Stimuli-responsive magnetic particles for biomedical applications.

PubMed

Medeiros, S F; Santos, A M; Fessi, H; Elaissari, A

2011-01-17

In recent years, magnetic nanoparticles have been studied due to their potential applications as magnetic carriers in biomedical area. These materials have been increasingly exploited as efficient delivery vectors, leading to opportunities of use as magnetic resonance imaging (MRI) agents, mediators of hyperthermia cancer treatment and in targeted therapies. Much attention has been also focused on "smart" polymers, which are able to respond to environmental changes, such as changes in the temperature and pH. In this context, this article reviews the state-of-the art in stimuli-responsive magnetic systems for biomedical applications. The paper describes different types of stimuli-sensitive systems, mainly temperature- and pH sensitive polymers, the combination of this characteristic with magnetic properties and, finally, it gives an account of their preparation methods. The article also discusses the main in vivo biomedical applications of such materials. A survey of the recent literature on various stimuli-responsive magnetic gels in biomedical applications is also included. Copyright © 2010 Elsevier B.V. All rights reserved.

A solid state actuator based on polypyrrole (PPy) and a solid electrolyte NBR working in air

NASA Astrophysics Data System (ADS)

Cho, Misuk; Nam, Jaedo; Choi, Hyouk Ryeol; Koo, Jachoon; Lee, Youngkwan

2005-05-01

The solid polymer electrolyte based conducting polymer actuator was presented. In the preparation of acutuator module, an ionic liquid impregnated a synthetic rubber (NBR) and PPy were used as a solid polymer electrolyte and conducting polymer, respectively. An ionic liquid, 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide (BMITFSI) is gradually dispersed into the NBR film and the conducting polymer, PPy was synthesized on the surface of NBR. The ionic conductivity of new type solid polymer electrolyte as a function of the immersion time was investigated. The cyclic voltammetry responsed and the redox switching dynamics of PEDOT in NBR matrix were studied. The displacement of the actuator was measured by laser beam.

Performance improvement of gel- and solid-state dye-sensitized solar cells by utilization the blending effect of poly (vinylidene fluoride-co-hexafluropropylene) and poly (acrylonitrile-co-vinyl acetate) co-polymers

NASA Astrophysics Data System (ADS)

Venkatesan, Shanmugam; Obadja, Nesia; Chang, Ting-Wei; Chen, Li-Tung; Lee, Yuh-Lang

2014-12-01

Poly (vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) and poly (acrylonitrile-co-vinyl acetate) (PAN-VA) are used as gelator to prepare gel- and solid-state polymer electrolytes for dye sensitized solar cells (DSSCs) applications. The electrolytes prepared using PVDF-HFP have higher conductivities than those prepared using PAN-VA. In blended polymers, the conductivities of the electrolytes increase with increasing composition of PVDF-HFP; at 75% PVDF-HFP, conductivity of the blended polymer surpassed that of pure polymers. It is also found that the viscosity of the electrolyte prepared by PAN-VA (1.2 kPaS) is much lower than that by PVDF-HFP (11 kPaS). Therefore, increasing PAN-VA composition can decrease the viscosity of the electrolyte, improving the penetration of electrolytes in the TiO2 matrix. By controlling the ratio of PVDF-HFP/PAN-VA, the conductivity and viscosity of the electrolyte can be regulated and an optimal ratio based on the conversion efficiency of the gel- and solid state DSSCs is obtained at the ratio of 3/1. The highest efficiency achieved by the gel- and solid-state cells using the blending polymers are 6.3% and 4.88%, respectively, which are higher than those prepared using pure polymers (5.53% and 4.56%, respectively). The introduction of TiO2 fillers to the solid electrolyte can further increase the cell efficiency to 5.34%.

Surface-modified multifunctional MIP nanoparticles

NASA Astrophysics Data System (ADS)

Moczko, Ewa; Poma, Alessandro; Guerreiro, Antonio; Perez de Vargas Sansalvador, Isabel; Caygill, Sarah; Canfarotta, Francesco; Whitcombe, Michael J.; Piletsky, Sergey

2013-04-01

The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as a protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity (PEG methacrylate); electro-activity (vinylferrocene); fluorescence (eosin acrylate); thiol groups (pentaerythritol tetrakis(3-mercaptopropionate)). The method has broad applicability and can be used to produce multifunctional imprinted nanoparticles with potential for further application in the biosensors, diagnostics and biomedical fields and as an alternative to natural receptors.The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as a protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity (PEG methacrylate); electro-activity (vinylferrocene); fluorescence (eosin acrylate); thiol groups (pentaerythritol tetrakis(3-mercaptopropionate)). The method has broad applicability and can be used to produce multifunctional imprinted nanoparticles with potential for further application in the biosensors, diagnostics and biomedical fields and as an alternative to natural receptors. Electronic supplementary information (ESI) available: Details of the synthesis of eosin O-acrylate monomer and 1H-NMR spectrum of MIP NPs post-derivatised with PEG shell. See DOI: 10.1039/c3nr00354j

Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

2016-02-01

The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

Porous inorganic-organic shape memory polymers.

PubMed

Zhang, Dawei; Burkes, William L; Schoener, Cody A; Grunlan, Melissa A

2012-06-21

Thermoresponsive shape memory polymers (SMPs) are a type of stimuli-sensitive materials that switch from a temporary shape back to their permanent shape upon exposure to heat. While the majority of SMPs have been fabricated in the solid form, porous SMP foams exhibit distinct properties and are better suited for certain applications, including some in the biomedical field. Like solid SMPs, SMP foams have been restricted to a limited group of organic polymer systems. In this study, we prepared inorganic-organic SMP foams based on the photochemical cure of a macromer comprised of inorganic polydimethylsiloxane (PDMS) segments and organic poly(ε-caprolactone) (PCL) segments, diacrylated PCL(40)-block-PDMS(37)-block-PCL(40). To achieve tunable pore size with high interconnectivity, the SMP foams were prepared via a refined solvent-casting/particulate-leaching (SCPL) method. By varying design parameters such as degree of salt fusion, macromer concentration in the solvent and salt particle size, the SMP foams with excellent shape memory behavior and tunable pore size, pore morphology, and modulus were obtained.

Application of Solid-State NMR Relaxometry for Characterization and Formulation Optimization of Grinding-Induced Drug Nanoparticle.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Moribe, Kunikazu

2016-03-07

The formation mechanism of drug nanoparticles was investigated using solid-state nuclear magnetic resonance (NMR) techniques for the efficient discovery of an optimized nanoparticle formulation. The cogrinding of nifedipine (NIF) with polymers, including hydroxypropyl methylcellulose (HPMC) and polyvinylpyrrolidone (PVP), and sodium dodecyl sulfate (SDS) was performed to prepare the NIF nanoparticle formulations. Then, solid-state NMR relaxometry was used for the nanometer-order characterization of NIF in the polymer matrix. Solid-state NMR measurements revealed that the crystal size of NIF was reduced to several tens of nanometers with amorphization of NIF by cogrinding with HPMC and SDS for 100 min. Similarly, the size of the NIF crystal was reduced to less than 90 nm in the 40 min ground mixture of NIF/PVP/SDS. Furthermore, 100 min grinding of NIF/PVP/SDS induced amorphization of almost all the NIF crystals followed by nanosizing. The hydrogen bond between NIF and PVP led to the efficient amorphization of NIF in the NIF/PVP/SDS system compared with NIF/HPMC/SDS system. The efficient nanosizing of the NIF crystal in the solid state, revealed by the solid-state NMR relaxation time measurements, enabled the formation of large amounts of NIF nanoparticles in water followed by the polymer dissolution. In contrast, excess amorphization of the NIF crystals failed to efficiently prepare the NIF nanoparticles. The solid-state characterization of the crystalline NIF revealed good correlation with the NIF nanoparticles formation during aqueous dispersion. Furthermore, the solid-state NMR measurements including relaxometry successfully elucidated the nanometer-order dispersion state of NIF in polymer matrix, leading to the discovery of optimized conditions for the preparation of suitable drug nanoparticles.

Fundamental characteristics of degradation-recoverable solid-state DFB polymer laser.

PubMed

Yoshioka, Hiroaki; Yang, Yu; Watanabe, Hirofumi; Oki, Yuji

2012-02-13

A novel solid-state dye laser with degradation recovery was proposed and demonstrated. Polydimethylsiloxane was used as a nanoporous solid matrix to enable the internal circulation of dye molecules in the solid state. An internal circulation model for the dye molecules was also proposed and verified numerically by assuming molecular mobility and using a proposed diffusion equation. The durability of the laser was increased 20.5-fold compared with that of a conventional polymethylmethacrylate laser. This novel laser solves the low-durability problem of dye-doped polymer lasers.

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

DOE PAGES

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.; ...

2017-11-30

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

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

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Solid-state radioluminescent compositions

DOEpatents

Clough, Roger L.; Gill, John T.; Hawkins, Daniel B.; Renschler, Clifford L.; Shepodd, Timothy J.; Smith, Henry M.

1991-01-01

A solid state radioluminescent composition for light source comprises an optically clear polymer organic matrix containing tritiated organic materials and dyes capable of "red" shifting primary scintillation emissions from the polymer matrix. The tritiated organic materials are made by reducing, with tritium, an unsaturated organic compound that prior to reduction contains olefinic or alkynylic bonds.

New Solid Polymer Electrolytes for Improved Lithium Batteries

NASA Technical Reports Server (NTRS)

Hehemann, David G.

2002-01-01

The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

PubMed

Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

2016-01-11

The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer translocation in solid-state nanopores: Dependence on hydrodynamic interactions and polymer configuration

NASA Astrophysics Data System (ADS)

Edmonds, Christopher M.; Hesketh, Peter J.; Nair, Sankar

2013-11-01

We present a Brownian dynamics investigation of 3-D Rouse and Zimm polymer translocation through solid-state nanopores. We obtain different scaling exponents α for both polymers using two initial configurations: minimum energy, and 'steady-state'. For forced translocation, Rouse polymers (no hydrodynamic interactions), shows a large dependence of α on initial configuration and voltage. Higher voltages result in crowding at the nanopore exit and reduced α. When the radius of gyration is in equilibrium at the beginning and end of translocation, α = 1 + υ where υ is the Flory exponent. For Zimm polymers (including hydrodynamic interactions), crowding is reduced and α = 2υ. Increased pore diameter does not affect α at moderate voltages that reduce diffusion effects. For unforced translocation using narrow pores, both polymers give α = 1 + 2υ. Due to increased polymer-pore interactions in the narrow pore, hydrodynamic drag effects are reduced, resulting in identical scaling.

Na3.4Zr1.8Mg0.2Si2PO12 filled poly(ethylene oxide)/Na(CF3SO2)2N as flexible composite polymer electrolyte for solid-state sodium batteries

NASA Astrophysics Data System (ADS)

Zhang, Zhizhen; Xu, Kaiqi; Rong, Xiaohui; Hu, Yong-Sheng; Li, Hong; Huang, Xuejie; Chen, Liquan

2017-12-01

Solid electrolytes with high ionic conductivity and excellent electrochemical stability are of prime significance to enable the application of solid-state batteries in energy storage and conversion. In this study, solid composite polymer electrolytes (CPEs) based on sodium bis(trifluorosulfonyl) imide (NaTFSI) and poly (ethylene oxide) (PEO) incorporated with active ceramic filler (NASICON) are reported for the first time. With the addition of NASICON fillers, the thermal stability and electrochemical stability of the CPEs are improved. A high conductivity of 2.8 mS/cm (at 80 °C) is readily achieved when the content of the NASICON filler in the composite polymer reaches 50 wt%. Furthermore, Na3V2(PO4)3/CPE/Na solid-state batteries using this composite electrolyte display good rate and excellent cycle performance.

[Fundamentals of plasma chemistry and its application to drug engineering].

PubMed

Kuzuya, M

1996-04-01

In this review, our novel research works in both low temperature plasma chemistry and solid state plasma chemistry were described. As for low temperature plasma, the ESR study on plasma-induced radicals of several selected conventional polymers was shown including the detailed analyses of the radical structure and the mechanism by which the radicals were formed on typical degradable methacrylic polymers and cross-linkable polystyrene. One of the pharmaceutical applications of the plasma processing for drug delivery system (DDS) was also described, which includes the preparations of double-compressed tablet consisting of drugs as a core material and various types of polymers as a wall material followed by plasma-irradiation on such a tablet. As for solid state plasma, the detailed reaction mechanism of solid state mechanochemical polymerization was shown including the solid state single electron transfer and the special feature of the resulting polymers. The structural criteria for polymerizable monomer derived from the quantum chemical considerations were also established. Based on the above findings, we synthesized various polymeric prodrugs by mechanochemical polymerization and studied the nature of hydrolyses (drug release).

Polycarbonate-based polyurethane as a polymer electrolyte matrix for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Bao, Junjie; Shi, Gaojian; Tao, Can; Wang, Chao; Zhu, Chen; Cheng, Liang; Qian, Gang; Chen, Chunhua

2018-06-01

Four kinds of polycarbonate-based polyurethane with 8-14 wt% hard segments content are synthesized via reactions of polycarbonatediol, hexamethylene diisocyanate and diethylene glycol. The mechanical strength of the polyurethanes increase with the increase of hard segments content. Solid polymer electrolytes composed of the polycarbonate-based polyurethanes and LiTFSI exhibits fascinating characteristics for all-solid-state lithium batteries with a high ionic conductivity of 1.12 × 10-4 S cm-1 at 80 °C, an electrochemical stability window up to 4.5 V (vs. Li+/Li), excellent mechanical strength and superior interfacial stability against lithium metal. The all-solid-state batteries using LiFePO4 cathode can deliver high discharge capacities (161, 158, 134 and 93 mAh g-1 at varied rates of 0.2, 0.5, 1 and 2 C) at 80 °C and excellent cycling performance (with 91% capacity retention after 600 cycles at 1 C). All the results indicate that such a polyurethane-based solid polymer electrolyte can be a promising candidate for all-solid-state lithium batteries.

Classification of solid dispersions: correlation to (i) stability and solubility (ii) preparation and characterization techniques.

PubMed

Meng, Fan; Gala, Urvi; Chauhan, Harsh

2015-01-01

Solid dispersion has been a topic of interest in recent years for its potential in improving oral bioavailability, especially for poorly water soluble drugs where dissolution could be the rate-limiting step of oral absorption. Understanding the physical state of the drug and polymers in solid dispersions is essential as it influences both the stability and solubility of these systems. This review emphasizes on the classification of solid dispersions based on the physical states of drug and polymer. Based on this classification, stability aspects such as crystallization tendency, glass transition temperature (Tg), drug polymer miscibility, molecular mobility, etc. and solubility aspects have been discussed. In addition, preparation and characterization methods for binary solid dispersions based on the classification have also been discussed.

Nano-sponge ionic liquid-polymer composite electrolytes for solid-state lithium power sources

NASA Astrophysics Data System (ADS)

Liao, Kang-Shyang; Sutto, Thomas E.; Andreoli, Enrico; Ajayan, Pulickel; McGrady, Karen A.; Curran, Seamus A.

Solid polymer gel electrolytes composed of 75 wt.% of the ionic liquid, 1- n-butyl-2,3-dimethylimidazolium bis-trifluoromethanesulfonylimide with 1.0 M lithium bis-trifluoromethanesulfonylimide and 25 wt.% poly(vinylidenedifluoro-hexafluoropropene) are characterized as the electrolyte/separator in solid-state lithium batteries. The ionic conductivity of these gels ranges from 1.5 to 2.0 mS cm -1, which is several orders of magnitude more conductive than any of the more commonly used solid polymers, and comparable to the best solid gel electrolytes currently used in industry. TGA indicates that these polymer gel electrolytes are thermally stable to over 280 °C, and do not begin to thermally decompose until over 300 °C; exhibiting a significant advancement in the safety of lithium batteries. Atomic force microscopy images of these solid thin films indicate that these polymer gel electrolytes have the structure of nano-sponges, with a sub-micron pore size. For these thin film batteries, 150 charge-discharge cycles are run for Li xCoO 2 where x is cycled between 0.95 down to 0.55. Minimal internal resistance effects are observed over the charging cycles, indicating the high ionic conductivity of the ionic liquid solid polymer gel electrolyte. The overall cell efficiency is approximately 98%, and no significant loss in battery efficiency is observed over the 150 cycles.

Preparation of redox polymer cathodes for thin film rechargeable batteries

DOEpatents

Skotheim, T.A.; Lee, H.S.; Okamoto, Yoshiyuki.

1994-11-08

The present invention relates to the manufacture of thin film solid state electrochemical devices using composite cathodes comprising a redox polymer capable of undergoing oxidation and reduction, a polymer solid electrolyte and conducting carbon. The polymeric cathode material is formed as a composite of radiation crosslinked polymer electrolytes and radiation crosslinked redox polymers based on polysiloxane backbones with attached organosulfur side groups capable of forming sulfur-sulfur bonds during electrochemical oxidation.

Pharmaceutical applications of dynamic mechanical thermal analysis.

PubMed

Jones, David S; Tian, Yiwei; Abu-Diak, Osama; Andrews, Gavin P

2012-04-01

The successful development of polymeric drug delivery and biomedical devices requires a comprehensive understanding of the viscoleastic properties of polymers as these have been shown to directly affect clinical efficacy. Dynamic mechanical thermal analysis (DMTA) is an accessible and versatile analytical technique in which an oscillating stress or strain is applied to a sample as a function of oscillatory frequency and temperature. Through cyclic application of a non-destructive stress or strain, a comprehensive understanding of the viscoelastic properties of polymers may be obtained. In this review, we provide a concise overview of the theory of DMTA and the basic instrumental/operating principles. Moreover, the application of DMTA for the characterization of solid pharmaceutical and biomedical systems has been discussed in detail. In particular we have described the potential of DMTA to measure and understand relaxation transitions and miscibility in binary and higher-order systems and describe the more recent applications of the technique for this purpose. © 2011 Elsevier B.V. All rights reserved.

Surface-modified multifunctional MIP nanoparticles.

PubMed

Moczko, Ewa; Poma, Alessandro; Guerreiro, Antonio; Perez de Vargas Sansalvador, Isabel; Caygill, Sarah; Canfarotta, Francesco; Whitcombe, Michael J; Piletsky, Sergey

2013-05-07

The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as a protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity (PEG methacrylate); electro-activity (vinylferrocene); fluorescence (eosin acrylate); thiol groups (pentaerythritol tetrakis(3-mercaptopropionate)). The method has broad applicability and can be used to produce multifunctional imprinted nanoparticles with potential for further application in the biosensors, diagnostics and biomedical fields and as an alternative to natural receptors.

Ultra-thin Solid-State Li-Ion Electrolyte Membrane Facilitated by a Self-Healing Polymer Matrix.

PubMed

Whiteley, Justin M; Taynton, Philip; Zhang, Wei; Lee, Se-Hee

2015-11-18

Thin solid membranes are formed by a new strategy, whereby an in situ derived self-healing polymer matrix that penetrates the void space of an inorganic solid is created. The concept is applied as a separator in an all-solid-state battery with an FeS2 -based cathode and achieves tremendous performance for over 200 cycles. Processing in dry conditions represents a paradigm shift for incorporating high active-material mass loadings into mixed-matrix membranes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advanced Coatings from Natural-Based Polymers for Metals

DTIC Science & Technology

2000-07-01

Polyimide Interfaces," J. surfaces using a simple dipping-withdrawing coating Vac. Sci. Technol., 3,1390 (1985).converted into the solid layers by heat...Tang, C.H., "Interface Reaction During Metalliza- more, the Al metal in the substrate favorably interacted tion of Cured Polyimide : An XPS Study," 1...property together with its biocompatability was the reason why CS is widely used in biomedical applications, for example, a bacteriostatic agent, a

Molecular mechanism of polymer-assisting supersaturation of poorly water-soluble loratadine based on experimental observations and molecular dynamic simulations.

PubMed

Zhang, Shenwu; Sun, Mengchi; Zhao, Yongshan; Song, Xuyang; He, Zhonggui; Wang, Jian; Sun, Jin

2017-10-01

Polymers have been usually used to retard nucleation and crystal growth in order to maintain supersaturation, yet their roles in inhibition of nucleation and crystal growth are poorly understood. In our work, the polymer-based supersaturation performances and molecular mechanisms of poorly aqueous soluble loratadine were investigated. Two common hydrophilic polymers (hydroxylpropylmethyl cellulose acetate succinate (HPMC-AS) and poly(vinylpyrrolidone-co-vinyl-acetate) (PVP-VA)) were used. It was found that HPMC-AS was a better polymer to prevent drug molecules from aggregation and to maintain the supersaturated state in solution than PVP-VA. The in vitro dissolution experiments showed that HPMC-AS solid dispersions had more rapid release at pH 4.5 and 6.8 media than PVP-VA solid dispersions under the un-sink condition. Moreover, molecular dynamic simulation results showed that HPMC-AS was more firmly absorbed onto a surface of the drug nanoparticles than PVP-VA due to bigger hydrophobic areas of HPMC-AS. Thereby, crystallization process of loratadine was inhibited in the presence of water to provide prolonged stability of the supersaturated state. In conclusion, polymers played a key role in maintaining supersaturation state of loratadine solid dispersions by strong drug-polymer interactions and the hydrophobic characteristic of polymers.

A Newly Designed Composite Gel Polymer Electrolyte Based on Poly(Vinylidene Fluoride-Hexafluoropropylene) (PVDF-HFP) for Enhanced Solid-State Lithium-Sulfur Batteries.

PubMed

Xia, Yan; Wang, Xiuli; Xia, Xinhui; Xu, Ruochen; Zhang, Shengzhao; Wu, Jianbo; Liang, Yanfei; Gu, Changdong; Tu, Jiangping

2017-10-26

Developing high-performance solid-state electrolytes is crucial for the innovation of next-generation lithium-sulfur batteries. Herein, a facile method for preparation of a novel gel polymer electrolyte (GPE) based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) is reported. Furthermore, Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 (LATP) nanoparticles as the active fillers are uniformly embedded into the GPE to form the final PVDF-HFP/LATP composite gel polymer electrolyte (CPE). Impressively, the obtained CPE demonstrates a high lithium ion transference number of 0.51 and improved electrochemical stability as compared to commercial liquid electrolyte. In addition, the assembled solid-sate Li-S battery with the composite gel polymer electrolyte membrane presents a high initial capacity of 918 mAh g -1 at 0.05 C, and better cycle performance than the counterparts with liquid electrolyte. Our designed PVDF-HFP/LATP composite can be a promising electrolyte for next-generation solid-state batteries with high cycling stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid polymer electrolytes

DOEpatents

Abraham, Kuzhikalail M.; Alamgir, Mohamed; Choe, Hyoun S.

1995-01-01

This invention relates to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF.sub.3 SO.sub.2).sub.2, LiAsF.sub.6, and LiClO.sub.4.

Progress in battery technology since the First CSULB Annual Battery Conference and prospects for the future

NASA Astrophysics Data System (ADS)

Pickett, David F., Jr.

1992-04-01

An evaluation is made of noteworthy trends in the development of advanced electrochemical cells since January 1986. The advancements noted encompass LiAr batteries, spacecraft power supply Ni-H and Li-SO2 batteries, battery-powered biomedical devices, rechargeable Li-ion batteries, and the development of ambient temperature rechargeable lithium polymer solid electrolyte batteries. Attention is given to OSHA regulatory guidelines for recently commercially introduced advanced battery systems.

Metal-containing and related polymers for biomedical applications.

PubMed

Yan, Yi; Zhang, Jiuyang; Ren, Lixia; Tang, Chuanbing

2016-10-07

A survey of the most recent progress in the biomedical applications of metal-containing polymers is given. Due to the unique optical, electrochemical, and magnetic properties, at least 30 different metal elements, most of them transition metals, are introduced into polymeric frameworks for interactions with biology-relevant substrates via various means. Inspired by the advance of metal-containing small molecular drugs and promoted by the great progress in polymer chemistry, metal-containing polymers have gained momentum during recent decades. According to their different applications, this review summarizes the following biomedical applications: (1) metal-containing polymers as drug delivery vehicles; (2) metal-containing polymeric drugs and biocides, including antimicrobial and antiviral agents, anticancer drugs, photodynamic therapy agents, radiotherapy agents and biocides; (3) metal-containing polymers as biosensors, and (4) metal-containing polymers in bioimaging.

Solid polymer electrolytes

DOEpatents

Abraham, K.M.; Alamgir, M.; Choe, H.S.

1995-12-12

This invention relates to Li ion (Li{sup +}) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF{sub 3}SO{sub 2}){sub 2}, LiAsF{sub 6}, and LiClO{sub 4}. 2 figs.

Synthesis and characterization of a Hyaluronan-polyethylene copolymer for biomedical applications.

PubMed

Oldinski, Rachael A; Cranson, Cody N; James, Susan P

2010-08-01

Hyaluronan (HA)-based biomaterials are of interest for bone and cartilage tissue engineering because HA plays an important role in orthopedic tissue development, function, and repair. The goal of this project was to develop a biomaterial that incorporated the constituents of both a hydrogel and a hydrophobic polymer for biomedical applications. A series of amphiphilic graft copolymers consisting of HA, a glycosaminoglycan, and high-density polyethylene (HDPE), that is, HA-co-HDPE, were fabricated. The chemical characteristics, physical and viscoelastic properties, and cytocompatibility of novel HA-co-HDPE materials were characterized via Fourier Transform infrared (FTIR) spectroscopy, solid state nuclear magnetic resonance (ssNMR) spectroscopy, differential scanning calorimetry (DSC), dynamic shear testing, and an in vitro human osteoblast cell study. The esterification reaction between HA and functionalized HDPE resulted in semicrystalline, insoluble powder. The dynamic shear properties of HA-co-HDPE concentrated solutions were more like natural proteoglycans than the HA control. HA-co-HDPE was successfully compression molded into disks that swelled upon hydration. Osteoblasts were viable and expressed the osteoblast phenotype after 7 days of culture on HA-co-HDPE materials. These HA-co-HDPE materials may have several biomaterial applications in saline suspension or molded form, including orthopedic tissue repair.

Recent development of antifouling polymers: structure, evaluation, and biomedical applications in nano/micro-structures.

PubMed

Liu, Lingyun; Li, Wenchen; Liu, Qingsheng

2014-01-01

Antifouling polymers have been proven to be vital to many biomedical applications such as medical implants, drug delivery, and biosensing. This review covers the major development of antifouling polymers in the last 2 decades, including the material chemistry, structural factors important to antifouling properties, and how to challenge or evaluate the antifouling performances. We then discuss the applications of antifouling polymers in nano/micro-biomedical applications in the form of nanoparticles, thin coatings for medical devices (e.g., artificial joint, catheter, wound dressing), and nano/microscale fibers. © 2014 Wiley Periodicals, Inc.

Nickel/metal hydride secondary batteries using an alkaline solid polymer electrolyte

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

Vassal, N.; Salmon, E.; Fauvarque, J.F.

1999-01-01

Sealed alkaline solid polymer electrolyte nickel/metal hydride laboratory cells have been constructed and tested to evaluate their properties. Studies of the cycle life, self-discharge, and behavior of cells at different temperatures were carried out. The first results on the electrochemical behavior of an alkaline solid polymer electrolyte [based on poly(ethylene oxide), potassium hydroxide, and water] medium are presented here and show good reversibility of this all-solid-state system for more than 500 cycles, without significant loss of capacity and with a reasonable average discharge efficiency (close to 80%). The temperature-dependence study allowed the determination of optimum operating conditions between 0 andmore » 40 C. Characteristics of the solid polymer electrolyte based Ni/MH cells are compared to those of several other rechargeable battery systems.« less

Recent Advances in Glycerol Polymers: Chemistry and Biomedical Applications

PubMed Central

Zhang, Heng

2015-01-01

Glycerol polymers are attracting increased attention due to the diversity of polymer compositions and architectures available. This article provides a brief chronological review on the current status of these polymers along with representative examples of their use for biomedical applications. First, we describe the underlying chemistry of glycerol, which provides access to a range of monomers for subsequent polymerizations. We then review the various synthetic methodologies to prepare glycerol-based polymers including polyethers, polycarbonates, polyesters, and so forth. Next, we describe several biomedical applications where glycerol polymers are being investigated including carriers for drug delivery, sealants or coatings for tissue repair, and agents possessing antibacterial activity. Fourth, we describe the growing market opportunity for the use of polymers in medicine. Finally we conclude and summarize the findings, as well as discuss potential opportunities for continued research efforts. PMID:25308354

The theory and design of piezoelectric/pyroelectric polymer film sensors for biomedical engineering applications.

PubMed

Brown, L F

1989-01-01

The unique properties of piezoelectric/pyroelectric polymers offer many new opportunities for biomedical engineering sensor applications. Since their discovery nearly 20 years ago, the polymer films have been used for many novel switching and sensor applications. Despite the prodigious exposure from many recent publications describing piezo film applications, methods of sensor fabrication and circuit interfacing still elude most engineers. This paper is presented as a tutorial guide to applying piezo polymers to biomedical engineering applications. A review of the fundamentals of piezoelectricity/pyroelectricity in piezo polymers is first presented. Their material properties are contrasted with piezoelectric ceramic materials. Some advantages and disadvantages of the films for biomedical sensors are discussed. Specific details on the fabrication of piezo film sensors are presented. Methods are described for forming, cutting, and mounting film sensors, and making lead connections. A brief discussion of equivalent circuit models for the design and simulation of piezoelectric/pyroelectric sensors is included, as well as common circuit interface techniques. Finally, several sources are recommended for further information on a variety of biomedical sensor applications.

Functional supramolecular polymers for biomedical applications.

PubMed

Dong, Ruijiao; Zhou, Yongfeng; Huang, Xiaohua; Zhu, Xinyuan; Lu, Yunfeng; Shen, Jian

2015-01-21

As a novel class of dynamic and non-covalent polymers, supramolecular polymers not only display specific structural and physicochemical properties, but also have the ability to undergo reversible changes of structure, shape, and function in response to diverse external stimuli, making them promising candidates for widespread applications ranging from academic research to industrial fields. By an elegant combination of dynamic/reversible structures with exceptional functions, functional supramolecular polymers are attracting increasing attention in various fields. In particular, functional supramolecular polymers offer several unique advantages, including inherent degradable polymer backbones, smart responsiveness to various biological stimuli, and the ease for the incorporation of multiple biofunctionalities (e.g., targeting and bioactivity), thereby showing great potential for a wide range of applications in the biomedical field. In this Review, the trends and representative achievements in the design and synthesis of supramolecular polymers with specific functions are summarized, as well as their wide-ranging biomedical applications such as drug delivery, gene transfection, protein delivery, bio-imaging and diagnosis, tissue engineering, and biomimetic chemistry. These achievements further inspire persistent efforts in an emerging interdisciplin-ary research area of supramolecular chemistry, polymer science, material science, biomedical engineering, and nanotechnology. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quasi-Solid-State Rechargeable Li-O2 Batteries with High Safety and Long Cycle Life at Room Temperature.

PubMed

Cho, Sung Man; Shim, Jimin; Cho, Sung Ho; Kim, Jiwoong; Son, Byung Dae; Lee, Jong-Chan; Yoon, Woo Young

2018-05-09

As interest in electric vehicles and mass energy storage systems continues to grow, Li-O 2 batteries are attracting much attention as a candidate for next-generation energy storage systems owing to their high energy density. However, safety problems related to the use of lithium metal anodes have hampered the commercialization of Li-O 2 batteries. Herein, we introduced a quasi-solid polymer electrolyte with excellent electrochemical, chemical, and thermal stabilities into Li-O 2 batteries. The ion-conducting QSPE was prepared by gelling a polymer network matrix consisting of poly(ethylene glycol) methyl ether methacrylate, methacrylated tannic acid, lithium trifluoromethanesulfonate, and nanofumed silica with a small amount of liquid electrolyte. The quasi-solid-state Li-O 2 cell consisted of a lithium powder anode, a quasi-solid polymer electrolyte, and a Pd 3 Co/multiwalled carbon nanotube cathode, which enhanced the electrochemical performance of the cell. This cell, which exhibited improved safety owing to the suppression of lithium dendrite growth, achieved a lifetime of 125 cycles at room temperature. These results show that the introduction of a quasi-solid electrolyte is a potentially new alternative for the commercialization of solid-state Li-O 2 batteries.

Present status of solid state photoelectrochemical solar cells and dye sensitized solar cells using PEO-based polymer electrolytes

NASA Astrophysics Data System (ADS)

Singh, Pramod Kumar; Nagarale, R. K.; Pandey, S. P.; Rhee, H. W.; Bhattacharya, Bhaskar

2011-06-01

Due to energy crises in the future, much effort is being directed towards alternate sources. Solar energy is accepted as a novel substitute for conventional sources of energy. Out of the long list of various types of solar cells available on the market, solid state photoelectrochemical solar cells (SSPECs) and dye sensitized solar cells (DSSCs) are proposed as an alternative to costly crystalline solar cell. This review provides a common platform for SSPECs and DSSCs using polymer electrolyte, particularly on polyethylene oxide (PEO)-based polymer electrolytes. Due to numerous advantageous properties of PEO, it is frequently used as an electrolyte in both SSPECs as well as DSSCs. In DSSCs, so far high efficiency (more than 11%) has been obtained only by using volatile liquid electrolyte, which suffers many disadvantages, such as corrosion, leakage and evaporation. The PEO-based solid polymer proves its importance and could be used to solve the problems stated above. The recent developments in SSPECs and DSSCs using modified PEO electrolytes by adding nano size inorganic fillers, blending with low molecular weight polymers and ionic liquid (IL) are discussed in detail. The role of ionic liquid in modifying the electrical, structural and photoelectrochemical properties of PEO polymer electrolytes is also described.

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

PubMed

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

2017-11-01

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

Polydopamine--a nature-inspired polymer coating for biomedical science.

PubMed

Lynge, Martin E; van der Westen, Rebecca; Postma, Almar; Städler, Brigitte

2011-12-01

Polymer coatings are of central importance for many biomedical applications. In the past few years, poly(dopamine) (PDA) has attracted considerable interest for various types of biomedical applications. This feature article outlines the basic chemistry and material science regarding PDA and discusses its successful application from coatings for interfacing with cells, to drug delivery and biosensing. Although many questions remain open, the primary aim of this feature article is to illustrate the advent of PDA on its way to become a popular polymer for bioengineering purposes.

Reconfigurable Solid-state Dye-doped Polymer Ring Resonator Lasers

NASA Astrophysics Data System (ADS)

Chandrahalim, Hengky; Fan, Xudong

2015-12-01

This paper presents wavelength configurable on-chip solid-state ring lasers fabricated by a single-mask standard lithography. The single- and coupled-ring resonator hosts were fabricated on a fused-silica wafer and filled with 3,3‧-Diethyloxacarbocyanine iodide (CY3), Rhodamine 6G (R6G), and 3,3‧-Diethylthiadicarbocyanine iodide (CY5)-doped polymer as the reconfigurable gain media. The recorded lasing threshold was ~220 nJ/mm2 per pulse for the single-ring resonator laser with R6G, marking the lowest threshold shown by solid-state dye-doped polymer lasers fabricated with a standard lithography process on a chip. A single-mode lasing from a coupled-ring resonator system with the lasing threshold of ~360 nJ/mm2 per pulse was also demonstrated through the Vernier effect. The renewability of the dye-doped polymer was examined by removing and redepositing the dye-doped polymer on the same resonator hosts for multiple cycles. We recorded consistent emissions from the devices for all trials, suggesting the feasibility of employing this technology for numerous photonic and biochemical sensing applications that entail for sustainable, reconfigurable, and low lasing threshold coherent light sources on a chip.

Reconfigurable Solid-state Dye-doped Polymer Ring Resonator Lasers

PubMed Central

Chandrahalim, Hengky; Fan, Xudong

2015-01-01

This paper presents wavelength configurable on-chip solid-state ring lasers fabricated by a single-mask standard lithography. The single- and coupled-ring resonator hosts were fabricated on a fused-silica wafer and filled with 3,3′-Diethyloxacarbocyanine iodide (CY3), Rhodamine 6G (R6G), and 3,3′-Diethylthiadicarbocyanine iodide (CY5)-doped polymer as the reconfigurable gain media. The recorded lasing threshold was ~220 nJ/mm2 per pulse for the single-ring resonator laser with R6G, marking the lowest threshold shown by solid-state dye-doped polymer lasers fabricated with a standard lithography process on a chip. A single-mode lasing from a coupled-ring resonator system with the lasing threshold of ~360 nJ/mm2 per pulse was also demonstrated through the Vernier effect. The renewability of the dye-doped polymer was examined by removing and redepositing the dye-doped polymer on the same resonator hosts for multiple cycles. We recorded consistent emissions from the devices for all trials, suggesting the feasibility of employing this technology for numerous photonic and biochemical sensing applications that entail for sustainable, reconfigurable, and low lasing threshold coherent light sources on a chip. PMID:26674508

Reconfigurable Solid-state Dye-doped Polymer Ring Resonator Lasers.

PubMed

Chandrahalim, Hengky; Fan, Xudong

2015-12-17

This paper presents wavelength configurable on-chip solid-state ring lasers fabricated by a single-mask standard lithography. The single- and coupled-ring resonator hosts were fabricated on a fused-silica wafer and filled with 3,3'-Diethyloxacarbocyanine iodide (CY3), Rhodamine 6G (R6G), and 3,3'-Diethylthiadicarbocyanine iodide (CY5)-doped polymer as the reconfigurable gain media. The recorded lasing threshold was ~220 nJ/mm(2) per pulse for the single-ring resonator laser with R6G, marking the lowest threshold shown by solid-state dye-doped polymer lasers fabricated with a standard lithography process on a chip. A single-mode lasing from a coupled-ring resonator system with the lasing threshold of ~360 nJ/mm(2) per pulse was also demonstrated through the Vernier effect. The renewability of the dye-doped polymer was examined by removing and redepositing the dye-doped polymer on the same resonator hosts for multiple cycles. We recorded consistent emissions from the devices for all trials, suggesting the feasibility of employing this technology for numerous photonic and biochemical sensing applications that entail for sustainable, reconfigurable, and low lasing threshold coherent light sources on a chip.

Surface-modified multifunctional MIP nanoparticles

PubMed Central

Moczko, Ewa; Poma, Alessandro; Guerreiro, Antonio; de Vargas Sansalvador, Isabel Perez; Caygill, Sarah; Canfarotta, Francesco; Whitcombe, Michael J.; Piletsky, Sergey

2015-01-01

The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly-sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity (PEG methacrylate); electro-activity (vinyl ferrocene); fluorescence (eosin acrylate); thiol groups (pentaerythritol tetrakis(3-mercaptopropionate)). The method has broad applicability and can be used to produce multifunctional imprinted nanoparticles with potential for further application in the biosensors, diagnostics and biomedical fields and as an alternative to natural receptors. PMID:23503559

Mathematical Modeling and Optimization Studies on Development of Fuel Cells for Multifarious Applications

DTIC Science & Technology

2010-05-12

multicomponent steady-state model for liquid -feed solid polymer electrolyte DBFCs. These fuel cells use sodium borohydride (NaBH4) in alkaline media...layers, diffusion layers and the polymer electrolyte membrane for a liquid feed DBFC. Diffusion of reactants within and between the pores is accounted...projected for futuristic portable applications. In this project we developed a three- dimensional, multicomponent steady-state model for liquid -feed solid

New strategy and easy fabrication of solid-state supercapacitor based on polypyrrole and nitrile rubber.

PubMed

Lee, Sangyool; Lee, Youngkwan; Cho, Mi-Suk; Nam, Jae-Do

2008-09-01

Solid state redox supercapacitors were fabricated using a solid polymer electrolyte, nitrile butadiene rubber (NBR)-KCI and chemically deposited polypyrrole (PPy) as the conducting polymer electrodes on both surfaces of a NBR film. The optimal conditions for the preparation of the PPy/NBR electrode were confirmed as functions of the uptake of pyrrole monomer into the NBR matrix as well as the immersion time in an oxidant solution. The morphology of the PPy-NBR-KCI capacitor was observed using scanning electron microscopy. The performance of the capacitors was characterized using a galvanostatic charge-discharge technique.

Organic Solid-State Tri-Wavelength Lasing from Holographic Polymer-Dispersed Liquid Crystal and a Distributed Feedback Laser with a Doped Laser Dye and a Semiconducting Polymer Film.

PubMed

Liu, Minghuan; Liu, Yonggang; Peng, Zenghui; Wang, Shaoxin; Wang, Qidong; Mu, Quanquan; Cao, Zhaoliang; Xuan, Li

2017-05-07

Organic solid-state tri-wavelength lasing was demonstrated from dye-doped holographic polymer-dispersed liquid crystal (HPDLC) distributed feedback (DFB) laser with semiconducting polymer poly[-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene-vinylene] (MEH-PPV) and laser dye [4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran] (DCM) by a one-step holography technique, which centered at 605.5 nm, 611.9 nm, and 671.1 nm. The temperature-dependence tuning range for the tri-wavelength dye-doped HPDLC DFB laser was as high as 8 nm. The lasing emission from the 9th order HPDLC DFB laser with MEH-PPV as active medium was also investigated, which showed excellent s-polarization characterization. The diffraction order is 9th and 8th for the dual-wavelength lasing with DCM as the active medium. The results of this work provide a method for constructing the compact and cost-effective all solid-state smart laser systems, which may find application in scientific and applied research where multi-wavelength radiation is required.

Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

2002-01-01

Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

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

Sakamoto, Y.; Ishii, Y.; Kawasaki, S., E-mail: kawasaki.shinji@nitech.ac.jp

2016-07-06

Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

Recent Advances in Fast Ion Conducting Materials and Devices - Proceedings of the 2nd Asian Conference on Solid State Ionics

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Liu, Qingguo; Chen, Liquan

The Table of Contents for the book is as follows: * Preface * Invited Papers * Recent Trends in Solid State Ionics * Theoretical Aspects of Fast Ion Conduction in Solids * Chemical Bonding and Intercalation Processes in Framework Structures * Extra-Large Near-Electrode Regions and Diffusion Length on the Solid Electrolyte-Electrode Interface as Studied by Photo-EMF Method * Frequency Response of Glasses * XPS Studies on Ion Conducting Glasses * Characterization of New Ambient Temperature Lithium Polymer-Electrolyte * Recent Development of Polymer Electrolytes: Solid State Voltammetry in Polymer Electrolytes * Secondary Solid State Batteries: From Material Properties to Commercial Development * Silver Vanadium Oxide Bronze and its Applications for Electrochemical Devices * Study on β''-Alumina Solid Electrolyte and β Battery in SIC * Materials for Solid Oxide Fuel Cells * Processing for Super Superionic Ceramics * Hydrogen Production Using Oxide Ionic or Protonic Conductor * Ionically Conductive Sulfide-Based Lithium Glasses * Relation of Conductivity to Structure and Structural Relaxation in Ion-Conducting Glasses * The Mechanism of Ionic Conductivity in Glass * The Role of Synthesis and Structure in Solid State Ionics - Electrodes to Superconductors * Electrochromism in Spin-Coated Thin Films from Peroxo-Poly tungstate Solutions * Electrochemical Studies on High Tc Superconductors * Multivalence Fast Ionic Conductors - Montmorillonites * Contributed Papers * Volt-Ampere Characteristics and Interface Charge Transport in Solid Electrolytes * Internal Friction of Silver Chalcogenides * Thermal Expansion of Ionic and Superionic Solids * Improvement of PEO-LiCF3SO3 Complex Electrolytes Using Additives * Ionic Conductivity of Modified Poly (Methoxy Polyethylene Glycol Methacrylate) s-Lithium Salt Complexes * Solid Polymer Electrolytes of Crosslinked Polyethylene Glycol and Lithium Salts * Single Ionic Conductors Prepared by in Situ Polymerization of Methacrylic Acid Alkali Metal Salts in Polyethylene Oxide * Redox Behavior of Alkyl Viologens in Ion Conductive Polymer Solid * Ionic Conductivity of Interpenetrating Polymer Networks Containing LiClO4 * Electrochemical Behaviors of Porphyrins Incorporated into Solid Polymer Electrolytes * Lithium Ion Conducting Polymer Electrolytes * Electrochemical Synthesis of Polyaniline Thin Film * Electrochemical Aspect of Polyaniline Electrode in Aqueous Electrolyte * Mixed Cation Effect in Epoxy Resin - PEO-IPN Containing Perchlorate Salts * Conductivity, Raman and IR Studies on the Doped PEO-PPG Polymer Blends * Proton Conducting Polymeric Electrolytes from Poly (Ethyleneoxide) System * Surface Structure of Polymer Solid Ionic Conductors Based on Segmented Polyether Polyurethaneureas * Study on Addition Products of LiI and Diethylene Glycol etc. * Solid State Rechargeable Battery Using Paper Form Copper Ion Conductive Solid Electrolyte * Characterization of Electrode/Electrolyte Interfaces in Battery Li/PVAC-Li-Mont./Li1+xV3O8 by AC Impedance Method * Investigation on Reversibility of Vanadium Oxide Cathode Materials in Solid-State Battery * Preparation and Characterization of Silver Boromolybdate Solid State Batteries * The Electric Properties of the Trinary Cathode Material and its Application in Magnisium Solid State Cell * Electrical Properties and Phase Relation of Na2Mo0.1S0.9O4 Doped with Rare Earth Sulfate * New Electrochemical Probe for Rapid Determination of Silicon Concentration in Hot Metals * A New Theoretical EMF Expression for SOx(x = 2, 3) Sensors Based on Na2SO4 Solid Electrolyte * Evaluation of the Electrochemical SOx(x = 2, 3) Sensor with a Tubular Nasicon Electrolyte * The Response Time of a Modified Oxygen Sensor Using Zirconia Electrolyte * Preparation, Characteristics and Sintering Behavior of MgO-PSZ Powder * Reaction between La0.9MnO3 and Yttria Doped Zirconia * Development of the Extended-Life Oxygen Sensor of Caβ''-Al2O3 * Caβ''-Al2O3 Ultra-Low Oxygen Sensor * Measurement of Sulfur Concentration with Zirconia-Based Electrolyte Cell in Molten Iron * Influence of SO2 on the Conductivity of Calcia Stabilized Zirconia * Reactions between YSZ and La1-xCaxMnO3 as a Cathode for SOFC * Preparation and Electrical Properties of Lithium β''-Alumina * Influence of Lithia Content on Properties of β''-Alumina Ceramics * Electrical Conductivity of Solid Solutions of Na2SO4 with Na2SeO4 * Effect of Antagonist XO42- = MoO42- and WO42- Ion Substitution on the Electrical Conductivity of Li2SO4 : Li2CO3 Eutectic System * Study on the Electrical Properties and Structure of Multicrystal Materials Li5+xGe1-xCrxV3O12 * Preliminary Study on Synthesis of Silver Zirconium Silicophosphates by Sol - Gel Process * Sodium Ion Conduction in Iron(III) Exchanged Y Zeolite * Electrical Properties of V5O9+x (x = 0, 1) and CuxV5O9.1 * Electrical Properties of the Tetragonal ZrO2 Stabilized with CeO2, CeO2 + Gd2O3 * Study of Preparation and Ionic Conduction of Doped Barium Cerate Perovskite * Preparing Fine Alumina Powder by Homogeneous Precipitation Method for Fabricating β''-Al2O3 * Amorphous Lithium Ion Conductors in Li2S-SiS2-LiBO2 System * Mixed Alkali Effect of Glass Super Ionic Conductors * Electrical Property and Phase Separation, Crystallization Behavior of A Cu+-Conducting Glass * Investigation of Phase Separation and Crystallization for 0.4CuI-0.3 Cu2O-0.3P2O5 Glass by SEM and XRD * Study on the Lithium Solid Electrolytes of Li3N-LiX(X = F, Cl, Br, I)-B2O3 Ternary Systems * Synthesis and Characterization of the Li2O : P2O5 : WO3 Glasses * The Electrochromic Properties of Electrodeposited Ni-O Films in Nonaqueous Electrolytes * All Solid-State WO3-MnO2 Based Electrochromic Window * Electrochromism in Nickel Oxide Films * E S R of X-Irradiated Melt Quenched Li2SO4 * Mixed-Alkali Effect in the Li2O-Na2O-TeO2 Glass System * Electrical and Thermal Studies on Silver Tellurite Glasses * Late Entries (Invited Papers) * Proton Conducting Polymers * Light Scattering Studies on Superionic Conductor YSZ * Development of Thin Film Surface Modified Solid State Electrochemical Gas Sensors * Author Index * List of Participants

Molecular engineering of polymer actuators for biomedical and industrial use

NASA Astrophysics Data System (ADS)

Banister, Mark; Eichorst, Rebecca; Gurr, Amy; Schweitzer, Georgette; Geronov, Yordan; Rao, Pavalli; McGrath, Dominic

2012-04-01

Five key materials engineering components and how each component impacted the working performance of a polymer actuator material are investigated. In our research we investigated the change of actuation performance that occurred with each change we made to the material. We investigated polymer crosslink density, polymer chain length, polymer gelation, type and density of reactive units, as well as the addition of binders to the polymer matrix. All five play a significant role and need to be addressed at the molecular level to optimize a polymer gel for use as a practical actuator material for biomedical and industrial use.

High-Resolution Solid-State NMR Spectroscopy: Characterization of Polymorphism in Cimetidine, a Pharmaceutical Compound

ERIC Educational Resources Information Center

Pacilio, Julia E.; Tokarski, John T.; Quiñones, Rosalynn; Iuliucci, Robbie J.

2014-01-01

High-resolution solid-state NMR (SSNMR) spectroscopy has many advantages as a tool to characterize solid-phase material that finds applications in polymer chemistry, nanotechnology, materials science, biomolecular structure determination, and others, including the pharmaceutical industry. The technology associated with achieving high resolution…

End-functionalized ROMP polymers for Biomedical Applications

PubMed Central

Madkour, Ahmad E.; Koch, Amelie H. R.; Lienkamp, Karen; Tew, Gregory N.

2010-01-01

We present two novel allyl-based terminating agents that can be used to end-functionalize living polymer chains obtained by ring-opening metathesis polymerization (ROMP) using Grubbs’ third generation catalyst. Both terminating agents can be easily synthesized and yield ROMP polymers with stable, storable activated ester groups at the chain-end. These end-functionalized ROMP polymers are attractive building blocks for advanced polymeric materials, especially in the biomedical field. Dye-labeling and surface-coupling of antimicrobially active polymers using these end-groups were demonstrated. PMID:21499549

Polymers in life sciences: Pharmaceutical and biomedical applications

NASA Astrophysics Data System (ADS)

Barba, Anna Angela; Dalmoro, Annalisa; d'Amore, Matteo; Lamberti, Gaetano; Cascone, Sara; Titomanlio, Giuseppe

2015-12-01

This paper deals with the work done by prof. Titomanlio and his group in the fields of pharmaceutical and biomedical applications of polymers. In particular, the main topics covered are: i) controlled drug release from pharmaceuticals based on hydrogel for oral delivery of drugs; ii) production and characterization of micro and nanoparticles based on stimuli-responsive polymers; iii) use of polymers for coronary stent gel-paving; iv) design and realization of novel methods (in-vitro and in-silico) to test polymer-based pharmaceuticals.

Experiment for validation of fluid-structure interaction models and algorithms.

PubMed

Hessenthaler, A; Gaddum, N R; Holub, O; Sinkus, R; Röhrle, O; Nordsletten, D

2017-09-01

In this paper a fluid-structure interaction (FSI) experiment is presented. The aim of this experiment is to provide a challenging yet easy-to-setup FSI test case that addresses the need for rigorous testing of FSI algorithms and modeling frameworks. Steady-state and periodic steady-state test cases with constant and periodic inflow were established. Focus of the experiment is on biomedical engineering applications with flow being in the laminar regime with Reynolds numbers 1283 and 651. Flow and solid domains were defined using computer-aided design (CAD) tools. The experimental design aimed at providing a straightforward boundary condition definition. Material parameters and mechanical response of a moderately viscous Newtonian fluid and a nonlinear incompressible solid were experimentally determined. A comprehensive data set was acquired by using magnetic resonance imaging to record the interaction between the fluid and the solid, quantifying flow and solid motion. Copyright © 2016 The Authors. International Journal for Numerical Methods in Biomedical Engineering published by John Wiley & Sons Ltd.

AIE Polymers: Synthesis, Properties, and Biological Applications.

PubMed

Zhan, Ruoyu; Pan, Yutong; Manghnani, Purnima Naresh; Liu, Bin

2017-05-01

Aggregation-caused quenching (ACQ) is a general phenomenon that is faced by traditional fluorescent polymers. Aggregation-induced emission (AIE) is exactly opposite to ACQ. AIE molecules are almost nonemissive in their molecularly dissolved state, but they can be induced to show high fluorescence in the aggregated or solid state. Incorporation of AIE phenomenon into polymer design has yielded various polymers with AIE characteristics. In this review, the recent progress of AIE polymers for biological applications is summarized. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Disentangled solid state and metastable polymer melt; a solvent free route to high-modulus high-strength tapes and films of UHMWPE

NASA Astrophysics Data System (ADS)

Rastogi, Sanjay

2013-03-01

Ultra High Molecular Weight Polyethylene (UHMWPE) having average molar mass greater than a million g/mol is an engineering polymer. Due to its light-weight, high abrasion resistance and biocompatibility it is used for demanding applications such as body armour, prostheses etc. At present, because of its high melt viscosity to achieve the uniaxial/biaxial properties in the form of fibers/films the polymer is processed via solution route where nearly 95wt% of the solvent is used to process 5wt% of the polymer. In past several attempts have been made to process the polymer without using any solvent. However, compared to the solvent processing route the achieved mechanical properties were rather poor. Here we show that by controlled synthesis it is feasible to obtain UHMWPE that could be processed free of solvent to make uniaxial tapes and biaxial films, having unprecedented mechanical properties, exceeding that of the solution spun fibers. We address some of the fundamental aspects of chemistry, physics, rheology and processing for the development of desired morphological features to achieve the ultimate mechanical properties in tapes and films. The paper will also address the metastable melt state obtained on melting of the disentangled crystals and its implication on rheology in linear and nonlinear viscoelastic region. Solid state NMR studies will be applied to establish disentangled state in solid state to the polymerisation conditions. References: Macromolecules 2011, 44(14), 5558-5568; Nature Materials 2005, 4, 635-641; Phys Rev Lett 2006, 96(21), 218303-218205. The authors acknowledge financial support by the Dutch Polymer Institute.

The Organic Solid State.

ERIC Educational Resources Information Center

Cowan, Dwaine O.; Wlygul, Frank M.

1986-01-01

Reviews interesting and useful electrical, magnetic, and optical properties of the organic solid state. Offers speculation as to areas of fruitful research. Discusses organic superconductors, conducting organic polymers, organic metals, and traces recent history of creation of organic metals. (JM)

Laser surface texturing of polymers for biomedical applications

NASA Astrophysics Data System (ADS)

Riveiro, Antonio; Maçon, Anthony L. B.; del Val, Jesus; Comesaña, Rafael; Pou, Juan

2018-02-01

Polymers are materials widely used in biomedical science because of their biocompatibility, and good mechanical properties (which, in some cases, are similar to those of human tissues); however, these materials are, in general, chemically and biologically inert. Surface characteristics, such as topography (at the macro-, micro, and nanoscale), surface chemistry, surface energy, charge or wettability are interrelated properties, and they cooperatively influence the biological performance of materials when used for biomedical applications. They regulate the biological response at the implant/tissue interface (e.g., influencing the cell adhesion, cell orientation, cell motility, etc.). Several surface processing techniques have been explored to modulate these properties for biomedical applications. Despite their potentials, these methods have limitations that prevent their applicability. In this regard, laser-based methods, in particular laser surface texturing (LST), can be an interesting alternative. Different works have showed the potentiality of this technique to control the surface properties of biomedical polymers and enhance their biological performance; however, more research is needed to obtain the desired biological response. This work provides a general overview of the basics and applications of LST for the surface modification of polymers currently used in the clinical practice (e.g. PEEK, UHMWPE, PP, etc.). The modification of roughness, wettability, and their impact on the biological response is addressed to offer new insights on the surface modification of biomedical polymers.

Fabricating Superhydrophobic Polymeric Materials for Biomedical Applications

PubMed Central

Kaplan, Jonah; Grinstaff, Mark

2015-01-01

Superhydrophobic materials, with surfaces possessing permanent or metastable non-wetted states, are of interest for a number of biomedical and industrial applications. Here we describe how electrospinning or electrospraying a polymer mixture containing a biodegradable, biocompatible aliphatic polyester (e.g., polycaprolactone and poly(lactide-co-glycolide)), as the major component, doped with a hydrophobic copolymer composed of the polyester and a stearate-modified poly(glycerol carbonate) affords a superhydrophobic biomaterial. The fabrication techniques of electrospinning or electrospraying provide the enhanced surface roughness and porosity on and within the fibers or the particles, respectively. The use of a low surface energy copolymer dopant that blends with the polyester and can be stably electrospun or electrosprayed affords these superhydrophobic materials. Important parameters such as fiber size, copolymer dopant composition and/or concentration, and their effects on wettability are discussed. This combination of polymer chemistry and process engineering affords a versatile approach to develop application-specific materials using scalable techniques, which are likely generalizable to a wider class of polymers for a variety of applications. PMID:26383018

Thermostable gel polymer electrolyte based on succinonitrile and ionic liquid for high-performance solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Pandey, Gaind P.; Liu, Tao; Hancock, Cody; Li, Yonghui; Sun, Xiuzhi Susan; Li, Jun

2016-10-01

A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10-4 S cm-1 at -30 °C up to ∼1.5 × 10-2 S cm-1 at 80 °C) with good electrochemical stability window (-2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from -30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g-1 at 0.18 A g-1 and 138 F g-1 at 8 A g-1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.

Enhanced PEDOT adhesion on solid substrates with electrografted P(EDOT-NH2)

PubMed Central

Ouyang, Liangqi; Wei, Bin; Kuo, Chin-chen; Pathak, Sheevangi; Farrell, Brendan; Martin, David C.

2017-01-01

Conjugated polymers, such as poly(3,4-ethylene dioxythiophene) (PEDOT), have emerged as promising materials for interfacing biomedical devices with tissue because of their relatively soft mechanical properties, versatile organic chemistry, and inherent ability to conduct both ions and electrons. However, their limited adhesion to substrates is a concern for in vivo applications. We report an electrografting method to create covalently bonded PEDOT on solid substrates. An amine-functionalized EDOT derivative (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanamine (EDOT-NH2), was synthesized and then electrografted onto conducting substrates including platinum, iridium, and indium tin oxide. The electrografting process was performed under slightly basic conditions with an overpotential of ~2 to 3 V. A nonconjugated, cross-linked, and well-adherent P(EDOT-NH2)–based polymer coating was obtained. We found that the P(EDOT-NH2) polymer coating did not block the charge transport through the interface. Subsequent PEDOT electrochemical deposition onto P(EDOT-NH2)–modified electrodes showed comparable electroactivity to pristine PEDOT coating. With P(EDOT-NH2) as an anchoring layer, PEDOT coating showed greatly enhanced adhesion. The modified coating could withstand extensive ultrasonication (1 hour) without significant cracking or delamination, whereas PEDOT typically delaminated after seconds of sonication. Therefore, this is an effective means to selectively modify microelectrodes with highly adherent and highly conductive polymer coatings as direct neural interfaces. PMID:28275726

Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

PubMed

Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

2017-10-04

We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

Solid-state supercapacitors with ionic liquid based gel polymer electrolyte: Effect of lithium salt addition

NASA Astrophysics Data System (ADS)

Pandey, G. P.; Hashmi, S. A.

2013-12-01

Performance characteristics of the solid-state supercapacitors fabricated with ionic liquid (IL) incorporated gel polymer electrolyte and acid treated multiwalled carbon nanotube (MWCNT) electrodes have been studied. The effect of Li-salt (LiPF6) addition in the IL (1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate, EMImFAP) based gel electrolyte on the performance of supercapacitors has been specifically investigated. The LiPF6/IL/poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) gel electrolyte film possesses excellent electrochemical window of 4 V (from -2.0 to 2.0 V), high ionic conductivity ∼2.6 × 10-3 S cm-1 at 20 °C and high enough thermal stability. The comparative performance of supercapacitors employing electrolytes with and without lithium salt has been evaluated by impedance spectroscopy and cyclic voltammetric studies. The acid-treated MWCNT electrodes show specific capacitance of ∼127 F g-1 with IL/LiPF6 containing gel polymer electrolyte as compared to that with the gel polymer electrolyte without Li-salt, showing the value of ∼76 F g-1. The long cycling stability of the solid state supercapacitor based on the Li-salt containing gel polymer electrolyte confirms the electrochemical stability of the electrolyte.

Defects in electro-optically active polymer solids

NASA Technical Reports Server (NTRS)

Martin, David C.

1993-01-01

There is considerable current interest in the application of organic and polymeric materials for electronic and photonic devices. The rapid, non-linear optical (NLO) response of these materials makes them attractive candidates for waveguides, interferometers, and frequency doublers. In order to realize the full potential of these systems, it is necessary to develop processing schemes which can fabricate these molecules into ordered arrangements. There is enormous potential for introducing well-defined, local variations in microstructure to control the photonic properties of organic materials by rational 'defect engineering.' This effort may eventually become as technologically important as the manipulation of the electronic structure of solid-state silicon based devices is at present. The success of this endeavor will require complimentary efforts in the synthesis, processing, and characterization of new materials. Detailed information about local microstructure will be necessary to understand the influence of symmetry breaking of the solid phases near point, line, and planar defects. In metallic and inorganic polycrystalline materials, defects play an important role in modifying macroscopic properties. To understand the influence of particular defects on the properties of materials, it has proven useful to isolate the defect by creating bicrystals between two-component single crystals. In this way the geometry of a grain boundary defect and its effect on macroscopic properties can be determined unambiguously. In crystalline polymers it would be valuable to establish a similar depth of understanding about the relationship between defect structure and macroscopic properties. Conventionally processed crystalline polymers have small crystallites (10-20 nm), which implies a large defect density in the solid state. Although this means that defects may play an important or even dominant role in crystalline or liquid crystalline polymer systems, it also makes it difficult to isolate the effect of a particular boundary on a macroscopically observed property. However, the development of solid-state and thin-film polymerization mechanisms have facilitated the synthesis of highly organized and ordered polymers. These systems provide a unique opportunity to isolate and investigate in detail the structure of covalently bonded solids near defects and the effect of these defects on the properties of the material. The study of defects in solid polymers has been the subject of a recent review (Martin, 1993).

Recycling and processing of several typical crosslinked polymer scraps with enhanced mechanical properties based on solid-state mechanochemical milling

NASA Astrophysics Data System (ADS)

Lu, Canhui; Zhang, Xinxing; Zhang, Wei

2015-05-01

The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. The results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps.

Molecular Strategies for Morphology Control in Semiconducting Polymers for Optoelectronics.

PubMed

Rahmanudin, Aiman; Sivula, Kevin

2017-06-28

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

PEELS of buckyballs: Synthesis and first investigations into properties

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

Schlueter, A.D.

The polymer analogous aromatization of double-stranded Diels-Alder polymers to give fully unsaturated, all-carbon ladder polymers by means of dehydration and dehydrogenation is described. The polymers obtained were characterized by solid state carbon NMR and UV-spectroscopy as well as elemental analysis. Investigations into optical and electrical properties will be discussed.

Current status of solid-state lithium batteries employing solid redox polymerization cathodes

NASA Astrophysics Data System (ADS)

Visco, S. J.; Doeff, M. M.; Dejonghe, L. C.

1991-03-01

The rapidly growing demand for secondary batteries having high specific energy and power has naturally led to increased efforts in lithium battery technology. Still, the increased safety risks associated with high energy density systems has tempered the enthusiasm of proponents of such systems for use in the consumer marketplace. The inherent advantages of all-solid-state batteries in regards to safety and reliability are strong factors in advocating their introduction to the marketplace. However, the low ionic conductivity of solid electrolytes relative to nonaqueous liquid electrolytes implies low power densities for solid state systems operating at ambient temperatures. Recent advances in polymer electrolytes have led to the introduction of solid electrolytes having conductivities in the range of 10(exp -4)/ohm cm at room temperature; this is still two orders of magnitude lower than liquid electrolytes. Although these improved ambient conductivities put solid state batteries in the realm of practical devices, it is clear that solid state batteries using such polymeric separators will be thin film devices. Fortunately, thin film fabrication techniques are well established in the plastics and paper industry, and present the possibility of continuous web-form manufacturing. This style of battery manufacture should make solid polymer batteries very cost-competitive with conventional secondary cells. In addition, the greater geometric flexibility of thin film solid state cells should provide benefits in terms of the end-use form factor in device design. This work discusses the status of solid redox polymerization cathodes.

Establishing a molecular relationship between chondritic and cometary organic solids

PubMed Central

Cody, George D.; Heying, Emily; Alexander, Conel M. O.; Nittler, Larry R.; Kilcoyne, A. L. David; Sandford, Scott A.

2011-01-01

Multidimensional solid-state NMR spectroscopy is used to refine the identification and abundance determination of functional groups in insoluble organic matter (IOM) isolated from a carbonaceous chondrite (Murchison, CM2). It is shown that IOM is composed primarily of highly substituted single ring aromatics, substituted furan/pyran moieties, highly branched oxygenated aliphatics, and carbonyl groups. A pathway for producing an IOM-like molecular structure through formaldehyde polymerization is proposed and tested experimentally. Solid-state 13C NMR analysis of aqueously altered formaldehyde polymer reveals considerable similarity with chondritic IOM. Carbon X-ray absorption near edge structure spectroscopy of formaldehyde polymer reveals the presence of similar functional groups across certain Comet 81P/Wild 2 organic solids, interplanetary dust particles, and primitive IOM. Variation in functional group concentration amongst these extraterrestrial materials is understood to be a result of various degrees of processing in the parent bodies, in space, during atmospheric entry, etc. These results support the hypothesis that chondritic IOM and cometary refractory organic solids are related chemically and likely were derived from formaldehyde polymer. The fine-scale morphology of formaldehyde polymer produced in the experiment reveals abundant nanospherules that are similar in size and shape to organic nanoglobules that are ubiquitous in primitive chondrites. PMID:21464292

Lithium Polymer Electrolytes and Solid State NMR

NASA Technical Reports Server (NTRS)

Berkeley, Emily R.

2004-01-01

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Highly flexible and all-solid-state paperlike polymer supercapacitors.

PubMed

Meng, Chuizhou; Liu, Changhong; Chen, Luzhuo; Hu, Chunhua; Fan, Shoushan

2010-10-13

In recent years, much effort have been dedicated to achieve thin, lightweight and even flexible energy-storage devices for wearable electronics. Here we demonstrate a novel kind of ultrathin all-solid-state supercapacitor configuration with an extremely simple process using two slightly separated polyaniline-based electrodes well solidified in the H(2)SO(4)-polyvinyl alcohol gel electrolyte. The thickness of the entire device is much comparable to that of a piece of commercial standard A4 print paper. Under its highly flexible (twisting) state, the integrate device shows a high specific capacitance of 350 F/g for the electrode materials, well cycle stability after 1000 cycles and a leakage current of as small as 17.2 μA. Furthermore, due to its polymer-based component structure, it has a specific capacitance of as high as 31.4 F/g for the entire device, which is more than 6 times that of current high-level commercial supercapacitor products. These highly flexible and all-solid-state paperlike polymer supercapacitors may bring new design opportunities of device configuration for energy-storage devices in the future wearable electronic area.

Molecular Structure of Humin and Melanoidin via Solid State NMR

PubMed Central

Herzfeld, Judith; Rand, Danielle; Matsuki, Yoh; Daviso, Eugenio; Mak-Jurkauskas, Melody; Mamajanov, Irena

2011-01-01

Sugar-derived humins and melanoidins figure significantly in food chemistry, agricultural chemistry, biochemistry and prebiotic chemistry. Despite wide interest and significant experimental attention, the amorphous and insoluble nature of the polymers has made them resistant to conventional structural characterization. Here we make use of solid-state NMR methods, including selective 13C substitution, 1H-dephasing, and double quantum filtration. The spectra, and their interpretation, are simplified by relying exclusively on hydronium for catalysis. The results for polymers derived from ribose, deoxyribose and fructose indicate diverse pathways to furans, suggest a simple route to pyrroles in the presence of amines, and reveal a heterogenous network-type polymer in which sugar molecules cross-link the heterocycles. PMID:21456563

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

PubMed

Zhang, Xi; Jiang, Hongrui

2015-03-09

Photo-self-charging cells (PSCs) are compact devices with dual functions of photoelectric conversion and energy storage. By introducing a scattering layer in polymer-based quasi-solid-state dye-sensitized solar cells, two-electrode PSCs with highly compact structure were obtained. The charge storage function stems from the formed ion channel network in the scattering layer/polymer electrolyte system. Both the photoelectric conversion and the energy storage functions are integrated in only the photoelectrode of such PSCs. This design of PSC could continuously output power as a solar cell with considerable efficiency after being photo-charged. Such PSCs could be applied in highly-compact mini power devices.

Thermosensitive chitosan/glycerophosphate-based hydrogel and its derivatives in pharmaceutical and biomedical applications.

PubMed

Supper, Stephanie; Anton, Nicolas; Seidel, Nina; Riemenschnitter, Marc; Curdy, Catherine; Vandamme, Thierry

2014-02-01

Thermogelling chitosan (CS)/glycerophosphate (GP) solutions have been reported as a new type of parenteral in situ forming depot system. These free-flowing solutions at ambient temperature turn into semi-solid hydrogels after parenteral administration. Formulation parameters such as CS physico-chemical characteristics, CS/gelling agent ratio or pH of the system, were acknowledged as key parameters affecting the solution stability, the sol/gel transition behavior and/or the final hydrogel structure. We discuss also the use of the standard CS/GP thermogels for various biomedical applications, including drug delivery and tissue engineering. Furthermore, this manuscript reviews the different strategies implemented to improve the hydrogel characteristics such as combination with carrier particles, replacement of GP, addition of a second polymer and chemical modification of CS. The recent advances in the formulation of CS-based thermogelling systems already overcame several challenges faced by the standard CS/GP system. Dispersion of drug-loaded carrier particles into the thermogels allowed achieving prolonged release profiles for low molecular weight drugs; incorporation of an additional polymer enabled to strengthen the network, while the use of chemically modified CS led to enhanced pH sensitivity or biodegradability of the matrix.

Solid-state supercapacitors with ionic liquid gel polymer electrolyte based on poly (3, 4-ethylenedioxythiophene), carbon nanotubes, and metal oxides nanocomposites for electrical energy storage

NASA Astrophysics Data System (ADS)

Obeidat, Amr M.

Clean and renewable energy systems have emerged as an important area of research having diverse and significant new applications. These systems utilize different energy storage methods such as the batteries and supercapacitors. Supercapacitors are electrochemical energy storage devices that are designed to bridge the gap between batteries and conventional capacitors. Supercapacitors which store electrical energy by electrical double layer capacitance are based on large surface area structured carbons. The materials systems in which the Faradaic reversible redox reactions store electrical energy are the transition metal oxides and electronically conducting polymers. Among the different types of conducting polymers, poly (3, 4- ethylenedioxythiophene) (PEDOT) is extensively investigated owing to its chemical and mechanical stability. Due to instability of aqueous electrolytes at high voltages and toxicity of organic electrolytes, potential of supercapacitors has not been fully exploited. A novel aspect of this work is in utilizing the ionic liquid gel polymer electrolyte to design solid-state supercapacitors for energy storage. Various electrochemical systems were investigated including graphene, PEDOT, PEDOT-carbon nanotubes, PEDOT-manganese oxide, and PEDOT-iron oxide nanocomposites. The electrochemical performance of solid-state supercapacitor devices was evaluated based on cyclic voltammetry (CV), charge-discharge (CD), prolonged cyclic tests, and electrochemical impedance spectroscopy (EIS) techniques. Raman spectroscopy technique was also utilized to analyze the bonding structure of the electrode materials. The graphene solid-state supercapacitor system displayed areal capacitance density of 141.83 mF cm-2 based on high potential window up to 4V. The PEDOT solid-state supercapacitor system was synthesized in acetonitrile and aqueous mediums achieving areal capacitance density of 219.17 mF cm-2. The hybrid structure of solid-state supercapacitors was also studied in solid-state design based on PEDOT and graphene electrodes that produced areal capacitance density of 198.26 mF cm-2. Symmetrical PEDOT-manganese oxide nanocomposites were synthesized by co-deposition and dip-coating techniques to fabricate solid-state supercapacitor systems achieving areal capacitance density of 122.08 mF cm-2 credited to the PEDOT-MnO2 supercapacitor that was synthesized by dipping the PEDOT electrode in pure KMnO4 solution. The electrochemical performance of PEDOT-carbon nanotube solid-state supercapacitors was also investigated in both acetonitrile and aqueous medium showing good dispersion characteristics with optimum CNT content of 1 mg. The PEDOT-CNT solid-state supercapacitor system synthesized in acetonitrile displayed areal capacitance density of 297.43 mF cm-2. PEDOT-Fe2O3 nanocomposites were synthesized by single-step co-deposition techniques, and these were used to fabricate solid-state supercapacitors achieving areal capacitance density of 96.89 mF cm-2. Furthermore, some of these thin flexible solid-state supercapacitors were integrated with solar cells for direct storage of solar electricity, which proved to be promising as autonomous power source for flexible and wearable electronics. This dissertation describes the electrode synthesis, design and properties of solid-state supercapacitors, and their electrochemical performance in the storage of electrical energy.

NMR characterization of polymers: Review and update

USDA-ARS?s Scientific Manuscript database

NMR spectroscopy is a major technique for the characterization and analysis of polymers. A large number of methodologies have been developed in both the liquid and the solid state, and the literature has grown considerably (1-5). The field now covers a broad spectrum of activities, including polym...

Elucidating the Charge Transfer Mechanism in Radical Polymer Thin Films

NASA Astrophysics Data System (ADS)

Mukherjee, Sanjoy; Boudouris, Bryan

The active role of polymers in organic electronics has attracted significant attention in recent decades. Beyond conventional conjugated polymers, recently radical polymers have received a great deal of consideration by the community. Radical polymers are redox-active macromolecules with non-conjugated backbones functionalized with persistent radical sites. Because of their nascent nature, many open questions regarding the physics of their solid-state charge transfer mechanism still exist. In order to address these questions, well-defined radical polymers were synthesized and blended in a manner such that there was tight control over the radical density within the conducting thin films. We demonstrate that the systematic manipulation of the radical-to-radical spacing in open-shell macromolecules leads to exponential changes in the macroscopic electrical conductivity, and temperature-independent charge transport behaviour. Thus, a clear picture emerges that charge transfer in radical polymers is dictated by a tunnelling mechanism between proximal sites. This behavior is consistent with a distinct mechanism similar to redox reactions in biological media, but is unique relative to transport in common conjugated polymers. These results constitute the first experimental insight into the mechanism of solid-state electrical conduction in radical polymers.

Towards improved solubility of poorly water-soluble drugs: cryogenic co-grinding of piroxicam with carrier polymers.

PubMed

Penkina, Anna; Semjonov, Kristian; Hakola, Maija; Vuorinen, Sirpa; Repo, Timo; Yliruusi, Jouko; Aruväli, Jaan; Kogermann, Karin; Veski, Peep; Heinämäki, Jyrki

2016-01-01

Amorphous solid dispersions (SDs) open up exciting opportunities in formulating poorly water-soluble active pharmaceutical ingredients (APIs). In the present study, novel catalytic pretreated softwood cellulose (CPSC) and polyvinylpyrrolidone (PVP) were investigated as carrier polymers for preparing and stabilizing cryogenic co-ground SDs of poorly water-soluble piroxicam (PRX). CPSC was isolated from pine wood (Pinus sylvestris). Raman and Fourier transform infrared (FTIR) spectroscopy, X-ray powder diffraction (XRPD) and differential scanning calorimetry (DSC) were used for characterizing the solid-state changes and drug-polymer interactions. High-resolution scanning electron microscope (SEM) was used to analyze the particle size and surface morphology of starting materials and final cryogenic co-ground SDs. In addition, the molecular aspects of drug-polymer interactions and stabilization mechanisms are presented. The results showed that the carrier polymer influenced both the degree of amorphization of PRX and stabilization against crystallization. The cryogenic co-ground SDs prepared from PVP showed an enhanced dissolution rate of PRX, while the corresponding SDs prepared from CPSC exhibited a clear sustained release behavior. In conclusion, cryogenic co-grinding provides a versatile method for preparing amorphous SDs of poorly water-soluble APIs. The solid-state stability and dissolution behavior of such co-ground SDs are to a great extent dependent on the carrier polymer used.

Recycling and processing of several typical crosslinked polymer scraps with enhanced mechanical properties based on solid-state mechanochemical milling

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

Lu, Canhui; Zhang, Xinxing; Zhang, Wei

The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. Themore » results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps.« less

Spatial Temperature Mapping within Polymer Nanocomposites Undergoing Ultrafast Photothermal Heating via Gold Nanorods

PubMed Central

Maity, Somsubhra; Wu, Wei-Chen; Xu, Chao; Tracy, Joseph B.; Gundogdu, Kenan; Bochinski, Jason R.; Clarke, Laura I.

2015-01-01

Heat emanates from gold nanorods (GNRs) under ultrafast optical excitation of the localized surface plasmon resonance. The steady state nanoscale temperature distribution formed within a polymer matrix embedded with GNRs undergoing pulsed femtosecond photothermal heating is determined experimentally using two independent ensemble optical techniques. Physical rotation of the nanorods reveals the average local temperature of the polymer melt in the immediate spatial volume surrounding them while fluorescence of homogeneously-distributed perylene molecules monitors temperature over sample regions at larger distances from the GNRs. Polarization-sensitive fluorescence measurements of the perylene probes provide an estimate of the average size of the quasi-molten region surrounding each nanorod (that is, the boundary between softened polymer and solid material as the temperature decreases radially away from each particle) and distinguishes the steady state temperature in the solid and melt regions. Combining these separate methods enables nanoscale spatial mapping of the average steady state temperature distribution caused by ultrafast excitation of the GNRs. These observations definitively demonstrate the presence of a steady-state temperature gradient and indicate that localized heating via the photothermal effect within materials enables nanoscale thermal manipulations without significantly altering the bulk sample temperature in these systems. These quantitative results are further verified by reorienting nanorods within a solid polymer nanofiber without inducing any morphological changes to the highly temperature-sensitive nanofiber surface. Temperature differences of 70 – 90 °C were observed over a distances of ~100 nm. PMID:25379775

Highly Conductive Solid-State Hybrid Electrolytes Operating at Subzero Temperatures.

PubMed

Kwon, Taeyoung; Choi, Ilyoung; Park, Moon Jeong

2017-07-19

We report a unique, highly conductive, dendrite-inhibited, solid-state polymer electrolyte platform that demonstrates excellent battery performance at subzero temperatures. A design based on functionalized inorganic nanoparticles with interconnected mesopores that contain surface nitrile groups is the key to this development. Solid-state hybrid polymer electrolytes based on succinonitrile (SN) electrolytes and porous nanoparticles were fabricated via a simple UV-curing process. SN electrolytes were effectively confined within the mesopores. This stimulated favorable interactions with lithium ions, reduced leakage of SN electrolytes over time, and improved mechanical strength of membranes. Inhibition of lithium dendrite growth and improved electrochemical stability up to 5.2 V were also demonstrated. The hybrid electrolytes exhibited high ionic conductivities of 2 × 10 -3 S cm -1 at room temperature and >10 -4 S cm -1 at subzero temperatures, leading to stable and improved battery performance at subzero temperatures. Li cells made with lithium titanate anodes exhibited stable discharge capacities of 151 mAh g -1 at temperatures below -10 °C. This corresponds to 92% of the capacity achieved at room temperature (164 mAh g -1 ). Our work represents a significant advance in solid-state polymer electrolyte technology and far exceeds the performance available with conventional polymeric battery separators.

Dye-impregnated polymer-filled porous glass: a new composite material for solid state dye lasers and laser beam control optical elements (Abstract Only)

NASA Astrophysics Data System (ADS)

Koldunov, M. F.; Manenkov, Alexander A.; Sitnikov, N. M.; Dolotov, S. M.

1994-07-01

Polymer-filled microporous glass (PFMG) composite materials have been recently proposed as a proper host for dyes to create solid-state dye lasers and laser beam control elements (Q-switchers, etc.) [1,2]. In this paper we report investigation of some laser-related properties of Polymethilmethacrylate (PMAA) - filled porous glass doped with Rhodamine 6G perchiorate (active lasing dye) and 1055 dye (passive bleachable dye): laser induced damage threshold, lasmg efficiency, bleaching efficiency, and microhardness have been measured. All these characteristics have been found to be rather high indicating that PFMG composite materials are perspective hosts for dye impregnation and fabrication highly effective solid-state dye lasers and other laser related elements (Q-switchers, mode-lockers, modeselectors, spatial filters).

Solid-State NMR Spectroscopy for the Physical Chemistry Laboratory

ERIC Educational Resources Information Center

Kinnun, Jacob J.; Leftin, Avigdor; Brown, Michael F.

2013-01-01

Solid-state nuclear magnetic resonance (NMR) spectroscopy finds growing application to inorganic and organic materials, biological samples, polymers, proteins, and cellular membranes. However, this technique is often neither included in laboratory curricula nor typically covered in undergraduate courses. On the other hand, spectroscopy and…

All-solid-state lithium organic battery with composite polymer electrolyte and pillar[5]quinone cathode.

PubMed

Zhu, Zhiqiang; Hong, Meiling; Guo, Dongsheng; Shi, Jifu; Tao, Zhanliang; Chen, Jun

2014-11-26

The cathode capacity of common lithium ion batteries (LIBs) using inorganic electrodes and liquid electrolytes must be further improved. Alternatively, all-solid-state lithium batteries comprising the electrode of organic compounds can offer much higher capacity. Herein, we successfully fabricated an all-solid-state lithium battery based on organic pillar[5]quinone (C35H20O10) cathode and composite polymer electrolyte (CPE). The poly(methacrylate) (PMA)/poly(ethylene glycol) (PEG)-LiClO4-3 wt % SiO2 CPE has an optimum ionic conductivity of 0.26 mS cm(-1) at room temperature. Furthermore, pillar[5]quinine cathode in all-solid-state battery rendered an average operation voltage of ∼2.6 V and a high initial capacity of 418 mAh g(-1) with a stable cyclability (94.7% capacity retention after 50 cycles at 0.2C rate) through the reversible redox reactions of enolate/quinonid carbonyl groups, showing favorable prospect for the device application with high capacity.

Etched Polymer Fibre Bragg Gratings and Their Biomedical Sensing Applications

PubMed Central

Rajan, Ginu; Bhowmik, Kishore; Xi, Jiangtao; Peng, Gang-Ding

2017-01-01

Bragg gratings in etched polymer fibres and their unique properties and characteristics are discussed in this paper. Due to the change in material and mechanical properties of the polymer fibre through etching, Bragg gratings inscribed in such fibres show high reflectivity and enhanced intrinsic sensitivity towards strain, temperature, and pressure. The short-term and long-term stability of the gratings and the effect of hysteresis on the dynamic characteristics are also discussed. The unique properties and enhanced intrinsic sensitivity of etched polymer fibre Bragg grating are ideal for the development of high-sensitivity sensors for biomedical applications. To demonstrate their biomedical sensing capabilities, a high-sensitivity pressure transducer that operates in the blood pressure range, and a breathing rate monitoring device are developed and presented. PMID:29027945

The Ten Outstanding Engineering Achievements of the Past 50 Years.

