide and N,N'-methylenebisacrylamide. When the channel was warmed by a Peltier device, a capillarity-based solution flow completely stopped because of the water-repellency of channel surfaces. On the other hand, the cooling of the channels allowed the restart of the solution flow through hydrophilic channels. Solution mixing downstream a T-junction was readily conducted by a Peltier device that had placed at the junction. The technique was applied to the fluorometric analysis of polyamines in saliva. The saliva sample was mixed with nickel(II) chloride solution at the first junction to mask amino acids and then mixed with o-phthalaldehyde solution at the second junction to form the fluorometric derivatives of polyamines. Blue fluorescence was observed downstream the second junction. Linear correlation was obtained between the emission intensity and the spermine concentration in the range of 20-100 microM. No mechanical pump or valve was required for the fluid manipulation.

  4. Compaction of amorphous iron–boron powder

    DEFF Research Database (Denmark)

    Hendriksen, Peter Vang; Mørup, Steen; Koch, Christian;


    report on attempts to compact amorphous iron–boron particles prepared by chemical reduction of Fe(II) ions in aqueous solution by NaBH4 (Ref. 2). The particles prepared in this way are pyrophoric, but can be passivated. The small particle size (10–100 nm), characteristic of this preparation technique...

  5. Amorphous Solid Water:

    DEFF Research Database (Denmark)

    Wenzel, Jack; Linderstrøm-Lang, C. U.; Rice, Stuart A.


    The structure factor of amorphous solid D2O deposited from the vapor at 10°K has been obtained by measuring the neutron diffraction spectrum in the wave vector transfer from 0.8 to 12.3 reciprocal angstroms. The results indicate that the phase investigated is amorphous and has a liquiid-like stru......The structure factor of amorphous solid D2O deposited from the vapor at 10°K has been obtained by measuring the neutron diffraction spectrum in the wave vector transfer from 0.8 to 12.3 reciprocal angstroms. The results indicate that the phase investigated is amorphous and has a liquiid...

  6. Amorphous pharmaceutical solids. (United States)

    Vranić, Edina


    Amorphous forms are, by definition, non-crystalline materials which possess no long-range order. Their structure can be thought of as being similar to that of a frozen liquid with the thermal fluctuations present in a liquid frozen out, leaving only "static" structural disorder. The amorphous solids have always been an essential part of pharmaceutical research, but the current interest has been raised by two developments: a growing attention to pharmaceutical solids in general, especially polymorphs and solvates and a revived interest in the science of glasses and the glass transition. Amorphous substances may be formed both intentionally and unintentionally during normal pharmaceutical manufacturing operations. The properties of amorphous materials can be exploited to improve the performance of pharmaceutical dosage forms, but these properties can also give rise to unwanted effects that need to be understood and managed in order for the systems to perform as required.

  7. Selecting polymers for two-phase partitioning bioreactors (TPPBs): Consideration of thermodynamic affinity, crystallinity, and glass transition temperature. (United States)

    Bacon, Stuart L; Peterson, Eric C; Daugulis, Andrew J; Parent, J Scott


    Two-phase partitioning bioreactor technology involves the use of a secondary immiscible phase to lower the concentration of cytotoxic solutes in the fermentation broth to subinhibitory levels. Although polymeric absorbents have attracted recent interest due to their low cost and biocompatibility, material selection requires the consideration of properties beyond those of small molecule absorbents (i.e., immiscible organic solvents). These include a polymer's (1) thermodynamic affinity for the target compound, (2) degree of crystallinity (wc ), and (3) glass transition temperature (Tg ). We have examined the capability of three thermodynamic models to predict the partition coefficient (PC) for n-butyric acid, a fermentation product, in 15 polymers. Whereas PC predictions for amorphous materials had an average absolute deviation (AAD) of ≥16%, predictions for semicrystalline polymers were less accurate (AAD ≥ 30%). Prediction errors were associated with uncertainties in determining the degree of crystallinity within a polymer and the effect of absorbed water on n-butyric acid partitioning. Further complications were found to arise for semicrystalline polymers, wherein strongly interacting solutes increased the polymer's absorptive capacity by actually dissolving the crystalline fraction. Finally, we determined that diffusion limitations may occur for polymers operating near their Tg , and that the Tg can be reduced by plasticization by water and/or solute. This study has demonstrated the impact of basic material properties that affects the performance of polymers as sequestering phases in TPPBs, and reflects the additional complexity of polymers that must be taken into account in material selection.

  8. Extraction of Gold(III) from Hydrochloric Acid Solutions with a PVC-based Polymer Inclusion Membrane (PIM) Containing Cyphos® IL 104



    Abstract: Poly(vinyl chloride) (PVC) based polymer inclusion membranes (PIMs), with different concentrations of Cyphos® IL 104 as the membrane extractant/carrier, were studied for their ability to extract Au(III) from hydrochloric acid solutions. Some of the PIMs also contained one of the following plasticizers or modifiers: 2-nitrophenyloctyl ether, dioctylphthalate, 1-dodecanol, 1-tetradecanol, or tri(2-ethylhexyl) phosphate. The best performance, in terms of extraction rate and amount of A...

  9. Development of Solid-Phase Extraction Using Molecularly Imprinted Polymer for the Analysis of Organophosphorus Pesticides-(Chlorpyrifos) in Aqueous Solution


    Binsalom, A.; Chianella, I.; Campbell, K.; Zourob, M.


    A new and selective sorbent for molecularly imprinted solid-phase extraction (MISPE) was prepared to extract chlorpyrifos (CPF) residue from solutions. The extracted analyte was analyzed by high performance liquid chromotography (HPLC) coupled with photodiode array detection. To synthesize the molecularly imprinted polymers, four different pyrogens (acetonitrile, toluene, dichloromethane and chloroform) were initially studied. CPF was used as the template molecule, methacrylic acid as the fun...

  10. Fabrication of solution-processed amorphous indium zinc oxide thin-film transistors at low temperatures using deep-UV irradiation under wet conditions (United States)

    Park, Jee Ho; Chae, Soo Sang; Yoo, Young Bum; Lee, Ji Hoon; Lee, Tae Il; Baik, Hong Koo


    We fabricated solution-processed indium zinc oxide (IZO) thin film transistors (TFTs) at annealing temperatures as low as 250 °C using deep UV (DUV) irradiation in water vapor medium. The DUV light decomposed the carbon compounds in the IZO films, and the hydroxyl radicals generated when water vapor reacted with ozone effectively oxidized the films. These phenomena were confirmed by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Finally, we fabricated DUV-treated IZO TFTs in water-vapor medium at 250 °C with a mobility of 1.2 cm2/Vs and an on/off current ratio of 2.66 × 106.

  11. The effect of surfactants on the dissolution behavior of amorphous formulations

    DEFF Research Database (Denmark)

    Mah, Pei T; Peltonen, Leena; Novakovic, Dunja


    in detail. The main aim of this study was to investigate the effect of surfactant on the dissolution behavior of neat amorphous drug and binary polymer based solid dispersion. Indomethacin was used as the model drug and the surfactants studied were polysorbate 80 and poloxamer 407. The presence...... studies of neat amorphous drugs requires prudent consideration. The design of amorphous formulations with optimal dissolution performance requires the appropriate selection of a combination of excipients and consideration of the method of introducing the excipients....

  12. Effect of shear force and solution pH on flocs breakage and re-growth formed by nano-Al(13) polymer. (United States)

    Xu, Weiying; Gao, Baoyu; Yue, Qinyan; Wang, Yan


    The breakage and re-growth of flocs formed by polyaluminum chloride (PAC) and the Al(13)O(4) (OH)(24)(7+) (Al(13) for short) polymer were comparatively evaluated for the coagulation of humic acid (HA). A series of jar experiments were conducted to investigate the impacts of shear rate and solution pH on flocs breakage and re-aggregation potential. Results indicated that the responses of flocs to the increasing shear force and solution pH depend on the coagulant used. The ability of flocs to resist breakage decreased with the increasing shear rate. For all levels of shear force investigated in this study, the flocs formed by Al(13) polymer were weaker than those of PAC, whereas Al(13) polymer displayed a better recoverability than PAC. The similar results were obtained when pH of solution was changed. The flocs generated in acidic conditions were stronger and more recoverable than those generated in alkaline conditions no matter which coagulant was used.

  13. Acid-base interactions in amorphous solid dispersions of lumefantrine prepared by spray-drying and hot-melt extrusion using X-ray photoelectron spectroscopy. (United States)

    Song, Yang; Zemlyanov, Dmitry; Chen, Xin; Su, Ziyang; Nie, Haichen; Lubach, Joseph W; Smith, Daniel; Byrn, Stephen; Pinal, Rodolfo


    This study investigates drug-excipient interactions in amorphous solid dispersions (ASDs) of the model basic compound lumefantrine (LMN), with five acidic polymers. X-ray photoelectron spectroscopy (XPS) was used to measure the extent of the protonation of the tertiary amine in LMN by the five acidic polymers. The extent/efficiency of protonation of the ASDs was assessed a function of polymer type, manufacturing process (hot-melt extrusion vs. spray drying), and drug loading (DL). The most strongly acidic polymer, polystyrene sulfonic acid (PSSA) was found to be the most efficient polymer in protonating LMN, independently of manufacturing method and DL. The rank order for the protonation extent of LMN by each polymer is roughtly the same for both manufacturing processes. However, protonation efficiency of polymers of similar acidic strength ranged from ∼0% to 75% (HPMCAS and Eudragit L100-55, respectively), suggesting an important role of molecular/mixing effects. For some polymers, including Eudragit L100 55 and HPMCP, spray-drying resulted in higher protonation efficiency compared to hot-melt extrusion. This result is attributable to a more favorable encounter between acid and base groups, when exposed to each other in solution phase. Increasing DL led to decreased protonation efficiency in most cases, particularly for polyacrylic acid, despite having the highest content of acidic groups per unit mass. These results indicate that the combined effects of acid strength and mixing phenomena regulate the efficiency of acid-base interactions in the ASDs.

  14. Hyperbranched Polymer-Based Electrolyte for Lithium Polymer Batteries

    Institute of Scientific and Technical Information of China (English)

    Takahito Itoh


    @@ 1Introduction Solid polymer electrolytes have attracted much attention as electrolyte materials for all solid-state recharge able lithium batteries, and poly ( ethylene oxide) ( PEO)-based polymer electrolytes are among the most intensively studied systems[1-3]. Hyperbranched polymers have unique properties such as completely amorphous, highly soluble in common organic solvent and processible because of the highly branched nature[4,5].