ERIC Educational Resources Information Center

Hightower, George

1984-01-01

Describes the outstanding achievement in each of 10 major engineering categories. These categories include synthetic fibers, nuclear energy, computers, solid state electronics, jet aircraft, biomedical engineering, lasers, communications satellites, the United States space program, and automation and control systems. (JN)

In-line NIR spectroscopy for the understanding of polymer-drug interaction during pharmaceutical hot-melt extrusion.

PubMed

Saerens, Lien; Dierickx, Lien; Quinten, Thomas; Adriaensens, Peter; Carleer, Robert; Vervaet, Chris; Remon, Jean Paul; De Beer, Thomas

2012-05-01

The aim was to evaluate near-infrared spectroscopy for the in-line determination of the drug concentration, the polymer-drug solid-state behaviour and molecular interactions during hot-melt extrusion. Kollidon® SR was extruded with varying metoprolol tartrate (MPT) concentrations (20%, 30% and 40%) and monitored using NIR spectroscopy. A PLS model allowed drug concentration determination. The correlation between predicted and real MPT concentrations was good (R(2)=0.97). The predictive performance of the model was evaluated by the root mean square error of prediction, which was 1.54%. Kollidon® SR with 40% MPT was extruded at 105°C and 135°C to evaluate NIR spectroscopy for in-line polymer-drug solid-state characterisation. NIR spectra indicated the presence of amorphous MPT and hydrogen bonds between drug and polymer in the extrudates. More amorphous MPT and interactions could be found in the extrudates produced at 135°C than at 105°C. Raman spectroscopy, DSC and ATR FT-IR were used to confirm the NIR observations. Due to the instability of the formulation, only in-line Raman spectroscopy was an adequate confirmation tool. NIR spectroscopy is a potential PAT-tool for the in-line determination of API concentration and for the polymer-drug solid-state behaviour monitoring during pharmaceutical hot-melt extrusion. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrospun aniline-tetramer-co-polycaprolactone fibres for conductive, biodegradable scaffolds.

PubMed

Guex, A G; Spicer, C D; Armgarth, A; Gelmi, A; Humphrey, E J; Terracciano, C M; Harding, S; Stevens, M M

2017-09-01

Conjugated polymers have been proposed as promising materials for scaffolds in tissue engineering applications. The restricted processability and biodegradability of conjugated polymers limit their use for biomedical applications however. Here we synthesised a block- co -polymer of aniline tetramer and PCL (AT-PCL), and processed it into fibrous non-woven scaffolds by electrospinning. We showed that fibronectin (Fn) adhesion was dependant on the AT-PCL oxidative state, with a reduced Fn unfolding length on doped membranes. Furthermore, we demonstrated the cytocompatibility and potential of these membranes to support the growth and osteogenic differentiation of MC3T3-E1 over 21 days.

Electropolymerized Conducting Polymer as Actuator and Sensor Device

ERIC Educational Resources Information Center

Cortes, Maria T.; Moreno, Juan C.

2005-01-01

A study demonstrates the potential application of conducting polymers to convert electrical energy into mechanical energy at low voltage or current. The performance of the device is explained using electrochemistry and solid-state chemistry.

Polymeric Amorphous Solid Dispersions: A Review of Amorphization, Crystallization, Stabilization, Solid-State Characterization, and Aqueous Solubilization of Biopharmaceutical Classification System Class II Drugs.

PubMed

Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

2016-09-01

Poor water solubility of many drugs has emerged as one of the major challenges in the pharmaceutical world. Polymer-based amorphous solid dispersions have been considered as the major advancement in overcoming limited aqueous solubility and oral absorption issues. The principle drawback of this approach is that they can lack necessary stability and revert to the crystalline form on storage. Significant upfront development is, therefore, required to generate stable amorphous formulations. A thorough understanding of the processes occurring at a molecular level is imperative for the rational design of amorphous solid dispersion products. This review attempts to address the critical molecular and thermodynamic aspects governing the physicochemical properties of such systems. A brief introduction to Biopharmaceutical Classification System, solid dispersions, glass transition, and solubility advantage of amorphous drugs is provided. The objective of this review is to weigh the current understanding of solid dispersion chemistry and to critically review the theoretical, technical, and molecular aspects of solid dispersions (amorphization and crystallization) and potential advantage of polymers (stabilization and solubilization) as inert, hydrophilic, pharmaceutical carrier matrices. In addition, different preformulation tools for the rational selection of polymers, state-of-the-art techniques for preparation and characterization of polymeric amorphous solid dispersions, and drug supersaturation in gastric media are also discussed. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

A solid-state NMR method to determine domain sizes in multi-component polymer formulations

NASA Astrophysics Data System (ADS)

Schlagnitweit, Judith; Tang, Mingxue; Baias, Maria; Richardson, Sara; Schantz, Staffan; Emsley, Lyndon

2015-12-01

Polymer domain sizes are related to many of the physical properties of polymers. Here we present a solid-state NMR experiment that is capable of measuring domain sizes in multi-component mixtures. The method combines selective excitation of carbon magnetization to isolate a specific component with proton spin diffusion to report on domain size. We demonstrate the method in the context of controlled release formulations, which represents one of today's challenges in pharmaceutical science. We show that we can measure domain sizes of interest in the different components of industrial pharmaceutical formulations at natural isotopic abundance containing various (modified) cellulose derivatives, such as microcrystalline cellulose matrixes that are film-coated with a mixture of ethyl cellulose (EC) and hydroxypropyl cellulose (HPC).

The structures and luminescence properties of lanthanide (Ln = Sm, Eu and Tb) metal-organic coordination polymers based on 5-(2-hydroxyethoxy)isophthalate ligand

NASA Astrophysics Data System (ADS)

Wang, Peng; Zhang, Yu-Jie; Qin, Jie; Chen, Yong; Zhao, Ying

2015-03-01

Three unreported isomorphous Ln-containing metal-organic coordination polymeric complexes {LnL(HL)ṡ(H2O)2}n (Ln = Sm (1), Eu (2) and Tb (3), CCDC 971815-971817) were synthesized based on 5-(2-hydroxyethoxy) isophthalic acid (H2L) under hydrothermal conditions. The obtained coordination polymers were characterized by IR, elemental analysis, thermal analysis and X-ray diffraction In solid state, these polymers featured 3-D supramolecular structures constructed by 2-D sheets through H-bonds. Investigation of photoluminescence properties of H2L and 1-3 showed all of them exhibited intense fluorescent emissions in the solid state at room temperature.

Photo-assisted generation of phospholipid polymer substrates for regiospecific protein conjugation and control of cell adhesion.

PubMed

Tanaka, Masako; Iwasaki, Yasuhiko

2016-08-01

Novel photo-reactive phospholipid polymers were synthesized for use in the preparation of nonfouling surfaces with protein conjugation capacity. Poly[2-methacryloyloxyethyl phosphorylcholine (MPC)-ran-N-methacryloyl-(l)-tyrosinemethylester (MAT)] (P(MPC/MAT)) was synthesized by conventional radical polymerization, with the MAT units capable of being oxidized by 254nm UV irradiation. Because of this photo-oxidation, active species such as catechol and quinone were alternately generated in the copolymer. A silicon wafer was subjected to surface modification through spin coating of P(MPC/MAT) from an aqueous solution for use as a model substrate. The surface was then irradiated several times with UV light. The thickness of the polymer layers formed on the Si wafers was influenced by various parameters such as polymer concentration, UV irradiation time, and composition of the MAT units in P(MPC/MAT). Oxidized MAT units were advantageous not only for polymer adhesion to a solid surface but also for protein conjugation with the adhered polymers. The amount of protein immobilized on UV-irradiated P(MPC/MAT) was dependent on the composition of the MAT units in the polymer. Furthermore, it was confirmed that protein immobilization on the polymer occurred through the oxidized MAT units because the protein adsorption was significantly reduced upon blocking these units through pretreatment with glycine. Conjugation of regiospecific protein could also be achieved through the use of a photomask. In addition, nonspecific protein adsorption was reduced on the non-irradiated regions whose surface was covered with physisorbed P(MPC/MAT). Therefore, P(MPC/MAT) can be used in the preparation of nonfouling substrates, which enable micrometer-sized manipulation of proteins through photo-irradiation. Function of proteins immobilized on MPC copolymers was also confirmed by cell adhesion test. As such, photo-reactive MPC copolymers are suitable for performing controlled protein conjugation and preparing polymer-protein hybrid platforms for use in biomedical and diagnostic devices. Novel photo-reactive phospholipid polymers have been synthesized for immobilization on solid surfaces and regiospecific protein conjugation. Tyrosine residues embedded in 2-methacryloyloxyethyl phosphorylcholine (MPC) copolymers could be photo-oxidized, resulting in polymers able to form layers on a solid surface and conjugate with proteins. Moreover, nonspecific biofouling on the surface significantly reduced when the oxidized tyrosine units in the polymer layers were blocked. Upon UV irradiation through a photomask, the UV-exposed tyrosine units were selectively oxidized, forming the only specific regions in which protein conjugation could occur. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

An experimental study on PEO polymer electrolyte based all-solid-state supercapacitor

NASA Astrophysics Data System (ADS)

Yijing, Yin

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I 2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.

Composite electrolytes of polyethylene oxides/garnets interfacially wetted by ionic liquid for room-temperature solid-state lithium battery

NASA Astrophysics Data System (ADS)

Huo, Hanyu; Zhao, Ning; Sun, Jiyang; Du, Fuming; Li, Yiqiu; Guo, Xiangxin

2017-12-01

Paramount attention has been paid on solid polymer electrolytes due to their potential in enhancement of energy density as well as improvement of safety. Herein, the composite electrolytes consisting of Li-salt-free polyethylene oxides and 200 nm-sized Li6.4La3Zr1.4Ta0.6O12 particles interfacially wetted by [BMIM]TF2N of 1.8 μL cm-2 have been prepared. Such wetted ionic liquid remains the solid state of membrane electrolytes and decreases the interface impedance between the electrodes and the electrolytes. There is no release of the liquid phase from the PEO matrix when the pressure of 5.0 × 104 Pa being applied for 24 h. The interfacially wetted membrane electrolytes show the conductivity of 2.2 × 10-4 S cm-1 at 20 °C, which is one order of magnitude greater than that of the membranes without the wetted ionic liquids. The conduction mechanism is related to a large number of lithium ions releasing from Li6.4La3Zr1.4Ta0.6O12 particles and the improved conductive paths along the ion-liquid-wetted interfaces between the polymer matrix and ceramic grains. When the membranes being used in the solid-state LiFePO4/Li and LiFe0.15Mn0.85PO4/Li cells at 25 °C, the excellent rate capability and superior cycle stability has been shown. The results provide a new prospect for solid polymer electrolytes used for room-temperature solid-state lithium batteries.

Tailoring Oxygen Sensitivity with Halide Substitution in Difluoroboron Dibenzoylmethane Polylactide Materials

PubMed Central

DeRosa, Christopher A.; Kerr, Caroline; Fan, Ziyi; Kolpaczynska, Milena; Mathew, Alexander S.; Evans, Ruffin E.; Zhang, Guoqing; Fraser, Cassandra L.

2015-01-01

The dual-emissive properties of solid-state difluoroboron β-diketonate-poly(lactic acid) (BF2bdkPLA) materials have been utilized for biological oxygen sensing. In this work, BF2dbm(X)PLA materials were synthesized, where X = H, F, Cl, Br, and I. The effects of changing the halide substituent and PLA polymer chain length on the optical properties in dilute CH2Cl2 solutions and solid-state polymer films were studied. These luminescent materials show fluorescence, phosphorescence, and lifetime tunability on the basis of molecular weight, as well as lifetime modulation via the halide substituent. Short BF2dbm(Br)PLA (6.0 kDa) and both short and long BF2dbm(I)PLA polymers (6.0 or 20.3 kDa) have fluorescence and intense phosphorescence ideal for ratiometric oxygen sensing. The lighter halide-dye polymers with hydrogen, fluorine, and chlorine substitution have longer phosphorescence lifetimes and can be utilized as ultrasensitive oxygen sensors. Photostability was also analyzed for the polymer films. PMID:26480236

Molecular level studies on interfacial hydration of zwitterionic and other antifouling polymers in situ.

PubMed

Leng, Chuan; Sun, Shuwen; Zhang, Kexin; Jiang, Shaoyi; Chen, Zhan

2016-08-01

Antifouling polymers have wide applications in biomedical engineering and marine industry. Recently, zwitterionic materials have been reported as promising candidates for antifouling applications, while strong hydration is believed to be the key antifouling mechanism. Zwitterionic materials can be designed with various molecular structures, which affect their hydration and antifouling performance. Although strong hydration has been proposed to occur at the material surfaces, probing the solid material/water interfaces is challenging with traditional analytical techniques. Here in this review, we will review our studies on surface hydration of zwitterionic materials and other antifouling materials by using sum frequency generation (SFG) vibrational spectroscopy, which provides molecular understanding of the water structures at various material surfaces. The materials studied include zwitterionic polymer brushes with different molecular structures, amphiphilic polymers with zwitterionic groups, uncharged hydrophilic polymer brushes, amphiphilic polypeptoids, and widely used antifouling material poly(ethylene glycol). We will compare the differences among zwitterionic materials with various molecular structures as well as the differences between antifouling materials and fouling surfaces of control samples. We will also discuss the effects of pH and biological molecules like proteins on the surface hydration of the zwitterionic materials. Using SFG spectroscopy, we have measured the hydration layers of antifouling materials and found that strong hydrogen bonds are key to the formation of strong hydration layers preventing protein fouling at the polymer interfaces. Antifouling polymers have wide applications in biomedical engineering and marine industry. Recently, zwitterionic materials have been reported as promising candidates for antifouling applications, while strong hydration is believed to be the key antifouling mechanism. However, zwitterionic materials can be designed with various molecular structures, which affect their hydration and antifouling performance. Moreover, although strong hydration has been proposed to occur at the material surfaces, probing the solid material/water interfaces is challenging with traditional analytical techniques. Here in this manuscript, we will review our studies on surface hydration of zwitterionic materials and other antifouling materials by using sum frequency generation (SFG) vibrational spectroscopy, which provides molecular understanding of the water structures at various material surfaces. The materials studied include zwitterionic polymer brushes with different molecular structures, amphiphilic polymers with zwitterionic groups, uncharged hydrophilic polymer brushes, amphiphilic polypeptoids, and widely used antifouling material poly(ethylene glycol). We will compare the differences among zwitterionic materials with various molecular structures as well as the differences between antifouling materials and fouling surfaces of control samples. We will also discuss the effects of pH and biological molecules like proteins on the surface hydration of the zwitterionic materials. All the SFG results indicate that strongly hydrogen-bonded water at the materials' surfaces (strong surface hydration) is closely correlated to the good antifouling properties of the materials. This review will be widely interested by readers of Acta Biomaterialia and will impact many different research fields in chemistry, materials, engineering, and beyond. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A nonconjugated radical polymer glass with high electrical conductivity

NASA Astrophysics Data System (ADS)

Joo, Yongho; Agarkar, Varad; Sung, Seung Hyun; Savoie, Brett M.; Boudouris, Bryan W.

2018-03-01

Solid-state conducting polymers usually have highly conjugated macromolecular backbones and require intentional doping in order to achieve high electrical conductivities. Conversely, single-component, charge-neutral macromolecules could be synthetically simpler and have improved processibility and ambient stability. We show that poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl), a nonconjugated radical polymer with a subambient glass transition temperature, underwent rapid solid-state charge transfer reactions and had an electrical conductivity of up to 28 siemens per meter over channel lengths up to 0.6 micrometers. The charge transport through the radical polymer film was enabled with thermal annealing at 80°C, which allowed for the formation of a percolating network of open-shell sites in electronic communication with one another. The electrical conductivity was not enhanced by intentional doping, and thin films of this material showed high optical transparency.

Matrix-assisted laser desorption/ionization mass spectrometric analysis of poly(3,4-ethylenedioxythiophene) in solid-state dye-sensitized solar cells: comparison of in situ photoelectrochemical polymerization in aqueous micellar and organic media.

PubMed

Zhang, Jinbao; Ellis, Hanna; Yang, Lei; Johansson, Erik M J; Boschloo, Gerrit; Vlachopoulos, Nick; Hagfeldt, Anders; Bergquist, Jonas; Shevchenko, Denys

2015-04-07

Solid-state dye-sensitized solar cells (sDSCs) are devoid of such issues as electrolyte evaporation or leakage and electrode corrosion, which are typical for traditional liquid electrolyte-based DSCs. Poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the most popular and efficient p-type conducting polymers that are used in sDSCs as a solid-state hole-transporting material. The most convenient way to deposit this insoluble polymer into the dye-sensitized mesoporous working electrode is in situ photoelectrochemical polymerization. Apparently, the structure and the physicochemical properties of the generated conducting polymer, which determine the photovoltaic performance of the corresponding solar cell, can be significantly affected by the preparation conditions. Therefore, a simple and fast analytical method that can reveal information on polymer chain length, possible chemical modifications, and impurities is strongly required for the rapid development of efficient solar energy-converting devices. In this contribution, we applied matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) for the analysis of PEDOT directly on sDSCs. It was found that the PEDOT generated in aqueous micellar medium possesses relatively shorter polymeric chains than the PEDOT deposited from an organic medium. Furthermore, the micellar electrolyte promotes a transformation of one of the thiophene terminal units to thiophenone. The introduction of a carbonyl group into the PEDOT molecule impedes the growth of the polymer chain and reduces the conductivity of the final polymer film. Both the simplicity of sample preparation (only application of the organic matrix onto the solar cell is needed) and the rapidity of analysis hold the promise of making MALDI MS an essential tool for the physicochemical characterization of conducting polymer-based sDSCs.

Electroactive polymers for healthcare and biomedical applications

NASA Astrophysics Data System (ADS)

Bauer, Siegfried

2017-04-01

Electroactivity was noticed early in biological substances, including proteins, polynucleotides and enzymes, even piezoand pyroelectricity were found in wool, hair, wood, bone and tendon. Recently, ferroelectricity has been identified in a surprisingly large number of biologically relevant materials, including hydroxyapatite, aortic walls and elastin. Inspired by the variety of natural electroactive materials, a wealth of new elastomers and polymers were designed recently, including an all organic elastomer electret and self-healing dielectric elastomers. Let's further draw inspiration from nature and widen the utilization of electroactive polymers towards (mobile) healthcare and biomedical applications. Ferroelectrets, internally charged polymer foams with a strong piezoelectric thickness coefficient are employed in biomedical sensing, for example as blood pressure and pulse sensor, as vital signs monitor or for the detection of tonicclonic seizures. Piezo- and pyroelectric polymers are booming in printed electronics research. They provide electronic skin the ability to "feel" pressure and temperature changes, or to generate electrical energy from vibrations and motions, even from contractile and relaxation motions of the heart and lung. Dielectric elastomers are pioneered by StretchSense as wearable motion capture sensors, monitoring pressure, stretch, bend and shear, quantifying comfort in sports and healthcare. On the cellular level, electroactive polymer arrays are used to study mechanotransduction of individual cells. Ionic electroactive polymers show potential to be used in implantable electroactive biomedical devices. Already with the currently available science and technology, we are at the verge of witnessing the demonstration of truly complex bionic systems.

The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers.

PubMed

Harman-Ware, Anne E; Happs, Renee M; Davison, Brian H; Davis, Mark F

2017-01-01

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H), and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10, and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid-state NMR spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.

Reconstituted Polymeric Materials Derived From Post-Consumer Waste, Industrial Scrap And Virgin Resins Made By Solid State Shear Pulverizat

DOEpatents

Khait, Klementina

2005-02-01

A method of making polymeric particulates wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatibilizing agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product.

Reconstituted polymeric materials derived from post-consumer waste, industrial scrap and virgin resins made by solid state pulverization

DOEpatents

Khait, K.

1998-09-29

A method of making polymeric particulates is described wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatible agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product. 29 figs.

Reconstituted polymeric materials derived from post-consumer waste, industrial scrap and virgin resins made by solid state shear pulverization

DOEpatents

Khait, Klementina

2001-01-30

A method of making polymeric particulates wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatibilizing agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product.

Reconstituted polymeric materials derived from post-consumer waste, industrial scrap and virgin resins made by solid state pulverization

DOEpatents

Khait, Klementina

1998-09-29

A method of making polymeric particulates wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatibilizing agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product.

How interfaces affect hydrophobically driven polymer folding.

PubMed

Jamadagni, Sumanth N; Godawat, Rahul; Dordick, Jonathan S; Garde, Shekhar

2009-04-02

Studies of folding-unfolding of hydrophobic polymers in water provide an excellent starting point to probe manybody hydrophobic interactions in the context of realistic self-assembly processes. Such studies in bulk water have highlighted the similarities between thermodynamics of polymer collapse and of protein folding, and emphasized the role of hydration-water structure, density, and fluctuations-in the folding kinetics. Hydrophobic polymers are interfacially active-that is, they prefer locations at aqueous interfaces relative to bulk water-consistent with their low solubility. How does the presence of a hydrophobic solid surface or an essentially hydrophobic vapor-water interface affect the structural, thermodynamic, and kinetic aspects of polymer folding? Using extensive molecular dynamics simulations, we show that the large hydrophobic driving force for polymer collapse in bulk water is reduced at a solid alkane-water interface and further reduced at a vapor-water interface. As a result, at the solid-water interface, folded structures are marginally stable, whereas the vapor-liquid interface unfolds polymers completely. Structural sampling is also significantly affected by the interface. For example, at the solid-water interface, polymer conformations are quasi-2- dimensional, with folded states being pancake-like structures. At the vapor-water interface, the hydrophobic polymer is significantly excluded from the water phase and freely samples a broad range of compact to extended structures. Interestingly, although the driving force for folding is considerably lower, kinetics of folding are faster at both interfaces, highlighting the role of enhanced water fluctuations and dynamics at a hydrophobic interface.

Initial Drug Dissolution from Amorphous Solid Dispersions Controlled by Polymer Dissolution and Drug-Polymer Interaction.

PubMed

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

2016-10-01

To identify the key formulation factors controlling the initial drug and polymer dissolution rates from an amorphous solid dispersion (ASD). Ketoconazole (KTZ) ASDs using PVP, PVP-VA, HMPC, or HPMC-AS as polymeric matrix were prepared. For each drug-polymer system, two types of formulations with the same composition were prepared: 1. Spray dried dispersion (SDD) that is homogenous at molecular level, 2. Physical blend of SDD (80% drug loading) and pure polymer (SDD-PB) that is homogenous only at powder level. Flory-Huggins interaction parameters (χ) between KTZ and the four polymers were obtained by Flory-Huggins model fitting. Solution (13)C NMR and FT-IR were conducted to investigate the specific drug-polymer interaction in the solution and solid state, respectively. Intrinsic dissolution of both the drug and the polymer from ASDs were studied using a Higuchi style intrinsic dissolution apparatus. PXRD and confocal Raman microscopy were used to confirm the absence of drug crystallinity on the tablet surface before and after dissolution study. In solid state, KTZ is completely miscible with PVP, PVP-VA, or HPMC-AS, demonstrated by the negative χ values of -0.36, -0.46, -1.68, respectively; while is poorly miscible with HPMC shown by a positive χ value of 0.23. According to solution (13)C NMR and FT-IR studies, KTZ interacts with HPMC-AS strongly through H-bonding and dipole induced interaction; with PVPs and PVP-VA moderately through dipole-induced interactions; and with HPMC weakly without detectable attractive interaction. Furthermore, the "apparent" strength of drug-polymer interaction, measured by the extent of peak shift on NMR or FT-IR spectra, increases with the increasing number of interacting drug-polymer pairs. For ASDs with the presence of considerable drug-polymer interactions, such as KTZ/PVPs, KTZ/PVP-VA, or KTZ /HPMC-AS systems, drug released at the same rate as the polymer when intimate drug-polymer mixing was ensured (i.e., the SDD systems); while drug released much slower than the polymer when molecular level mixing or drug-polymer interaction was absent (SDD-PB systems). For ASDs without drug-polymer interaction (i.e., KTZ/HPMC systems), the mixing homogeneity had little impact on the release rate of either the drug or the polymer thus SDD and SDD-PB demonstrated the same drug or polymer release rate, while the drug released slowly and independently of polymer release. The initial drug release from an ASD was controlled by 1) the polymer release rate; 2) the strength of drug-polymer interaction, including the intrinsic interaction caused by the chemistry of the drug and the polymer (measured by the χ value), as well as that the apparent interaction caused by the drug-polymer ratio (measure by the extent of peak shift on spectroscopic analysis); and 3) the level of mixing homogeneity between the drug and polymer. In summary, the selection of polymer, drug-polymer ratio, and ASD processing conditions have profound impacts on the dissolution behavior of ASDs. Graphical Abstract Relationship between initial drug and polymer dissolution rates from amorphous solid dispersions with different mixing uniformity and drug-polymer interactions.

Shape-Memory Polymers for Biomedical Applications

NASA Astrophysics Data System (ADS)

Yakacki, Christopher M.; Gall, Ken

Shape-memory polymers (SMPs) are a class of mechanically functional "smart" materials that have generated substantial interest for biomedical applications. SMPs offer the ability to promote minimally invasive surgery, provide structural support, exert stabilizing forces, elute therapeutic agents, and biodegrade. This review focuses on several areas of biomedicine including vascular, orthopedic, and neuronal applications with respect to the progress and potential for SMPs to improve the standard of treatment in these areas. Fundamental studies on proposed biomedical SMP systems are discussed with regards to biodegradability, tailorability, sterilization, and biocompatibility. Lastly, a proposed research and development pathway for SMP-based biomedical devices is proposed based on trends in the recent literature.

Optimized performance of quasi-solid-state DSSC with PEO-bismaleimide polymer blend electrolytes filled with a novel procedure.

PubMed

Lee, Dong Ha; Sun, Kyung Chul; Qadir, Muhammad Bilal; Jeong, Sung Hoon

2014-12-01

Dye-sensitized solar cell (DSSC) is an attractive renewable energy technology currently under intense investigation. Electrolyte plays an important role in the photovoltaic performance of the DSSCs and many efforts have been contributed to study different kinds of electrolytes with various characteristics such as liquid electrolytes, polymer electrolytes and so on. In this study, DSSC is developed by using quasi-solid electrolyte and a novel procedure is adopted for filling this electrolyte. The quasi-solid-state electrolyte was prepared by mixing Poly ethylene oxide (PEO) and bismaleimide together and constitution was taken as PEO (15 wt%) at various bismaleimide concentrations (1, 3, 5 wt%). The novel procedure of filling electrolyte consists of three major steps (first step: filling liquid electrolyte, second step: vaporization of liquid electrolyte, third step: refilling quasi-solid-state electrolyte). The electrochemical and photovoltaic performances of DSSCs with these electrolytes were also investigated. The electrochemical impedance spectroscopy (EIS) indicated that TiO2/Dye/electrolyte impedance is reduced and electron lifetime is increased, and consequently efficiency of cell has been improved after using this novel procedure. The photovoltaic power conversion efficiency of 6.39% has been achieved under AM 1.5 simulated sunlight (100 W/cm2) through this novel procedure and by using specified blend of polymers.

Setting the Record Straight: Bottom-Up Carbon Nanostructures via Solid-State Reactions

NASA Astrophysics Data System (ADS)

Jordan, Robert Stanley

Chapter 1 describes the development and spectroscopic investigation of a novel synthetic route to N = 8 armchair graphene nanoribbons from polydiacetylene polymers. Four distinct diphenyl polydiacetylene polymers are produced from the crystal-phase topochemical polymerization of their corresponding diphenyl-1,4-butadiynes. These polydiacetylene polymers are transformed into spectroscopically indistinguishable N = 8 armchair graphene nanoribbons via simple heating in the bulk, solid-state. The stepwise transformation of polydiacetylenes to graphene nanoribbons is examined in detail by the use of complementary spectroscopic methods, namely solid-state nuclear magnetic resonance, infrared, Raman and X-ray photoelectron spectroscopy. The final morphology and width of the nanoribbons is established through the use of high-resolution transmission electron microscopy. Chapter 2 chronicles the implementation of a similar approach to N = 12 armchair graphene nanoribbons from a dinaphthyl substituted polydiacetylene polymer. The mild nature of the process and pristine structure of the nanoribbons is again confirmed with the use of spectroscopic and microscopic methods. The chapter concludes with preliminary electrical measurements of the nanoribbons confirming that they are indeed conductive. Chapter 3 details the development of a synthetic route to diaryl trans-enediynes as structural models of individual reactive units within a polydiacetylene polymer. The trans-enediynes described are found to undergo three distinct annulation reactions depending on reaction conditions. Finally, the synthetic routes developed are utilized to access diethynyl [5]helicenes and phenanthrenes which fueled studies on the mechanism of the Bergman polymerization reaction.

Molecular mechanism of melting of a helical polymer crystal: Role of conformational order, packing and mobility of polymers

NASA Astrophysics Data System (ADS)

Cheerla, Ramesh; Krishnan, Marimuthu

2018-03-01

The molecular mechanism of melting of a superheated helical polymer crystal has been investigated using isothermal-isobaric molecular dynamics simulation that allows anisotropic deformation of the crystal lattice. A detailed microscopic analysis of the onset and progression of melting and accompanying changes in the polymer conformational order, translational, and orientation order of the solid along the melting pathway is presented. Upon gradual heating from room temperature to beyond the melting point at ambient pressure, the crystal exhibits signatures of premelting well below the solid-to-liquid melting transition at the melting point. The melting transition is manifested by abrupt changes in the crystal volume, lattice energy, polymer conformation, and dynamical properties. In the premelting stage, the crystal lattice structure and backbone orientation of the polymer chains are retained but with the onset of weakening of long-range helical order and interchain packing of polymers perpendicular to the fibre axis of the crystal. The premelting also marks the onset of conformational defects and anisotropic solid-state diffusion of polymers along the fibre axis. The present study underscores the importance of the interplay between intermolecular packing, interactions, and conformational dynamics at the atomic level in determining the macroscopic melting behavior of polymer crystals.

Constrasting Conductance/Viscosity Relations in Liquid States of Vitreous and Polymer Solid Electrolytes.

DTIC Science & Technology

1987-11-01

State lonics, 9 & 10, 617 (1983). 17. 11. Tweer, N. Laberge , and P.B. Macedo, J. Am. Ceram. Soc., 54, 121 (1971). p 18. R. Weiler, S. Blaser, and P.B...Bressel, Ph.D. Thesis, Purdue University, (1971). 25. S. Schantz, J. Sandahl, L. Borjesson, L.M. Torell and J.R. Stevens . Solid State lonics (in press). 26

Rechargeable solid polymer electrolyte battery cell

DOEpatents

Skotheim, Terji

1985-01-01

A rechargeable battery cell comprising first and second electrodes sandwiching a solid polymer electrolyte comprising a layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte adjacent said polymer blend and a layer of dry solid polymer electrolyte adjacent said layer of polymer blend and said second electrode.

The Use of Solid States Ionic Materials and Devices in Medical Applications

NASA Astrophysics Data System (ADS)

Linford, R. G.

2006-06-01

Electrolyte materials used in solid state polymer batteries can also be utilised in a special type of drug delivery system called an iontophoretic device. This review will describe the history, applications and limitations of iontophoretic and related systems and also the use of batteries and biofuel cells in medicine.

Dispersion of the Photosensitizer 5,10,15,20-Tetrakis(4-Sulfonatophenyl)-porphyrin by the Amphiphilic Polymer Poly(vinylpirrolidone) in Highly Porous Solid Materials Designed for Photodynamic Therapy.

PubMed

Díaz, Claudia; Catalán-Toledo, José; Flores, Mario E; Orellana, Sandra L; Pesenti, Héctor; Lisoni, Judit; Moreno-Villoslada, Ignacio

2017-08-03

The ability of the amphiphilic and biocompatible poly(vinylpyrrolidone) to avoid self-aggregation of the photosensitizer 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous solution in the presence of the biocompatible polycation chitosan, polymer that induces the dye self-aggregation, is shown. This is related to the tendency of the dye to undergo preferential solvation by the amphiphilic polymer. Importantly, the dispersant ability of this polymer is transferred to the solid state. Thus, aerogels made of the biocompatible polymers chitosan and chondroitin sulfate, and containing the photosensitizer dispersed by the amphiphilic polymer have been synthesized. Production of reactive oxygen species by the aerogel containing the amphiphilic polymer was faster than when the polymer was absent, correlating with the relative concentration of dyes dispersed as monomers. The aerogels presented here constitute low cost biocompatible materials bearing a conventional photosensitizer for photodynamic therapy, easy to produce, store, transport, and manage in clinical practice.

Effective Infiltration of Gel Polymer Electrolyte into Silicon-Coated Vertically Aligned Carbon Nanofibers as Anodes for Solid-State Lithium-Ion Batteries.

PubMed

Pandey, Gaind P; Klankowski, Steven A; Li, Yonghui; Sun, Xiuzhi Susan; Wu, Judy; Rojeski, Ronald A; Li, Jun

2015-09-23

This study demonstrates the full infiltration of gel polymer electrolyte into silicon-coated vertically aligned carbon nanofibers (Si-VACNFs), a high-capacity 3D nanostructured anode, and the electrochemical characterization of its properties as an effective electrolyte/separator for future all-solid-state lithium-ion batteries. Two fabrication methods have been employed to form a stable interface between the gel polymer electrolyte and the Si-VACNF anode. In the first method, the drop-casted gel polymer electrolyte is able to fully infiltrate into the open space between the vertically aligned core-shell nanofibers and encapsulate/stabilize each individual nanofiber in the polymer matrix. The 3D nanostructured Si-VACNF anode shows a very high capacity of 3450 mAh g(-1) at C/10.5 (or 0.36 A g(-1)) rate and 1732 mAh g(-1) at 1C (or 3.8 A g(-1)) rate. In the second method, a preformed gel electrolyte film is sandwiched between an Si-VACNF electrode and a Li foil to form a half-cell. Most of the vertical core-shell nanofibers of the Si-VACNF anode are able to penetrate into the gel polymer film while retaining their structural integrity. The slightly lower capacity of 2800 mAh g(-1) at C/11 rate and ∼1070 mAh g(-1) at C/1.5 (or 2.6 A g(-1)) rate have been obtained, with almost no capacity fade for up to 100 cycles. Electrochemical impedance spectroscopy does not show noticeable changes after 110 cycles, further revealing the stable interface between the gel polymer electrolyte and the Si-VACNFs anode. These results show that the infiltrated flexible gel polymer electrolyte can effectively accommodate the stress/strain of the Si shell due to the large volume expansion/contraction during the charge-discharge processes, which is particularly useful for developing future flexible solid-state lithium-ion batteries incorporating Si-anodes.

Post-polymerization C-H Borylation of Donor-Acceptor Materials Gives Highly Efficient Solid State Near-Infrared Emitters for Near-IR-OLEDs and Effective Biological Imaging.

PubMed

Crossley, Daniel L; Urbano, Laura; Neumann, Robert; Bourke, Struan; Jones, Jennifer; Dailey, Lea Ann; Green, Mark; Humphries, Martin J; King, Simon M; Turner, Michael L; Ingleson, Michael J

2017-08-30

Post-polymerization modification of the donor-acceptor polymer, poly(9,9-dioctylfluorene-alt-benzothiadiazole), PF8-BT, by electrophilic C-H borylation is a simple method to introduce controllable quantities of near-infrared (near-IR) emitting chromophore units into the backbone of a conjugated polymer. The highly stable borylated unit possesses a significantly lower LUMO energy than the pristine polymer resulting in a reduction in the band gap of the polymer by up to 0.63 eV and a red shift in emission of more than 150 nm. Extensively borylated polymers absorb strongly in the deep red/near-IR and are highly emissive in the near-IR region of the spectrum in solution and solid state. Photoluminescence quantum yield (PLQY) values are extremely high in the solid state for materials with emission maxima ≥ 700 nm with PLQY values of 44% at 700 nm and 11% at 757 nm for PF8-BT with different borylation levels. This high brightness enables efficient solution processed near-IR emitting OLEDs to be fabricated and highly emissive borylated polymer loaded conjugated polymer nanoparticles (CPNPs) to be prepared. The latter are bright, photostable, low toxicity bioimaging agents that in phantom mouse studies show higher signal to background ratios for emission at 820 nm than the ubiquitous near-IR emissive bioimaging agent indocyanine green. This methodology represents a general approach for the post-polymerization functionalization of donor-acceptor polymers to reduce the band gap as confirmed by the C-H borylation of poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2c,2cc-diyl) (PF8TBT) resulting in a red shift in emission of >150 nm, thereby shifting the emission maximum to 810 nm.

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

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

Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solidmore » state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.« less

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

DOE PAGES

Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry

2018-02-19

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solidmore » state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.« less

Near-infrared (NIR) emitting conjugated polymers for biomedical applications (Presentation Recording)

NASA Astrophysics Data System (ADS)

Repenko, Tatjana; Kuehne, Alexander J. C.

2015-10-01

Fluorescent biomedical markers of today such as dye-infiltrated colloids, microgels and quantum dots suffer from fast bleaching, lack surface functionality (for targets or pharmaceutical agents) and potentially leach heavy metals in case of quantum dots (e.g. Cd). By contrast, conjugated polymer particles are non-cytotoxic, exhibit reduced bleaching, as the entire particle consists of fluorophore, they are hydrophobic and show high quantum yields. Consequently, conjugated polymer particles represent ideal materials for biological applications and imaging. However currently, conjugated polymer particles for biomedical imaging usually lack near-infrared (NIR) emission and are polydisperse. Fluorescent agents with emission in the NIR spectrum are interesting for biomedical applications due to their low photo-damage towards biological species and the ability of NIR radiation to penetrate deep into biological tissue.. I will present the development and synthesis of new conjugated polymers particles with fluorescence in the NIR spectral region for bio-imaging and clinical diagnosis. The particle synthesis proceeds in a one-step Pd or Ni-catalyzed dispersion polymerization of functional NIR emitters. The resulting monodisperse conjugated polymer particles are obtained as a dispersion in a non-hazardous solvent. Different sizes in the sub-micrometer range with a narrow size distribution can be produced. Furthermore biological recognition motifs can be easily attached to the conjugated polymers via thiol-yne click-chemistry providing specific tumor targeting without quenching of the fluorescence. References [1] Kuehne AJC, Gather MC, Sprakel J., Nature Commun. 2012, 3, 1088. [2] Repenko T, Fokong S, De Laporte L, Go D, Kiessling F, Lammers T, Kuehne AJC.,Chem Commun 2015, accepted.

A summary of the research program in the broad field of electronics

NASA Technical Reports Server (NTRS)

1972-01-01

Summary reports of research projects covering solid state materials, semiconductors and devices, quantum electronics, plasmas, applied electromagnetics, electrical engineering systems to include control communication, computer and power systems, biomedical engineering and mathematical biosciences.

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors.

PubMed

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-04-07

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br - in PIL-M-(Br) and TFSI - in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br - and TFSI - , respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g - ¹, 40 and 48 kW·kg - ¹, and 107 and 59.9 Wh·kg - ¹ were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively.

Conducting Polymers and Their Applications in Diabetes Management.

PubMed

Zhao, Yu; Cao, Luyao; Li, Lanlan; Cheng, Wen; Xu, Liangliang; Ping, Xinyu; Pan, Lijia; Shi, Yi

2016-10-26

Advances in conducting polymers (CPs) have promoted the development of diabetic monitoring and treatment, which is of great significance in human healthcare and modern medicine. CPs are special polymers with physical and electrochemical features resembling metals, inorganic semiconductors and non-conducting polymers. To improve and extend their properties, the fabrication of CPs and CP composites has attracted intensive attention in recent decades. Some CPs are biocompatible and suitable for biomedical use. Thus, the intriguing properties of CPs make wearable, noninvasive, continuous diabetes managing devices and other potential applications in diabetes possible in the near future. To highlight the recent advances of CPs and their derived materials (especially in conducting polymer hydrogels), here we discuss their fabrication and characterization, review the current state-of-the-art research in diabetes management based on these materials and describe current challenges as well as future potential research directions.

Conducting Polymers and Their Applications in Diabetes Management

PubMed Central

Zhao, Yu; Cao, Luyao; Li, Lanlan; Cheng, Wen; Xu, Liangliang; Ping, Xinyu; Pan, Lijia; Shi, Yi

2016-01-01

Advances in conducting polymers (CPs) have promoted the development of diabetic monitoring and treatment, which is of great significance in human healthcare and modern medicine. CPs are special polymers with physical and electrochemical features resembling metals, inorganic semiconductors and non-conducting polymers. To improve and extend their properties, the fabrication of CPs and CP composites has attracted intensive attention in recent decades. Some CPs are biocompatible and suitable for biomedical use. Thus, the intriguing properties of CPs make wearable, noninvasive, continuous diabetes managing devices and other potential applications in diabetes possible in the near future. To highlight the recent advances of CPs and their derived materials (especially in conducting polymer hydrogels), here we discuss their fabrication and characterization, review the current state-of-the-art research in diabetes management based on these materials and describe current challenges as well as future potential research directions. PMID:27792179

Degradable vinyl polymers for biomedical applications.

PubMed

Delplace, Vianney; Nicolas, Julien

2015-10-01

Vinyl polymers have been the focus of intensive research over the past few decades and are attractive materials owing to their ease of synthesis and their broad diversity of architectures, compositions and functionalities. Their carbon-carbon backbones are extremely resistant to degradation, however, and this property limits their uses. Degradable polymers are an important field of research in polymer science and have been used in a wide range of applications spanning from (nano)medicine to microelectronics and environmental protection. The development of synthetic strategies to enable complete or partial degradation of vinyl polymers is, therefore, of great importance because it will offer new opportunities for the application of these materials. This Review captures the most recent and promising approaches to the design of degradable vinyl polymers and discusses the potential of these materials for biomedical applications.