  15. Characterization of Amorphous and Co-Amorphous Simvastatin Formulations Prepared by Spray Drying

    DEFF Research Database (Denmark)

    Craye, Goedele; Löbmann, Korbinian; Grohganz, Holger;


    In this study, spray drying from aqueous solutions, using the surface-active agent sodium lauryl sulfate (SLS) as a solubilizer, was explored as a production method for co-amorphous simvastatin-lysine (SVS-LYS) at 1:1 molar mixtures, which previously have been observed to form a co......-amorphous mixture upon ball milling. In addition, a spray-dried formulation of SVS without LYS was prepared. Energy-dispersive X-ray spectroscopy (EDS) revealed that SLS coated the SVS and SVS-LYS particles upon spray drying. X-ray powder diffraction (XRPD) and differential scanning calorimetry (DSC) showed...... the studied formulations were able to significantly extend the stability of amorphous SVS compared to previous co-amorphous formulations of SVS. The best stability (at least 12 months in dry conditions) was observed when SLS was spray-dried with SVS (and LYS). In conclusion, spray drying of SVS and LYS from...

  16. Controlling charge injection properties in polymer field-effect transistors by incorporation of solution processed molybdenum trioxide. (United States)

    Long, Dang Xuan; Xu, Yong; Wei, Huai-xin; Liu, Chuan; Noh, Yong-Young


    A simply and facilely synthesized MoO3 solution was developed to fabricate charge injection layers for improving the charge-injection properties in p-type organic field-effect transistors (OFETs). By dissolving MoO3 powder in ammonium (NH3) solvent under an air atmosphere, an intermediate ammonium molybdate ((NH4)2MoO4) precursor is made stable, transparent and spin-coated to form the MoO3 interfacial layers, the thickness and morphology of which can be well-controlled. When the MoO3 layer was applied to OFETs with a cost-effective molybdenum (Mo) electrode, the field-effect mobility (μFET) was significantly improved to 0.17 or 1.85 cm(2) V(-1)s(-1) for polymer semiconductors, regioregular poly(3-hexylthiophene) (P3HT) or 3,6-bis-(5bromo-thiophen-2-yl)-N,N'-bis(2-octyl-1-dodecyl)-1,4-dioxo-pyrrolo[3,4-c]pyrrole (DPPT-TT), respectively. Device analysis indicates that the MoO3-deposited Mo contact exhibits a contact resistance RC of 1.2 MΩ cm comparable to that in a device with the noble Au electrode. Kelvin-probe measurements show that the work function of the Mo electrode did not exhibit a dependence on the thickness of MoO3 film. Instead, ultraviolet photoemission spectroscopy results show that a doping effect is probably induced by casting the MoO3 layer on the P3HT semiconductor, which leads to the improved hole injection.

  17. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal recovery from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Fish, R.H.


    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe{sup 3+} ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, Mg{sup 2+}, Al{sup 3+}, and Cr{sup 3+} ions at pH 1--3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe{sup 3+} (for example, Hg{sup 2+} at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe{sup 3+}, Al{sup 3+} ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads used determined are useful as well as equilibrium selectivity coefficient (K{sub m}) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe{sup 3+} ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2,6-LICAMS series of polymer pendant ligands are more selective to divalent metal ions Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, and Mg{sup 2+}, than either PS-CATS or PS-3,3-LICAMS. However, Fe{sup 3+} ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe{sup 3+}, the polymer ligand is selective for Al{sup 3+}, Cu{sup 2+} or Hg{sup 2+}. The changing of the cavity size from two CH{sub 2} groups to six CH{sub 2} groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect

  18. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal recovery from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Fish, Richard H. (Berkeley, CA)


    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe.sup.3+ ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+, Mg.sup.2+, Al.sup.3+, and Cr.sup.3+ ions at pH 1-3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe.sup.3+ (for example, Hg.sup.2+ at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe.sup.3+ Al.sup.3+ ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads used determined are useful as well as equilibrium selectivity coefficient (K.sub.m) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe.sup.3+ ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2,6-LICAMS series of polymer pendant ligands are more selective to divalent metal ions Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+, and Mg.sup.2+, than either PS-CATS or PS-3,3-LICAMS. However, Fe.sup.3+ ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe.sup.3+, the polymer ligand is selective for Al.sup.3+, Cu.sup.2+ or Hg.sup.2+. The changing of the cavity size from two CH.sub.2 groups to six CH.sub.2 groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect the order of metal ion

  19. Structure-Processing Relationships in Solution Processable Polymer Thin Film Transistors and Small Molecule Bulk Heterojunction Solar Cells (United States)

    Perez, Louis A.

    A regio-regular (RR) conjugated copolymer based on cyclopenta[2,1-b:3,4- b]dithiophene (CDT) and pyridal[2,1,3]thiadiazole (PT) structural units was prepared by using polymerization reactions involving reactants specifically designed to avoid random orientation of the asymmetric PT heterocycle. Compared to its regio-irregular (RI) counterpart, the RR polymer exhibits a two orders of magnitude increase in hole mobility from 0.005 to 0.6 cm2V -1s-1. To probe the reason for this difference in mobility, we examined the crystalline structure and its orientation in thin films of both copolymers as a function of depth via grazing incidence wide angle X-ray scattering (GIWAXS). In the RI film, the pi-pi stacking direction of the crystallites is mainly perpendicular to the substrate normal (edge-on orientation) while in the RR film the crystallites adopt a mixed pi-pi stacking orientation in the center of the film as well as near the interface between the polymer and the dielectric layer. These results demonstrate that control of backbone regularity is another important design criterion to consider in the synthesis and optimization of new conjugated copolymers with asymmetric structural units. Solution processed organic photovoltaic devices (OPVs) have emerged as a promising sustainable energy technology due to their ease of fabrication, potential to enable low-cost manufacturing, and ability to be incorporated onto light-weight flexible substrates. To date, the most efficacious OPV device architecture, the bulk heterojunction (BHJ), consists of a blend of a light-harvesting conjugated organic electron donating molecule and a strong electron-accepting compound (usually a soluble fullerene derivative e.g. [6,6]-phenyl C71 butyric acid methyl ester (PC71BM). BHJ layer morphology, which has been shown to be highly dependent on processing, has a significant effect on OPV performance. It is postulated that optimal BHJ morphologies consist of discrete bicontinuous nanoscale

  20. Concurrent multiscale modeling of amorphous materials (United States)

    Tan, Vincent


    An approach to multiscale modeling of amorphous materials is presented whereby atomistic scale domains coexist with continuum-like domains. The atomistic domains faithfully predict severe deformation while the continuum domains allow the computation to scale up the size of the model without incurring excessive computational costs associated with fully atomistic models and without the introduction of spurious forces across the boundary of atomistic and continuum-like domains. The material domain is firstly constructed as a tessellation of Amorphous Cells (AC). For regions of small deformation, the number of degrees of freedom is then reduced by computing the displacements of only the vertices of the ACs instead of the atoms within. This is achieved by determining, a priori, the atomistic displacements within such Pseudo Amorphous Cells associated with orthogonal deformation modes of the cell. Simulations of nanoscale polymer tribology using full molecular mechanics computation and our multiscale approach give almost identical prediction of indentation force and the strain contours of the polymer. We further demonstrate the capability of performing adaptive simulations during which domains that were discretized into cells revert to full atomistic domains when their strain attain a predetermined threshold. The authors would like to acknowledge the financial support given to this study by the Agency of Science, Technology and Research (ASTAR), Singapore (SERC Grant No. 092 137 0013).

  1. Nanofabrication in Polymer Solutions

    Institute of Scientific and Technical Information of China (English)


    This review covers recent advances in fabrication of nanomaterials in polymersolutions with emphasis on using the self-assembled amphiphilic block copolymers in solutionto fabricate organic/inorganic composites with nanoscale modifications. The phase behaviorof block copolymers in water and the use of templates to form ordered nanostructures arereviewed in detail. Modern physical techniques for nanoscale characterization are alsointroduced. The authors suggested that this approach should provide new routes to creatematerials with interesting morphologies for many different applications.

  2. Structural and ionic conductivity behavior in hydroxypropylmethylcellulose (HPMC) polymer films complexed with sodium iodide (NaI) (United States)

    Rani, N. Sandhya; Sannappa, J.; Demappa, T.; Mahadevaiah


    Solid polymer electrolyte films based on Hydroxypropylmethylcellulose (HPMC) complexed with Sodium Iodide (NaI) were prepared using solution cast method. The dissolution of the salt into the polymer host and the micro structural properties of pure and NaI complexed HPMC polymer electrolyte films were confirmed by X - Ray diffraction (XRD) studies. The XRD results revealed that the amorphous domains of HPMC polymer matrix was increased with increase in the NaI salt concentration. The degree of crystallanity and crystallite size is high for pure HPMC samples. Direct current (dc) conductivity was measured in the temperature range of 313-383k. Temperature dependence of dc electrical conductivity and activation energy regions data indicated the dominance of ion type charge transport in these polymer electrolyte films.

  3. Characterization of Amorphous and Co-Amorphous Simvastatin Formulations Prepared by Spray Drying. (United States)

    Craye, Goedele; Löbmann, Korbinian; Grohganz, Holger; Rades, Thomas; Laitinen, Riikka


    In this study, spray drying from aqueous solutions, using the surface-active agent sodium lauryl sulfate (SLS) as a solubilizer, was explored as a production method for co-amorphous simvastatin-lysine (SVS-LYS) at 1:1 molar mixtures, which previously have been observed to form a co-amorphous mixture upon ball milling. In addition, a spray-dried formulation of SVS without LYS was prepared. Energy-dispersive X-ray spectroscopy (EDS) revealed that SLS coated the SVS and SVS-LYS particles upon spray drying. X-ray powder diffraction (XRPD) and differential scanning calorimetry (DSC) showed that in the spray-dried formulations the remaining crystallinity originated from SLS only. The best dissolution properties and a "spring and parachute" effect were found for SVS spray-dried from a 5% SLS solution without LYS. Despite the presence of at least partially crystalline SLS in the mixtures, all the studied formulations were able to significantly extend the stability of amorphous SVS compared to previous co-amorphous formulations of SVS. The best stability (at least 12 months in dry conditions) was observed when SLS was spray-dried with SVS (and LYS). In conclusion, spray drying of SVS and LYS from aqueous surfactant solutions was able to produce formulations with improved physical stability for amorphous SVS.