A Novel Silicone-Magnetite Composite Material Used in the Fabrication of Biomimetic Cilia

NASA Astrophysics Data System (ADS)

Carstens, B. L.; Evans, B. A.; Shields, A. R.; Su, J.; Washburn, S.; Falvo, M. R.; Superfine, R.

2008-10-01

We have developed a novel polymer-magnetite composite that we use to fabricate arrays of magnetically actuable biomimetic cilia. Biomimetic cilia are flexible nanorods 750 nm in diameter and 25 microns tall. They generate fluid flows similar to those produced by biological cilia. Polymer-magnetic nanoparticle materials such as ours are becoming increasingly useful in biomedical applications and microelectromechanical systems (MEMS). Comprised of magnetite (Fe3O4), the nanoparticles have a diameter of 5-7 nm and are complexed with a silicone copolymer and crosslinked into a flexible, magnetic solid. Amine groups make up 6-7 percent of the silicone copolymer, providing a simple means of functionalization. We present a detailed mechanical and magnetic analysis of our bulk crosslinked material. The high-aspect ratio biomimetic cilia we create with this magnetite-copolymer complex may have applications in microfluidic mixing, biofouling, and MEMS.

Co-assembly of Zn(SPh){sub 2} and organic linkers into helical and zig-zag polymer chains

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

Liu Yi; Yu Lingmin; Loo, Say Chye Joachim

2012-07-15

Two novel one-dimensional coordination polymers, single helicate [Zn(SPh){sub 2}(TPyTA)(EG)]{sub n} (EG=ethylene glycol) (1) and zig-zag structure [Zn(SPh){sub 2}(BPyVB)]{sub n} (2), were synthesized under solvothermal conditions at 150 Degree-Sign C or room temperature by the co-assembly of Zn(SPh){sub 2} and organic linkers such as 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPyTA) and 1,3-bis(trans-4-pyridylvinyl)benzene (BPyVB). X-ray crystallography study reveals that both polymers 1 and 2 crystallize in space group P2{sub 1}/c of the monoclinic system. The solid-state UV-vis absorption spectra show that 1 and 2 have maxium absorption onsets at 400 nm and 420 nm, respectively. TGA analysis indicates that 1 and 2 are stable up tomore » 110 Degree-Sign C and 210 Degree-Sign C. - Graphical abstract: Two novel one-dimensional coordination polymers, single helicate [Zn(SPh){sub 2}(TPyTA)(EG)]{sub n} (1) and zig-zag structure [Zn(SPh){sub 2}(BPyVB)]{sub n} (2), were synthesized. Solid-state UV-vis absorptions show that 1 and 2 have maxium absorption onsets at 400 nm and 420 nm, respectively. TGA analysis indicates that 1 and 2 are stable up to 110 Degree-Sign C and 210 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Two novel one-dimensional coordination polymers have been synthesized. Black-Right-Pointing-Pointer TPyTA results in helical structures in 1 while BPyVB leads to zig-zag chains in 2. Black-Right-Pointing-Pointer Solid-state UV-vis absorption spectra and TGA analysis of the title polymers were studied.« less

A Silica-Aerogel-Reinforced Composite Polymer Electrolyte with High Ionic Conductivity and High Modulus.

PubMed

Lin, Dingchang; Yuen, Pak Yan; Liu, Yayuan; Liu, Wei; Liu, Nian; Dauskardt, Reinhold H; Cui, Yi

2018-06-25

High-energy all-solid-state lithium (Li) batteries have great potential as next-generation energy-storage devices. Among all choices of electrolytes, polymer-based systems have attracted widespread attention due to their low density, low cost, and excellent processability. However, they are generally mechanically too weak to effectively suppress Li dendrites and have lower ionic conductivity for reasonable kinetics at ambient temperature. Herein, an ultrastrong reinforced composite polymer electrolyte (CPE) is successfully designed and fabricated by introducing a stiff mesoporous SiO 2 aerogel as the backbone for a polymer-based electrolyte. The interconnected SiO 2 aerogel not only performs as a strong backbone strengthening the whole composite, but also offers large and continuous surfaces for strong anion adsorption, which produces a highly conductive pathway across the composite. As a consequence, a high modulus of ≈0.43 GPa and high ionic conductivity of ≈0.6 mS cm -1 at 30 °C are simultaneously achieved. Furthermore, LiFePO 4 -Li full cells with good cyclability and rate capability at ambient temperature are obtained. Full cells with cathode capacity up to 2.1 mAh cm -2 are also demonstrated. The aerogel-reinforced CPE represents a new design principle for solid-state electrolytes and offers opportunities for future all-solid-state Li batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular Chemistry and Engineering of Boron-Modified Polyorganosilazanes as New Processable and Functional SiBCN Precursors.

PubMed

Viard, Antoine; Fonblanc, Diane; Schmidt, Marion; Lale, Abhijeet; Salameh, Chrystelle; Soleilhavoup, Anne; Wynn, Mélanie; Champagne, Philippe; Cerneaux, Sophie; Babonneau, Florence; Chollon, Georges; Rossignol, Fabrice; Gervais, Christel; Bernard, Samuel

2017-07-06

A series of boron-modified polyorganosilazanes was synthesized from a poly(vinylmethyl-co-methyl)silazane and controlled amounts of borane dimethyl sulfide. The role of the chemistry behind their synthesis has been studied in detail by using solid-state NMR spectroscopy, FTIR spectroscopy, and elemental analysis. The intimate relationship between the chemistry and the processability of these polymers is discussed. Polymers with low boron contents displayed appropriate requirements for facile processing in solution, such as impregnation of host carbon materials, which resulted in the design of mesoporous monoliths with a high specific surface area after pyrolysis. Polymers with high boron content are more appropriate for solid-state processing to design mechanically robust monolith-type macroporous and dense structures after pyrolysis. Boron acts as a crosslinking element, which offers the possibility to extend the processability of polyorganosilazanes and suppress the distillation of oligomeric fragments in the low-temperature region of their thermal decomposition (i.e., pyrolysis) at 1000 °C under nitrogen. Polymers with controlled and high ceramic yields were generated. We provide a comprehensive mechanistic study of the two-step thermal decomposition based on a combination of thermogravimetric experiments coupled with elemental analysis, solid-state NMR spectroscopy, and FTIR spectroscopy. Selected characterization tools allowed the investigation of specific properties of the monolith-type SiBCN materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improving the chemical stability of amorphous solid dispersion with cocrystal technique by hot melt extrusion.

PubMed

Liu, Xu; Lu, Ming; Guo, Zhefei; Huang, Lin; Feng, Xin; Wu, Chuanbin

2012-03-01

To explore in-situ forming cocrystal as a single-step, efficient method to significantly depress the processing temperature and thus minimize the thermal degradation of heat-sensitive drug in preparation of solid dispersions by melting method (MM) and hot melt extrusion (HME). Carbamazepine (CBZ)-nicotinamide (NIC) cocrystal solid dispersions were prepared with polymer carriers PVP/VA, SOLUPLUS and HPMC by MM and/or HME. The formation of cocrystal was investigated by differential scanning calorimetry and hot stage polarized optical microscopy. State of CBZ in solid dispersion was characterized by X-ray powder diffraction and optical microscopy. Interactions between CBZ, NIC and polymers were investigated by FTIR. Dissolution behaviors of solid dispersions were compared with that of pure CBZ. CBZ-NIC cocrystal with melting point of 160°C was formed in polymer carriers during heating process, and the preparation temperature of amorphous CBZ solid dispersion was therefore depressed to 160°C. The dissolution rate of CBZ-NIC cocrystal solid dispersion was significantly increased. By in-situ forming cocrystal, chemically stable amorphous solid dispersions were prepared by MM and HME at a depressed processing temperature. This method provides an attractive opportunity for HME of heat-sensitive drugs.

The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers

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

Harman-Ware, Anne E.; Happs, Renee M.; Davison, Brian H.

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H) and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10 and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid state NMRmore » spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.« less

The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers

DOE PAGES

Harman-Ware, Anne E.; Happs, Renee M.; Davison, Brian H.; ...

2017-11-30

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H) and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10 and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid state NMRmore » spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.« less

Polymer space-charge-limited transistor as a solid-state vacuum tube triode

NASA Astrophysics Data System (ADS)

Chao, Yu-Chiang; Ku, Ming-Che; Tsai, Wu-Wei; Zan, Hsiao-Wen; Meng, Hsin-Fei; Tsai, Hung-Kuo; Horng, Sheng-Fu

2010-11-01

We report the construction of a polymer space-charge-limited transistor (SCLT), a solid-state version of vacuum tube triode. The SCLT achieves a high on/off ratio of 3×105 at a low operation voltage of 1.5 V by using high quality insulators both above and below the grid base electrode. Applying a greater bias to the base increases the barrier potential, and turns off the channel current, without introducing a large parasitic leakage current. Simulation result verifies the influence of base bias on channel potential distribution. The output current density is 1.7 mA/cm2 with current gain greater than 1000.

Design and development of low cost polyurethane biopolymer based on castor oil and glycerol for biomedical applications

PubMed Central

Tan, A. C. W.; Polo‐Cambronell, B. J.; Provaggi, E.; Ardila‐Suárez, C.; Ramirez‐Caballero, G. E.; Baldovino‐Medrano, V. G.

2017-01-01

Abstract In the current study, we present the synthesis of novel low cost bio‐polyurethane compositions with variable mechanical properties based on castor oil and glycerol for biomedical applications. A detailed investigation of the physicochemical properties of the polymer was carried out by using mechanical testing, ATR‐FTIR, and X‐ray photoelectron spectroscopy (XPS). Polymers were also tested in short term in‐vitro cell culture with human mesenchymal stem cells to evaluate their biocompatibility for potential applications as biomaterial. FTIR analysis confirmed the synthesis of castor oil and glycerol based PU polymers. FTIR also showed that the addition of glycerol as co‐polyol increases crosslinking within the polymer backbone hence enhancing the bulk mechanical properties of the polymer. XPS data showed that glycerol incorporation leads to an enrichment of oxidized organic species on the surface of the polymers. Preliminary investigation into in vitro biocompatibility showed that serum protein adsorption can be controlled by varying the glycerol content with polymer backbone. An alamar blue assay looking at the metabolic activity of the cells indicated that castor oil based PU and its variants containing glycerol are non‐toxic to the cells. This study opens an avenue for using low cost bio‐polyurethane based on castor oil and glycerol for biomedical applications. PMID:29159831

Novel ether-linkages containing aliphatic copolyesters of poly(butylene 1,4-cyclohexanedicarboxylate) as promising candidates for biomedical applications.

PubMed

Gigli, Matteo; Lotti, Nadia; Vercellino, Marco; Visai, Livia; Munari, Andrea

2014-01-01

A new class of biodegradable and biocompatible poly(butylene 1,4-cyclohexanedicarboxylate) based random copolymers are proposed for biomedical applications. The introduction of ether-oxygen containing BDG sequences along the PBCE macromolecular chain is expected to remarkably improve chain flexibility and surface hydrophilicity due to the presence of highly electronegative oxygen atoms. P(BCExBDGy) copolymers were synthesized by polycondensation. The homopolymer PBCE and three copolymers, namely (P(BCE70BDG30), P(BCE55BDG45) and P(BCE40BDG60)) were characterized from the molecular, thermal, structural and mechanical point of view. Hydrolytic degradation studies in the presence and absence of hog-pancreas lipase were performed under physiological conditions. To evaluate the diffusion profile of small molecules through the polymer matrix, the release behaviour of fluorescein isothiocyanate (FITC) was investigated. For biocompatibility studies, cell adhesion and proliferation of murine fibroblast (L929) and endocrine pancreatic (INS-1) cells were performed on each polymeric film. Results showed that solid-state properties can be tailored by simply varying copolymers' composition. Crystallinity degree and hydrophobicity significantly decreased with the increase of BDG co-unit mol%. Moreover, mechanical properties and biodegradability of PBCE, both depending on crystallinity degree, were remarkably improved: P(BCE40BDG60) showed an elastomeric behaviour with εb over 600% and, as regard to biodegradability, after 98days it lost over 60% of its initial weight if incubated in the presence of the pancreatic lipase. Lastly, the newly developed biomaterials resulted not cytotoxic with both types of cells and could be properly tailored for biomedical applications varying the content of BDG co-unit mol%. © 2013.

Biopolymer-based thermoplastic mixture for producing solid biodegradable shaped bodies and its photo degradation stability

NASA Astrophysics Data System (ADS)

Sulong, Nurulsaidatulsyida; Rus, Anika Zafiah M.

2013-12-01

In recent years, biopolymers with controllable lifetimes have become increasingly important for many applications in the areas of agriculture, biomedical implants and drug release, forestry, wild life conservation and waste management. Natural oils are considered to be the most important class of renewable sources. They can be obtained from naturally occurring plants, such as sunflower, cotton, linseed and palm oil. In Malaysia, palm oil is an inexpensive and commodity material. Biopolymer produced from palm oil (Bio-VOP) is a naturally occurring biodegradable polymer and readily available from agriculture. For packaging use however, Bio-VOP is not thermoplastic and its granular form is unsuitable for most uses in the plastics industry, mainly due to processing difficulties during extrusion or injection moulding. Thus, research workers have developed several methods to blend Bio-VOP appropriately for industrial uses. In particular, injections moulding processes, graft copolymerisation, and preparation of blends with thermoplastic polymers have been studied to produce solid biodegradable shaped bodies. HDPE was chosen as commercial thermoplastic materials and was added with 10% Bio-VOP for the preparation of solid biodegradable shaped bodies named as HD-VOP. The UV light exposure of HD-VOP at 12 minutes upon gives the highest strength of this material that is 17.6 MPa. The morphological structure of HD-VOP shows dwi structure surface fracture which is brittle and ductile properties.

Polymer-Enriched 3D Graphene Foams for Biomedical Applications.

PubMed

Wang, Jun Kit; Xiong, Gordon Minru; Zhu, Minmin; Özyilmaz, Barbaros; Castro Neto, Antonio Helio; Tan, Nguan Soon; Choong, Cleo

2015-04-22

Graphene foams (GFs) are versatile nanoplatforms for biomedical applications because of their excellent physical, chemical, and mechanical properties. However, the brittleness and inflexibility of pristine GF (pGF) are some of the important factors restricting their widespread application. Here, a chemical-vapor-deposition-assisted method was used to synthesize 3D GFs, which were subsequently spin-coated with polymer to produce polymer-enriched 3D GFs with high conductivity and flexibility. Compared to pGF, both poly(vinylidene fluoride)-enriched GF (PVDF/GF) and polycaprolactone-enriched GF (PCL/GF) scaffolds showed improved flexibility and handleability. Despite the presence of the polymers, the polymer-enriched 3D GF scaffolds retained high levels of electrical conductivity because of the presence of microcracks that allowed for the flow of electrons through the material. In addition, polymer enrichment of GF led to an enhancement in the formation of calcium phosphate (Ca-P) compounds when the scaffolds were exposed to simulated body fluid. Between the two polymers tested, PCL enrichment of GF resulted in a higher in vitro mineralization nucleation rate because the oxygen-containing functional group of PCL had a higher affinity for Ca-P deposition and formation compared to the polar carbon-fluorine (C-F) bond in PVDF. Taken together, our current findings are a stepping stone toward future applications of polymer-enriched 3D GFs in the treatment of bone defects as well as other biomedical applications.

Phase-Change Thermoplastic Elastomer Blends for Tunable Shape Memory by Physical Design

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

Mineart, Kenneth P.; Tallury, Syamal S.; Li, Tao

Shape-memory polymers (SMPs) change shape upon exposure to an environmental stimulus.1-3 They are of considerable importance in the ongoing development of stimuli-responsive biomedical4,5 and deployable6 devices, and their function depends on the presence of two components.7 The first provides mechanical rigidity to ensure retention of one or more temporary strain states and also serves as a switch capable of releasing a temporary strain state. The second, a network-forming component, is required to restore the polymer to a prior strain state upon stimulation. In thermally-activated SMPs, the switching element typically relies on a melting or glass transition temperature,1-3,7 and broad ormore » multiple switches permit several temporary strain states.8-10 Chemical integration of network-forming and switching species endows SMPs with specific properties.8,10,11 Here, we demonstrate that phase-change materials incorporated into network-forming macromolecules yield shape-memory polymer blends (SMPBs) with physically tunable switching temperatures and recovery kinetics for use in multi-responsive laminates and shape-change electronics.« less

Chlorine-rich plasma polymer coating for the prevention of attachment of pathogenic fungal cells onto materials surfaces

NASA Astrophysics Data System (ADS)

Lamont-Friedrich, Stephanie J.; Michl, Thomas D.; Giles, Carla; Griesser, Hans J.; Coad, Bryan R.

2016-07-01

The attachment of pathogenic fungal cells onto materials surfaces, which is often followed by biofilm formation, causes adverse consequences in a wide range of areas. Here we have investigated the ability of thin film coatings from chlorinated molecules to deter fungal colonization of solid materials by contact killing of fungal cells reaching the surface of the coating. Coatings were deposited onto various substrate materials via plasma polymerization, which is a substrate-independent process widely used for industrial coating applications, using 1,1,2-trichloroethane as the process vapour. XPS surface analysis showed that the coatings were characterized by a highly chlorinated hydrocarbon polymer nature, with only a very small amount of oxygen incorporated. The activity of these coatings against human fungal pathogens was quantified using a recently developed, modified yeast assay and excellent antifungal activity was observed against Candida albicans and Candida glabrata. Plasma polymer surface coatings derived from chlorinated hydrocarbon molecules may therefore offer a promising solution to preventing yeast and mould biofilm formation on materials surfaces, for applications such as air conditioners, biomedical devices, food processing equipment, and others.

The synthesis and protein resistance of amphiphilic PDMS-b-(PDMS-g-cysteine) copolymers

NASA Astrophysics Data System (ADS)

Lei, Yufeng; Lin, Yaling; Zhang, Anqiang

2017-10-01

Zwitterionic polymers have been used to cope with nonspecific protein adsorption and bio-fouling problems for a wide range of materials, including biomedical devices, marine coatings and membrane separation. However, direct surface modification with highly water-soluble zwitterionic polymers is rather difficult due to their poor attachment to hydrophobic solid surfaces. In this work, we utilize the hydrophobic interaction to anchor zwitterionic polysiloxanes grafted with cysteine onto surfaces by adding an hydrophobic block of polydimethylsiloxanes, referred as PDMS-b-(PDMS-g-Cys)s. The synthesis involves only three steps of reactions, and the structures of each product were characterized using GPC, FT-IR and 1H NMR. The adsorption and protein resistance of PDMS-b-(PDMS-g-Cys)s on a gold surface are investigated with QCM-D. The results show that the hydrophobic interaction moieties of the additional PDMS blocks help the hydrophilic cysteine-grafted blocks stably attach and then function on the sensor. These findings suggest that the addition of hydrophobic moieties provides an effective approach to construct anti-fouling interfaces with zwitterionic polymers in aqueous solution.

Recent advances in conjugated polymers for light emitting devices.

PubMed

Alsalhi, Mohamad Saleh; Alam, Javed; Dass, Lawrence Arockiasamy; Raja, Mohan

2011-01-01

A recent advance in the field of light emitting polymers has been the discovery of electroluminescent conjugated polymers, that is, kind of fluorescent polymers that emit light when excited by the flow of an electric current. These new generation fluorescent materials may now challenge the domination by inorganic semiconductor materials of the commercial market in light-emitting devices such as light-emitting diodes (LED) and polymer laser devices. This review provides information on unique properties of conjugated polymers and how they have been optimized to generate these properties. The review is organized in three sections focusing on the major advances in light emitting materials, recent literature survey and understanding the desirable properties as well as modern solid state lighting and displays. Recently, developed conjugated polymers are also functioning as roll-up displays for computers and mobile phones, flexible solar panels for power portable equipment as well as organic light emitting diodes in displays, in which television screens, luminous traffic, information signs, and light-emitting wallpaper in homes are also expected to broaden the use of conjugated polymers as light emitting polymers. The purpose of this review paper is to examine conjugated polymers in light emitting diodes (LEDs) in addition to organic solid state laser. Furthermore, since conjugated polymers have been approved as light-emitting organic materials similar to inorganic semiconductors, it is clear to motivate these organic light-emitting devices (OLEDs) and organic lasers for modern lighting in terms of energy saving ability. In addition, future aspects of conjugated polymers in LEDs were also highlighted in this review.

Recent Advances in Conjugated Polymers for Light Emitting Devices

PubMed Central

AlSalhi, Mohamad Saleh; Alam, Javed; Dass, Lawrence Arockiasamy; Raja, Mohan

2011-01-01

A recent advance in the field of light emitting polymers has been the discovery of electroluminescent conjugated polymers, that is, kind of fluorescent polymers that emit light when excited by the flow of an electric current. These new generation fluorescent materials may now challenge the domination by inorganic semiconductor materials of the commercial market in light-emitting devices such as light-emitting diodes (LED) and polymer laser devices. This review provides information on unique properties of conjugated polymers and how they have been optimized to generate these properties. The review is organized in three sections focusing on the major advances in light emitting materials, recent literature survey and understanding the desirable properties as well as modern solid state lighting and displays. Recently, developed conjugated polymers are also functioning as roll-up displays for computers and mobile phones, flexible solar panels for power portable equipment as well as organic light emitting diodes in displays, in which television screens, luminous traffic, information signs, and light-emitting wallpaper in homes are also expected to broaden the use of conjugated polymers as light emitting polymers. The purpose of this review paper is to examine conjugated polymers in light emitting diodes (LEDs) in addition to organic solid state laser. Furthermore, since conjugated polymers have been approved as light-emitting organic materials similar to inorganic semiconductors, it is clear to motivate these organic light-emitting devices (OLEDs) and organic lasers for modern lighting in terms of energy saving ability. In addition, future aspects of conjugated polymers in LEDs were also highlighted in this review. PMID:21673938

Polymer Electrolyte Through Enzyme Catalysis for High Performance Lithium-Ion Batteries

DTIC Science & Technology

1998-10-16

by block number) FIELD GROUP SUB-GROUP Polymer Electrolyte, Solid State, Enzyme Catalysis, Lithium - Ion Battery , Sol Gel, High Conductivity 19...excellent candidates for lithium - ion battery development. Furthermore, the processes used to achieve the final product yield very good mechanical properties...Objectives This research was initiated to investigate synthesis of improved polymer electrolytes for lithium - ion battery applications. The overall

New Polymer Electrolyte Cell Systems

NASA Technical Reports Server (NTRS)

Smyrl, William H.; Owens, Boone B.; Mann, Kent; Pappenfus, T.; Henderson, W.

2004-01-01

PAPERS PUBLISHED: 1. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials. Journal of the Electrochemical Society (2004), 15 1 (2), A209-A2 15. 2. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Ionic-liquidlpolymer electrolyte composite materials for electrochemical device applications. Polymeric Materials Science and Engineering (2003), 88 302. 3. Pappenfus, Ted R.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; and Smyrl, William H. Ionic Conductivity of a poly(vinylpyridinium)/Silver Iodide Solid Polymer Electrolyte System. Solid State Ionics (in press 2004). 4. Pappenfus Ted M.; Mann, Kent R; Smyrl, William H. Polyelectrolyte Composite Materials with LiPFs and Tetraglyme. Electrochemical and Solid State Letters, (2004), 7(8), A254.

Compact Ozone Differential Absorption Lidar (DIAL) Transmitter Using Solid-State Dye Polymers

NASA Technical Reports Server (NTRS)

Jones, Alton L., Jr.; DeYoung, Russell J.; Elsayid-Ele, Hani

2001-01-01

A new potential DIAL laser transmitter is described that uses solid-state dye laser materials to make a simpler, more compact, lower mass laser system. Two solid-state dye laser materials were tested to evaluate their performance in a laser oscillator cavity end pumped by a pulsed Nd:YAG laser at 532 nm. The polymer host polymethyl-methacrylate was injected with a pyrromethene laser dye, PM 580, or PM 597. A narrowband laser oscillator cavity was constructed to produce visible wavelengths of 578 and 600 nm which were frequency doubled into the UV region (299 or 300 nm) by using a BBO crystal, resulting in a maximum energy of 11 mJ at a wavelength of 578 nm when pumped by the Nd:YAG laser at an energy of 100 mJ (532 nm). A maximum output energy of 378 microJ was achieved in the UV region at a wavelength of 289 nm but lasted only 2000 laser shots at a repetition rate of 10 Hz. The results are promising and show that a solid-state dye laser based ozone DIAL system is possible with improvements in the design of the laser transmitter.

Process to produce lithium-polymer batteries

DOEpatents

MacFadden, Kenneth Orville

1998-01-01

A polymer bonded sheet product suitable for use as an electrode in a non-aqueous battery system. A porous electrode sheet is impregnated with a solid polymer electrolyte, so as to diffuse into the pores of the electrode. The composite is allowed to cool, and the electrolyte is entrapped in the porous electrode. The sheet products composed have the solid polymer electrolyte composition diffused into the active electrode material by melt-application of the solid polymer electrolyte composition into the porous electrode material sheet. The solid polymer electrolyte is maintained at a temperature that allows for rapid diffusion into the pores of the electrode. The composite electrolyte-electrode sheets are formed on current collectors and can be coated with solid polymer electrolyte prior to battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte coating has low resistance.

Preparation of the polyelectrolyte complex hydrogel of biopolymers via a semi-dissolution acidification sol-gel transition method and its application in solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Zhao, Jian; Chen, Yu; Yao, Ying; Tong, Zong-Rui; Li, Pu-Wang; Yang, Zi-Ming; Jin, Shao-Hua

2018-02-01

Hydrogels have drawn many attentions as the solid-state electrolytes in flexible solid-state supercapacitors (SCs) recently. Among them, the polyelectrolyte complex hydrogel (PECH) electrolytes of natural polymers are more competitive because of their environmentally friendly property and low cost. However, while mixing two biopolymer solutions with opposite charges, the strong electrostatic interactions between the cationic and anionic biopolymers may result in precipitates instead of hydrogels. Here we report a novel method, semi-dissolution acidification sol-gel transition (SD-A-SGT), for the preparation of the PECH of chitosan (CTS) and sodium alginate (SA), with the controllable sol-gel transition and uniform composition and successfully apply it as the hydrogel electrolyte of solid-state supercapacitors (SCs). The CTS-SA PECH exhibits an extremely high ionic conductivity of 0.051 S·cm-1 and reasonable mechanical properties with a tensile strength of 0.29 MPa and elongation at break of 109.5%. The solid-state SC fabricated with the CTS-SA PECH and conventional polyaniline (PANI) nanowire electrodes provided a high specific capacitance of 234.6 F·g-1 at 5 mV·s-1 and exhibited excellent cycling stability with 95.3% capacitance retention after 1000 cycles. Our work may pave a novel avenue to the preparation of biodegradable PECHs of full natural polymers, and promote the development of environmentally friendly electronic devices.

One-step synthesis of solid state luminescent carbon-based silica nanohybrids for imaging of latent fingerprints

NASA Astrophysics Data System (ADS)

Li, Feng; Li, Hongren; Cui, Tianfang

2017-11-01

Fluorescent carbon-based nanomaterials(CNs) with tunable visible emission are biocompatible, environment friendly and most suitable for various biomedical applications. Despite the successes in preparing strongly fluorescent CNs, preserving the luminescence in solid materials is still challenging because of the serious emission quenching of CNs in solid state materials. In this work, fluorescent carbon and silica nanohybrids (SiCNHs) were synthesized via a simple one-step hydrothermal approach by carbonizing sodium citrate and (3-aminopropyl)triethoxysilane(APTES), and hydrolysis of tetraethyl orthosilicate(TEOS). The resultant SiCNs were characterized through X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectroscopy. The SiCNs exhibited strong fluorescence in both aqueous and solid states. The luminescent solid state SiCNs power were successfully used as a fluorescent labeling material for enhanced imaging of latent fingerprints(LFPs) on single background colour and multi-coloured surfaces substrates in forensic science for individual identification.

Small lasers in flow cytometry.

PubMed

Telford, William G

2004-01-01

Laser technology has made tremendous advances in recent years, particularly in the area of diode and diode-pumped solid state sources. Flow cytometry has been a direct beneficiary of these advances, as these small, low-maintenance, inexpensive lasers with reasonable power outputs are integrated into flow cytometers. In this chapter we review the contribution and potential of solid-state lasers to flow cytometry, and show several examples of these novel sources integrated into production flow cytometers. Technical details and critical parameters for successful application of these lasers for biomedical analysis are reviewed.

Human pathogens, nosocomial infections, heat-sensitive textile implants, and an innovative approach to deal with them.

PubMed

Cinquemani, Claudio

2011-01-01

Implantable polymers, as used for biomedical applications, inherently have to be sterile. Nonetheless, most implants, particularly those comprised of biomaterials developed in recent years for tissue engineering, are heat sensitive. Therefore, use of hazardous (radio)chemicals--due to lack of alternative methods--is still state of the art for sterilization processes. The drawbacks of these techniques, both drastic and well known, lead to the demand for an alternative sterilization method, which is equally obvious and urgent. High-pressure fluid treatment is a low-temperature technique that is already in use for pasteurization of liquid food products. This paper explores inactivation of vegetative microorganisms, spores, and endotoxins adherent to solid surfaces using compressed CO(2). Pressures ranging from 50 to 100 bar and temperatures from 25 °C to 50 °C were explored to investigate liquid, gaseous or supercritical state. Analysis of variance (ANOVA) and statistical modeling were used to identify the optimum parameter settings for inactivation of pathogenic bacteria and fungi (Candida albicans, Staphylococcus aureus). The addition of small amounts of ozone ensures inactivation of persistent spores (Bacillus stearothermophilus, B. subtilis) up to 10(6) cfu/ml, while endotoxins remain in practically unchanged concentration on the polymer surface. We then discuss environmental issues of the process and inactivation mechanisms. The replacement of conventional chemicals with nonpersistent ones resolves organizational and safety-related issues and protects natural resources as well as handling staff. The pressurized-fluid-based method exhibits mild treatment parameters, thus protecting sensitive textures. Finally, an outlook on possible applications of this innovative technique is presented.

Theoretical and experimental investigation of drug-polymer interaction and miscibility and its impact on drug supersaturation in aqueous medium.

PubMed

Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

2016-10-01

Amorphous solid dispersions (ASDs) have the potential to offer higher apparent solubility and bioavailability of BCS class II drugs. Knowledge of the solid state drug-polymer solubility/miscibility and their mutual interaction are fundamental requirements for the effective design and development of such systems. To this end, we have carried out a comprehensive investigation of various ASD systems of dipyridamole and cinnarizine in polyvinylpyrrolidone (PVP) and polyacrylic acid (PAA) at different drug loadings. Theoretical and experimental examinations (by implementing binary and ternary Flory-Huggins (F-H) theory) related to drug-polymer interaction/miscibility including solubility parameter approach, melting point depression method, phase diagram, drug-polymer interaction in the presence of moisture and the effect of drug loading on interaction parameter were performed. The information obtained from this study was used to predict the stability of ASDs at different drug loadings and under different thermal and moisture conditions. Thermal and moisture sorption analysis not only provided the composition-dependent interaction parameter but also predicted the composition dependent miscibility. DPM-PVP, DPM-PAA and CNZ-PAA systems have shown molecular level mixing over the complete range of drug loading. For CNZ-PVP, the presence of a single Tg at lower drug loadings (10, 20 and 35%w/w) indicates the formation of solid solution. However, drug recrystallization was observed for samples with higher drug weight fractions (50 and 65%w/w). Finally, the role of polymer in maintaining drug supersaturation has also been explored. It has been found that drug-polymer combinations capable of hydrogen-bonding in the solution state (DPM-PVP, DPM-PAA and CNZ-PAA) are more effective in preventing drug crystallization compared to the drug-polymer systems without such interaction (CNZ-PVP). The DPM-PAA system outperformed all other ASDs in various stability conditions (dry-state, in the presence of moisture and in solution state), which was attributed to the drug's low crystallization tendency, the strong DPM-PAA interaction, the robustness of this interaction against moisture or water and the ability of PAA in maintaining DPM supersaturation. Copyright © 2016 Elsevier B.V. All rights reserved.

High Ionic Conductivity of Composite Solid Polymer Electrolyte via In Situ Synthesis of Monodispersed SiO2 Nanospheres in Poly(ethylene oxide).

PubMed

Lin, Dingchang; Liu, Wei; Liu, Yayuan; Lee, Hye Ryoung; Hsu, Po-Chun; Liu, Kai; Cui, Yi

2016-01-13

High ionic conductivity solid polymer electrolyte (SPE) has long been desired for the next generation high energy and safe rechargeable lithium batteries. Among all of the SPEs, composite polymer electrolyte (CPE) with ceramic fillers has garnered great interest due to the enhancement of ionic conductivity. However, the high degree of polymer crystallinity, agglomeration of ceramic fillers, and weak polymer-ceramic interaction limit the further improvement of ionic conductivity. Different from the existing methods of blending preformed ceramic particles with polymers, here we introduce an in situ synthesis of ceramic filler particles in polymer electrolyte. Much stronger chemical/mechanical interactions between monodispersed 12 nm diameter SiO2 nanospheres and poly(ethylene oxide) (PEO) chains were produced by in situ hydrolysis, which significantly suppresses the crystallization of PEO and thus facilitates polymer segmental motion for ionic conduction. In addition, an improved degree of LiClO4 dissociation can also be achieved. All of these lead to good ionic conductivity (1.2 × 10(-3) S cm(-1) at 60 °C, 4.4 × 10(-5) S cm(-1) at 30 °C). At the same time, largely extended electrochemical stability window up to 5.5 V can be observed. We further demonstrated all-solid-state lithium batteries showing excellent rate capability as well as good cycling performance.

Direct growth of high crystallinity graphene from water-soluble polymer powders

NASA Astrophysics Data System (ADS)

Chen, Qiao; Zhong, Yujia; Huang, Meirong; Zhao, Guoke; Zhen, Zhen; Zhu, Hongwei

2018-07-01

The use of solid-state carbon sources is effective to produce graphene by safe and low-cost chemical vapor deposition (CVD) process. Water-soluble polymers are generally environmentally friendly and have great potential on large-scale green production of graphene. Here, we systematically study the growth of graphene from water-soluble polymers on copper foils. Two different conversion ways are adopted to investigate the growth mechanism of graphene from water-soluble polymers. We find that the metal-binding functional group hydroxyl strongly influences the vaporization of water-soluble polymers on Cu foils, which hinders the formation of graphene films by rapid thermal treatment. In direct CVD process using water-soluble polymer powders as precursors, oxygenated functional groups in polymers can enhance the crystallinity of as-grown graphene in contrast to solid hydrocarbons without containing oxygen (e.g. polyethylene). Large and continuous graphene films of high quality are synthesized from polyvinyl alcohol and polyethylene glycol. Nitrogen doping in graphene can be easily realized by using nitrogen-containing water-soluble polymers (e.g. polyvinyl pyrrolidone).

Molecular-Level Control of Ciclopirox Olamine Release from Poly(ethylene oxide)-Based Mucoadhesive Buccal Films: Exploration of Structure-Property Relationships with Solid-State NMR.

PubMed

Urbanova, Martina; Gajdosova, Marketa; Steinhart, Miloš; Vetchy, David; Brus, Jiri

2016-05-02

Mucoadhesive buccal films (MBFs) provide an innovative way to facilitate the efficient site-specific delivery of active compounds while simultaneously separating the lesions from the environment of the oral cavity. The structural diversity of these complex multicomponent and mostly multiphase systems as well as an experimental strategy for their structural characterization at molecular scale with atomic resolution were demonstrated using MBFs of ciclopirox olamine (CPX) in a poly(ethylene oxide) (PEO) matrix as a case study. A detailed description of each component of the CPX/PEO films was followed by an analysis of the relationships between each component and the physicochemical properties of the MBFs. Two distinct MBFs were identified by solid-state NMR spectroscopy: (i) at low API (active pharmaceutical ingredient) loading, a nanoheterogeneous solid solution of CPX molecularly dispersed in an amorphous PEO matrix was created; and (ii) at high API loading, a pseudoco-crystalline system containing CPX-2-aminoethanol nanocrystals incorporated into the interlamellar space of a crystalline PEO matrix was revealed. These structural differences were found to be closely related to the mechanical and physicochemical properties of the prepared MBFs. At low API loading, the polymer chains of PEO provided sufficient quantities of binding sites to stabilize the CPX that was molecularly dispersed in the highly amorphous semiflexible polymer matrix. Consequently, the resulting MBFs were soft, with low tensile strength, plasticity, and swelling index, supporting rapid drug release. At high CPX content, however, the active compounds and the polymer chains simultaneously cocrystallized, leaving the CPX to form nanocrystals grown directly inside the spherulites of PEO. Interfacial polymer-drug interactions were thus responsible not only for the considerably enhanced plasticity of the system but also for the exclusive crystallization of CPX in the thermodynamically most stable polymorphic form, Form I, which exhibited reduced dissolution kinetics. The bioavailability of CPX olamine formulated as PEO-based MBFs can thus be effectively controlled by inducing the complete dispersion and/or microsegregation and nanocrystallization of CPX olamine in the polymer matrix. Solid-state NMR spectroscopy is an efficient tool for exploring structure-property relationships in these complex pharmaceutical solids.

Tritium containing polymers having a polymer backbone substantially void of tritium

DOEpatents

Jensen, G.A.; Nelson, D.A.; Molton, P.M.

1992-03-31

A radioluminescent light source comprises a solid mixture of a phosphorescent substance and a tritiated polymer. The solid mixture forms a solid mass having length, width, and thickness dimensions, and is capable of self-support. In one aspect of the invention, the phosphorescent substance comprises solid phosphor particles supported or surrounded within a solid matrix by a tritium containing polymer. The tritium containing polymer comprises a polymer backbone which is essentially void of tritium. 2 figs.

Tritium containing polymers having a polymer backbone substantially void of tritium

DOEpatents

Jensen, George A.; Nelson, David A.; Molton, Peter M.

1992-01-01

A radioluminescent light source comprises a solid mixture of a phosphorescent substance and a tritiated polymer. The solid mixture forms a solid mass having length, width, and thickness dimensions, and is capable of self-support. In one aspect of the invention, the phosphorescent substance comprises solid phosphor particles supported or surrounded within a solid matrix by a tritium containing polymer. The tritium containing polymer comprises a polymer backbone which is essentially void of tritium.

Method of forming a foamed thermoplastic polymer

DOEpatents

Duchane, D.V.; Cash, D.L.

1984-11-21

A solid thermoplastic polymer is immersed in an immersant solution comprising a compatible carrier solvent and an infusant solution containing an incompatible liquid blowing agent for a time sufficient for the immersant solution to infuse into the polymer. The carrier solvent is then selectively extracted, preferably by a solvent exchange process in which the immersant solution is gradually diluted with and replaced by the infusant solution, so as to selectively leave behind the infustant solution permanently entrapped in the polymer. The polymer is then heated to volatilize the blowing agent and expand the polymer into a foamed state.

Self-organization of glucose oxidase-polymer surfactant nanoconstructs in solvent-free soft solids and liquids.

PubMed

Sharma, Kamendra P; Zhang, Yixiong; Thomas, Michael R; Brogan, Alex P S; Perriman, Adam W; Mann, Stephen

2014-10-02

An anisotropic glucose oxidase-polymer surfactant nanoconjugate is synthesized and shown to exhibit complex temperature-dependent phase behavior in the solvent-free state. At close to room temperature, the nanoconjugate crystallizes as a mesolamellar soft solid with an expanded interlayer spacing of ca. 12 nm and interchain correlation lengths consistent with alkyl tail-tail and PEO-PEO ordering. The soft solid displays a birefringent spherulitic texture and melts at 40 °C to produce a solvent-free liquid protein without loss of enzyme secondary structure. The nanoconjugate melt exhibits a birefringent dendritic texture below the conformation transition temperature (Tc) of glucose oxidase (58 °C) and retains interchain PEO-PEO ordering. Our results indicate that the shape anisotropy of the protein-polymer surfactant globular building block plays a key role in directing mesolamellar formation in the solvent-free solid and suggests that the microstructure observed in the solvent-free liquid protein below Tc is associated with restrictions in the intramolecular motions of the protein core of the nanoconjugate.

Grafted functional groups on expanded tetrafluoroethylene (ePTFE) support for fuel cell and water transport membranes

DOEpatents

Fuller, Timothy J.; Jiang, Ruichun

2017-01-24

A method for forming a modified solid polymer includes a step of contacting a solid fluorinated polymer with a sodium sodium-naphthalenide solution to form a treated fluorinated solid polymer. The treated fluorinated solid polymer is contacted with carbon dioxide, sulfur dioxide, or sulfur trioxide to form a solid grafted fluorinated polymer. Characteristically, the grafted fluorinated polymer includes appended CO.sub.2H or SO.sub.2H or SO.sub.3H groups. The solid grafted fluorinated polymer is advantageously incorporated into a fuel cell as part of the ion-conducting membrane or a water transport membrane in a humidifier.

α-Amino acid containing degradable polymers as functional biomaterials: rational design, synthetic pathway, and biomedical applications.

PubMed

Sun, Huanli; Meng, Fenghua; Dias, Aylvin A; Hendriks, Marc; Feijen, Jan; Zhong, Zhiyuan

2011-06-13

Currently, biomedical engineering is rapidly expanding, especially in the areas of drug delivery, gene transfer, tissue engineering, and regenerative medicine. A prerequisite for further development is the design and synthesis of novel multifunctional biomaterials that are biocompatible and biologically active, are biodegradable with a controlled degradation rate, and have tunable mechanical properties. In the past decades, different types of α-amino acid-containing degradable polymers have been actively developed with the aim to obtain biomimicking functional biomaterials. The use of α-amino acids as building units for degradable polymers may offer several advantages: (i) imparting chemical functionality, such as hydroxyl, amine, carboxyl, and thiol groups, which not only results in improved hydrophilicity and possible interactions with proteins and genes, but also facilitates further modification with bioactive molecules (e.g., drugs or biological cues); (ii) possibly improving materials biological properties, including cell-materials interactions (e.g., cell adhesion, migration) and degradability; (iii) enhancing thermal and mechanical properties; and (iv) providing metabolizable building units/blocks. In this paper, recent developments in the field of α-amino acid-containing degradable polymers are reviewed. First, synthetic approaches to prepare α-amino acid-containing degradable polymers will be discussed. Subsequently, the biomedical applications of these polymers in areas such as drug delivery, gene delivery and tissue engineering will be reviewed. Finally, the future perspectives of α-amino acid-containing degradable polymers will be evaluated.