  4. Exact solution of the thermodynamics and size parameters of a polymer confined to a lattice of finite size: Large chain limit

    Energy Technology Data Exchange (ETDEWEB)

    Snyder, Chad R., E-mail:; Guttman, Charles M., E-mail: [Materials Science and Engineering Division, National Institute of Standards and Technology (NIST), Gaithersburg, Maryland 20899 (United States); Di Marzio, Edmund A., E-mail: [Materials Science and Engineering Division, National Institute of Standards and Technology (NIST), Gaithersburg, Maryland 20899 (United States); Bio-Poly-Phase, 14205 Parkvale Road, Rockville, Maryland 20853 (United States)


    We extend the exact solutions of the Di Marzio-Rubin matrix method for the thermodynamic properties, including chain density, of a linear polymer molecule confined to walk on a lattice of finite size. Our extensions enable (a) the use of higher dimensions (explicit 2D and 3D lattices), (b) lattice boundaries of arbitrary shape, and (c) the flexibility to allow each monomer to have its own energy of attraction for each lattice site. In the case of the large chain limit, we demonstrate how periodic boundary conditions can also be employed to reduce computation time. Advantages to this method include easy definition of chemical and physical structure (or surface roughness) of the lattice and site-specific monomer-specific energetics, and straightforward relatively fast computations. We show the usefulness and ease of implementation of this extension by examining the effect of energy variation along the lattice walls of an infinite rectangular cylinder with the idea of studying the changes in properties caused by chemical inhomogeneities on the surface of the box. Herein, we look particularly at the polymer density profile as a function of temperature in the confined region for very long polymers. One particularly striking result is the shift in the critical condition for adsorption due to surface energy inhomogeneities and the length scale of the inhomogeneities; an observation that could have important implications for polymer chromatography. Our method should have applications to both copolymers and biopolymers of arbitrary molar mass.

  5. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal and recovery from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Fish, Richard H. (Berkeley, CA)


    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe.sup.3+ ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+,Mg.sup.2+, Al.sup.3+, and Cr.sup.3+ ions at pH 1-3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe.sup.3+ (for example, Hg.sup.2+ at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe.sup.3+ Al.sup.3+ ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads use determined are useful as well as equilibrium selectivity coefficient (K.sub.m) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe.sup.3+ ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2-6-Mn.sup.2+, Ni.sup.2+, and Mg.sup.2+, than either PS-CATS or PS-3,3-LICAMS. However, Fe.sup.3+ ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe.sup.3+, the polymer ligand is selective for Al.sup.3+, Cu.sup.2+ or Hg.sup.2+. The changing of the cavity size from two CH.sub.2 groups to six CH.sub.2 groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect the order of metal ion selectivity.

  6. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal and recovery from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Fish, R.H.


    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe{sup 3+} ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, Mg{sup 2+}, Al{sup 3+}, and Cr{sup 3+} ions at pH 1--3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe{sup 3+} (for example, Hg{sup 2+} at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe{sup 3+}, Al{sup 3+} ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads use determined are useful as well as equilibrium selectivity coefficient (K{sub m}) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe{sup 3+} ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2-6-Mn{sup 2+}, Ni{sup 2+}, and Mg{sup 2+}, than either PS-CATS or PS-3,3-LICAMS. However, Fe{sup 3+} ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe{sup 3+}, the polymer ligand is selective for Al{sup 3+}, Cu{sup 2+} or Hg{sup 2+}. The changing of the cavity size from two CH{sub 2} groups to six CH{sub 2} groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect the order of metal ion selectivity. 9 figs.

  7. Development of Silicate Polymers

    DEFF Research Database (Denmark)

    Søgaard, Erik Gydesen; Simonsen, Morten Enggrob

      The development of inorganic polymers is a new promising technology that may be used in many applications. The syntheses of inorganic polymers are normally carried out either by mixing an amorphous material for example silicium dioxide with a mineral base or dissolving metal oxids or metal...... hydroxide in acid and increase pH to saturation of the metal hydroxide. It is assumed that the syntheses of the inorganic polymer are carried out through polymerisation of oligomers (dimer, trimer) which provide the actual unit structures of the three dimensional macromolecular structure. In this work...

  8. Low band-gap polymers incorporating benzotriazole and 5,6-dialkoxy-benzothiadiazole as solution processable electrochromic materials

    Directory of Open Access Journals (Sweden)

    W. T. Neo


    Full Text Available Two series of donor-acceptor type conjugated polymers bearing benzotriazole or 5,6-dialkoxy-benzothiadiazole as acceptors unit are synthesized via Stille coupling. The optical, electrochemical, spectroelectrochemical characterizations and theoretical calculations are carried out. The polymers display excellent solubility in common organic solvents upon the introduction of long aliphatic side chains. The electrochromic performances of the polymers are also studied. Upon oxidation, the polymers switch from magenta or blue to a transmissive light blue state. In particular, respectable optical contrasts of about 44 and 40% are obtained in the visible and near infrared (NIR region respectively for P2. The polymers also reveal fast switching of about from one second to a few seconds. In addition, P2 exhibits a high coloration efficiency of 518 and 561 cm2/C in the visible and NIR region respectively. The promising electrochromic behaviour of these polymers, together with the enhanced solubility will allow large-scale processing and advancement towards real applications.

  9. Low temperature dynamics in amorphous solids : A photon echo study

    NARCIS (Netherlands)

    Meijers, Hans C.; Wiersma, Douwe A.


    The long-lived stimulated photon echo is put forward as a powerful technique to probe structural dynamics in glasses and other amorphous solids. We present results of optical dephasing measurements on several doped organic glasses (deuterated ethanol, toluene, and triethylamine) and polymers (polyst

  10. Synthesis and application of reduced graphene oxide and molecularly imprinted polymers composite in chemo sensor for trichloroacetic acid detection in aqueous solution (United States)

    Kibechu, Rose W.; Mamo, Messai A.; Msagati, Titus A. M.; Sampath, S.; Mamba, Bhekie B.

    This work presents the fabrication of a simple, cheap and fast thin film chemo sensor for detection of trichloroacetic acid (TCAA) in aqueous solutions. Reduced graphene oxide (RGO) based molecular imprinted polymers (MIP) chemo-sensor has been developed. The recognition of TCAA was achieved by imprinted polymers synthesized by copolymerization of 4-vinylpyridine (4-VP) and a crosslinking monomer ethylene glycol dimethacrylate (EDGMA) in acetonitrile using bulk polymerization method. Adsorption studies to determine the rebinding properties of the MIP with the template were conducted using UV Visible spectrophotometer. The fabricated sensor exhibited high recognition ability and affinity for HAA in comparison with the non-imprinted one which was employed as a control, this indicated that the MIP could selectively rebind with TCAA. Reduced graphene oxide (RGO) was used to improve conductivity of the sensor; RGO was obtained from reduction of graphene oxide (GO) synthesized using modified Stauddmer and Hummers method. Polysulphone was used in solution blending of MIP and RGO to form a hybrid which was deposited between two gold plated electrodes by spin coating to form a thin film. The performance of the imprinted sensor was studied using a homemade circuit. The results demonstrate that the sensor based on TCAA-imprinted polymer is fast, cheap and sensitive screening method of TCAA in drinking water.

  11. Study of amorphous semiconductors doped with rare earths (Gd and Er) and conducting polymers by EPR techniques and magnetic susceptibility; Estudo de semicondutores amorfos dopados com terras raras (Gd e Er) e de polimeros condutores atraves das tecnicas de RPE e susceptibilidade magnetica

    Energy Technology Data Exchange (ETDEWEB)

    Sercheli, Mauricio da Silva


    This thesis involves the study of amorphous semiconductors and conducting polymers, which have been characterized by EPR and magnetic susceptibility measurements, and to a lesser extent by Raman spectroscopy and RBS. The semiconductors were studied using thin films of silicon doped with rare earth metals, e.g. erbium and gadolinium, which had their magnetic properties studied. Using these studies we could determine the state of valence of the rare earths as well as their concentrations in the silicon matrix. According to our results, the valence of the rare earth metal ions is 3+, and we were able to conclude that 4f electronic shells could not be used for the calculation of the conducting band in this system. Furthermore, the analysis of the data on the magnetic susceptibility of the Er{sup 3+} ion with cubic crystalline acting field, gave us the opportunity to estimate the overall splitting of their electronic states for the first time. The conducting polymers were studied using samples of poly(3-methylthiophene) doped with ClO{sub 4}{sup -}, which show a phase transition in the range of 230 K to 130 K. The electron paramagnetic resonance also gives important information on the crystallization, doping level and the presence of polarons or bipolarons in conducting polymers. (author)

  12. Triazatruxene-containing hyperbranched polymers:Microwave-assisted synthesis and optoelectronic properties

    Institute of Scientific and Technical Information of China (English)


    Hyperbranched polymer structures represent a class of high-functionality building blocks with excellent three-dimensional topology for the construction of highly substituted conjugated polymers.In this contribution,an efficient microwave synthesis protocol toward the synthesis of conjugated hyperbranched polymers is presented.A novel series of soluble hyperbranched polyfluorenes (PTF1-PTF3) incorporating triazatruxene moiety as the branch units with various branching degrees have thus been successfully constructed with good yields and high molecular weight via a facile "A2+B2+C3" approach.The structures of the hyperbranched polymers were confirmed by NMR and GPC.Their thermal,optical,and electrochemical properties of the hyperbranched polymers were also investigated.The results showed that introduction of triazatruxene units into the hyperbranched structure endowed the polymer with good thermal stability and highly amorphous properties.Photophysical investigation of PTFx revealed strong blue emission in both solution and solid states.Hyperbranched polymers with higher degree of branching and proper content of linear fluorene units exhibited better photophysical properties in terms of narrow emission spectra and relatively high quantum efficiency as well as improved thermal spectral stability.The triazatruxene branching unit also played a role in raising the HOMO energy levels relative to those of polyfluorenes that would help to improve the charge injection and transport properties.The incorporation of triazatruxene unit into hyperbranched polymers has thus explored an effective avenue for constructing optoelectronic polymers with improved functional characteristics.