Design and development of low cost polyurethane biopolymer based on castor oil and glycerol for biomedical applications.

PubMed

Tan, A C W; Polo-Cambronell, B J; Provaggi, E; Ardila-Suárez, C; Ramirez-Caballero, G E; Baldovino-Medrano, V G; Kalaskar, D M

2018-02-01

In the current study, we present the synthesis of novel low cost bio-polyurethane compositions with variable mechanical properties based on castor oil and glycerol for biomedical applications. A detailed investigation of the physicochemical properties of the polymer was carried out by using mechanical testing, ATR-FTIR, and X-ray photoelectron spectroscopy (XPS). Polymers were also tested in short term in-vitro cell culture with human mesenchymal stem cells to evaluate their biocompatibility for potential applications as biomaterial. FTIR analysis confirmed the synthesis of castor oil and glycerol based PU polymers. FTIR also showed that the addition of glycerol as co-polyol increases crosslinking within the polymer backbone hence enhancing the bulk mechanical properties of the polymer. XPS data showed that glycerol incorporation leads to an enrichment of oxidized organic species on the surface of the polymers. Preliminary investigation into in vitro biocompatibility showed that serum protein adsorption can be controlled by varying the glycerol content with polymer backbone. An alamar blue assay looking at the metabolic activity of the cells indicated that castor oil based PU and its variants containing glycerol are non-toxic to the cells. This study opens an avenue for using low cost bio-polyurethane based on castor oil and glycerol for biomedical applications. © 2017 The Authors Biopolymers Published by Wiley Periodicals, Inc.

Facile synthesis of polymeric fluorescent organic nanoparticles based on the self-polymerization of dopamine for biological imaging.

PubMed

Shi, Yingge; Jiang, Ruming; Liu, Meiying; Fu, Lihua; Zeng, Guangjian; Wan, Qing; Mao, Liucheng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-08-01

Polymeric fluorescent organic nanoparticles (polymer-FONs) have raised considerable research attention for biomedical applications owing to their advantages as compared with fluorescent inorganic nanoparticles and small organic molecules. In this study, we presented an efficient, facile and environment-friendly strategy to produce polymer-FONs, which relied on the self-polymerization of dopamine and polyethyleneimine (PEI) in rather mild conditions. To obtain the final polymer-FONs, aldehyde group-containing copolymers (named as poly(UA-co-PEGMA)) were synthesized by reversible addition-fragmentation chain-transfer polymerization using polyethylene glycol methyl ether methacrylate (PEGMA) and 1-undecen-10-al (UA) as monomers. The dopamine was conjugated onto poly(UA-co-PEGMA) through a multicomponent reaction between UA and dopamine to obtain poly(UA-co-PEGMA)-DA, which was further utilized for preparation of polymer-FONs through self-polymerization of dopamine and PEI. 1 H nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy and fluorescence spectroscopy were employed to characterize the structure, morphology, compositions and optical properties of these polymer-FONs. Cell viability and cell uptake behavior results suggested that these polymer-FONs possess good biocompatibility and can be potentially utilized for biomedical applications. More importantly, the method can be also applied to fabricate many other multifunctional polymer-FONs with great potential for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Process to produce lithium-polymer batteries

DOEpatents

MacFadden, K.O.

1998-06-30

A polymer bonded sheet product is described suitable for use as an electrode in a non-aqueous battery system. A porous electrode sheet is impregnated with a solid polymer electrolyte, so as to diffuse into the pores of the electrode. The composite is allowed to cool, and the electrolyte is entrapped in the porous electrode. The sheet products composed have the solid polymer electrolyte composition diffused into the active electrode material by melt-application of the solid polymer electrolyte composition into the porous electrode material sheet. The solid polymer electrolyte is maintained at a temperature that allows for rapid diffusion into the pores of the electrode. The composite electrolyte-electrode sheets are formed on current collectors and can be coated with solid polymer electrolyte prior to battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte coating has low resistance. 1 fig.

Ion conducting organic/inorganic hybrid polymers

NASA Technical Reports Server (NTRS)

Meador, Maryann B. (Inventor); Kinder, James D. (Inventor)

2010-01-01

This invention relates to a series of organic/inorganic hybrid polymers that are easy to fabricate into dimensionally stable films with good ion-conductivity over a wide range of temperatures for use in a variety of applications. The polymers are prepared by the reaction of amines, preferably diamines and mixtures thereof with monoamines with epoxy-functionalized alkoxysilanes. The products of the reaction are polymerized by hydrolysis of the alkoxysilane groups to produce an organic-containing silica network. Suitable functionality introduced into the amine and alkoxysilane groups produce solid polymeric membranes which conduct ions for use in fuel cells, high-performance solid state batteries, chemical sensors, electrochemical capacitors, electro-chromic windows or displays, analog memory devices and the like.

Backbone-Degradable Polymers Prepared by Chemical Vapor Deposition.

PubMed

Xie, Fan; Deng, Xiaopei; Kratzer, Domenic; Cheng, Kenneth C K; Friedmann, Christian; Qi, Shuhua; Solorio, Luis; Lahann, Joerg

2017-01-02

Polymers prepared by chemical vapor deposition (CVD) polymerization have found broad acceptance in research and industrial applications. However, their intrinsic lack of degradability has limited wider applicability in many areas, such as biomedical devices or regenerative medicine. Herein, we demonstrate, for the first time, a backbone-degradable polymer directly synthesized via CVD. The CVD co-polymerization of [2.2]para-cyclophanes with cyclic ketene acetals, specifically 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), results in well-defined, hydrolytically degradable polymers, as confirmed by FTIR spectroscopy and ellipsometry. The degradation kinetics are dependent on the ratio of ketene acetals to [2.2]para-cyclophanes as well as the hydrophobicity of the films. These coatings address an unmet need in the biomedical polymer field, as they provide access to a wide range of reactive polymer coatings that combine interfacial multifunctionality with degradability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer mobility in cell walls of cucumber hypocotyls

NASA Technical Reports Server (NTRS)

Fenwick, K. M.; Apperley, D. C.; Cosgrove, D. J.; Jarvis, M. C.

1999-01-01

Cell walls were prepared from the growing region of cucumber (Cucumis sativus) hypocotyls and examined by solid-state 13C NMR spectroscopy, in both enzymically active and inactivated states. The rigidity of individual polymer segments within the hydrated cell walls was assessed from the proton magnetic relaxation parameter, T2, and from the kinetics of cross-polarisation from 1H to 13C. The microfibrils, including most of the xyloglucan in the cell wall, as well as cellulose, behaved as very rigid solids. A minor xyloglucan fraction, which may correspond to cross-links between microfibrils, shared a lower level of rigidity with some of the pectic galacturonan. Other pectins, including most of the galactan side-chain residues of rhamnogalacturonan I, were much more mobile and behaved in a manner intermediate between the solid and liquid states. The only difference observed between the enzymically active and inactive cell walls, was the loss of a highly mobile, methyl-esterified galacturonan fraction, as the result of pectinesterase activity.

Monolithic quasi-solid-state dye-sensitized solar cells based on graphene-modified mesoscopic carbon-counter electrodes

NASA Astrophysics Data System (ADS)

Rong, Yaoguang; Han, Hongwei

2013-01-01

A monolithic quasi-solid-state dye-sensitized solar cell (DSSC) based on graphene-modified mesoscopic carbon-counter electrode is developed. A TiO2-working electrode layer, ZrO2 spacer layer, and carbon counter electrode layer were constructed on a single conducting glass substrate by screen printing. The quasi-solid-state polymer gel electrolyte employed a polymer composite as the gelator, and effectively infiltrated the porous layers. Fabricated with normal carbon-counter electrode (NC-CE) containing graphite and carbon black, the DSSC had a power conversion efficiency (PCE) of 5.09% with the fill factor of 0.63 at 100 mW cm-2 AM1.5 illumination. When the NC-CE was modified with graphene sheets, the PCE and fill factor were enhanced to 6.27% and 0.71, respectively. This improvement indicates excellent conductivity and high electrocatalytic activity of the graphene sheets, which have been considered as a promising platinum-free electrode material for DSSCs.

High cation transport polymer electrolyte

DOEpatents

Gerald, II, Rex E.; Rathke, Jerome W [Homer Glen, IL; Klingler, Robert J [Westmont, IL

2007-06-05

A solid state ion conducting electrolyte and a battery incorporating same. The electrolyte includes a polymer matrix with an alkali metal salt dissolved therein, the salt having an anion with a long or branched chain having not less than 5 carbon or silicon atoms therein. The polymer is preferably a polyether and the salt anion is preferably an alkyl or silyl moiety of from 5 to about 150 carbon/silicon atoms.

Correlating Transport with Nanostructure and Chemical Identity in Radical Polymer Conducting Glasses

NASA Astrophysics Data System (ADS)

Boudouris, Bryan; Rostro, Lizbeth; Baradwaj, Aditya; Hay, Martha

2015-03-01

Radical polymers are an emerging class of macromolecules that are composed of non-conjugated backbones which bear stable radical groups at the pendant positions. Because of these stable radical sites, these glassy materials are able to conduct charge in the solid state through a series of oxidation-reduction (redox) reactions. Importantly, the redox-active behavior is controlled by both the local chemical environment of the radical polymer groups and by the nanoscale structure of the materials. Here, we demonstrate that proper control of the pendant group chemical functionality allows for the fabrication of transparent and conducting amorphous thin films which have solid-state hole mobility and electrical conductivity values on the same order as those seen in common conjugated, semicrystalline polymer systems [e.g., poly(3-hexylthiophene) (P3HT)]. Furthermore, we show that control of the nanostructure of the materials aids in facilitating transport in these radical polymer thin films. In turn, we implement simultaneous spectroscopic and electrical characterization measurements in order to elucidate the exact mechanism of charge transport in radical polymers. Finally, we demonstrate that, because there is ready control over the molecular properties of these materials, developing bendable and stretchable transparent conducting thin films is relatively straightforward with this unique class of organic electronic materials.

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

PubMed

Abraham, Anuji; Crull, George

2014-10-06

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.

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors

PubMed Central

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-01-01

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br) and TFSI− in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively. PMID:29642456

In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment

DOE PAGES

Kroning, Annika; Furchner, Andreas; Aulich, Dennis; ...

2015-02-10

The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes with high potential for biosensing and biomedical applications are studied by in-situ infrared-spectroscopic ellipsometry (IRSE). IRSE as a highly sensitive non-destructive technique allows us to investigate protein adsorption on polymer brushes in aqueous environment in dependence of external stimuli like temperature and pH. These stimuli are, for instance, relevant in switchable mixed brushes containing poly(N-isopropyl acrylamide) and poly(acrylic acid), respectively. We use such brushes as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. IRSE can distinguish between polymer-specific vibrational bands, which yield insights intomore » the hydration state of the brushes, and changes in the protein-specific amide bands, which are related to changes of the protein secondary structure.« less

Structural Modifications and Photophysical Studies of Fluorescent Conjugated Polymers for Solid State Sensor Development

NASA Astrophysics Data System (ADS)

Chen, Anting

Fluorescent conjugated polymers (FCPs) represent an exciting area of research in chemosensors and biosensors. Previously, the polymer tmeda-PPETE, N,N,N'-trimethylethylenediamino (tmeda) receptors on a poly[2,5-thiophenediyl-1,2-ethynediyl-1,4-phenylenediyl-1,2-ethynediyl] (PPETE) backbone, showed significant quenching when copper(II) was added. Tmeda-PPETE polymer preloaded with copper(II) was found to be a fluorescent "turn-on" sensor for iron cations. Additional investigation of this metallopolymer revealed a selective sensory system toward carbonate and phosphorus anions through a competitive binding of copper(II) between the polymer tmeda-PPETE and the anions. Fluorescent turn-on response under systematically varied pH was affected by the equilibrium shift of the ionization of polyprotic ions. A sterically hindered pentiptycene group was introduced to the PPETE polymer backbone aiming to reduce aggregation and self-quenching in the solid state. A new FCP, tmeda-PPpETE (poly[(pentiptycene ethynylene)-alt-(thienylene ethynylene)] with tmeda receptors, has been designed and synthesized via Sonogashira cross-coupling reaction. Absorption and emission spectra of tmeda-PPpETE showed blue shifting from tmeda-PPETE, suggesting increased rigidity of polymer backbone. Tmeda-PPpETE showed a high selectivity towards copper(II) with improved sensitivity compared to tmeda-PPETE. The fluorescent quenching response is over 120-fold at emission maximum, and the detection limit is 1.04 ppb, significantly lower than the EPA action level of 1.3 ppm for copper(II). A small turn-off fluorescent response of tmeda-PPpETE was also observed upon addition of iron cations. To further investigate the interaction between pentiptycene containing polymers and iron cations, tmpda-PPpETE containing N,N,N'-trimethylpropylenediamino (tmpda) receptors was designed and synthesized. The absorption and emission spectra for tmpda-PPpETE were analogous to those of tmeda-PPpETE, with a higher quantum yield for tmpda-PPpETE. The cation selectivity test in solution showed selective fluorescent quenching for iron cations. Investigation of the polymer-iron interaction showed that two binding mechanisms were involved. This is the first report of pentiptycene-derived polymer participating in a metal complex formation. By using 1,3,5-triethynylbenzene as the linker group, a network of PPETE polymer backbone loaded with tmeda receptors was designed and synthesized. This transformed the linear FCP, tmeda-PPETE into a network polymer. Two derivatives of this polymer were also successfully synthesized. The metal cation selectivity test showed similar fluorescent response as tmeda-PPETE, which revealed the potential in developing solid state sensors.

Garnet-type solid-state fast Li ion conductors for Li batteries: critical review.

PubMed

Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana

2014-07-07

Batteries are electrochemical devices that store electrical energy in the form of chemical energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and electric vehicles. Conventional LiBs use an organic polymer electrolyte, which exhibits several safety issues including leakage, poor chemical stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power density. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compounds are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion conductivity of ∼10(-6) at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion conductivity of 10(-3) S cm(-1) at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chemically stable at higher temperatures and voltages compared to polymer electrolytes. Here, we discuss the chemical composition-structure-ionic conductivity relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism.

Triclosan antimicrobial polymers

PubMed Central

Petersen, Richard C.

2016-01-01

Triclosan antimicrobial molecular fluctuating energies of nonbonding electron pairs for the oxygen atom by ether bond rotations are reviewed with conformational computational chemistry analyses. Subsequent understanding of triclosan alternating ether bond rotations is able to help explain several material properties in Polymer Science. Unique bond rotation entanglements between triclosan and the polymer chains increase both the mechanical properties of polymer toughness and strength that are enhanced even better through secondary bonding relationships. Further, polymer blend compatibilization is considered due to similar molecular relationships and polarities. With compatibilization of triclosan in polymers a more uniform stability for nonpolar triclosan in the polymer solid state is retained by the antimicrobial for extremely low release with minimum solubility into aqueous solution. As a result, triclosan is projected for long extended lifetimes as an antimicrobial polymer additive. Further, triclosan rapid alternating ether bond rotations disrupt secondary bonding between chain monomers in the resin state to reduce viscosity and enhance polymer blending. Thus, triclosan is considered for a polymer additive with multiple properties to be an antimicrobial with additional benefits as a nonpolar toughening agent and a hydrophobic wetting agent. The triclosan material relationships with alternating ether bond rotations are described through a complete different form of medium by comparisons with known antimicrobial properties that upset bacterial cell membranes through rapid fluctuating mechanomolecular energies. Also, triclosan bond entanglements with secondary bonding can produce structural defects in weak bacterial lipid membranes requiring pliability that can then interfere with cell division. Regarding applications with polymers, triclosan can be incorporated by mixing into a resin system before cure, melt mixed with thermoplastic polymers that set on cooling into a solid or alternatively applied as a coating through several different methods with dissolving into an organic solvent and dried on by evaporation as a common means. PMID:27280150

An Extraordinary Sulfonated-Graphenal-Polymer-Based Electrolyte Separator for All-Solid-State Supercapacitors.

PubMed

Liu, Xubo; Men, Chuanling; Zhang, Xiaohua; Li, Qingwen

2016-09-01

Sulfonated graphenal polymers can be assembled up by poly(vinyl alcohol) adhesion. The porous assembly structure results in a remarkably improved ionic conductivity and thus enhances electrochemical performances such as specific capacitance, capacitance retention, and cycling stability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Characterization of Electroactive Polymers Based on Pyrrole

DTIC Science & Technology

1989-10-01

169. 5. E.T. Kang, K.G. Neoh and H.C. Ti, Solid State Communications, 1986, 60, 457. 6. Osamu Niwa, Masami Kakuchi, and Toshiaki Tamamura, 7...1987, 18, 49. 8. Keiko Koga, Takao lino, Shigeyuki Ueta, and Motowo Takayanagi , Polymer. Journal, 1989, 21, 499. 9. S.E. Lindesey and G.B. Street

Smart polymers as surface modifiers for bioanalytical devices and biomaterials: theory and practice

NASA Astrophysics Data System (ADS)

Ivanov, A. E.; Zubov, V. P.

2016-06-01

Smart, or responsive polymers can reversibly change their state of aggregation, thus switching from water-soluble to insoluble state, in response to minor changes in temperature, pH or solvent composition. Grafting of these polymers to solid surfaces imparts the surfaces with controllable wettability and adsorption behaviour. The review summarizes the theoretical models and the results of physical measurements of the conformational transitions in grafted polymer chains and polymer brushes. Primary attention is paid to the grafting density and the length and spatial arrangement of grafted chains, the role of polystyrene, organosilane or alkanethiol sublayers and their effects on adsorption of proteins and adhesion of cells. The key applications of grafted smart polymers such as cell culture and tissue engineering, cell and protein separation, biosensing and targeted drug delivery are surveyed. The bibliography includes 174 references.

2D coherent charge transport in highly ordered conducting polymers doped by solid state diffusion

NASA Astrophysics Data System (ADS)

Kang, Keehoon; Watanabe, Shun; Broch, Katharina; Sepe, Alessandro; Brown, Adam; Nasrallah, Iyad; Nikolka, Mark; Fei, Zhuping; Heeney, Martin; Matsumoto, Daisuke; Marumoto, Kazuhiro; Tanaka, Hisaaki; Kuroda, Shin-Ichi; Sirringhaus, Henning

2016-08-01

Doping is one of the most important methods to control charge carrier concentration in semiconductors. Ideally, the introduction of dopants should not perturb the ordered microstructure of the semiconducting host. In some systems, such as modulation-doped inorganic semiconductors or molecular charge transfer crystals, this can be achieved by spatially separating the dopants from the charge transport pathways. However, in conducting polymers, dopants tend to be randomly distributed within the conjugated polymer, and as a result the transport properties are strongly affected by the resulting structural and electronic disorder. Here, we show that in the highly ordered lamellar microstructure of a regioregular thiophene-based conjugated polymer, a small-molecule p-type dopant can be incorporated by solid state diffusion into the layers of solubilizing side chains without disrupting the conjugated layers. In contrast to more disordered systems, this allows us to observe coherent, free-electron-like charge transport properties, including a nearly ideal Hall effect in a wide temperature range, a positive magnetoconductance due to weak localization and the Pauli paramagnetic spin susceptibility.

Screening and evaluation of polymers as flocculation aids for the treatment of aquacultural effluents

USGS Publications Warehouse

Ebeling, J.M.; Rishel, K.L.; Sibrell, P.L.

2005-01-01

As environmental regulations become more stringent, environmentally sound waste management and disposal are becoming increasingly more important in all aquaculture operations. One of the primary water quality parameters of concern is the suspended solids concentration in the discharged effluent. For example, EPA initially considered the establishment of numerical limitations for only one single pollutant: total suspended solids (TSS). For recirculation systems, the proposed TSS limitations would have applied to solids polishing or secondary solids removal technology. The new rules and regulations from EPA (August 23, 2004) require only qualitative TSS limits, in the form of solids control best management practices (BMP), allowing individual regional and site specific conditions to be addressed by existing state or regional programs through NPDES permits. In recirculation systems, microscreen filters are commonly used to remove the suspended solids from the process water. Further concentration of suspended solids from the backwash water of the microscreen filter could significantly reduce quantity of discharge water. And in some cases, the backwash water from microscreen filters needs to be further concentrated to minimize storage volume during over wintering for land disposal or other final disposal options. In addition, this may be required to meet local, state, and regional discharge water quality. The objective of this research was an initial screening of several commercially available polymers routinely used as coagulation-flocculation aids in the drinking and wastewater treatment industry and determination of their effectiveness for the treatment of aquaculture wastewater. Based on the results of the initial screening, a further evaluation of six polymers was conducted to estimate the optimum polymer dosage for flocculation of aquaculture microscreen effluent and overall solids removal efficiency. Results of these evaluations show TSS removal was close to 99% via settling, with final TSS values ranging from as low as 10-17 mg/L. Although not intended to be used for reactive phosphorus (RP) removal, RP was reduced by 92-95% by removing most of the TSS in the wastewater to approximately 1 mg/L-P. Dosage requirements were fairly uniform, requiring between 15 and 20 mg/L of polymer. Using these dosages, estimated costs range from $4.38 to $13.08 per metric tonne of feed. ?? 2005 Elsevier B.V. All rights reserved.

Responsive Biomaterials: Advances in Materials Based on Shape-Memory Polymers.

PubMed

Hardy, John G; Palma, Matteo; Wind, Shalom J; Biggs, Manus J

2016-07-01

Shape-memory polymers (SMPs) are morphologically responsive materials with potential for a variety of biomedical applications, particularly as devices for minimally invasive surgery and the delivery of therapeutics and cells for tissue engineering. A brief introduction to SMPs is followed by a discussion of the current progress toward the development of SMP-based biomaterials for clinically relevant biomedical applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of the Strength of Drug-Polymer Interactions on the Molecular Mobility and Crystallization Inhibition in Ketoconazole Solid Dispersions.

PubMed

Mistry, Pinal; Mohapatra, Sarat; Gopinath, Tata; Vogt, Frederick G; Suryanarayanan, Raj

2015-09-08

The effects of specific drug-polymer interactions (ionic or hydrogen-bonding) on the molecular mobility of model amorphous solid dispersions (ASDs) were investigated. ASDs of ketoconazole (KTZ), a weakly basic drug, with each of poly(acrylic acid) (PAA), poly(2-hydroxyethyl methacrylate) (PHEMA), and polyvinylpyrrolidone (PVP) were prepared. Drug-polymer interactions in the ASDs were evaluated by infrared and solid-state NMR, the molecular mobility quantified by dielectric spectroscopy, and crystallization onset monitored by differential scanning calorimetry (DSC) and variable temperature X-ray diffractometry (VTXRD). KTZ likely exhibited ionic interactions with PAA, hydrogen-bonding with PHEMA, and weaker dipole-dipole interactions with PVP. On the basis of dielectric spectroscopy, the α-relaxation times of the ASDs followed the order: PAA > PHEMA > PVP. In addition, the presence of ionic interactions also translated to a dramatic and disproportionate decrease in mobility as a function of polymer concentration. On the basis of both DSC and VTXRD, an increase in strength of interaction translated to higher crystallization onset temperature and a decrease in extent of crystallization. Stronger drug-polymer interactions, by reducing the molecular mobility, can potentially delay the crystallization onset temperature as well as crystallization extent.

Toward highly stable solid-state unconventional thin-film battery-supercapacitor hybrid devices: Interfacing vertical core-shell array electrodes with a gel polymer electrolyte

NASA Astrophysics Data System (ADS)

Pandey, Gaind P.; Klankowski, Steven A.; Liu, Tao; Wu, Judy; Li, Jun

2017-02-01

A novel solid-state battery-supercapacitor hybrid device is fabricated for high-performance electrical energy storage using a Si anode and a TiO2 cathode in conjunction with a flexible, solid-like gel polymer electrolyte film as the electrolyte and separator. The electrodes were fabricated as three-dimensional nanostructured vertical arrays by sputtering active materials as conformal shells on vertically aligned carbon nanofibers (VACNFs) which serve as the current collector and structural template. Such nanostructured vertical core-shell array-electrodes enable short Li-ion diffusion path and large pseudocapacitive contribution by fast surface reactions, leading to the hybrid features of batteries and supercapacitors that can provide high specific energy over a wide range of power rates. Due to the improved mechanical stability of the infiltrated composite structure, the hybrid cell shows excellent cycling stability and is able to retain more than 95% of the original capacity after 3500 cycles. More importantly, this solid-state device can stably operate in a temperature range from -20 to 60 °C with a very low self-discharge rate and an excellent shelf life. This solid-state architecture is promising for the development of highly stable thin-film hybrid energy storage devices for unconventional applications requiring largely varied power, wider operation temperature, long shelf-life and higher safety standards.

Crystallization features of normal alkanes in confined geometry.

PubMed

Su, Yunlan; Liu, Guoming; Xie, Baoquan; Fu, Dongsheng; Wang, Dujin

2014-01-21

How polymers crystallize can greatly affect their thermal and mechanical properties, which influence the practical applications of these materials. Polymeric materials, such as block copolymers, graft polymers, and polymer blends, have complex molecular structures. Due to the multiple hierarchical structures and different size domains in polymer systems, confined hard environments for polymer crystallization exist widely in these materials. The confined geometry is closely related to both the phase metastability and lifetime of polymer. This affects the phase miscibility, microphase separation, and crystallization behaviors and determines both the performance of polymer materials and how easily these materials can be processed. Furthermore, the size effect of metastable states needs to be clarified in polymers. However, scientists find it difficult to propose a quantitative formula to describe the transition dynamics of metastable states in these complex systems. Normal alkanes [CnH2n+2, n-alkanes], especially linear saturated hydrocarbons, can provide a well-defined model system for studying the complex crystallization behaviors of polymer materials, surfactants, and lipids. Therefore, a deeper investigation of normal alkane phase behavior in confinement will help scientists to understand the crystalline phase transition and ultimate properties of many polymeric materials, especially polyolefins. In this Account, we provide an in-depth look at the research concerning the confined crystallization behavior of n-alkanes and binary mixtures in microcapsules by our laboratory and others. Since 2006, our group has developed a technique for synthesizing nearly monodispersed n-alkane containing microcapsules with controllable size and surface porous morphology. We applied an in situ polymerization method, using melamine-formaldehyde resin as shell material and nonionic surfactants as emulsifiers. The solid shell of microcapsules can provide a stable three-dimensional (3-D) confining environment. We have studied multiple parameters of these microencapsulated n-alkanes, including surface freezing, metastability of the rotator phase, and the phase separation behaviors of n-alkane mixtures using differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD), and variable-temperature solid-state nuclear magnetic resonance (NMR). Our investigations revealed new direct evidence for the existence of surface freezing in microencapsulated n-alkanes. By examining the differences among chain packing and nucleation kinetics between bulk alkane solid solutions and their microencapsulated counterparts, we also discovered a mechanism responsible for the formation of a new metastable bulk phase. In addition, we found that confinement suppresses lamellar ordering and longitudinal diffusion, which play an important role in stabilizing the binary n-alkane solid solution in microcapsules. Our work also provided new insights into the phase separation of other mixed system, such as waxes, lipids, and polymer blends in confined geometry. These works provide a profound understanding of the relationship between molecular structure and material properties in the context of crystallization and therefore advance our ability to improve applications incorporating polymeric and molecular materials.

The Concept of Solid Solvent as Processing Aid.

DTIC Science & Technology

1984-09-20

3 presents the DSC results of acetanilide . Acetanilide shows a sharp melting peak at 116C, very close to the melting point (Tm) reported by Fisher...should become compatible with a polymer and act as a solvent in the liquid state above its melting point , significantly reducing the viscosity of the...polymer, but should become incompatible and crystallize out of the polymer as discrete domains below its melting point without adversely affecting

Developments in the use of rare earth metal complexes as efficient catalysts for ring-opening polymerization of cyclic esters used in biomedical applications

NASA Astrophysics Data System (ADS)

Cota, Iuliana

2017-04-01

Biodegradable polymers represent a class of particularly useful materials for many biomedical and pharmaceutical applications. Among these types of polyesters, poly(ɛ-caprolactone) and polylactides are considered very promising for controlled drug delivery devices. These polymers are mainly produced by ring-opening polymerization of their respective cyclic esters, since this method allows a strict control of the molecular parameters (molecular weight and distribution) of the obtained polymers. The most widely used catalysts for ring-opening polymerization of cyclic esters are tin- and aluminium-based organometallic complexes; however since the contamination of the aliphatic polyesters by potentially toxic metallic residues is particularly of concern for biomedical applications, the possibility of replacing organometallic initiators by novel less toxic or more efficient organometallic complexes has been intensively studied. Thus, in the recent years, the use of highly reactive rare earth initiators/catalysts leading to lower polymer contamination has been developed. The use of rare earth complexes is considered a valuable strategy to decrease the polyester contamination by metallic residues and represents an attractive alternative to traditional organometallic complexes.

Prediction of Phase Behavior of Spray-Dried Amorphous Solid Dispersions: Assessment of Thermodynamic Models, Standard Screening Methods and a Novel Atomization Screening Device with Regard to Prediction Accuracy

PubMed Central

Chavez, Pierre-François; Meeus, Joke; Robin, Florent; Schubert, Martin Alexander; Somville, Pascal

2018-01-01

The evaluation of drug–polymer miscibility in the early phase of drug development is essential to ensure successful amorphous solid dispersion (ASD) manufacturing. This work investigates the comparison of thermodynamic models, conventional experimental screening methods (solvent casting, quench cooling), and a novel atomization screening device based on their ability to predict drug–polymer miscibility, solid state properties (Tg value and width), and adequate polymer selection during the development of spray-dried amorphous solid dispersions (SDASDs). Binary ASDs of four drugs and seven polymers were produced at 20:80, 40:60, 60:40, and 80:20 (w/w). Samples were systematically analyzed using modulated differential scanning calorimetry (mDSC) and X-ray powder diffraction (XRPD). Principal component analysis (PCA) was used to qualitatively assess the predictability of screening methods with regards to SDASD development. Poor correlation was found between theoretical models and experimentally-obtained results. Additionally, the limited ability of usual screening methods to predict the miscibility of SDASDs did not guarantee the appropriate selection of lead excipient for the manufacturing of robust SDASDs. Contrary to standard approaches, our novel screening device allowed the selection of optimal polymer and drug loading and established insight into the final properties and performance of SDASDs at an early stage, therefore enabling the optimization of the scaled-up late-stage development. PMID:29518936

Understanding the generation and maintenance of supersaturation during the dissolution of amorphous solid dispersions using modulated DSC and 1H NMR.

PubMed

Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

2018-01-30

In this study, the dissolution behaviour of dipyridamole (DPM) and cinnarizine (CNZ) spray-dried amorphous solid dispersions (ASDs) using polyvinyl pyrrolidone (PVP) and polyacrylic acid (PAA) as a carrier matrix were evaluated and compared. The drug concentrations achieved from the dissolution of PVP and PAA solid dispersions were significantly greater than the equilibrium solubility of crystalline DPM and CNZ in phosphate buffer pH 6.8 (PBS 6.8). The maximum drug concentration achieved by dissolution of PVP and PAA solid dispersions did not exceed the theoretically calculated apparent solubility of amorphous DPM and CNZ. However, the degree of supersaturation of DPM and CNZ increased considerably as the polymer weight fraction within the solid dispersion increased. In addition, the supersaturation profile of DPM and CNZ were studied in the presence and absence of the polymers. PAA was found to maintain a higher level of supersaturation compared to PVP. The enhanced drug solution concentration following dissolution of ASDs can be attributed to the reduced crystal growth rates of DPM and CNZ at an equivalent supersaturation. We have also shown that, for drugs having high crystallization tendency and weak drug-polymer interaction, the feasible way to increase dissolution might be increase the polymer weight fraction in the ASD. Solution 1 H NMR spectra were used to understand dissolution mechanism and to identify drug-polymer interaction. The change in electron densities of proton attached to different groups in DPM and CNZ suggested drug-polymer interaction in solution. The relative intensities of peak shift and nature of interaction between drug and polymer in different systems are different. These different effects suggest that DPM and CNZ interacts in a different way with PVP and PAA in solution which goes some way towards explaining the different polymeric effect, particularly in terms of inhibition of drug recrystallization and dissolution of DPM and CNZ ASDs. These results established that the different drug/polymer interactions in the solid state and in solution give rise to the variation in dissolution profile observed for different systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Method of forming a foamed thermoplastic polymer

DOEpatents

Duchane, David V.; Cash, David L.

1986-01-01

A method of forming a foamed thermoplastic polymer. A solid thermoplastic lymer is immersed in an immersant solution comprising a compatible carrier solvent and an infusant solution containing an incompatible liquid blowing agent for a time sufficient for the immersant solution to infuse into the polymer. The carrier solvent is then selectively extracted, preferably by a solvent exchange process in which the immersant solution is gradually diluted with and replaced by the infusant solution, so as to selectively leave behind the infusant solution permanently entrapped in the polymer. The polymer is then heated to volatilize the blowing agent and expand the polymer into a foamed state.

Synthesis and characterization of poly(L-alanine)-block-poly(ethylene glycol) monomethyl ether as amphiphilic biodegradable co-polymers.

PubMed

Zhang, Guolin; Ma, Jianbiao; Li, Yanhong; Wang, Yinong

2003-01-01

Di-block co-polymers of poly(L-alanine) with poly(ethylene glycol) monomethyl ether (MPEG) were synthesized as amphiphilic biodegradable co-polymers. The ring-opening polymerization of N-carboxy-L-alanine anhydride (NCA) in dichloromethane was initiated by amino-terminated poly(ethylene glycol) monomethyl ether (MPEG-NH2, M(n) = 2000) to afford poly(L-alanine)-block-MPEG. The weight ratio of two blocks in the co-polymers could be altered by adjusting the feeding ratio of NCA to MPEG-NH2. Their chemical structures were characterized on the basis of infrared spectrometry and nuclear magnetic resonance. According to circular dichroism measurement, the poly(L-alanine) chain on the co-polymers in an aqueous medium had a alpha-helix conformation. Two melting points from MPEG block and poly(L-alanine), respectively, could be observed in differential scanning calorimetry curves of the co-polymers, suggesting that a micro-domain phase separation appeared in their bulky states. The co-polymers could take up some water and the capacity was dependent on the ratio of poly(L-alanine) block to MPEG. Such co-polymers might be useful in drug-delivery systems and other biomedical applications.

A Quasi-Solid-State Sodium-Ion Capacitor with High Energy Density.

PubMed

Wang, Faxing; Wang, Xiaowei; Chang, Zheng; Wu, Xiongwei; Liu, Xiang; Fu, Lijun; Zhu, Yusong; Wu, Yuping; Huang, Wei

2015-11-18

A quasi-solid-state sodium-ion capacitor is demonstrated with nanoporous disordered carbon and macroporous graphene as the negative and positive electrodes, respectively, using a sodium-ion-conducting gel polymer electrolyte. It can operate at a cell voltage as high as 4.2 V with an energy density of record high 168 W h kg(-1). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adaptation of ion beam technology to microfabrication of solid state devices and transducers

NASA Technical Reports Server (NTRS)

Topich, J. A.

1978-01-01

A number of areas were investigated to determine the potential uses of ion beam techniques in the construction of solid state devices and transducers and the packaging of implantable electronics for biomedical applications. The five areas investigated during the past year were: (1) diode-like devices fabricated on textured silicon; (2) a photolithographic technique for patterning ion beam sputtered PVC (polyvinyl chloride); (3) use of sputtered Teflon as a protective coating for implantable pressure sensors; (4) the sputtering of Macor to seal implantable hybrid circuits; and (5) the use of sputtered Teflon to immobilize enzymes.

Charge and discharge characteristics of lithium-ion graphite electrodes in solid-state cells

NASA Astrophysics Data System (ADS)

Lemont, S.; Billaud, D.

Lithium ions have been electrochemically intercalated into graphite in solid-state cells operating with solid polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO 4). The working composite electrode is composed of active-divided natural graphite associated with P(EO) 8-LiClO 4 acting as a binder and a Li + ionic conductor. Intercalation and de-intercalation of Li + were performed using galvanostatic or voltammetry techniques. The curves obtained in our solid-state cells were compared with those performed in liquid ethylene carbonate-LiClO 4 electrolyte. It is shown that in solid-state cells, side reactions occur both in the reduction and in the oxidation processes which leads to some uncertainty in the determination of the maximum reversible capacity of the graphite material.

Affects of Microgravity on the Polymerization and Material Properties of Biomedical Grade Polymers

NASA Astrophysics Data System (ADS)

Crane, Deborah J.

2002-01-01

the material of choice in the production of acetabular cups for hip and tibial cradles for knee orthopeadic implant components for over 30 years. Although UHMWPE is used for more than 1.5 million implants a year in the United States alone and more than 3 million implant surgeries a year worldwide, problems with debris particle formation, pitting and fracture continue to induce premature failure of implant components. chains produced during polymerization are capable of packing into crystalline structures called lamellae, which are embedded within randomly oriented amorphous regions. Crosslinks, or tie molecules bridge the crystalline structures, which contribute to the materials' toughness and strength as a biomedical material. Research has been conducted providing evidence that a crosslinked gradient at the articulating surface of the polymer component provides resistance to surface degradation and subsequent debris formation. Recently, the introduction of highly crosslinked UHMWPE had proven to reduce some of the problems associated with the applications of this polymer as a biomedical material and was seen as the answer to solving the continuing problems associated with UHMWPE implant components. Yet current research into the fatigue characteristics of highly crosslinked UHMWPE has shown that subsurface crack propagation and subsequent delamination continues to produce problematic debris generation. Studies have shown that various sterilization and accelerated aging (to emulate natural oxidation rates) protocols adversely effects the material properties. Additional research has shown that alignment of the lamellae, caused by processing technique, fabrication or surface articulation may be the precursor to debris particle formation. Processing techniques performed under high pressure has proven to effect the width of the crystalline lamellae and therefore, the material's response to wear and fracture. UHMWP due to a microgravity environment, which could be extended to include other polymers. Polymerization as well as polymer processing in a microgravity environment may affect the length and orientation of the molecular chains, the degree of crosslinking, and distribution of amorphous to crystalline portions of the material, thus changing the ultimate properties of the polymer. Small polymer samples would be produced from the resin for testing and analysis. This research would include the effect of micro-g processing by compression molded vs. ram extruded samples for analysis. Morphological alterations in the material could be monitored using Transmission Electron Microscopy and associated properties such as toughness, density and crystallinity could be determined and compared to terra produced materials using conventional mechanical testing, density gradient columns and calorimetry techniques. If alterations are evident, fatigue testing can be performed on small specimens in order to determine the material's resistance to crack initiation and propagation. number of orthopaedic implant recipients and could be extended for use in robotics and other beneficial applications. Although polymers exhibit the greatest biocompatibility, problems with debris particle generation continue to reduce the effectiveness of UHMWPE as a biomedical material. Further polymer research in a microgravity environment may prove to produce the desired alterations in the materials' morphology and associated properties, therefore providing millions of people with superior orthopaedic implant components and lessen the occurrences of repeat surgery.

Solution behavior of PVP-VA and HPMC-AS-based amorphous solid dispersions and their bioavailability implications.

PubMed

Qian, Feng; Wang, Jennifer; Hartley, Ruiling; Tao, Jing; Haddadin, Raja; Mathias, Neil; Hussain, Munir

2012-10-01

To identify the mechanism behind the unexpected bio-performance of two amorphous solid dispersions: BMS-A/PVP-VA and BMS-A/HPMC-AS. Solubility of crystalline BMS-A in PVP-VA and HPMC-AS was measured by DSC. Drug-polymer interaction parameters were obtained by Flory-Huggins model fitting. Drug dissolution kinetics of spray-dried dispersions were studied under sink and non-sink conditions. BMS-A supersaturation was studied in the presence of pre-dissolved PVP-VA and HPMC-AS. Potency and crystallinity of undissolved solid dispersions were determined by HPLC and DSC. Polymer dissolution kinetics were obtained by mass balance calculation. Bioavailability of solid dispersions was assessed in dogs. In solid state, both polymers are miscible with BMS-A, while PVP-VA solublizes the drug better. BMS-A dissolves similarly from both solid dispersions in vitro regardless of dissolution method, while the HPMC-AS dispersion performed much better in vivo. At the same concentration, HPMC-AS is more effective in prolonging BMS-A supersaturation; this effect was negated by the slow dissolution rate of HPMC-AS. Further study revealed that fast PVP-VA dissolution resulted in elevated drug loading in undissolved dispersions and facilitated drug recrystallization before complete release. In contrast, the hydrophobicity and slower HPMC-AS dissolution prevented BMS-A recrystallization within the HPMC-AS matrix for >24 h. The lower bioavailability of PVP-VA dispersion was attributed to BMS-A recrystallization within the undissolved dispersion, due to hydrophilicity and fast PVP-VA dissolution rate. Polymer selection for solid dispersion development has significant impact on in vivo performance besides physical stability.

Temperature-Responsive Polymers for Biological Applications

DTIC Science & Technology

2003-06-01

polymer temperature response in water by varying chemical composition of the monomer. In order to achieve this a series of polymers were designed and...varying the m/n composition and polymer type. Polymer grafting onto the silicon surface exhibits similar solubility behaviour. Adhesion energy...Driven by the high promise for biomedical applications, polymers that exhibit a response in water at about 37ºC are of particular interest. Taylor and

The Use of Polymer Design in Resorbable Colloids

NASA Astrophysics Data System (ADS)

Finne-Wistrand, Anna; Albertsson, Ann-Christine

2006-08-01

During the past decade, researchers in the field of polymer chemistry have developed a wide range of very powerful procedures for constructing ever-more-sophisticated polymers. These methods subsequently have been used in suitable systems to solve specific medical problems. This is complicated, and many key factors such as mechanical properties, biocompatibility, biodegradation, stability, and degradation profile must be considered. Colloid particle systems can be used to solve many biomedical- and pharmaceutical-related problems, and it is expected that nanotechnology can be used to develop these materials, devices, and systems even further. For example, an injectible scaffold system with a defined release and degradation profile has huge potential for the repair and regeneration of damaged tissues. This short, nonexhaustive review presents examples of polymer architecture in resorbable particles that have been compared and tested in biomedical applications. We also discuss the design of polymers for core-shell structures.

Use of X-Ray Diffraction, Molecular Simulations, and Spectroscopy to Determine the Molecular Packing in a Polymer-Fullerene Bimolecular Crystal

DTIC Science & Technology

2012-09-05

Richter , M. F. Toney , M. Heeney , I. McCulloch , ACS Nano 2009 , 3 , 780 . [ 19 ] H. W. Spiess , Macromolecules 43 , 5479 . [ 20 ] K...Schmidt-Rohr , H. W. Spiess , Multidimensional Solid-State NMR and Polymers , Academic Press , London 1994 . [ 21 ] C. Yang , J. G. Hu

Evaluation of Eudragit® Retard Polymers for the Microencapsulation of Alpha-Lipoic Acid.

PubMed

Pecora, Tiziana M G; Musumeci, Teresa; Musumeci, Lucrezia; Fresta, Massimo; Pignatello, Rosario

2016-01-01

Microencapsulation of natural antioxidants in polymeric systems represents a possible strategy for improving the oral bioavailability of compounds that are otherwise poorly soluble. α-lipoic acid (ALA) was microencapsulated with polymethacrylate polymers (blends at various ratios of Eudragit® RS100 and RL100 resins). Microspheres were produced by solvent displacement of an ethanol cosolution of ALA and polymers; the microsuspensions were then freeze-dried, using trehalose as a cryoprotector. Microspheres were characterized in the solid state for micromeritic properties and drug loading, as well as by infrared spectroscopy, powder X-ray diffractometry and differential scanning calorimetry. The antioxidant activity of free and encapsulated ALA was assessed by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. In vitro release studies, performed in simulated gastric (pH 1.2) and intestinal fluid (pH 6.8), showed that, depending on polymer composition and drug-to-polymer ratio, ALA release can be slowed down, compared to the dissolution pattern of the free drug. Solid-state characterization confirmed the chemical stability of ALA in the microspheres, suggesting that ALA did not develop strong interactions with the polymer and was present in an amorphous or a disordered-crystalline state within the polymer network. As indicated by the DPPH assay, the microencapsulation of ALA in Eudragit® Retard matrices did not alter its antioxidant activity. ALA was effectively encapsulated in Eudragit® Retard matrices, showing a chemical stability up to 6 months at room conditions and at 40°C. Moreover, since the drug maintained its antioxidant activity in vitro, the potential application of these microparticulate systems for oral administration would deserve further studies.

The Production of Solid Dosage Forms from Non-Degradable Polymers.

PubMed

Major, Ian; Fuenmayor, Evert; McConville, Christopher

2016-01-01

Non-degradable polymers have an important function in medicine. Solid dosage forms for longer term implantation require to be constructed from materials that will not degrade or erode over time and also offer the utmost biocompatibility and biostability. This review details the three most important non-degradable polymers for the production of solid dosage forms - silicone elastomer, ethylene vinyl acetate and thermoplastic polyurethane. The hydrophobic, thermoset silicone elastomer is utilised in the production of a broad range of devices, from urinary catheter tubing for the prevention of biofilm to intravaginal rings used to prevent HIV transmission. Ethylene vinyl acetate, a hydrophobic thermoplastic, is the material of choice of two of the world's leading forms of contraception - Nuvaring® and Implanon®. Thermoplastic polyurethane has such a diverse range of building blocks that this one polymer can be hydrophilic or hydrophobic. Yet, in spite of this versatility, it is only now finding utility in commercialised drug delivery systems. Separately then one polymer has a unique ability that differentiates it from the others and can be applied in a specific drug delivery application; but collectively these polymers provide a rich palette of material and drug delivery options to empower formulation scientists in meeting even the most demanding of unmet clinical needs. Therefore, these polymers have had a long history in controlled release, from the very beginning even, and it is pertinent that this review examines briefly this history while also detailing the state-of-the-art academic studies and inventions exploiting these materials. The paper also outlines the different production methods required to manufacture these solid dosage forms as many of the processes are uncommon to the wider pharmaceutical industry.

Two-Dimensional Polymer Synthesized via Solid-State Polymerization for High-Performance Supercapacitors.

PubMed

Liu, Wei; Ulaganathan, Mani; Abdelwahab, Ibrahim; Luo, Xin; Chen, Zhongxin; Rong Tan, Sherman Jun; Wang, Xiaowei; Liu, Yanpeng; Geng, Dechao; Bao, Yang; Chen, Jianyi; Loh, Kian Ping

2018-01-23

Two-dimensional (2-D) polymer has properties that are attractive for energy storage applications because of its combination of heteroatoms, porosities and layered structure, which provides redox chemistry and ion diffusion routes through the 2-D planes and 1-D channels. Here, conjugated aromatic polymers (CAPs) were synthesized in quantitative yield via solid-state polymerization of phenazine-based precursor crystals. By choosing flat molecules (2-TBTBP and 3-TBQP) with different positions of bromine substituents on a phenazine-derived scaffold, C-C cross coupling was induced following thermal debromination. CAP-2 is polymerized from monomers that have been prepacked into layered structure (3-TBQP). It can be mechanically exfoliated into micrometer-sized ultrathin sheets that show sharp Raman peaks which reflect conformational ordering. CAP-2 has a dominant pore size of ∼0.8 nm; when applied as an asymmetric supercapacitor, it delivers a specific capacitance of 233 F g -1 at a current density of 1.0 A g -1 , and shows outstanding cycle performance.

High degree of polymerization in a fullerene-containing supramolecular polymer.

PubMed

Isla, Helena; Pérez, Emilio M; Martín, Nazario

2014-05-26

Supramolecular polymers based on dispersion forces typically show lower molecular weights (MW) than those based on hydrogen bonding or metal-ligand coordination. We present the synthesis and self-assembling properties of a monomer featuring two complementary units, a C60 derivative and an exTTF-based macrocycle, that interact mainly through π-π, charge-transfer, and van der Waals interactions. Thanks to the preorganization in the host part, a remarkable log K(a)=5.1±0.5 in CHCl3 at room temperature is determined for the host-guest couple. In accordance with the large binding constant, the monomer self-assembles in the gas phase, in solution, and in the solid state to form linear supramolecular polymers with a very high degree of polymerization. A MW above 150 kDa has been found experimentally in solution, while in the solid state the monomer forms extraordinarily long, straight, and uniform fibers with lengths reaching several microns. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A stable perovskite electrolyte in moist air for Li-ion batteries.

PubMed

Li, Yutao; Xu, Henghui; Chien, Po-Hsiu; Wu, Nan; Xin, Sen; Xue, Leigang; Park, Kyusung; Hu, Yan-Yan; Goodenough, John B

2018-05-07

Solid-oxide Li+ electrolytes of a rechargeable cell are generally sensitive to moisture in the air, H+ exchanges for the mobile Li+ of the electrolyte and forms insulating surface phases at the electrolyte interfaces and in the grain boundaries of a polycrystalline membrane. These surface phases dominate the total interfacial resistance of a conventional rechargeable cell having a solid-electrolyte separator. We report a new perovskite Li+ solid electrolyte, Li0.38Sr0.44Ta0.7Hf0.3O2.95F0.05, having a Li-ion conductivity σLi = 4.8×10-4 S cm-1 at 25 oC that does not react with water having 3≤pH≤14. The solid electrolyte with a thin Li+-conducting polymer on its surface to prevent reduction of Ta5+ is wet by metallic lithium and provides low-impedance dendrite-free plating/stripping of a lithium anode. It is also stable on contact with a composite polymer cathode. With this solid electrolyte, we demonstrate excellent cycling performance of an all-solid-state Li/LiFePO4 cell, a Li-S cell with a polymer-gel cathode, and a supercapacitor. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

DOEpatents

Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

2015-02-24

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

A Comprehensive Approach to Evaluating Hazards of Microplastics in the Marine Environment

NASA Astrophysics Data System (ADS)

Noble, A. E.; Lewis, A. S.; Butler, C. H.; Lunsman, T. D.; Verslycke, T.

2016-02-01

Plastic debris in the environment is a growing global concern, and the past decade has brought particular attention to a small size range of plastic debris, often referred to as microplastics. The potential environmental effects of microplastics are complex and, as yet, poorly understood. Emerging research suggests that specific plastic types pose environmental risks primarily via indirect toxicity caused by hazardous compounds associated with microplastics (e.g., monomers, additives, and sorbed environmental pollutants). However, our understanding of the physicochemical properties that determine the environmental fate and toxicity of microplastics is limited. Some recent regulatory initiatives have been broad, seeking to regulate all solid synthetic polymers ≤5 mm despite the lack of a sound technical basis for using solely a size-based cutoff. Such broad regulation of all solid synthetic polymers may actually discourage the use and innovation of less hazardous synthetic polymers and "greener" substitutes. We propose a polymer-specific approach to evaluating potential hazards of microplastics, informed by the state of the science and current research needs. This approach relies on identifying focused tests and analyses to set criteria for determining the degree to which a solid synthetic polymer is likely to pose environmental risk. Important considerations include degradation, sorptive capacity, and monomer/additive content. Our approach is a first step toward a more comprehensive way to evaluate the environmental hazards and risks of microplastics. Our goals are to develop clearer criteria to assess future solid synthetic polymers of unknown concern, inform microplastics regulation, and drive innovation of greener solutions to this global concern.

Study on the Antimicrobial Properties of Citrate-Based Biodegradable Polymers

PubMed Central

Su, Lee-Chun; Xie, Zhiwei; Zhang, Yi; Nguyen, Kytai Truong; Yang, Jian

2014-01-01

Citrate-based polymers possess unique advantages for various biomedical applications since citric acid is a natural metabolism product, which is biocompatible and antimicrobial. In polymer synthesis, citric acid also provides multiple functional groups to control the crosslinking of polymers and active binding sites for further conjugation of biomolecules. Our group recently developed a number of citrate-based polymers for various biomedical applications by taking advantage of their controllable chemical, mechanical, and biological characteristics. In this study, various citric acid derived biodegradable polymers were synthesized and investigated for their physicochemical and antimicrobial properties. Results indicate that citric acid derived polymers reduced bacterial proliferation to different degrees based on their chemical composition. Among the studied polymers, poly(octamethylene citrate) showed ~70–80% suppression to microbe proliferation, owing to its relatively higher ratio of citric acid contents. Crosslinked urethane-doped polyester elastomers and biodegradable photoluminescent polymers also exhibited significant bacteria reduction of ~20 and ~50% for Staphylococcus aureus and Escherichia coli, respectively. Thus, the intrinsic antibacterial properties in citrate-based polymers enable them to inhibit bacteria growth without incorporation of antibiotics, silver nanoparticles, and other traditional bacteria-killing agents suggesting that the citrate-based polymers are unique beneficial materials for wound dressing, tissue engineering, and other potential medical applications where antimicrobial property is desired. PMID:25023605

Conjugated amplifying polymers for optical sensing applications.

PubMed

Rochat, Sébastien; Swager, Timothy M

2013-06-12

Thanks to their unique optical and electrochemical properties, conjugated polymers have attracted considerable attention over the last two decades and resulted in numerous technological innovations. In particular, their implementation in sensing schemes and devices was widely investigated and produced a multitude of sensory systems and transduction mechanisms. Conjugated polymers possess numerous attractive features that make them particularly suitable for a broad variety of sensing tasks. They display sensory signal amplification (compared to their small-molecule counterparts) and their structures can easily be tailored to adjust solubility, absorption/emission wavelengths, energy offsets for excited state electron transfer, and/or for use in solution or in the solid state. This versatility has made conjugated polymers a fluorescence sensory platform of choice in the recent years. In this review, we highlight a variety of conjugated polymer-based sensory mechanisms together with selected examples from the recent literature.

Development of traceable measurement of the diffuse optical properties of solid reference standards for biomedical optics at National Institute of Standards and Technology.

PubMed

Lemaillet, Paul; Bouchard, Jean-Pierre; Allen, David W

2015-07-01

The development of a national reference instrument dedicated to the measurement of the scattering and absorption properties of solid tissue-mimicking phantoms used as reference standards is presented. The optical properties of the phantoms are measured with a double-integrating sphere setup in the steady-state domain, coupled with an inversion routine of the adding-doubling procedure that allows for the computation of the uncertainty budget for the measurements. The results are compared to the phantom manufacturer's values obtained by a time-resolved approach. The results suggest that the agreement between these two independent methods is within the estimated uncertainties. This new reference instrument will provide optical biomedical research laboratories with reference values for absolute diffuse optical properties of phantom materials.

Rechargeable sodium all-solid-state battery

DOE PAGES

Zhou, Weidong; Li, Yutao; Xin, Sen; ...

2017-01-03

A reversible plating/stripping of a dendrite-free metallic-sodium anode with a reduced anode/ceramic interfacial resistance is created by a thin interfacial interlayer formed in situ or by the introduction of a dry polymer film. Wetting of the sodium on the interfacial interlayer suppresses dendrite formation and growth at different discharge/charge C-rates. Furthermore, all-solid-state batteries were obtained with a high cycling stability and Coulombic efficiency at 65 °C.

Rechargeable Sodium All-Solid-State Battery

PubMed Central

2017-01-01

A reversible plating/stripping of a dendrite-free metallic-sodium anode with a reduced anode/ceramic interfacial resistance is created by a thin interfacial interlayer formed in situ or by the introduction of a dry polymer film. Wetting of the sodium on the interfacial interlayer suppresses dendrite formation and growth at different discharge/charge C-rates. All-solid-state batteries were obtained with a high cycling stability and Coulombic efficiency at 65 °C. PMID:28149953

Engineering the Membrane/Electrode Interface To Improve the Performance of Solid-State Supercapacitors.

PubMed

Huang, Chun; Zhang, Jin; Snaith, Henry J; Grant, Patrick S

2016-08-17

This paper investigates the effect of adding a 450 nm layer based on porous TiO2 at the interface between a 4.5 μm carbon/TiO2 nanoparticle-based electrode and a polymer electrolyte membrane as a route to improve energy storage performance in solid-state supercapacitors. Electrochemical characterization showed that adding the interface layer reduced charge transfer resistance, promoted more efficient ion transfer across the interface, and significantly improved charge/discharge dynamics in a solid-state supercapacitor, resulting in an increased areal capacitance from 45.3 to 111.1 mF cm(-2) per electrode at 0.4 mA cm(-2).

Solid State Humidity Sensors

NASA Astrophysics Data System (ADS)

Chang, Song-Lin

There are only a few solid state humidity sensors available today. Most of those sensors use a porous oxide material as a principal part of the device. The devices work on the basis of a change in resistance as the moisture in the air varies. In this experiment, two solid state humidity sensors have been developed for use under practical conditions. One is a Polymer Oxide Semiconductor device with a POLYOX film that absorbs the moisture from the air. The amount of water dipoles absorbed by the polymer is a function of relative humidity. This sensor can measure relative humidity from 20% to 90%. The other is a Dew Point sensor. The sensor is in contact with the upper surface of a miniature Peltier cooler. Water molecules deposited on the sensor surface cause the electrical current through the sensor to increase. The operator adjusts the temperature of the Peltier cooler until a saturated current through the sensor is reached. About one min. is required to measure low relative humidities. The Dew Point sensor can measure a range of relative humidities of 30% to 80%.

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

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

Kong, Zueqian

2010-01-01

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

Monolithic quasi-solid-state dye-sensitized solar cells based on graphene modified mesoscopic carbon counter electrodes

NASA Astrophysics Data System (ADS)

Rong, Yaoguang; Li, Xiong; Liu, Guanghui; Wang, Heng; Ku, Zhiliang; Xu, Mi; Liu, Linfeng; Hu, Min; Yang, Ying; Han, Hongwei

2013-03-01

We have developed a monolithic quasi-solid-state dye-sensitized solar cell (DSSC) based on graphene modified mesoscopic carbon counter electrode (GC-CE), which offers a promising prospect for commercial applications. Based on the design of a triple layer structure, the TiO2 working electrode layer, ZrO2 spacer layer and carbon counter electrode (CE) layer are constructed on a single conducting glass substrate by screen-printing. The quasi-solid-state polymer gel electrolyte employs a polymer composite as the gelator and could effectively infiltrate into the porous layers. Fabricated with normal carbon counter electrode (NC-CE) containing graphite and carbon black, the device shows a power conversion efficiency (PCE) of 5.09% with the fill factor (FF) of 0.63 at 100 mW cm-2 AM1.5 illumination. When the NC-CE is modified with graphene sheets, the PCE and FF could be enhanced to 6.27% and 0.71, respectively. This improvement indicates excellent conductivity and high electrocatalytic activity of the graphene sheets, which have been considered as a promising platinum-free electrode material for DSSCs.

Temperature-responsive magnetite/PEO-PPO-PEO block copolymer nanoparticles for controlled drug targeting delivery.

PubMed

Chen, Shu; Li, Ying; Guo, Chen; Wang, Jing; Ma, Junhe; Liang, Xiangfeng; Yang, Liang-Rong; Liu, Hui-Zhou

2007-12-04

In this study, temperature-responsive magnetite/polymer nanoparticles were developed from iron oxide nanoparticles and poly(ethyleneimine)-modified poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer. The particles were characterized by TEM, XRD, DLS, VSM, FTIR, and TGA. A typical product has an approximately 20 nm magnetite core and an approximately 40 nm hydrodynamic diameter with a narrow size distribution and is superparamagnetic with large saturation magnetization (51.34 emu/g) at room temperature. The most attractive feature of the nanoparticles is their temperature-responsive volume-transition property. DLS results indicated that their average hydrodynamic diameter underwent a sharp decrease from 45 to 25 nm while evaluating the temperature from 20 to 35 degrees C. The temperature-dependent evolution of the C-O stretching band in the FTIR spectra of the aqueous nanoparticles solution revealed that thermo-induced self-assembly of the immobilized block copolymers occurred on the magnetite solid surfaces, which is accompanied by a conformational change from a fully extended state to a highly coiled state of the copolymer. Consequently, the copolymer shell could act as a temperature-controlled "gate" for the transit of guest substance. The uptake and release of both hydrophobic and hydrophilic model drugs were well controlled by switching the transient opening and closing of the polymer shell at different temperatures. A sustained release of about 3 days was achieved in simulated human body conditions. In primary mouse experiments, drug-entrapped magnetic nanoparticles showed good biocompatibility and effective therapy for spinal cord damage. Such intelligent magnetic nanoparticles are attractive candidates for widespread biomedical applications, particularly in controlled drug-targeting delivery.

Solid polymer electrolyte lithium batteries

DOEpatents

Alamgir, M.; Abraham, K.M.

1993-10-12

This invention pertains to Lithium batteries using Li ion (Li[sup +]) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride). 3 figures.

Solid polymer electrolyte lithium batteries

DOEpatents

Alamgir, Mohamed; Abraham, Kuzhikalail M.

1993-01-01

This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

Semi-interpenetrating solid polymer electrolyte based on thiol-ene cross-linker for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Suk, Jungdon; Lee, Yu Hwa; Kim, Do Youb; Kim, Dong Wook; Cho, Song Yun; Kim, Ji Man; Kang, Yongku

2016-12-01

We developed highly promising solid polymer electrolytes (SPEs) based on a novel cross-linker containing star-shaped phosphazene with poly(ethylene oxide) (PEO) branches with very high ionic conductivity (7.6 × 10-4 S cm-1), improved mechanical stability, and good electrochemical stability for all-solid-state lithium batteries. In particular, allyl groups were introduced at the ends of the cross-linker in order to overcome the easy self-polymerization of existing cross-linking acrylate end groups. A novel semi-interpenetrating network (semi-IPN) SPE was prepared by in-situ radical polymerization of a precursor solution containing lithium salt, poly(ethylene glycol) dimethyl ether as a plasticizer, and a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and a synthesized hexakis(allyloxy)cyclotriphosphazene (thiol-ene PAL) as the cross-linker. Batteries employing LiFePO4 as the cathode, lithium foil as the anode, and the SPE thin film as the electrolyte were assembled and tested. At ambient temperature, the initial discharge capacity was 147 mAh/g at 0.1 °C and 132 mAh/g at 0.5 °C, and 97% of the capacity was retained at the 100th cycle. All-solid-state pouch-package lithium cells assembled with the SPEs exhibited stable electrochemical performance, even under a severely wrinkled state. These outstanding properties of SPEs based on thiol-ene PAL demonstrate feasibility for practical battery applications with improved reliability and safety.

Surface functionalization of solid state ultra-high molecular weight polyethylene through chemical grafting

NASA Astrophysics Data System (ADS)

Sherazi, Tauqir A.; Rehman, Tayyiba; Naqvi, Syed Ali Raza; Shaikh, Ahson Jabbar; Shahzad, Sohail Anjum; Abbas, Ghazanfar; Raza, Rizwan; Waseem, Amir

2015-12-01

The surface of ultra-high molecular weight polyethylene (UHMWPE) powder was functionalized with styrene using chemical grafting technique. The grafting process was initiated through radical generation on base polymer matrix in the solid state by sodium thiosulfate, while peroxides formed at radical sites during this process were dissociated by ceric ammonium nitrate. Various factors were optimized and reasonably high level of monomer grafting was achieved, i.e., 15.6%. The effect of different acids as additive and divinyl benzene (DVB) as a cross-linking agent was also studied. Post-grafting sulfonation was conducted to introduce the ionic moieties to the grafted polymer. Ion-exchange capacity (IEC) was measured experimentally and is found to be 1.04 meq g-1, which is in close agreement with the theoretical IEC values. The chemical structure of grafted and functionalized polymer was characterized by attenuated total reflection infrared spectroscopy (ATR-FTIR) and thermal properties were investigated by thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC). Thermal analysis depicts that the presence of radicals on the polymer chain accelerates the thermal decomposition process. The results signify that the chemical grafting is an effective tool for substantial surface modification and subsequent functionalization of polyethylene.

Composite Polymer-Garnet Solid State Electrolytes

NASA Astrophysics Data System (ADS)

Villa, Andres; Oduncu, Muhammed R.; Scofield, Gregory D.; Marinero, Ernesto E.; Forbey, Scott

Solid-state electrolytes provide a potential solution to the safety and reliability issues of Li-ion batteries. We have synthesized cubic-phase Li7-xLa3Zr2-xBixO12 compounds utilizing inexpensive, scalable Sol-gel synthesis and obtained ionic conductivities 1.2 x 10-4 S/cm at RT in not-fully densified pellets. In this work we report on the fabrication of composite polymer-garnet ceramic particle electrolytes to produce flexible membranes that can be integrated with standard battery electrodes without the need for a separator. As a first step we incorporated the ceramic particles into polyethylene oxide polymers (PEO) to form flexible membranes. Early results are encouraging yielding ionic conductivity values 1.0 x 10-5 S/cm at RT. To increment the conductivity in the membranes, we are optimizing amongst other: the ceramic particle size distribution and weight load, the polymer molecular weight and chemical composition and the solvated Li-salt composition and content. Unhindered ion transport across interfaces between the composites and the battery electrode materials is paramount for battery performance. To this end, we are investigating the effect of interface morphology, its atomic composition and exploring novel electrode structures that facilitate ionic transport.

Thermal aging of interfacial polymer chains in ethylene-propylene-diene terpolymer/aluminum hydroxide composites: solid-state NMR study.

PubMed

Gabrielle, Brice; Lorthioir, Cédric; Lauprêtre, Françoise

2011-11-03

The possible influence of micrometric-size filler particles on the thermo-oxidative degradation behavior of the polymer chains at polymer/filler interfaces is still an open question. In this study, a cross-linked ethylene-propylene-diene (EPDM) terpolymer filled by aluminum trihydrate (ATH) particles is investigated using (1)H solid-state NMR. The time evolution of the EPDM network microstructure under thermal aging at 80 °C is monitored as a function of the exposure time and compared to that of an unfilled EPDM network displaying a similar initial structure. While nearly no variations of the topology are observed on the neat EPDM network over 5 days at 80 °C, a significant amount of chain scission phenomena are evidenced in EPDM/ATH. A specific surface effect induced by ATH on the thermodegradative properties of the polymer chains located in their vicinity is thus pointed out. Close to the filler particles, a higher amount of chain scissions are detected, and the characteristic length scale related to these interfacial regions displaying a significant thermo-oxidation process is determined as a function of the aging time.

Nucleation, Growth, and Alignment of Poly(3-hexylthiophene) Nanofibers for High-Performance OFETs.

PubMed

Persson, Nils E; Chu, Ping-Hsun; McBride, Michael; Grover, Martha; Reichmanis, Elsa

2017-04-18

Conjugated semiconducting polymers have been the subject of intense study for over two decades with promising advances toward a printable electronics manufacturing ecosystem. These materials will deliver functional electronic devices that are lightweight, flexible, large-area, and cost-effective, with applications ranging from biomedical sensors to solar cells. Synthesis of novel molecules has led to significant improvements in charge carrier mobility, a defining electrical performance metric for many applications. However, the solution processing and thin film deposition of conjugated polymers must also be properly controlled to obtain reproducible device performance. This has led to an abundance of research on the process-structure-property relationships governing the microstructural evolution of the model semicrystalline poly(3-hexylthiophene) (P3HT) as applied to organic field effect transistor (OFET) fabrication. What followed was the production of an expansive body of work on the crystallization, self-assembly, and charge transport behavior of this semiflexible polymer whose strong π-π stacking interactions allow for highly creative methods of structural control, including the modulation of solvent and solution properties, flow-induced crystallization and alignment techniques, structural templating, and solid-state thermal and mechanical processing. This Account relates recent progress in the microstructural control of P3HT thin films through the nucleation, growth, and alignment of P3HT nanofibers. Solution-based nanofiber formation allows one to develop structural order prior to thin film deposition, mitigating the need for intricate deposition processes and enabling the use of batch and continuous chemical processing steps. Fiber growth is framed as a traditional crystallization problem, with the balance between nucleation and growth rates determining the fiber size and ultimately the distribution of grain boundaries in the solid state. Control of nucleation can be accomplished through a sonication-based seeding procedure, while growth can be modulated through supersaturation control via the tuning of solvent quality, the use of UV irradiation or through aging. These principles carry over to the flow-induced growth of P3HT nanofibers in a continuous microfluidic processing system, leading to thin films with significantly enhanced mobility. Further gains can be made by promoting long-range polymer chain alignment, achieved by depositing nanofibers through shear-based coating methods that promote high fiber packing density and alignment. All of these developments in processing were carried out on a standard OFET platform, enabling us to generalize quantitative structure-property relationships from structural data sources such as UV-vis, AFM, and GIWAXS. It is shown that a linear correlation exists between mobility and the in-plane orientational order of nanofibers, as extracted from AFM images using advanced computer vision software developed by our group. Herein, we discuss data-driven approaches to the determination of process-structure-property relationships, as well as the transferability of structural control strategies for P3HT to other conjugated polymer systems and applications.

Systems for production of polymer encapsuated solids

DOEpatents

Bourcier, William L.; Aines, Roger D.; Baker, Sarah E.; Duoss, Eric B.; Maiti, Amitesh; Roberts, Jeffery J.; Spadaccini, Christopher M.; Stolaroff, Joshuah K.; Vericella, John J.; Lewis, Jennifer A.; Hardin, IV, James O.; Floyd, III, William C.

2017-11-21

Encapsulated solids are made by first encapsulating precursor materials in a polymer shell. The precursors are some combination of solids, liquids, gases, and/or gels. The precursors are then transformed into solids by emplacement of the capsule in an environment where gas or fluid transport into or out of the polymer shell causes transformation into solids.

Elucidation and visualization of solid-state transformation and mixing in a pharmaceutical mini hot melt extrusion process using in-line Raman spectroscopy.

PubMed

Van Renterghem, Jeroen; Kumar, Ashish; Vervaet, Chris; Remon, Jean Paul; Nopens, Ingmar; Vander Heyden, Yvan; De Beer, Thomas

2017-01-30

Mixing of raw materials (drug+polymer) in the investigated mini pharma melt extruder is achieved by using co-rotating conical twin screws and an internal recirculation channel. In-line Raman spectroscopy was implemented in the barrels, allowing monitoring of the melt during processing. The aim of this study was twofold: to investigate (I) the influence of key process parameters (screw speed - barrel temperature) upon the product solid-state transformation during processing of a sustained release formulation in recirculation mode; (II) the influence of process parameters (screw speed - barrel temperature - recirculation time) upon mixing of a crystalline drug (tracer) in an amorphous polymer carrier by means of residence time distribution (RTD) measurements. The results indicated a faster mixing endpoint with increasing screw speed. Processing a high drug load formulation above the drug melting temperature resulted in the production of amorphous drug whereas processing below the drug melting point produced solid dispersions with partially amorphous/crystalline drug. Furthermore, increasing the screw speed resulted in lower drug crystallinity of the solid dispersion. RTD measurements elucidated the improved mixing capacity when using the recirculation channel. In-line Raman spectroscopy has shown to be an adequate PAT-tool for product solid-state monitoring and elucidation of the mixing behavior during processing in a mini extruder. Copyright © 2016 Elsevier B.V. All rights reserved.

Continuous process to produce lithium-polymer batteries

DOEpatents

Chern, Terry Song-Hsing; Keller, David Gerard; MacFadden, Kenneth Orville

1998-01-01

Solid polymer electrolytes are extruded with active electrode material in a continuous, one-step process to form composite electrolyte-electrodes ready for assembly into battery cells. The composite electrolyte-electrode sheets are extruded onto current collectors to form electrodes. The composite electrodes, as extruded, are electronically and ionically conductive. The composite electrodes can be overcoated with a solid polymer electrolyte, which acts as a separator upon battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte separator has low resistance.

Synthesis, Characterization and Conductivity Study of Poly(vinyl 4-HYDROXY-3-METHOXY Benzal) and its Sodio Salt in Solid State

NASA Astrophysics Data System (ADS)

Borah, P.; Hussain, S.; Dutta, A.

Among the various ion-conducting materials, polymer salt complexes are of current interest due to their possible application as solid electrolyte as well as their physical nature in advanced high-energy electrochemical devices such as batteries, fuel cells, electrochromic display devices, photo electro-chemical solar cells52-55 etc. The main advantages of polymeric electrolytes are their mechanical properties, ease of fabrication of thin films of desired sizes and their ability to form proper electrode-electrolyte contact. Polymer electrolyte usually consists of a polymer and a salt and is considered to be solid solutions in which the polymer functions as solvent. In the present paper the synthesis, characterization and the conductivity study of the polymer poly (vinyl 4-hydroxy-3-methoxy benzal) (PV-HMB) and its sodio salt (PV-HMB-Na) have been reported. The polymer was prepared by carrying out homogenous acetalization between the prepolymer poly vinylalcohol (PVA) and 4-hydroxy-3-methoxy benzaldehyde (vanilline). PVA was dissolved in dimethyl formamide (DMF) and lithium chloride (LiCl) system i.e., in non-aqueous medium. The sodio salt was prepared by alkalization. The polymer and its salt were characterized by IR, 1H NMR and DSC. Frequency and temperature dependence of ac conductivity has been studied to learn about the electrical conduction behaviour in this material. The electrical conductivity of the new polymeric salt was found to be in the range 10-4 to 10-6 Scm-1. There is about 103 to 104 fold increase in the conductivity of the new polymer salt. Apparent activation energy of the polymer and its salt were found to be 0.139 and 0.08998 ev respectively.

Modelling Viscoelastic Behaviour of Polymer by A Mixed Velocity, Displacement Formulation - Numerical and Experimental Results

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

Pham, VT.; Silva, L.; Digonnet, H.

2011-05-04

The objective of this work is to model the viscoelastic behaviour of polymer from the solid state to the liquid state. With this objective, we perform experimental tensile tests and compare with simulation results. The chosen polymer is a PMMA whose behaviour depends on its temperature. The computation simulation is based on Navier-Stokes equations where we propose a mixed finite element method with an interpolation P1+/P1 using displacement (or velocity) and pressure as principal variables. The implemented technique uses a mesh composed of triangles (2D) or tetrahedra (3D). The goal of this approach is to model the viscoelastic behaviour ofmore » polymers through a fluid-structure coupling technique with a multiphase approach.« less

Multilevel description of the DNA molecule translocation in solid-state synthetic nanopores

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

Nosik, V. L., E-mail: v-nosik@yandex.ru; Rudakova, E. B.

2016-07-15

Interest of researchers in micro- and nanofluidics of polymer solutions and, in particular, DNA ionic solutions is constantly increasing. The use of DNA translocation with a controlled velocity through solid-state nanopores and pulsed X-ray beams in new sequencing schemes opens up new possibilities for studying the structure of DNA and other biopolymers. The problems related to the description of DNA molecular motion in a limited volume of nanopore are considered.

Miniature biotelemeter gives multichannel wideband biomedical data

NASA Technical Reports Server (NTRS)

Carraway, J. B.

1972-01-01

A miniature biotelemeter was developed for sensing and transmitting multiple channels of biomedical data over a radio link. The design of this miniature, 10-channel, wideband (5 kHz/channel), pulse amplitude modulation/ frequency modulation biotelemeter takes advantage of modern device technology (e.g., integrated circuit operational amplifiers, complementary symmetry/metal oxide semiconductor logic, and solid state switches) and hybrid packaging techniques. The telemeter is being used to monitor 10 channels of neuron firings from specific regions of the brain in rats implanted with chronic electrodes. Design, fabrication, and testing of an engineering model biotelemeter are described.

Reciprocated suppression of polymer crystallization toward improved solid polymer electrolytes: Higher ion conductivity and tunable mechanical properties

DOE PAGES

Bi, Sheng; Sun, Che-Nan; Zawodzinski, Thomas A.; ...

2015-08-06

Solid polymer electrolytes based on lithium bis(trifluoromethanesulfonyl) imide and polymer matrix were extensively studied in the past due to their excellent potential in a broad range of energy related applications. Poly(vinylidene fluoride) (PVDF) and polyethylene oxide (PEO) are among the most examined polymer candidates as solid polymer electrolyte matrix. In this paper, we study the effect of reciprocated suppression of polymer crystallization in PVDF/PEO binary matrix on ion transport and mechanical properties of the resultant solid polymer electrolytes. With electron and X-ray diffractions as well as energy filtered transmission electron microscopy, we identify and examine the appropriate blending composition thatmore » is responsible for the diminishment of both PVDF and PEO crystallites. Laslty, a three-fold conductivity enhancement is achieved along with a highly tunable elastic modulus ranging from 20 to 200 MPa, which is expected to contribute toward future designs of solid polymer electrolytes with high room-temperature ion conductivities and mechanical flexibility.« less

Polymer Self-Assembly into Unique Fractal Nanostructures in Solution by a One-Shot Synthetic Procedure.

PubMed

Shin, Suyong; Gu, Ming-Long; Yu, Chin-Yang; Jeon, Jongseol; Lee, Eunji; Choi, Tae-Lim

2018-01-10

A fractal nanostructure having a high surface area is potentially useful in sensors, catalysts, functional coatings, and biomedical and electronic applications. Preparation of fractal nanostructures on solid substrates has been reported using various inorganic or organic compounds. However, achieving such a process using polymers in solution has been extremely challenging. Here, we report a simple one-shot preparation of polymer fractal nanostructures in solution via an unprecedented assembly mechanism controlled by polymerization and self-assembly kinetics. This was possible only because one monomer was significantly more reactive than the other, thereby easily forming a diblock copolymer microstructure. Then, the second insoluble block containing poly(p-phenylenevinylene) (PPV) without any side chains spontaneously underwent self-assembly during polymerization by an in situ nanoparticlization of conjugated polymers (INCP) method. The formation of fractal structures in solution was confirmed by various imaging techniques such as atomic force microscopy, transmission electron microscopy (TEM), and cryogenic TEM. The diffusion-limited aggregation theory was adopted to explain the branching patterns of the fractal nanostructures according to the changes in polymerization conditions such as the monomer concentration and the presence of additives. Finally, after detailed kinetic analyses, we proposed a plausible mechanism for the formation of unique fractal nanostructures, where the gradual formation and continuous growth of micelles in a chain-growth-like manner were accounted for.

Room temperature solid-state synthesis of a conductive polymer for applications in stable I₂-free dye-sensitized solar cells.

PubMed

Kim, Byeonggwan; Koh, Jong Kwan; Kim, Jeonghun; Chi, Won Seok; Kim, Jong Hak; Kim, Eunkyoung

2012-11-01

A solid-state polymerizable monomer, 2,5-dibromo-3,4-propylenedioxythiophene (DBProDOT), was synthesized at 25 °C to produce a conducting polymer, poly(3,4-propylenedioxythiophene) (PProDOT). Crystallographic studies revealed a short interplane distance between DBProDOT molecules, which was responsible for polymerization at low temperature with a lower activation energy and higher exothermic reaction than 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) or its derivatives. Upon solid-state polymerization (SSP) of DBProDOT at 25 °C, PProDOT was obtained in a self-doped state with tribromide ions and an electrical conductivity of 0.05 S cm⁻¹, which is considerably higher than that of chemically-polymerized PProDOT (2×10⁻⁶ S cm⁻¹). Solid-state ¹³C NMR spectroscopy and DFT calculations revealed polarons in PProDOT and a strong perturbation of carbon nuclei in thiophenes as a result of paramagnetic broadening. DBProDOT molecules deeply penetrated and polymerized to fill nanocrystalline TiO₂ pores with PProDOT, which functioned as a hole-transporting material (HTM) for I₂-free solid-state dye-sensitized solar cells (ssDSSCs). With the introduction of an organized mesoporous TiO₂ (OM-TiO₂) layer, the energy conversion efficiency reached 3.5 % at 100 mW cm⁻², which was quite stable up to at least 1500 h. The cell performance and stability was attributed to the high stability of PProDOT, with the high conductivity and improved interfacial contact of the electrode/HTM resulting in reduced interfacial resistance and enhanced electron lifetime. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mussel-Inspired Adhesives and Coatings

PubMed Central

Lee, Bruce P.; Messersmith, P.B.; Israelachvili, J.N.; Waite, J.H.

2011-01-01

Mussels attach to solid surfaces in the sea. Their adhesion must be rapid, strong, and tough, or else they will be dislodged and dashed to pieces by the next incoming wave. Given the dearth of synthetic adhesives for wet polar surfaces, much effort has been directed to characterizing and mimicking essential features of the adhesive chemistry practiced by mussels. Studies of these organisms have uncovered important adaptive strategies that help to circumvent the high dielectric and solvation properties of water that typically frustrate adhesion. In a chemical vein, the adhesive proteins of mussels are heavily decorated with Dopa, a catecholic functionality. Various synthetic polymers have been functionalized with catechols to provide diverse adhesive, sealant, coating, and anchoring properties, particularly for critical biomedical applications. PMID:22058660

Chemically durable polymer electrolytes for solid-state alkaline water electrolysis

NASA Astrophysics Data System (ADS)

Park, Eun Joo; Capuano, Christopher B.; Ayers, Katherine E.; Bae, Chulsung

2018-01-01

Generation of high purity hydrogen using electrochemical splitting of water is one of the most promising methods for sustainable fuel production. The materials to be used as solid-state electrolytes for alkaline water electrolyzer require high thermochemical stability against hydroxide ion attack in alkaline environment during the operation of electrolysis. In this study, two quaternary ammonium-tethered aromatic polymers were synthesized and investigated for anion exchange membrane (AEM)-based alkaline water electrolyzer. The membranes properties including ion exchange capacity (IEC), water uptake, swelling degree, and anion conductivity were studied. The membranes composed of all C-C bond polymer backbones and flexible side chain terminated by cation head groups exhibited remarkably good chemical stability by maintaining structural integrity in 1 M NaOH solution at 95 °C for 60 days. Initial electrochemical performance and steady-state operation performance were evaluated, and both membranes showed a good stabilization of the cell voltage during the steady-state operation at the constant current density at 200 mA/cm2. Although both membranes in current form require improvement in mechanical stability to afford better durability in electrolysis operation, the next generation AEMs based on this report could lead to potentially viable AEM candidates which can provide high electrolysis performance under alkaline operating condition.

Continuous process to produce lithium-polymer batteries

DOEpatents

Chern, T.S.H.; Keller, D.G.; MacFadden, K.O.

1998-05-12

Solid polymer electrolytes are extruded with active electrode material in a continuous, one-step process to form composite electrolyte-electrodes ready for assembly into battery cells. The composite electrolyte electrode sheets are extruded onto current collectors to form electrodes. The composite electrodes, as extruded, are electronically and ionically conductive. The composite electrodes can be over coated with a solid polymer electrolyte, which acts as a separator upon battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte separator has low resistance. 1 fig.

Solid polymer electrolyte composite membrane comprising laser micromachined porous support

DOEpatents

Liu, Han [Waltham, MA; LaConti, Anthony B [Lynnfield, MA; Mittelsteadt, Cortney K [Natick, MA; McCallum, Thomas J [Ashland, MA

2011-01-11

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 5 microns, are made by laser micromachining and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

Solid polymer electrolyte composite membrane comprising plasma etched porous support

DOEpatents

Liu, Han; LaConti, Anthony B.

2010-10-05

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 0.1 to 5 microns, are made by plasma etching and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

Nanoparticles of conjugated polymers prepared from phase-separated films of phospholipids and polymers for biomedical applications.