  13. Novel conjugated polymers based on dithieno[3,2-b:6,7-b]carbazole for solution processed thin-film transistors. (United States)

    Chen, Yagang; Liu, Chengfang; Tian, Hongkun; Bao, Cheng; Zhang, Xiaojie; Yan, Donghang; Geng, Yanhou; Wang, Fosong


    Two conjugated polymers (CPs) P-tCzC12 and P-tCzC16 comprising alternating dithieno[3,2-b:6,7-b]carbazole and 4,4'-dihexadecyl-2,2'-bithiophene units have been designed and synthesized. Upon thermal annealing, they can form ordered thin films in which the polymer backbones dominantly adopted an edge-on orientation respective to the substrate with a lamellar spacing of ≈24 Å and a π-stacking distance of ≈3.7 Å. Organic thin-film transistors (OTFTs) were fabricated by solution casting. A hole mobility of 0.39 cm(2) V(-1) s(-1) has been demonstrated with P-tCzC16. This value is the highest among the CPs containing heteroacenes larger than 4 rings.

  14. Investigation of the amorphous to crystalline phase transition of chemical solution deposited Pb(Zr30Ti70)O3 thin films by soft x-ray absorption and soft x-ray emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Schneller, T.; Schneller, T.; Kohlstedt, H.; Petraru, A.; Waser, R.; Guo, J.; Denlinger, J.; Learmonth, T.; Glans, Per-Andres; Smith, K. E.


    Chemical solution deposited (CSD) complex oxide thin films attract considerable interest in various emerging fields as for example, fuel cells, ferroelectric random access memories or coated conductors. In the present paper the results of soft-x-ray spectroscopy between 100 eV and 500 eV on the amorphous to crystalline phase transition of ferroelectric PbZr{sub 0.3}Ti{sub 0.7}O{sub 3} (PZT) thin films are presented. Five CSD samples derived from the same wafer coated with a PZT film pyrolyzed at 350 C were heat treated at different temperatures between 400 C and 700 C. At first the sample were morphologically and electrically characterized. Subsequently the soft-x-ray absorption and emission experiments were performed at the undulator beamline 8.0 of the Advanced Light Source of the Lawrence Berkeley National Laboratory. Soft-x-ray absorption spectra were acquired for the Ti L{sub 2,3-}, O K-, and C K-edge thresholds by using simultaneously the total electron yield (TEY) and total fluorescence yield (TFY) detection methods. For two samples, annealed at 400 C and 700 C, respectively, the resonant inelastic soft-x-ray spectroscopy (RIXS) was applied for various excitation energies near the Ti L-, O K-edges. We observed clear evidence of a rutile phase at untypically low temperatures. This rutile phase transforms into the perovskite phase upon increasing annealing temperature. These results are discussed in the framework of current microscopic models of the PZT (111) texture selection.

  15. Electrodeposition of amorphous gold alloy films

    Energy Technology Data Exchange (ETDEWEB)

    Kato, Masaru; Senda, Kazutaka [Central Research Laboratory, Kanto Chemical Co., Inc., Saitama 340-0003 (Japan); Advanced Research Institute for Science and Engineering, Waseda University, Tokyo 169-8555 (Japan); Musha, Yuta [Department of Applied Chemistry, School of Science and Engineering, Waseda University, Tokyo 169-8555 (Japan); Sasano, Junji [Kagami Memorial Laboratory for Materials Science and Technology, Waseda University, Tokyo 169-0051 (Japan); Okinaka, Yutaka [Advanced Research Institute for Science and Engineering, Waseda University, Tokyo 169-8555 (Japan); Osaka, Tetsuya [Department of Applied Chemistry, School of Science and Engineering, Waseda University, Tokyo 169-8555 (Japan); Kagami Memorial Laboratory for Materials Science and Technology, Waseda University, Tokyo 169-0051 (Japan); Advanced Research Institute for Science and Engineering, Waseda University, Tokyo 169-8555 (Japan)], E-mail:


    The process for electroplating amorphous gold-nickel-tungsten alloy that we developed previously based on the addition of a gold salt to a known amorphous Ni-W electroplating solution was investigated further using the X-ray diffraction (XRD) method for the purpose of quickly surveying the effects of various experimental variables on the microstructure of the alloy. In this system the gold concentration in the plating bath was found to be critical; i.e., when it is either very low or very high, the deposit becomes crystalline to XRD. The deposit composition varies linearly with the mole ratio of Au to Ni in solution, and the alloy deposit is amorphous to XRD when the atomic ratio of Au/Ni in the deposit is between 0.5 and 1.5. At suitable concentrations of the metal ions, the deposit contains essentially no tungsten. By extending the work on the Au-Ni-W system, an amorphous Au-Co alloy plating process was also developed.