PubMed

Yoon, Jungju; Kwag, Jungheon; Shin, Tae Joo; Park, Joonhyuck; Lee, Yong Man; Lee, Yebin; Park, Jonghyup; Heo, Jung; Joo, Chulmin; Park, Tae Jung; Yoo, Pil J; Kim, Sungjee; Park, Juhyun

2014-07-09

Phase separation in films of phospholipids and conjugated polymers results in nanoassemblies because of a difference in the physicochemical properties between the hydrophobic polymers and the polar lipid heads, together with the comparable polymer side-chain lengths to lipid tail lengths, thus producing nanoparticles of conjugated polymers upon disassembly in aqueous media by the penetration of water into polar regions of the lipid heads. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The mechanisms of drug release from solid dispersions in water-soluble polymers.

PubMed

Craig, Duncan Q M

2002-01-14

Solid dispersions in water-soluble carriers have attracted considerable interest as a means of improving the dissolution rate, and hence possibly bioavailability, of a range of hydrophobic drugs. However, despite the publication of numerous original papers and reviews on the subject, the mechanisms underpinning the observed improvements in dissolution rate are not yet understood. In this review the current consensus with regard to the solid-state structure and dissolution properties of solid dispersions is critically assessed. In particular the theories of carrier- and drug-controlled dissolution are highlighted. A model is proposed whereby the release behaviour from the dispersions may be understood in terms of the dissolution or otherwise of the drug into the concentrated aqueous polymer layer adjacent to the solid surface, including a derivation of an expression to describe the release of intact particles from the dispersions. The implications of a deeper understanding of the dissolution mechanisms are discussed, with particular emphasis on optimising the choice of carrier and manufacturing method and the prediction of stability problems.

Interfaces in polymer nanocomposites – An NMR study

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

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

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

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

PubMed

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

2015-11-02

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.

Fluorescence probe techniques to monitor protein adsorption-induced conformation changes on biodegradable polymers.

PubMed

Benesch, Johan; Hungerford, Graham; Suhling, Klaus; Tregidgo, Carolyn; Mano, João F; Reis, Rui L

2007-08-15

The study of protein adsorption and any associated conformational changes on interaction with biomaterials is of great importance in the area of implants and tissue constructs. This study aimed to evaluate some fluorescent techniques to probe protein conformation on a selection of biodegradable polymers currently under investigation for biomedical applications. Because of the fluorescence emanating from the polymers, the use of monitoring intrinsic protein fluorescence was precluded. A highly solvatochromic fluorescent dye, Nile red, and a well-known protein label, fluorescein isothiocyanate, were employed to study the adsorption of serum albumin to polycaprolactone and to some extent also to two starch-containing polymer blends (SPCL and SEVA-C). A variety of fluorescence techniques, steady state, time resolved, and imaging were employed. Nile red was found to leach from the protein, while fluorescein isothiocyanate proved useful in elucidating a conformational change in the protein and the observation of protein aggregates adsorbed to the polymer surface. These effects were seen by making use of the phenomenon of energy migration between the fluorescent tags to monitor interprobe distance and the use of fluorescence lifetime imaging to ascertain the surface packing of the protein on polymer.

Biopolymers and supramolecular polymers as biomaterials for biomedical applications

PubMed Central

Freeman, Ronit; Boekhoven, Job; Dickerson, Matthew B.; Naik, Rajesh R.

2015-01-01

Protein- and peptide-based structural biopolymers are abundant building blocks of biological systems. Either in their natural forms, such as collagen, silk or fibronectin, or as related synthetic materials they can be used in various technologies. An emerging area is that of biomimetic materials inspired by protein-based biopolymers, which are made up of small molecules rather than macromolecules and can therefore be described as supramolecular polymers. These materials are very useful in biomedical applications because of their ability to imitate the extracellular matrix both in architecture and their capacity to signal cells. This article describes important features of the natural extracellular matrix and highlight how these features are being incorporated into biomaterials composed of biopolymers and supramolecular polymers. We particularly focus on the structures, properties, and functions of collagen, fibronectin, silk, and the supramolecular polymers inspired by them as biomaterials for regenerative medicine. PMID:26989295

Glycoproteins functionalized natural and synthetic polymers for prospective biomedical applications: A review.

PubMed

Tabasum, Shazia; Noreen, Aqdas; Kanwal, Arooj; Zuber, Mohammad; Anjum, Muhammad Naveed; Zia, Khalid Mahmood

2017-05-01

Glycoproteins have multidimensional properties such as biodegradability, biocompatibility, non-toxicity, antimicrobial and adsorption properties; therefore, they have wide range of applications. They are blended with different polymers such as chitosan, carboxymethyl cellulose (CMC), polyvinyl pyrrolidone (PVP), polycaprolactone (PCL), heparin, polystyrene fluorescent nanoparticles (PS-NPs) and carboxyl pullulan (PC) to improve their properties like thermal stability, mechanical properties, resistance to pH, chemical stability and toughness. Considering the versatile charateristics of glycoprotein based polymers, this review sheds light on synthesis and characterization of blends and composites of glycoproteins, with natural and synthetic polymers and their potential applications in biomedical field such as drug delivery system, insulin delivery, antimicrobial wound dressing uses, targeting of cancer cells, development of anticancer vaccines, development of new biopolymers, glycoproteome research, food product and detection of dengue glycoproteins. All the technical scientific issues have been addressed; highlighting the recent advancement. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

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

2017-12-19

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

Designing a Novel Polymer Electrolyte for Improving the Electrode/Electrolyte Interface in Flexible All-Solid-State Electrical Double-Layer Capacitors.

PubMed

Wang, Jeng-An; Lu, Yi-Ting; Lin, Sheng-Chi; Wang, Yu-Sheng; Ma, Chen-Chi M; Hu, Chi-Chang

2018-05-30

A novel copolymer, polyurethane-poly(acrylic acid) (PAA), is successfully synthesized from poly(acrylic acid) (PAA) backbone cross-linked with waterborne polyurethane (WPU). This sticky polymer, which is neutralized with 1 M KOH and then soaked in 1 M KOH (denoted as WPU-PAAK-K), provides an ionic conductivity greater than 10 -2 S cm -1 and acts as a gel electrolyte perfectly improving the electrode/electrolyte interfaces in a flexible all-solid-state electrical double-layer capacitor (EDLC). The PAA backbone chains in the copolymer increase the amount of carboxyl groups and promote the segmental motion. The carboxyl groups enhance the water-uptake capacity, which facilitates the ion transport and promotes the ionic conductivity. The cross-linked agent, WPU chains, effectively maintains the rich water content and provides mechanical stickiness to bind two electrodes together. An acid-treated carbon paper (denoted as ACP) combining with such a gel polymer electrolyte demonstrates excellent capacitive behavior with a high areal capacitance of 211.6 mF cm -2 at 10 mV s -1 . A full cell consisting of ACP/WPU-PAAK-K/ACP displays a low equivalent series resistance of 0.44 Ω from the electrochemical impedance spectroscopic results. An all-solid-state ACP/WPU-PAAK-K/ACP EDLC provides an areal specific capacitance of 94.6 mF cm -2 at 1 mA cm -2 . This device under 180° bending shows a capacitance retention over 90%, revealing its remarkable flexibility.

Poly(naphthalene diimide) vinylene: solid state red emission and semiconducting properties for transistors

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

Liang, Xianfeng; Tan, Luxi; Liu, Zitong

Here in this work, a conjugated polymer PNV is developed, linking naphthalene diimide with a vinyl linkage. Owing to the C-H ∙∙∙O hydrogen bond between the carbonyl and the vinyl, PNV exhibits a high red emission with a quantum yield of 33.4% in the solid state while it shows n-type properties with an electron mobility up to 1.5 x 10 -3 cm 2 V -1 s -1 in organic field effect transistors, simultaneously.

Poly(naphthalene diimide) vinylene: solid state red emission and semiconducting properties for transistors

DOE PAGES

Liang, Xianfeng; Tan, Luxi; Liu, Zitong; ...

2017-04-06

Here in this work, a conjugated polymer PNV is developed, linking naphthalene diimide with a vinyl linkage. Owing to the C-H ∙∙∙O hydrogen bond between the carbonyl and the vinyl, PNV exhibits a high red emission with a quantum yield of 33.4% in the solid state while it shows n-type properties with an electron mobility up to 1.5 x 10 -3 cm 2 V -1 s -1 in organic field effect transistors, simultaneously.

Optical limiting in Pluronic F-127 hydrogel with nanocarbon inclusions

NASA Astrophysics Data System (ADS)

Nikolaeva, A. L.; Povarov, S. A.; Bocharov, V. N.

2017-02-01

Characteristics of nonlinear optical limiting (limiting curves) of laser radiation in aqueous polymer systems with nanocarbon inclusions have been studied. Suspensions of nanotubes and soot stabilized by the amphiphilic polymer Pluronic F-127, the additives of which provide the system's transition to a solid-like hydrogel aggregate state at room temperature, have been considered. The limiting materials after their optical breakdown by high-intensity radiation in the gel state have been regenerated using the thermoreversible hydrogel-isotropic solution phase transition. These systems are shown to be promising for self-healing optical materials.

An epistemology on the nature of polymers.

PubMed

Laridjani, Mortéza; Leboucher, Pierre

2014-01-01

Liquids have neither a periodic structure nor the completely random character of gases therefore the detailed study of their x-ray scattering diagram encounters many difficulties. The idea of periodic regularity in molecules of liquid polymers has been an attractive proposition for the simple interpretation of liquid polymer x-ray diagrams. The categorisation of polymer substances as being between a crystal phase with a perfect order and an amorphous disordered state is an over simplification of the complex reality. For obtaining structural information, during the early stages of the application of x-ray diffraction, a near crystalline model of the molecular arrangements in liquids was utilised. However, the results from these investigations led to just an approximation of the crystalline state. Our studies have analysed the real image of Fourier space of liquid polymers, for the first time, using anomalous diffractometry. The findings show the precise atomic structure of liquid polymers when transformed, by cooling, to solid polymers. We demonstrate that there is an intermediate ordered structure, characterised by the real full image of Fourier space. This prominent state of matter, an intermediate ordered structure, is defined by a regular unit cell with a five-fold symmetry. These structural atomic studies contribute to a more detailed understanding of the properties of polymers than the traditional studies of the degree of crystallinity.

An Epistemology on the Nature of Polymers

PubMed Central

Laridjani, Mortéza; Leboucher, Pierre

2014-01-01

Liquids have neither a periodic structure nor the completely random character of gases therefore the detailed study of their x-ray scattering diagram encounters many difficulties. The idea of periodic regularity in molecules of liquid polymers has been an attractive proposition for the simple interpretation of liquid polymer x-ray diagrams. The categorisation of polymer substances as being between a crystal phase with a perfect order and an amorphous disordered state is an over simplification of the complex reality. For obtaining structural information, during the early stages of the application of x-ray diffraction, a near crystalline model of the molecular arrangements in liquids was utilised. However, the results from these investigations led to just an approximation of the crystalline state. Our studies have analysed the real image of Fourier space of liquid polymers, for the first time, using anomalous diffractometry. The findings show the precise atomic structure of liquid polymers when transformed, by cooling, to solid polymers. We demonstrate that there is an intermediate ordered structure, characterised by the real full image of Fourier space. This prominent state of matter, an intermediate ordered structure, is defined by a regular unit cell with a five-fold symmetry. These structural atomic studies contribute to a more detailed understanding of the properties of polymers than the traditional studies of the degree of crystallinity. PMID:25329440

Vertically Aligned and Continuous Nanoscale Ceramic-Polymer Interfaces in Composite Solid Polymer Electrolytes for Enhanced Ionic Conductivity.

PubMed

Zhang, Xiaokun; Xie, Jin; Shi, Feifei; Lin, Dingchang; Liu, Yayuan; Liu, Wei; Pei, Allen; Gong, Yongji; Wang, Hongxia; Liu, Kai; Xiang, Yong; Cui, Yi

2018-06-13

Among all solid electrolytes, composite solid polymer electrolytes, comprised of polymer matrix and ceramic fillers, garner great interest due to the enhancement of ionic conductivity and mechanical properties derived from ceramic-polymer interactions. Here, we report a composite electrolyte with densely packed, vertically aligned, and continuous nanoscale ceramic-polymer interfaces, using surface-modified anodized aluminum oxide as the ceramic scaffold and poly(ethylene oxide) as the polymer matrix. The fast Li + transport along the ceramic-polymer interfaces was proven experimentally for the first time, and an interfacial ionic conductivity higher than 10 -3 S/cm at 0 °C was predicted. The presented composite solid electrolyte achieved an ionic conductivity as high as 5.82 × 10 -4 S/cm at the electrode level. The vertically aligned interfacial structure in the composite electrolytes enables the viable application of the composite solid electrolyte with superior ionic conductivity and high hardness, allowing Li-Li cells to be cycled at a small polarization without Li dendrite penetration.

Applications of Natural Polymeric Materials in Solid Oral Modified-Release Dosage Forms.

PubMed

Li, Liang; Zhang, Xin; Gu, Xiangqin; Mao, Shirui

2015-01-01

Solid oral modified-release dosage forms provide numerous advantages for drug delivery compared to dosage forms where the drugs are released and absorbed rapidly following ingestion. Natural polymers are of particular interest as drug carriers due to their good safety profile, biocompatibility, biodegradability, and rich sources. This review described the current applications of important natural polymers, such as chitosan, alginate, pectin, guar gum, and xanthan gum, in solid oral modified-release dosage forms. It was shown that natural polymers have been widely used to fabricate solid oral modified-release dosage forms such as matrix tablets, pellets and beads, and especially oral drug delivery systems such as gastroretentive and colon drug delivery systems. Moreover, chemical modifications could overcome the shortcomings associated with the use of natural polymers, and the combination of two or more polymers presented further advantages compared with that of single polymer. In conclusion, natural polymers and modified natural polymers have promising applications in solid oral modified-release dosage forms. However, commercial products based on them are still limited. To accelerate the application of natural polymers in commercial products, in vivo behavior of natural polymers-based solid oral modified-release dosage forms should be deeply investigated, and meanwhile quality of the natural polymers should be controlled strictly, and the influence of formulation and process parameters need to be understood intensively.

Curcumin-Eudragit® E PO solid dispersion: A simple and potent method to solve the problems of curcumin.

PubMed

Li, Jinglei; Lee, Il Woo; Shin, Gye Hwa; Chen, Xiguang; Park, Hyun Jin

2015-08-01

Using a simple solution mixing method, curcumin was dispersed in the matrix of Eudragit® E PO polymer. Water solubility of curcumin in curcumin-Eudragit® E PO solid dispersion (Cur@EPO) was greatly increased. Based on the results of several tests, curcumin was demonstrated to exist in the polymer matrix in amorphous state. The interaction between curcumin and the polymer was investigated through Fourier transform infrared spectroscopy and (1)H NMR which implied that OH group of curcumin and carbonyl group of the polymer involved in the H bonding formation. Cur@EPO also provided protection function for curcumin as verified by the pH challenge and UV irradiation test. The pH value influenced curcumin release profile in which sustained release pattern was revealed. Additionally, in vitro transdermal test was conducted to assess the potential of Cur@EPO as a vehicle to deliver curcumin through this alternative administration route. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2015-08-30

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

Investigating buried polymer interfaces using sum frequency generation vibrational spectroscopy

PubMed Central

Chen, Zhan

2010-01-01

This paper reviews recent progress in the studies of buried polymer interfaces using sum frequency generation (SFG) vibrational spectroscopy. Both buried solid/liquid and solid/solid interfaces involving polymeric materials are discussed. SFG studies of polymer/water interfaces show that different polymers exhibit varied surface restructuring behavior in water, indicating the importance of probing polymer/water interfaces in situ. SFG has also been applied to the investigation of interfaces between polymers and other liquids. It has been found that molecular interactions at such polymer/liquid interfaces dictate interfacial polymer structures. The molecular structures of silane molecules, which are widely used as adhesion promoters, have been investigated using SFG at buried polymer/silane and polymer/polymer interfaces, providing molecular-level understanding of polymer adhesion promotion. The molecular structures of polymer/solid interfaces have been examined using SFG with several different experimental geometries. These results have provided molecular-level information about polymer friction, adhesion, interfacial chemical reactions, interfacial electronic properties, and the structure of layer-by-layer deposited polymers. Such research has demonstrated that SFG is a powerful tool to probe buried interfaces involving polymeric materials, which are difficult to study by conventional surface sensitive analytical techniques. PMID:21113334

Singlet and triplet energy transfer in a benzil-doped, light emitting, solid-state conjugated polymer

NASA Astrophysics Data System (ADS)

Rothe, C.; Pålsson, L. O.; Monkman, A. P.

2002-12-01

The luminescence emitted from pure and benzil-doped thin films of the conjugated polymer polyfluorene [PF2/6] are compared. The prompt fluorescence from the first singlet-excited state of the polymer is quenched by 90% in the presence of 10% per weight benzil. In addition to the prompt fluorescence, time-resolved spectroscopy at low temperature also allows the detection of phosphorescence and delayed fluorescence from the host polymer. Again the delayed fluorescence is strongly quenched but the phosphorescence is enhanced in doped samples. An explanation of the results is given in terms of singlet energy transfer from the host to benzil and triplet energy transfer from the dopant back to PF2/6. We have applied this to enable better understanding of the photophysics in PF2/6 doped with a platinum porphyrin complex.

Redox-Active Hydrogel Polymer Electrolytes with Different pH Values for Enhancing the Energy Density of the Hybrid Solid-State Supercapacitor.

PubMed

Tang, Xiaohui; Lui, Yu Hui; Merhi, Abdul Rahman; Chen, Bolin; Ding, Shaowei; Zhang, Bowei; Hu, Shan

2017-12-27

To enhance the energy density of solid-state supercapacitors, a novel solid-state cell, made of redox-active poly(vinyl alcohol) (PVA) hydrogel electrolytes and functionalized carbon nanotube-coated cellulose paper electrodes, was investigated in this work. Briefly, acidic PVA-[BMIM]Cl-lactic acid-LiBr and neutral PVA-[BMIM]Cl-sodium acetate-LiBr hydrogel polymer electrolytes are used as catholyte and anolyte, respectively. The acidic condition of the catholyte contributes to suppression of the undesired irreversible reaction of Br - and extension of the oxygen evolution reaction potential to a higher value than that of the redox potential of Br - /Br 3 - reaction. The observed Br - /Br 3 - redox activity at the cathode contributes to enhance the cathode capacitance. The neutral condition of the anolyte helps extend the operating voltage window of the supercapacitor by introducing hydrogen evolution reaction overpotential to the anode. The electrosorption of nascent H on the negative electrode also increases the anode capacitance. As a result, the prepared solid-state hybrid supercapacitor shows a broad voltage window of 1.6 V, with a high Coulombic efficiency of 97.6% and the highest energy density of 16.3 Wh/kg with power density of 932.6 W/kg at 2 A/g obtained. After 10 000 cycles of galvanostatic charge and discharge tests at the current density of 10 A/g, it exhibits great cyclic stability with 93.4% retention of the initial capacitance. In addition, a robust capacitive performance can also be observed from the solid-state supercapacitor at different bending angles, indicating its great potential as a flexible energy storage device.

A novel quasi-solid state electrolyte with highly effective polysulfide diffusion inhibition for lithium-sulfur batteries

PubMed Central

Zhong, Hai; Wang, Chunhua; Xu, Zhibin; Ding, Fei; Liu, Xinjiang

2016-01-01

Polymer solid state electrolytes are actively sought for their potential application in energy storage devices, particularly lithium metal rechargeable batteries. Herein, we report a polymer with high concentration salts as a quasi-solid state electrolyte used for lithium-sulfur cells, which shows an ionic conductivity of 1.6 mS cm−1 at room temperature. The cycling performance of Li-S battery with this electrolyte shows a long cycle life (300 cycles) and high coulombic efficiency (>98%), without any consuming additives in the electrolyte. Moreover, it also shows a remarkably decreased self-discharge (only 0.2%) after storage for two weeks at room temperature. The reason can be attributed to that the electrolyte can suppress polysulfide anions diffusion, due to the high ratio oxygen atoms with negative charges which induce an electrical repulsion to the polysulfide anions, and their relatively long chains which can provide additional steric hindrance. Thus, the polysulfide anions can be located around carbon particles, which result in remarkably improved overall electrochemical performance, and also the electrolyte have a function of suppress the formation of lithium dendrites on the lithium anode surface. PMID:27146645

Rheology Guided Rational Selection of Processing Temperature To Prepare Copovidone-Nifedipine Amorphous Solid Dispersions via Hot Melt Extrusion (HME).

PubMed

Yang, Fengyuan; Su, Yongchao; Zhang, Jingtao; DiNunzio, James; Leone, Anthony; Huang, Chengbin; Brown, Chad D

2016-10-03

The production of amorphous solid dispersions via hot melt extrusion (HME) relies on elevated temperature and prolonged residence time, which can result in potential degradation and decomposition of thermally sensitive components. Herein, the rheological properties of a physical mixture of polymer and an active pharmaceutical ingredient (API) were utilized to guide the selection of appropriate HME processing temperature. In the currently studied copovidone-nifedipine system, a critical temperature, which is substantially lower (∼13 °C) than the melting point of crystalline API, was captured during a temperature ramp examination and regarded as the critical point at which the API could molecularly dissolve into the polymer. Based on the identification of this critical point, various solid dispersions were prepared by HME processing below, at, and above the critical temperature (both below and above the melting temperature (T m ) of crystalline API). In addition, the resultant extrudates along with two control solid dispersions prepared by physical mixing and cryogenic milling were assessed by X-ray diffraction, differential scanning calorimetry, hot stage microscopy, rheology, and solid-state NMR. Physicochemical properties of resultant solid dispersions indicated that the identified critical temperature is sufficient for the polymer-API system to reach a molecular-level mixing, manifested by the transparent and smooth appearance of extrudates, the absence of API crystalline diffraction and melting peaks, dramatically decreased rheological properties, and significantly improved polymer-API miscibility. Once the critical temperature has been achieved, further raising the processing temperature only results in limited improvement of API dispersion, reflected by slightly reduced storage modulus and complex viscosity and limited improvement in miscibility.

Nanoporous metal organic frameworks as hybrid polymer-metal composites for drug delivery and biomedical applications.

PubMed

Beg, Sarwar; Rahman, Mahfoozur; Jain, Atul; Saini, Sumant; Midoux, Patrick; Pichon, Chantal; Ahmad, Farhan Jalees; Akhter, Sohail

2017-04-01

Metal organic frameworks (MOFs), porous hybrid polymer-metal composites at the nanoscale, are recent innovations in the field of chemistry; they are novel polymeric materials with diverse biomedical applications. MOFs are nanoporous materials, consisting of metal ions linked together by organic bridging ligands. The unique physical and chemical characteristics of MOFs have attracted wider attention from the scientific community, exploring their utility in the field of material science, biology, nanotechnology and drug delivery. The practical feasibility of MOFs is possible owing to their abilities for biodegradability, excellent porosity, high loading capacity, ease of surface modification, among others. In this regard, this review provides an account of various types of MOFs, their physiochemical characteristics and use in diverse disciplines of biomedical sciences - with special emphasis on drug delivery and theranostics. Moreover, this review also highlights the stability and toxicity issues of MOFs, along with their market potential for biomedical applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

RNA as a stable polymer to build controllable and defined nanostructures for material and biomedical applications

PubMed Central

Li, Hui; Lee, Taek; Dziubla, Thomas; Pi, Fengmei; Guo, Sijin; Xu, Jing; Li, Chan; Haque, Farzin; Liang, Xing-Jie; Guo, Peixuan

2015-01-01

Summary The value of polymers is manifested in their vital use as building blocks in material and life sciences. Ribonucleic acid (RNA) is a polynucleic acid, but its polymeric nature in materials and technological applications is often overlooked due to an impression that RNA is seemingly unstable. Recent findings that certain modifications can make RNA resistant to RNase degradation while retaining its authentic folding property and biological function, and the discovery of ultra-thermostable RNA motifs have adequately addressed the concerns of RNA unstability. RNA can serve as a unique polymeric material to build varieties of nanostructures including nanoparticles, polygons, arrays, bundles, membrane, and microsponges that have potential applications in biomedical and material sciences. Since 2005, more than a thousand publications on RNA nanostructures have been published in diverse fields, indicating a remarkable increase of interest in the emerging field of RNA nanotechnology. In this review, we aim to: delineate the physical and chemical properties of polymers that can be applied to RNA; introduce the unique properties of RNA as a polymer; review the current methods for the construction of RNA nanostructures; describe its applications in material, biomedical and computer sciences; and, discuss the challenges and future prospects in this field. PMID:26770259

Preparation of a deuterated polymer: Simulating to produce a solid tritium radioactive source

NASA Astrophysics Data System (ADS)

Hu, Rui; Kan, Wentao; Xiong, Xiaoling; Wei, Hongyuan

2017-08-01

The preparation of a deuterated polymer was performed in order to simulate the production of the corresponding tritiated polymer as a solid tritium radioactive source. Substitution and addition reaction were used to introduce deuterium into the polymer. Proton nuclear magnetic resonance and FT-IR spectroscopy were used to investigate the extent and location of deuterium in the polymer, indicating an effectively deuterated polymer was produced. The thermal analysis showed that the final polymer product could tolerate the environmental temperature below 125 °C in its application. This research provides a prosperous method to prepare solid tritium radioactive source.

Infrared Mass Spectrometry for Environmental and Biomedical Applications

NASA Astrophysics Data System (ADS)

Baltz-Knorr, M. L.; Papantonakis, M. R.; Ermer Haglund, D. R., Jr.

2000-11-01

Matrix-assisted laser desorption and ionization (MALDI) mass spectrometry (MS) using a tunable, ultrashort pulse, mid-infrared free electron laser (FEL) has many applications for both environmental and biomedical research. Environmentally, the characterization of stored nuclear materials has been an important area of research. We are developing a method to determine nuclear tank waste constituents using MALDI MS. This includes desorption and ionization of small organic molecules from sodium nitrate solids and slurries (similar to the salt cake found in some tanks) and also from traditional MALDI matrices. Important aspects of the technique are that it does not produce a secondary waste stream and it is potentially field-deployable using solid-state lasers. Biomedically, the ability to do proteomics is being enhanced by the sensitivity and mass accuracy provided by MALDI MS. We are using MALDI MS to identify proteins embedded in liquid matrix materials, which provide a more natural environment for the biomolecules. We are also working on coupling MALDI MS to traditional protein identification and sequencing techniques for rapid analysis of large numbers of proteins. Research supported by the Office of Naval Research and the U.S. Department of Energy

Seven years of radionuclide laboratory at IMC - important achievements.

PubMed

Hrubý, M; Kučka, J; Pánek, J; Štěpánek, P

2016-10-20

For many important research topics in polymer science the use of radionuclides brings significant benefits concerning nanotechnology, polymer drug delivery systems, tissue engineering etc. This contribution describes important achievements of the radionuclide laboratory at Institute of Macromolecular Chemistry of the Academy of Sciences of the Czech Republic (IMC) in the area of polymers for biomedical applications. Particular emphasis will be given to water-soluble polymer carriers of radionuclides, thermoresponsive polymer radionuclide carriers, thermoresponsive polymers for local brachytherapy, polymer scaffolds modified with (radiolabeled) peptides and polymer copper chelators for the therapy of Wilson´s disease.

Effect of Molecular Weight on Mechanical and Electrochemical Performance of All Solid-State Polymer Electrolyte Membranes

NASA Astrophysics Data System (ADS)

He, Ruixuan; Ward, Daniel; Echeverri, Mauricio; Kyu, Thein

2015-03-01

Guided by ternary phase diagrams of polyethylene glycol diacrylate (PEGDA), succinonitrile plasticizer, and LiTFSI salt, completely amorphous solid-state transparent polymer electrolyte membranes (ss-PEM) were fabricated by UV irradiation in the isotropic melt state. Effects of PEGDA molecular weight (700 vs 6000 g/mol) on ss-PEM performance were investigated. These amorphous PEMs have superionic room temperature ionic conductivity of ~10-3 S/cm, whereby PEGDA6000-PEM outperforms its PEGDA700 counterpart, which may be ascribed to lower crosslinking density and greater segmental mobility. The longer chain between crosslinked points of PEGDA6000-PEM is responsible for greater extensibility of ~80% versus ~7% of PEGDA700-PEM. Besides, both PEMs exhibited thermal stability up to 120 °C and electrochemical stability versus Li+/Li up to 4.7V. LiFePO4/PEM/Li and Li4Ti5O12 /PEM/Li half-cells exhibited stable cyclic behavior up to 50 cycles tested with a capacity of ~140mAh/g, suggesting that LiFePO4/PEM/Li4Ti5O12 may be a promising full-cell for all solid-state lithium battery. We thank NSF-DMR 1161070 for providing funding of this project.

Processing of Fine-Scale Piezoelectric Ceramic/Polymer Composites for Sensors and Actuators

NASA Technical Reports Server (NTRS)

Janas, V. F.; Safari, A.

1996-01-01

The objective of the research effort at Rutgers is the development of lead zirconate titanate (PZT) ceramic/polymer composites with different designs for transducer applications including hydrophones, biomedical imaging, non-destructive testing, and air imaging. In this review, methods for processing both large area and multifunctional ceramic/polymer composites for acoustic transducers were discussed.

Diels-Alder Trapping of Photochemically Generated o-Xylenols: Application in the Synthesis of Novel Organic Molecules and Polymers

NASA Technical Reports Server (NTRS)

Meador, Michael A.

2003-01-01

Bis(o-xylenol) equivalents are useful synthetic intermediates in the construction of polymers and hydroxyl substituted organic molecules which can organize by hydrogen bonded self-assembly into unique supramolecular structures. These polymers and supramolecular materials have potential use as coatings and thin films in aerospace, electronic and biomedical applications.

Photoswitching of glass transition temperatures of azobenzene-containing polymers induces reversible solid-to-liquid transitions.

PubMed

Zhou, Hongwei; Xue, Changguo; Weis, Philipp; Suzuki, Yasuhito; Huang, Shilin; Koynov, Kaloian; Auernhammer, Günter K; Berger, Rüdiger; Butt, Hans-Jürgen; Wu, Si

2017-02-01

The development of polymers with switchable glass transition temperatures (T g ) can address scientific challenges such as the healing of cracks in high-T g polymers and the processing of hard polymers at room temperature without using plasticizing solvents. Here, we demonstrate that light can switch the T g of azobenzene-containing polymers (azopolymers) and induce reversible solid-to-liquid transitions of the polymers. The azobenzene groups in the polymers exhibit reversible cis-trans photoisomerization abilities. Trans azopolymers are solids with T g above room temperature, whereas cis azopolymers are liquids with T g below room temperature. Because of the photoinduced solid-to-liquid transitions of these polymers, light can reduce the surface roughness of azopolymer films by almost 600%, repeatedly heal cracks in azopolymers, and control the adhesion of azopolymers for transfer printing. The photoswitching of T g provides a new strategy for designing healable polymers with high T g and allows for control over the mechanical properties of polymers with high spatiotemporal resolution.

Preparation and characterization of triple shape memory composite foams.

PubMed

Nejad, Hossein Birjandi; Baker, Richard M; Mather, Patrick T

2014-10-28

Foams prepared from shape memory polymers (SMPs) offer the potential for low density materials that can be triggered to deploy with a large volume change, unlike their solid counterparts that do so at near-constant volume. While examples of shape memory foams have been reported in the past, they have been limited to dual SMPs: those polymers featuring one switching transition between an arbitrarily programmed shape and a single permanent shape established by constituent crosslinks. Meanwhile, advances by SMP researchers have led to several approaches toward triple- or multi-shape polymers that feature more than one switching phase and thus a multitude of temporary shapes allowing for a complex sequence of shape deployments. Here, we report the design, preparation, and characterization of a triple shape memory polymeric foam that is open cell in nature and features a two phase, crosslinked SMP with a glass transition temperature of one phase at a temperature lower than a melting transition of the second phase. The soft materials were observed to feature high fidelity, repeatable triple shape behavior, characterized in compression and demonstrated for complex deployment by fixing a combination of foam compression and bending. We further explored the wettability of the foams, revealing composition-dependent behavior favorable for future work in biomedical investigations.

Soft templating strategies for the synthesis of mesoporous materials: inorganic, organic-inorganic hybrid and purely organic solids.

PubMed

Pal, Nabanita; Bhaumik, Asim

2013-03-01

With the discovery of MCM-41 by Mobil researchers in 1992 the journey of the research on mesoporous materials started and in the 21st century this area of scientific investigation have extended into numerous branches, many of which contribute significantly in emerging areas like catalysis, energy, environment and biomedical research. As a consequence thousands of publications came out in large varieties of national and international journals. In this review, we have tried to summarize the published works on various synthetic pathways and formation mechanisms of different mesoporous materials viz. inorganic, organic-inorganic hybrid and purely organic solids via soft templating pathways. Generation of nanoscale porosity in a solid material usually requires participation of organic template (more specifically surfactants and their supramolecular assemblies) called structure-directing agent (SDA) in the bottom-up chemical reaction process. Different techniques employed for the syntheses of inorganic mesoporous solids, like silicas, metal doped silicas, transition and non-transition metal oxides, mixed oxides, metallophosphates, organic-inorganic hybrids as well as purely organic mesoporous materials like carbons, polymers etc. using surfactants are depicted schematically and elaborately in this paper. Moreover, some of the frontline applications of these mesoporous solids, which are directly related to their functionality, composition and surface properties are discussed at the appropriate places. Copyright © 2012 Elsevier B.V. All rights reserved.

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

PubMed

Prasad, Dev; Chauhan, Harsh; Atef, Eman

2014-11-01

The purpose of this study was to understand the combined effect of two polymers showing drug-polymer interactions on amorphous stabilization and dissolution enhancement of indomethacin (IND) in amorphous ternary solid dispersions. The mechanism responsible for the enhanced stability and dissolution of IND in amorphous ternary systems was studied by exploring the miscibility and intermolecular interactions between IND and polymers through thermal and spectroscopic analysis. Eudragit E100 and PVP K90 at low concentrations (2.5%-40%, w/w) were used to prepare amorphous binary and ternary solid dispersions by solvent evaporation. Stability results showed that amorphous ternary solid dispersions have better stability compared with amorphous binary solid dispersions. The dissolution of IND from the ternary dispersion was substantially higher than the binary dispersions as well as amorphous drug. Melting point depression of physical mixtures reveals that the drug was miscible in both the polymers; however, greater miscibility was observed in ternary physical mixtures. The IR analysis confirmed intermolecular interactions between IND and individual polymers. These interactions were found to be intact in ternary systems. These results suggest that the combination of two polymers showing drug-polymer interaction offers synergistic enhancement in amorphous stability and dissolution in ternary solid dispersions. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Enhanced corrosion resistance and hemocompatibility of biomedical NiTi alloy by atmospheric-pressure plasma polymerized fluorine-rich coating

NASA Astrophysics Data System (ADS)

Li, Penghui; Li, Limin; Wang, Wenhao; Jin, Weihong; Liu, Xiangmei; Yeung, Kelvin W. K.; Chu, Paul K.

2014-04-01

To improve the corrosion resistance and hemocompatibility of biomedical NiTi alloy, hydrophobic polymer coatings are deposited by plasma polymerization in the presence of a fluorine-containing precursor using an atmospheric-pressure plasma jet. This process takes place at a low temperature in air and can be used to deposit fluoropolymer films using organic compounds that cannot be achieved by conventional polymerization techniques. The composition and chemical states of the polymer coatings are characterized by fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The corrosion behavior of the coated and bare NiTi samples is assessed and compared by polarization tests and electrochemical impedance spectroscopy (EIS) in physiological solutions including simulated body fluids (SBF) and Dulbecco's Modified Eagle's medium (DMEM). The corrosion resistance of the coated NiTi alloy is evidently improved. Protein adsorption and platelet adhesion tests reveal that the adsorption ratio of albumin to fibrinogen is increased and the number of adherent platelets on the coating is greatly reduced. The plasma polymerized coating renders NiTi better in vitro hemocompatibility and is promising as a protective and hemocompatible coating on cardiovascular implants.

Effect of solid boundaries on a motile microorganism in a viscoelastic fluid

NASA Astrophysics Data System (ADS)

Karimi, Alireza; Li, Gaojin; Ardekani, Arezoo

2014-11-01

Microorganisms swimming in viscoelastic fluids are ubiquitous in nature; this includes biofilms grown on surfaces, Helicobacter pylori colonizing in the mucus layer covering the stomach and spermatozoa swimming through cervical mucus inside the mammalian female reproductive tract. Previous studies have focused on the locomotion of microorganisms in an unbounded viscoelastic fluid. However in many situations, microorganisms interact with solid boundaries and their hydrodynamic interaction is poorly understood. In this work, we numerically study the effect of solid boundaries on the swimming behavior of an archetypal low-Reynolds number swimmer, called ``squirmer,'' in a viscoelastic fluid. A Giesekus constitutive equation is used to model both viscoelasticity and shear-thinning behavior of the background fluid. We found that the time a neutral squirmer spends in the close proximity of the wall increases with polymer relaxation time and reaches a maximum at Weissenberg number of unity. A pusher is found to be trapped near the wall in a viscoelastic fluid, but the puller is less affected. This publication was made possible, in part, with support from NSF (Grant No. CBET-1150348-CAREER) and Indiana Clinical and Translational Sciences Institute Collaboration in Biomedical/Translational Research (Grant No. TR000006) from NIH.

Photoelectrochemical cells for conversion of solar energy to electricity and methods of their manufacture

DOEpatents

Skotheim, Terje

1984-04-10

A photoelectric device is disclosed which comprises first and second layers of semiconductive material, each of a different bandgap, with a layer of dry solid polymer electrolyte disposed between the two semiconductor layers. A layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte is further interposed between the dry solid polymer electrolyte and the first semiconductor layer. A method of manufacturing such devices is also disclosed.

Tailoring the physical properties of homopolymers and polymer nanocomposites via solid-state processing

NASA Astrophysics Data System (ADS)

Pierre, Cynthia

Numerous approaches can be used to modify polymer properties. In this thesis, it is demonstrated that an innovative, continuous, industrially scalable process called solid-state shear pulverization (SSSP) can be used to enhance polymer properties with and without the addition of nanofillers. The SSSP process employs a modified twin-screw extruder in which the barrel is cooled rather than heated, resulting in the polymer being processed at a temperature below its glass transition temperature, if the polymer is amorphous, or its melt transition temperature, if the polymer is semi-crystalline. The material processed via SSSP experiences high levels of shear and compressive stresses, resulting in many repeated fragmentation and fusion steps during pulverization, which can lead to mechanochemistry. This research provides the first in-depth study on the effect of SSSP processing on the molecular structure as well as physical properties of homopolymers. Rheological characterization has demonstrated an increase in the melt viscosity of pulverized poly(ethylene terephthalate) (PET), which can be ascribed to the in situ formation of lightly branched PET. Further evidence of branched PET is provided via a dramatic increase in the rate of crystallization of the pulverized samples. These results suggest that SSSP processing can enhance the reuse and recyclability of PET. While SSSP processing has dramatic effects on the structure of polyesters and consequently their properties, a mild effect is observed for polyolefins. This thesis also demonstrates via a combination of methods that the well-exfoliated state can be achieved via SSSP processing of various polymer nanocomposites, using as-received, unmodified fillers. For example, extensive comparisons are made concerning the thermal stability in air or nitrogen atmosphere of polypropylene (PP)/clay, PP/graphite, and PP/carbon nanotube (CNT) nanocomposites made by SSSP. These comparisons suggest that the mechanism by which CNTs enhance the thermal stability of PP differs from the mechanism associated with clay and graphite.

Thermal Processing of PVP- and HPMC-Based Amorphous Solid Dispersions.

PubMed

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

2016-02-01

Thermal processing technologies continue to gain interest in pharmaceutical manufacturing. However, the types and grades of polymers that can be utilized in common thermal processing technologies, such as hot-melt extrusion (HME), are often limited by thermal or rheological factors. The objectives of the present study were to compare and contrast two thermal processing methods, HME and KinetiSol® Dispersing (KSD), and investigate the influence of polymer type, polymer molecular weight, and drug loading on the ability to produce amorphous solid dispersions (ASDs) containing the model compound griseofulvin (GRIS). Dispersions were analyzed by a variety of imaging, solid-state, thermal, and solution-state techniques. Dispersions were prepared by both HME and KSD using polyvinylpyrrolidone (PVP) K17 or hydroxypropyl methylcellulose (HPMC) E5. Dispersions were only prepared by KSD using higher molecular weight grades of HPMC and PVP, as these could not be extruded under the conditions selected. Powder X-ray diffraction (PXRD) analysis showed that dispersions prepared by HME were amorphous at 10% and 20% drug load; however, it showed significant crystallinity at 40% drug load. PXRD analysis of KSD samples showed all formulations and drug loads to be amorphous with the exception of trace crystallinity seen in PVP K17 and PVP K30 samples at 40% drug load. These results were further supported by other analytical techniques. KSD produced amorphous dispersions at higher drug loads than could be prepared by HME, as well as with higher molecular weight polymers that were not processable by HME, due to its higher rate of shear and torque output.

Advanced biohybrid materials based on nanoclays for biomedical applications

NASA Astrophysics Data System (ADS)

Ruiz-Hitzky, Eduardo; Darder, Margarita; Wicklein, Bernd; Fernandes, Francisco M.; Castro-Smirnov, Fidel A.; Martín del Burgo, M. Angeles; del Real, Gustavo; Aranda, Pilar

2012-10-01

Bio-nanohybrids prepared by assembling natural polymers (polysaccharides, proteins, nucleic acids, etc) to nanosized silicates (nanoclays) and related solids (layered double hydroxides, LDHs) give rise to the so-called bionanocomposites constituting a group of biomaterials with potential applications in medicine. In this way, biopolymers, including chitosan, pectin, alginate, xanthan gum, ι-carrageenan, gelatin, zein, and DNA, as well as phospholipids such as phosphatidylcholine, have been incorporated in layered host matrices by means of ion-exchange mechanisms producing intercalation composites. Also bio-nanohybrids have been prepared by the assembly of diverse bio-polymers with sepiolite, a natural microfibrous magnesium silicate, in this case through interactions affecting the external surface of this silicate. The properties and applications of these resulting biomaterials as active phases of ion-sensors and biosensors, for potential uses as scaffolds for tissue engineering, drug delivery, and gene transfection systems, are introduced and discussed in this work. It is also considered the use of synthetic bionanocomposites as new substrates to immobilize microorganisms, as for instance to bind Influenza virus particles, allowing their application as effective low-cost vaccine adjuvants and carriers.