  16. Novel supercritical carbon dioxide impregnation technique for the production of amorphous solid drug dispersions: a comparison to hot melt extrusion. (United States)

    Potter, Catherine; Tian, Yiwei; Walker, Gavin; McCoy, Colin; Hornsby, Peter; Donnelly, Conor; Jones, David S; Andrews, Gavin P


    The formulation of BCS Class II drugs as amorphous solid dispersions has been shown to provide advantages with respect to improving the aqueous solubility of these compounds. While hot melt extrusion (HME) and spray drying (SD) are among the most common methods for the production of amorphous solid dispersions (ASDs), the high temperatures often required for HME can restrict the processing of thermally labile drugs, while the use of toxic organic solvents during SD can impact on end-product toxicity. In this study, we investigated the potential of supercritical fluid impregnation (SFI) using carbon dioxide as an alternative process for ASD production of a model poorly water-soluble drug, indomethacin (INM). In doing so, we produced ASDs without the use of organic solvents and at temperatures considerably lower than those required for HME. Previous studies have concentrated on the characterization of ASDs produced using HME or SFI but have not considered both processes together. Dispersions were manufactured using two different polymers, Soluplus and polyvinylpyrrolidone K15 using both SFI and HME and characterized for drug morphology, homogeneity, presence of drug-polymer interactions, glass transition temperature, amorphous stability of the drug within the formulation, and nonsink drug release to measure the ability of each formulation to create a supersaturated drug solution. Fully amorphous dispersions were successfully produced at 50% w/w drug loading using HME and 30% w/w drug loading using SFI. For both polymers, formulations containing 50% w/w INM, manufactured via SFI, contained the drug in the γ-crystalline form. Interestingly, there were lower levels of crystallinity in PVP dispersions relative to SOL. FTIR was used to probe for the presence of drug-polymer interactions within both polymer systems. For PVP systems, the nature of these interactions depended upon processing method; however, for Soluplus formulations this was not the case. The area under

  17. Solution-processable deep red-emitting supramolecular phosphorescent polymer with novel iridium complex for organic light-emitting diodes (United States)

    Liang, Aihui; Huang, Gui; Wang, Zhiping; Wu, Wenjin; Zhong, Yu; Zhao, Shan


    A novel bis(dibenzo-24-crown-8)-functionalized iridium complex with an emission peak at 665 nm was synthesized. Several deep red-emitting supramolecualr phosphorescent polymers (SPPs) as a class of solutionprocessable electroluminescent (EL) emitters were formed by utilizing the efficient non-bonding self-assembly between the resulting iridium complex and bis(dibenzylammonium)-tethered monomers. These SPPs show an intrinsic glass transition with a T g of ca. 90 °C. The photophysical and electroluminescent properties are strongly dependent on the hosts' structures of the supramolecular phosphorescent polymers. The polymer light-emitting diode based on SPP3 displayed a maximal external quantum efficiency (EQE) of 2.14% ph·el-1 and the Commission Internationale de L'Eclairage (CIE) coordinates of (0.70, 0.29).

  18. A Molecular-Level View of the Physical Stability of Amorphous Solid Dispersions (United States)

    Yuan, Xiaoda

    Many pharmaceutical compounds being developed in recent years are poorly soluble in water. This has led to insufficient oral bioavailability of many compounds in vitro. The amorphous formulation is one of the promising techniques to increase the oral bioavailability of these poorly water-soluble compounds. However, an amorphous drug substance is inherently unstable because it is a high energy form. In order to increase the physical stability, the amorphous drug is often formulated with a suitable polymer to form an amorphous solid dispersion. Previous research has suggested that the formation of an intimately mixed drug-polymer mixture contributes to the stabilization of the amorphous drug compound. The goal of this research is to better understand the role of miscibility, molecular interactions and mobility on the physical stability of amorphous solid dispersions. Methods were developed to detect different degrees of miscibility on nanometer scale and to quantify the extent of hydrogen-bonding interactions between the drug and the polymer. Miscibility, hydrogen-bonding interactions and molecular mobility were correlated with physical stability during a six-month period using three model systems. Overall, this research provides molecular-level insights into many factors that govern the physical stability of amorphous solid dispersions which can lead to a more effective design of stable amorphous formulations.

  19. Containerless synthesis of amorphous and nanophase organic materials

    Energy Technology Data Exchange (ETDEWEB)

    Benmore, Chris J.; Weber, Johann R.


    The invention provides a method for producing a mixture of amorphous compounds, the method comprising supplying a solution containing the compounds; and allowing at least a portion of the solvent of the solution to evaporate while preventing the solute of the solution from contacting a nucleation point. Also provided is a method for transforming solids to amorphous material, the method comprising heating the solids in an environment to form a melt, wherein the environment contains no nucleation points; and cooling the melt in the environment.

  20. Optimization of charge carrier transport balance for performance improvement of PDPP3T-based polymer solar cells prepared using a hot solution. (United States)

    Wang, Jian; Zhang, Fujun; Zhang, Miao; Wang, Wenbin; An, Qiaoshi; Li, Lingliang; Sun, Qianqian; Tang, Weihua; Zhang, Jian


    Polymer solar cells (PSCs), with poly(diketopyrrolopyrrole-terthiophene) (PDPP3T):[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as the active layers, were fabricated using solutions of different temperatures. The best power conversion efficiency (PCE) of the PSCs prepared using a hot solution was about 6.22%, which is better than 5.54% for PSCs prepared using cool (room temperature) solutions and 5.85% for PSCs prepared using cool solutions with a 1,8-diiodooctane (DIO) solvent additive. The underlying reasons for the improved PCE of the PSCs prepared using a hot solution could be attributed to the more dispersive donor and acceptor distribution in the active layer, resulting in a better bi-continuous interpenetrating network for exciton dissociation and charge carrier transport. An enhanced and more balanced charge carrier transport in the active layer is obtained for the PSCs prepared using a hot solution, which can be determined from the J-V curves of the related hole-only and electron-only devices.