Solid state NMR: The essential technology for helical membrane protein structural characterization

PubMed Central

Cross, Timothy A.; Ekanayake, Vindana; Paulino, Joana; Wright, Anna

2014-01-01

NMR spectroscopy of helical membrane proteins has been very challenging on multiple fronts. The expression and purification of these proteins while maintaining functionality has consumed countless graduate student hours. Sample preparations have depended on whether solution or solid-state NMR spectroscopy was to be performed – neither have been easy. In recent years it has become increasingly apparent that membrane mimic environments influence the structural result. Indeed, in these recent years we have rediscovered that Nobel laureate, Christian Anfinsen, did not say that protein structure was exclusively dictated by the amino acid sequence, but rather by the sequence in a given environment (Anfinsen, 1973) [106]. The environment matters, molecular interactions with the membrane environment are significant and many examples of distorted, non-native membrane protein structures have recently been documented in the literature. However, solid-state NMR structures of helical membrane proteins in proteoliposomes and bilayers are proving to be native structures that permit a high resolution characterization of their functional states. Indeed, solid-state NMR is uniquely able to characterize helical membrane protein structures in lipid environments without detergents. Recent progress in expression, purification, reconstitution, sample preparation and in the solid-state NMR spectroscopy of both oriented samples and magic angle spinning samples has demonstrated that helical membrane protein structures can be achieved in a timely fashion. Indeed, this is a spectacular opportunity for the NMR community to have a major impact on biomedical research through the solid-state NMR spectroscopy of these proteins. PMID:24412099

Solid state NMR: The essential technology for helical membrane protein structural characterization

NASA Astrophysics Data System (ADS)

Cross, Timothy A.; Ekanayake, Vindana; Paulino, Joana; Wright, Anna

2014-02-01

NMR spectroscopy of helical membrane proteins has been very challenging on multiple fronts. The expression and purification of these proteins while maintaining functionality has consumed countless graduate student hours. Sample preparations have depended on whether solution or solid-state NMR spectroscopy was to be performed - neither have been easy. In recent years it has become increasingly apparent that membrane mimic environments influence the structural result. Indeed, in these recent years we have rediscovered that Nobel laureate, Christian Anfinsen, did not say that protein structure was exclusively dictated by the amino acid sequence, but rather by the sequence in a given environment (Anfinsen, 1973) [106]. The environment matters, molecular interactions with the membrane environment are significant and many examples of distorted, non-native membrane protein structures have recently been documented in the literature. However, solid-state NMR structures of helical membrane proteins in proteoliposomes and bilayers are proving to be native structures that permit a high resolution characterization of their functional states. Indeed, solid-state NMR is uniquely able to characterize helical membrane protein structures in lipid environments without detergents. Recent progress in expression, purification, reconstitution, sample preparation and in the solid-state NMR spectroscopy of both oriented samples and magic angle spinning samples has demonstrated that helical membrane protein structures can be achieved in a timely fashion. Indeed, this is a spectacular opportunity for the NMR community to have a major impact on biomedical research through the solid-state NMR spectroscopy of these proteins.

Solid State Ionics Advanced Materials for Emerging Technologies

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Careem, M. A.; Dissanayake, M. A. K. L.; Rajapakse, R. M. G.; Seneviratne, V. A.

2006-06-01

Keynote lecture. Challenges and opportunities of solid state ionic devices / W. Weppner -- pt. I. Ionically conducting inorganic solids. Invited papers. Multinuclear NMR studies of mass transport of phosphoric acid in water / J. R. P. Jayakody ... [et al.]. Crystalline glassy and polymeric electrolytes: similarities and differences in ionic transport mechanisms / J.-L. Souquet. 30 years of NMR/NQR experiments in solid electrolytes / D. Brinkmann. Analysis of conductivity and NMR measurements in Li[symbol]La[symbol]TiO[symbol] fast Li[symbol] ionic conductor: evidence for correlated Li[symbol] motion / O. Bohnké ... [et al.]. Transport pathways for ions in disordered solids from bond valence mismatch landscapes / S. Adams. Proton conductivity in condensed phases of water: implications on linear and ball lightning / K. Tennakone -- Contributed papers. Proton transport in nanocrystalline bioceramic materials: an investigative study of synthetic bone with that of natural bone / H. Jena, B. Rambabu. Synthesis and properties of the nanostructured fast ionic conductor Li[symbol]La[symbol]TiO[symbol] / Q. N. Pham ... [et al.]. Hydrogen production: ceramic materials for high temperature water electrolysis / A. Hammou. Influence of the sintering temperature on pH sensor ability of Li[symbol]La[symbol]TiO[symbol]. Relationship between potentiometric and impedance spectroscopy measurements / Q. N. Pham ... [et al.]. Microstructure chracterization and ionic conductivity of nano-sized CeO[symbol]-Sm[symbol]O[symbol] system (x=0.05 - 0.2) prepared by combustion route / K. Singh, S. A. Acharya, S. S. Bhoga. Red soil in Northern Sri Lanka is a natural magnetic ceramic / K. Ahilan ... [et al.]. Neutron scattering of LiNiO[symbol] / K. Basar ... [et al.]. Preparation and properties of LiFePO[symbol] nanorods / L. Q. Mai ... [et al.]. Structural and electrochemical properties of monoclinic and othorhombic MoO[symbol] phases / O. M. Hussain ... [et al.]. Preparation of Zircon (ZrSiO[symbol]) ceramics via solid state sintering of Zr)[symbol] and SiO[symbol] and the effect of dopants on the zircon yield / U. Dhanayake, B. S. B. Karunaratne. Preparation and properties of vanadium doped ZnTe cermet thin films / M. S. Hossain, R. Islam, K. A. Khan. Dynamical properties and electronic structure of lithium-ion conductor / M. Kobayashi ... [et al.]. Cuprous ion conducting Montmorillonite-Polypyrrole nanocomposites / D. M. M. Krishantha ... [et al.]. Frequency dependence of conductivity studies on a newly synthesized superionic solid solution/mixed system: [0.75AgI: 0.25AgCl] / R. K. Nagarch, R. Kumar. Diffuse X-ray and neutron scattering from Powder PbS / X. Lian ... [et al.]. Electron affinity and work function of Pyrolytic MnO[symbol] thin films prepared from Mn(C[symbol]H[symbol]O[symbol])[symbol].4H[symbol]) / A. K. M. Farid Ul Islam, R. Islam, K. A. Khan. Crystal structure and heat capacity of Ba[symbol]Ca[symbol]Nb[symbol]O[symbol] / T. Shimoyama ... [et al.]. XPS and impedance investigations on amorphous vanadium oxide thin films / M. Kamalanathan ... [et al.]. Sintering and mixed electronic-ionic conducting properties of La[symbol]Sr[symbol]NiO[symbol] derived from a polyaminocarboxylate complex precursor / D.-P. Huang ... [et al.]. Preparation and characteristics of ball milled MgH[symbol] + M (M= Fe, VF[symbol] and FeF[symbol]) nanocomposites for hydrogen storage / N. W. B. Balasooriya, Ch. Poinsignon. Structural studies of oxysulfide glasses by X-ray diffraction and molecular dynamics simulation / R. Prasada Rao, M. Seshasayee, J. Dheepa. Synthesis, sintering and oxygen ionic conducting properties of Bi[symbol]V[symbol]Cu[symbol]O[symbol] / F. Zhang ... [et al.]. Synthesis and transport characteristics of PbI[symbol]-Ag[symbol]O-Cr[symbol]O[symbol] superioninc system / S. A. Suthanthiraraj, V. Mathew. Electronic conductivity of La[symbol]Sr[symbol]Ga[symbol]Mg[symbol]Co[symbol]O[symbol] electrolytes / K. Yamaji ... [et al.] -- pt. II. Electrode materials. Invited papers. Cathodic properties of Al-doped LiCoO[symbol] prepared by molten salt method Li-Ion batteries / M. V. Reddy, G. V. Subba Rao, B. V. R. Chowdari. Layered ion-electron conducting materials / M. A. Santa Ana, E. Benavente, G. González. LiNi[symbol]Co[symbol]O[symbol] cathode thin-film prepared by RF sputtering for all-solid-state rechargeable microbatteries / X. J. Zhu ... [et al.] -- Contributed papers. Contributed papers. Nanocomposite cathode for SOFCs prepared by electrostatic spray deposition / A. Princivalle, E. Djurado. Effect of the addition of nanoporous carbon black on the cycling characteristics of Li[symbol]Co[symbol](MoO[symbol])[symbol] for lithium batteries / K. M. Begam, S. R. S. Prabaharan. Protonic conduction in TiP[symbol]O[symbol] / V. Nalini, T. Norby, A. M. Anuradha. Preparation and electrochemical LiMn[symbol]O[symbol] thin film by a solution deposition method / X. Y. Gan ... [et al.]. Synthesis and characterization LiMPO[symbol] (M = Ni, Co) / T. Savitha, S. Selvasekarapandian, C. S. Ramya. Synthesis and electrical characterization of LiCoO[symbol] LiFeO[symbol] and NiO compositions / A. Wijayasinghe, B. Bergman. Natural Sri Lanka graphite as conducting enhancer in manganese dioxide (Emd type) cathode of alkaline batteries / N. W. B. Balasooriya ... [et al.]. Electrochemical properties of LiNi[symbol]Al[symbol]Zn[symbol]O[symbol] cathode material synthesized by emulsion method / B.-H. Kim ... [et al.]. LiNi[symbol]Co[symbol]O[symbol] cathode materials synthesized by particulate sol-gel method for lithium ion batteries / X. J. Zhu ... [et al.]. Pulsed laser deposition of highly oriented LiCoO[symbol] and LiMn[symbol]O[symbol] thin films for microbattery applications / O. M. Hussain ... [et al.]. Preparation of LiNi[symbol]Co[symbol]O[symbol] thin films by a sol-gel method / X. J. Zhu ... [et al.]. Electrochemical lithium insertion into a manganese dioxide electrode in aqueous solutions / M. Minakshi ... [et al.]. AC impedance spectroscopic analysis of thin film LiNiVO[symbol] prepared by pulsed laser deposition technique / S. Selvasekarapandian ... [et al.]. Synthesis and characterization of LiFePO[symbol] cathode materials by microwave processing / J. Zhou ... [et al.]. Characterization of Nd[symbol]Sr[symbol]CoO[symbol] including Pt second phase as the cathode material for low-temperature SOFCs / J. W. Choi ... [et al.]. Thermodynamic behavior of lithium intercalation into natural vein and synthetic graphite / N. W. B. Balasooriya, P. W. S. K. Bandaranayake, Ph. Touzain -- pt. III. Electroactive polymers. Invited papers. Organised or disorganised? looking at polymer electrolytes from both points of view / Y.-P. Liao ... [et al.]. Polymer electrolytes - simple low permittivity solutions? / I. Albinsson, B.-E. Mellander. Dependence of conductivity enhancement on the dielectric constant of the dispersoid in polymer-ferroelectric composite electrolytes / A. Chandra, P. K. Singh, S. Chandra. Design and application of boron compounds for high-performance polymer electrolytes / T. Fujinami. Structural, vibrational and AC impedance analysis of nano composite polymer electrolytes based on PVAC / S. Selvasekarapandian ... [et al.]. Absorption intensity variation with ion association in PEO based electrolytes / J. E. Furneaux ... [et al.]. Study of ion-polymer interactions in cationic and anionic ionomers from the dependence of conductivity on pressure and temperature / M. Duclot ... [et al.]. Triol based polyurethane gel electrolytes for electrochemical devices / A. R. Kulkarni. Contributed papers. Accurate conductivity measurements to solvation energies in nafion / M. Maréchal, J.-L Souquet. Ion conducting behaviour of composite polymer gel electrolyte: PEG-PVA-(NH[symbol]CH[symbol]CO[symbol])[symbol] system / S. L. Agrawal, A. Awadhia, S. K. Patel. Impedance spectroscopy and DSC studies of poly(vinylalcohol)/ silicotungstic acid crosslinked composite membranes / A. Anis, A. K. Banthia. (PEO)[symbol]:Na[symbol]P[symbol]O[symbol]: a report on complex formation / A. Bhide, K. Hariharan. Experimental studies on (PVC+LiClO[symbol]+DMP) polymer electrolyte systems for lithium battery / Ch. V. S. Reddy. Stability of the gel electrolyte, PAN: EC: PC: LiCF[symbol]SO[symbol] towards lithium / K. Perera ... [et al.]. Montmorillonite as a conductivity enhancer in (PEO)[symbol]LiCF[symbol]SO[symbol] polymer electrolyte / C. H. Manoratne ... [et al.]. Polymeric gel electrolytes for electrochemical capacitors / M. Morita ... [et al.]. Electrical conductivity studies on proton conducting polymer electrolytes based on poly (viniyl acetate) / D. Arun Kumar ... [et al.]. Conductivity and thermal studies on plasticized PEO:LiTf-Al[symbol]O[symbol] composite polymer electrolyte / H. M. J. C. Pitawala, M. A. K. L. Dissanayake, V. A. Seneviratne. Investigation of transport properties of a new biomaterials - gum mangosteen / S. S. Pradhan, A. Sarkar. Investigation of ionic conductivity of PEO-MgCl[symbol] based solid polymer electrolyte / M. Sundar ... [et al.]. [symbol]H NMR and Raman analysis of proton conducting polymer electrolytes based on partially hydrolyzed poly (vinyl alcohol) / G. Hirankumar ... [et al.]. Influence of Al[symbol]O[symbol] nanoparticles on the phase matrix of polyethylene oxide-silver triflate polymer electrolytes / S. Austin Suthanthiraraj, D. Joice Sheeba. Effect of different types of ceramic fillers on thermal, dielectric and transport properties of PEO[symbol]LiTf solid polymer electrolyte / K. Vignarooban ... [et al.]. Characterization of PVP based solid polymer electrolytes using spectroscopic techniques / C. S. Ramya ... [et al.]. Electrochemical and structural properties of poly vinylidene fluoride - silver triflate solid polymer electrolyte system / S. Austin Suthanthiraraj, B. Joseph Paul. Micro Raman, Li NMR and AC impedance analysis of PVAC:LiClO[symbol] solid polymer eectrolytes / R. Baskaran ... [et al.].Study of Na+ ion conduction in PVA-NaSCN solid polymer electrolytes / G. M. Brahmanandhan ... [et al.]. Effect of filler addition on plasticized polymer electrolyte systems / M. Sundar, S. Selladurai. Ionic motion in PEDOT and PPy conducting polymer bilayers / U. L. Zainudeen, S. Skaarup, M. A. Careem. Film formation mechanism and electrochemical characterization of V[symbol]O[symbol] xerogel intercalated by polyaniniline / Q. Zhu ... [et al.]. Effect of NH[symbol]NO[symbol] concentration on the conductivity of PVA based solid polymer electrolyte / M. Hema ... [et al.]. Dielectric and conductivity studies of PVA-KSCN based solid polymer electrolytes / J. Malathi ... [et al.] -- pt. IV. Emerging applications. Invited papers. The use of solid state ionic materials and devices in medical applications / R. Linford. Development of all-solid-state lithium batteries / V. Thangadurai, J. Schwenzei, W. Weppner. Reversible intermediate temperature solid oxide fuel cells / B.-E. Mellander, I. Albinsson. Nano-size effects in lithium batteries / P. Balaya, Y. Hu, J. Maier. Electrochromics: fundamentals and applications / C. G. Granqvist. Electrochemical CO[symbol] gas sensor / K. Singh. Polypyrrole for artificial muscles: ionic mechanisms / S. Skaarup. Development and characterization of polyfluorene based light emitting diodes and their colour tuning using Forster resonance energy transfer / P. C. Mattur ... [et al.]. Mesoporous and nanoparticulate metal oxides: applications in new photocatalysis / C. Boxall. Proton Conducting (PC) perovskite membranes for hydrogen separation and PC-SOFC electrodes and electrolytes / H. Jena, B. Rambabu. Contributed papers. Electroceramic materials for the development of natural gas fuelled SOFC/GT plant in developing country (Trinidad and Tobogo (T&T)) / R. Saunders, H. Jena, B. Rambabu. Thin film SOFC supported on nano-porous substrate / J. Hoon Joo, G. M. Choi. Characterization and fabrication of silver solid state battery Ag/AGI-AgPO[symbol]/I[symbol], C / E. Kartini ... [et al.]. Performance of lithium polymer cells with polyacrylonitrile based electrolyte / K. Perera ... [et al.]. Hydrothermal synthesis and electrochemical behavior of MoO[symbol] nanobelts for lithium batteries / Y. Qi ... [et al.]. Electrochemical behaviour of a PPy (DBS)/polyacrylonitrile: LiTF:EC:PC/Li cell / K. Vidanapathirana ... [et al.]. Characteristics of thick film CO[symbol] sensors based on NASICON using Li[symbol]CO[symbol]-CaCO[symbol] auxiliary phases / H. J. Kim ... [et al.]. Solid state battery discharge characteristic study on fast silver ion conducting composite system: 0.9[0.75AgI:0.25AgCl]: 0.1TiO[symbol] / R. K. Nagarch, R. Kumar, P. Rawat. Intercalating protonic solid-state batteries with series and parallel combination / K. Singh, S. S. Bhoga, S. M. Bansod. Synthesis and characterization of ZnO fiber by microwave processing / Lin Wang ... [et al.]. Preparation of Sn-Ge alloy coated Ge nanoparticles and Sn-Si alloy coated Si nanoparticles by ball-milling / J. K. D. S. Jayanett, S. M. Heald. Synthesis of ultrafine and crystallized TiO[symbol] by alalkoxied free polymerizable precursor method / M. Vijayakumar ... [et al.]. Development and characterization of polythiophene/fullerene composite solar cells and their degradation studies / P. K. Bhatnagar ... [et al.].

Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode

NASA Astrophysics Data System (ADS)

Gao, Jing; Sun, Chunshui; Xu, Lei; Chen, Jian; Wang, Chong; Guo, Decai; Chen, Hao

2018-04-01

Due to flexible property and light weight, the lithiated Nafion membrane swollen with PC (PC-Li-Nafion) has been employed as both solid-state electrolyte and separator to fabricate solid-state Li-S cells. The electrochemical measurements of PC-Li-Nafion membrane show that its Li-ion transference number is 0.928, ionic conductivity of 2.1 × 10-4 S cm-1 can be achieved at 70 °C and its electrochemical window is 0 ∼ +4.1 V vs. Li+/Li. It is observed that the Li dendrites are suppressed by using PC-Li-Nafion membrane due to its single-ion conducting property. The amounts of Li-Nafion resin binder and conductive carbon in the cathode are optimized as 40% and 10% respectively to make a balance of ionic and electronic conductivities. A thin-layer Li-Nafion resin with a thickness of around 2 μm is fabricated between the cathode and PC-Li-Nafion membrane to improve the interfacial contact and further enhance the specific capacity of the cell. When measured at 70 °C, the Li-S cell delivers a reversible specific capacity of 1072.8 mAh g-1 (S) at 0.05 C and 895 mAh g-1 (S) at 1 C. The capacity retention at 1 C is 89% after 100 cycles. These results suggest that high-performance solid-state Li-S cells can be fabricated with the Li-Nafion polymer electrolyte.

Use of Atomic Oxygen for Increased Water Contact Angles of Various Polymers for Biomedical Applications

NASA Technical Reports Server (NTRS)

Beger, Lauren; Roberts, Lily; deGroh, Kim; Banks, Bruce

2007-01-01

In the low Earth orbit (LEO) space environment, spacecraft surfaces can be altered during atomic oxygen exposure through oxidation and erosion. There can be terrestrial benefits of such interactions, such as the modification of hydrophobic or hydrophilic properties of polymers due to chemical modification and texturing. Such modification of the surface may be useful for biomedical applications. For example, atomic oxygen texturing may increase the hydrophilicity of polymers, such as chlorotrifluoroethylene (Aclar), thus allowing increased adhesion and spreading of cells on textured Petri dishes. The purpose of this study was to determine the effect of atomic oxygen exposure on the hydrophilicity of nine different polymers. To determine whether hydrophilicity remains static after atomic oxygen exposure or changes with exposure, the contact angles between the polymer and a water droplet placed on the polymer s surface were measured. The polymers were exposed to atomic oxygen in a radio frequency (RF) plasma asher. Atomic oxygen plasma treatment was found to significantly alter the hydrophilicity of non-fluorinated polymers. Significant decreases in the water contact angle occurred with atomic oxygen exposure. Fluorinated polymers were found to be less sensitive to changes in hydrophilicity for equivalent atomic oxygen exposures, and two of the fluorinated polymers became more hydrophobic. The majority of change in water contact angle of the non-fluorinated polymers was found to occur with very low fluence exposures, indicating potential cell culturing benefit with short treatment time.

A Unique Hybrid Quasi-Solid-State Electrolyte for Li-O2 Batteries with Improved Cycle Life and Safety.

PubMed

Yi, Jin; Zhou, Haoshen

2016-09-08

In the context of the development of electric vehicle to solve the contemporary energy and environmental issues, the possibility of pushing future application of Li-O2 batteries as a power source for electric vehicles is particularly attractive. However, safety concerns, mainly derived from the use of flammable organic liquid electrolytes, become a major bottleneck for the strategically crucial applications of Li-O2 batteries. To overcome this issue, rechargeable solid-state Li-O2 batteries with enhanced safety is regarded as an appealing candidate. In this study, a hybrid quasi-solid-state electrolyte combing a polymer electrolyte with a ceramic electrolyte is first designed and explored for Li-O2 batteries. The proposed rechargeable solid-state Li-O2 battery delivers improved cycle life (>100 cycles) and safety. The feasibility study demonstrates that the hybrid quasi-solid-state electrolytes could be employed as a promising alternative strategy for the development of rechargeable Li-O2 batteries, hence encouraging more efforts devoted to explore other hybrid solid-state electrolytes for Li-O2 batteries upon future application. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biomedical Applications of Thermally Activated Shape Memory Polymers

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

Small IV, W; Singhal, P; Wilson, T S

2009-04-10

Shape memory polymers (SMPs) are smart materials that can remember a primary shape and can return to this primary shape from a deformed secondary shape when given an appropriate stimulus. This property allows them to be delivered in a compact form via minimally invasive surgeries in humans, and deployed to achieve complex final shapes. Here we review the various biomedical applications of SMPs and the challenges they face with respect to actuation and biocompatibility. While shape memory behavior has been demonstrated with heat, light and chemical environment, here we focus our discussion on thermally stimulated SMPs.

Soluplus®/TPGS-based solid dispersions prepared by hot-melt extrusion equipped with twin-screw systems for enhancing oral bioavailability of valsartan.

PubMed

Lee, Jae-Young; Kang, Wie-Soo; Piao, Jingpei; Yoon, In-Soo; Kim, Dae-Duk; Cho, Hyun-Jong

2015-01-01

Soluplus(®) (SP) and D-alpha-tocopherol polyethylene glycol 1000 succinate (TPGS)-based solid dispersion (SD) formulations were developed by hot-melt extrusion (HME) to improve oral bioavailability of valsartan (VST). HME process with twin-screw configuration for generating a high shear stress was used to prepare VST SD formulations. The thermodynamic state of the drug and its dispersion in the polymers were evaluated by solid-state studies, including Fourier-transform infrared, X-ray diffraction, and differential scanning calorimetry. Drug release from the SD formulations was assessed at pH values of 1.2, 4.0, and 6.8. Pharmacokinetic study was performed in rats to estimate the oral absorption of VST. HME with a high shear rate produced by the twin-screw system was successfully applied to prepare VST-loaded SD formulations. Drug amorphization and its molecular dispersion in the polymer matrix were verified by several solid-state studies. Drug release from SD formulations was improved, compared to the pure drug, particularly at pH 6.8. Oral absorption of drug in rats was also enhanced in SP and TPGS-based SD groups compared to that in the pure drug group. SP and TPGS-based SDs, prepared by the HME process, could be used to improve aqueous solubility, dissolution, and oral absorption of poorly water-soluble drugs.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity

DOEpatents

Skotheim, Terje

1986-01-01

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity

DOEpatents

Skotheim, T.

1984-09-28

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Methods of improving mechanical and biomedical properties of Ca-Si-based ceramics and scaffolds.

PubMed

Wu, Chengtie

2009-05-01

CaSiO3 ceramics and porous scaffolds are regarded as potential materials for bone tissue regeneration owing to their excellent bioactivity. However, their low mechanical strength and high dissolution limit their further biomedical application. In this report, we introduce three methods to improve the mechanical and biomedical properties of CaSiO3 ceramics and scaffolds. Positive ions and polymer modification are two promising ways to improve the mechanical and biomedical properties of CaSiO3 ceramics and scaffolds for bone tissue regeneration.

Effect of zirconium oxide nanofiller and dibutyl phthalate plasticizer on ionic conductivity and optical properties of solid polymer electrolyte.

PubMed

Yasin, Siti Mariah Mohd; Ibrahim, Suriani; Johan, Mohd Rafie

2014-01-01

New solid polymer electrolytes (SPE) based on poly(ethylene oxide) (PEO) doped with lithium trifluoromethanesulfonate (LiCF3SO3), dibutyl phthalate (DBP) plasticizer, and zirconium oxide (ZrO2) nanoparticles were prepared by solution-casting technique. The conductivity was enhanced by addition of dibutyl phthalate (DBP) plasticizer and ZrO2 nanofiller with maximum conductivity (1.38 × 10(-4) Scm(-1)). The absorption edge and band gap values showed decreases upon addition of LiSO3CF3, DBP, and ZrO2 due to the formation of localized states in the SPE and the degree of disorder in the films increased.

Effect of Zirconium Oxide Nanofiller and Dibutyl Phthalate Plasticizer on Ionic Conductivity and Optical Properties of Solid Polymer Electrolyte

PubMed Central

Yasin, Siti Mariah Mohd; Ibrahim, Suriani

2014-01-01

New solid polymer electrolytes (SPE) based on poly(ethylene oxide) (PEO) doped with lithium trifluoromethanesulfonate (LiCF3SO3), dibutyl phthalate (DBP) plasticizer, and zirconium oxide (ZrO2) nanoparticles were prepared by solution-casting technique. The conductivity was enhanced by addition of dibutyl phthalate (DBP) plasticizer and ZrO2 nanofiller with maximum conductivity (1.38 × 10−4 Scm−1). The absorption edge and band gap values showed decreases upon addition of LiSO3CF3, DBP, and ZrO2 due to the formation of localized states in the SPE and the degree of disorder in the films increased. PMID:25133244

Fast Lithium-Ion Transportation in Crystalline Polymer Electrolytes.

PubMed

Fu, Xiao-Bin; Yang, Guang; Wu, Jin-Ze; Wang, Jia-Chen; Chen, Qun; Yao, Ye-Feng

2018-01-05

Fast lithium-ion transportation is found in the crystalline polymer electrolytes, α-CD-PEO n /Li + (n=12, 40), prepared by self-assembly of α-cyclodextrin (CD), polyethylene oxide (PEO) and Li + salts. A detailed solid-state NMR study combined with the X-ray diffraction technique reveals the unique structural features of the samples, that is, a) the tunnel structure formed by the assembled CDs, providing the ordered long-range pathway for Li + ion transportation; b) the all-trans conformational sequence of the PEO chains in the tunnels, attenuating significantly the coordination between Li + and the EO segments. The origin of the fast lithium-ion transportation has been attributed to these unique structural features. This work demonstrates the first example in solid polymer electrolytes (SPEs) for "creating" fast ion transportation through material design and will find potential applications in the design of new ionconducting SPE materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physical aging in pharmaceutical polymers and the effect on solid oral dosage form stability.

PubMed

Kucera, Shawn A; Felton, Linda A; McGinity, James W

2013-12-05

The application of a polymeric film to a solid oral dosage form can be an effective technique to modify drug release. Most polymers used for such purposes are amorphous in nature and are subject to physical aging. This physical aging phenomenon has been shown to cause changes not only in the mechanical and drug release properties of polymeric films, but also the permeability of these films due to a densification and decrease in free volume of the polymer as the material relaxes to an equilibrated thermodynamic state. Temperature, humidity, and additional excipients in the coating formulations have been shown to influence the aging process. This review article discusses the process of physical aging in films prepared from aqueous dispersions, describes various analytical techniques that can be used to investigate the aging process, and highlights strategies to prevent such aging. Copyright © 2013 Elsevier B.V. All rights reserved.

Ionic liquids in a poly ethylene oxide cross-linked gel polymer as an electrolyte for electrical double layer capacitor

NASA Astrophysics Data System (ADS)

Chaudoy, V.; Tran Van, F.; Deschamps, M.; Ghamouss, F.

2017-02-01

In the present work, we developed a gel polymer electrolyte via the incorporation of a room temperature ionic liquid into a cross-linked polymer matrix. The cross-linked gel electrolyte was prepared using a free radical polymerization of methacrylate and dimethacrylate oligomers dissolved in 1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide. Combining the advantages of the ionic liquids and of conventional polymers, the cross-linked gel polymer electrolyte was used both as a separator and as an electrolyte for a leakage-free and non-flammable EDLC supercapacitor. The quasi-all solid-state supercapacitors showed rather good capacitance, power and energy densities by comparison to a liquid electrolyte-based EDLC.

Polymer-Based Electrospun Nanofibers for Biomedical Applications

PubMed Central

Al-Enizi, Abdullah M.; Zagho, Moustafa M.

2018-01-01

Electrospinning has been considered a promising and novel procedure to fabricate polymer nanofibers due to its simplicity, cost effectiveness, and high production rate, making this technique highly relevant for both industry and academia. It is used to fabricate non-woven fibers with unique characteristics such as high permeability, stability, porosity, surface area to volume ratio, ease of functionalization, and excellent mechanical performance. Nanofibers can be synthesized and tailored to suit a wide range of applications including energy, biotechnology, healthcare, and environmental engineering. A comprehensive outlook on the recent developments, and the influence of electrospinning on biomedical uses such as wound dressing, drug release, and tissue engineering, has been presented. Concerns regarding the procedural restrictions and research contests are addressed, in addition to providing insights about the future of this fabrication technique in the biomedical field. PMID:29677145

Flexible all-solid-state asymmetric supercapacitors based on free-standing carbon nanotube/graphene and Mn3O4 nanoparticle/graphene paper electrodes.

PubMed

Gao, Hongcai; Xiao, Fei; Ching, Chi Bun; Duan, Hongwei

2012-12-01

We report the design of all-solid-state asymmetric supercapacitors based on free-standing carbon nanotube/graphene (CNTG) and Mn(3)O(4) nanoparticles/graphene (MG) paper electrodes with a polymer gel electrolyte of potassium polyacrylate/KCl. The composite paper electrodes with carbon nanotubes or Mn(3)O(4) nanoparticles uniformly intercalated between the graphene nanosheets exhibited excellent mechanical stability, greatly improved active surface areas, and enhanced ion transportation, in comparison with the pristine graphene paper. The combination of the two paper electrodes with the polymer gel electrolyte endowed our asymmetric supercapacitor of CNTG//MG an increased cell voltage of 1.8 V, a stable cycling performance (capacitance retention of 86.0% after 10,000 continuous charge/discharge cycles), more than 2-fold increase of energy density (32.7 Wh/kg) compared with the symmetric supercapacitors, and importantly a distinguished mechanical flexibility.

Ionically conducting PVA-LiClO4 gel electrolyte for high performance flexible solid state supercapacitors.

PubMed

Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Lokhande, Chandrakant D

2015-12-15

The synthesis of polymer gel electrolyte having high ionic conductivity, excellent compatibility with active electrode material, mechanical tractability and long life is crucial to obtain majestic electrochemical performance for flexible solid state supercapacitors (FSS-SCs). Our present work describes effect of different polymers gel electrolytes on electrochemical properties of MnO2 based FSS-SCs device. It is revealed that, MnO2-FSS-SCs with polyvinyl alcohol (PVA)-Lithium perchlorate (LiClO4) gel electrolyte demonstrate excellent electrochemical features such as maximum operating potential window (1.2V), specific capacitance of 112Fg(-1) and energy density of 15Whkg(-1) with extended cycling stability up to 2500CV cycles. Moreover, the calendar life suggests negligible decrease in the electrochemical performance of MnO2-FSS-SCs after 20days. Copyright © 2015 Elsevier Inc. All rights reserved.

Nonenzymatic all-solid-state coated wire electrode for acetylcholine determination in vitro.

PubMed

He, Cheng; Wang, Zhan; Wang, You; Hu, Ruifen; Li, Guang

2016-11-15

A nonenzymatic all-solid-state coated wire acetylcholine electrode was investigated. Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT/PSS) as conducting polymer was coated on one end of a gold wire (0.5mm in diameter). The acetylcholine selective membrane containing heptakis(2,3,6-tri-Ο-methyl)-β-cyclodextrin as an ionophore covered the conducting polymer layer. The electrode could work stably in a pH range of 6.5-8.5 and a temperature range of 15-40°C. It covered an acetylcholine concentration range of 10(-5)-10(-1)M with a slope of 54.04±1.70mV/decade, while detection limit was 5.69±1.06µM. The selectivity, dynamic response, reproducibility and stability were evaluated. The electrode could work properly in the rat brain homogenate to detect different concentrations of acetylcholine. Copyright © 2016 Elsevier B.V. All rights reserved.

Durable and water-floatable ionic polymer actuator with hydrophobic and asymmetrically laser-scribed reduced graphene oxide paper electrodes.

PubMed

Kim, Jaehwan; Jeon, Jin-Han; Kim, Hyun-Jun; Lim, Hyuneui; Oh, Il-Kwon

2014-03-25

Ionic polymer actuators driven by electrical stimuli have been widely investigated for use in practical applications such as bioinspired robots, sensors, and biomedical devices. However, conventional ionic polymer-metal composite actuators have a serious drawback of poor durability under long-term actuation in open air, mainly because of the leakage of the inner electrolyte and hydrated cations through cracks in the metallic electrodes. Here, we developed a highly durable and water-floatable ionic polymer artificial muscle by employing hydrophobic and asymmetrically laser-scribed reduced graphene oxide paper electrodes (HLrGOP). The highly conductive, flexible, and cost-effective HLrGOP electrodes have asymmetrically smooth hydrophobic outer and rough inner surfaces, resulting in liquid-impermeable and water-floatable functionalities and strong bonding between an ionic polymer and the electrodes. More interestingly, the HLrGOP electrode, which has a unique functionality to prevent the leakage of the vaporized or liquid electrolyte and mobile ions during electrical stimuli, greatly contributes to an exceptionally durable ionic polymer-graphene composite actuator that is a prerequisite for practical applications in active biomedical devices, biomimetic robots, touch-feedback haptic systems, and flexible soft electronics.

Dipole moment, solution, and solid state structure (-)-epicatechin, a monomer unit of procyanidin polymers

Treesearch

Frank R. Fronczek; Garret Gannuch; Wayne L. Mattice; Fred L. Tobiason; Jeff L. Broker; Richard W. Hemingway

1984-01-01

The structure of (-)-epicatechin has been determined in the crystalline state. Crystals are orthorhombic. P212121, a=670.8(1), b=1329.1 (3), c=1426.2(4) pm, Z=4. Dc=1.516 g cm-3, R=0.041 for 1624 observations. Intramolecular hydrogen bonds are absent. The...

Fundamentals of Atom Transfer Radical Polymerization

ERIC Educational Resources Information Center

Coessens, Veerle M. C.; Matyjaszewski, Krzysztof

2010-01-01

Today's market increasingly demands sophisticated materials for advanced technologies and high-value applications, such as nanocomposites, optoelectronic, or biomedical materials. Therefore, the demand for well-defined polymers with very specific molecular architecture and properties increases. Until recently, these kinds of polymers could only be…

Silk constructs for delivery of muskuloskeletal therapeutics

PubMed Central

Meinel, Lorenz; Kaplan, David L.

2012-01-01

Silk fibroin (SF) is a biopolymer with distinguishing features from many other bio- as well as synthetic polymers. From a biomechanical and drug delivery perspective, SF combines remarkable versatility for scaffolding (solid implants, hydrogels, threads, solutions), with advanced mechanical properties and good stabilization and controlled delivery of entrapped protein and small molecule drugs, respectively. It is this combination of mechanical and pharmaceutical features which render SF so exciting for biomedical applications. his pattern along with the versatility of this biopolymer have been translated into progress for musculoskeletal applications. We review the use and potential of silk fibroin for systemic and localized delivery of therapeutics in diseases affecting the musculoskeletal system. We also present future directions for this biopolymer as well as the necessary research and development steps for their achievement. PMID:22522139

Method of synthesizing polymers from a solid electrolyte

DOEpatents

Skotheim, Terje A.

1985-01-01

A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte wherein an assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

Method of synthesizing polymers from a solid electrolyte

DOEpatents

Skotheim, T.A.

1984-10-19

A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte is disclosed. An assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

Shape-memory effect by specific biodegradable polymer blending for biomedical applications.

PubMed

Cha, Kook Jin; Lih, Eugene; Choi, Jiyeon; Joung, Yoon Ki; Ahn, Dong Jun; Han, Dong Keun

2014-05-01

Specific biodegradable polymers having shape-memory properties through "polymer-blend" method are investigated and their shape-switching in body temperature (37 °C) is characterized. Poly(L-lactide-co-caprolactone) (PLCL) and poly(L-lactide-co-glycolide) (PLGA) are dissolved in chloroform and the films of several blending ratios of PLCL/PLGA are prepared by solvent casting. The shape-memory properties of films are also examined using dynamic mechanical analysis (DMA). Among the blending ratios, the PLCL50/PLGA50 film shows good performance of shape-fixity and shape-recovery based on glass transition temperature. It displays that the degree of shape recovery is 100% at 37 °C and the shape recovery proceeds within only 15 s. In vitro biocompatibility studies are shown to have good blood compatibility and cytocompatibility for the PLCL50/PLGA50 films. It is expected that this blended biodegradable polymer can be potentially used as a material for blood-contacting medical devices such as a self-expended vascular polymer stents and vascular closure devices in biomedical applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polyurethane with Tethered Copper(II)-Cyclen Complex: Preparation, Characterization and Catalytic Generation of Nitric Oxide from S-Nitrosothiols

PubMed Central

Hwang, Sangyeul

2008-01-01

The preparation and characterization of a commercial biomedical grade polyurethane (Tecophilic, SP-93A-100) material possessing covalently linked copper(II)-cyclen moieties as a nitric oxide (NO) generating polymer are described. Chemiluminescence NO measurements demonstrate that the prepared polymer can decompose endogenous S-nitrosothiols (RSNOs) such as S-nitrosoglutathione and S-nitrosocysteine to NO in the presence of thiol reducing agents (RSHs; e.g., glutathione and cysteine) at physiological pH. Since such RSNO and RSH already exist in blood, the proposed polymer is capable of spontaneously generating NO when in contact with fresh blood. This is demonstrated by utilizing the polymer as an outer coating at the distal end of an amperometric NO sensor to create a device that generates response toward the RSNO species in the blood. This polymer possesses the combined benefits of a commercial biomedical grade polyurethane with the ability to generate biologically active NO when on contact with blood, and thus may serve as a useful coating to improve the hemocompatibility of various medical devices. PMID:18314189

Method of altering the effective bulk density of solid material and the resulting product

DOEpatents

Kool, Lawrence B.; Nolen, Robert L.; Solomon, David E.

1983-01-01

A method of adjustably tailoring the effective bulk density of a solid material in which a mixture comprising the solid material, a film-forming polymer and a volatile solvent are sprayed into a drying chamber such that the solvent evaporates and the polymer dries into hollow shells having the solid material captured within the shell walls. Shell density may be varied as a function of solid/polymer concentration, droplet size and drying temperature.

Achieving High-Energy-High-Power Density in a Flexible Quasi-Solid-State Sodium Ion Capacitor.

PubMed

Li, Hongsen; Peng, Lele; Zhu, Yue; Zhang, Xiaogang; Yu, Guihua

2016-09-14

Simultaneous integration of high-energy output with high-power delivery is a major challenge for electrochemical energy storage systems, limiting dual fine attributes on a device. We introduce a quasi-solid-state sodium ion capacitor (NIC) based on a battery type urchin-like Na2Ti3O7 anode and a capacitor type peanut shell derived carbon cathode, using a sodium ion conducting gel polymer as electrolyte, achieving high-energy-high-power characteristics in solid state. Energy densities can reach 111.2 Wh kg(-1) at power density of 800 W kg(-1), and 33.2 Wh kg(-1) at power density of 11200 W kg(-1), which are among the best reported state-of-the-art NICs. The designed device also exhibits long-term cycling stability over 3000 cycles with capacity retention ∼86%. Furthermore, we demonstrate the assembly of a highly flexible quasi-solid-state NIC and it shows no obvious capacity loss under different bending conditions.

Stabilization of a supersaturated solution of mefenamic acid from a solid dispersion with EUDRAGIT(®) EPO.

PubMed

Kojima, Taro; Higashi, Kenjirou; Suzuki, Toyofumi; Tomono, Kazuo; Moribe, Kunikazu; Yamamoto, Keiji

2012-10-01

The stabilization mechanism of a supersaturated solution of mefenamic acid (MFA) from a solid dispersion with EUDRAGIT(®) EPO (EPO) was investigated. The solid dispersions were prepared by cryogenic grinding method. Powder X-ray diffractometry, in vitro dissolution test, in vivo oral absorption study, infrared spectroscopy, and solid- and solution-state NMR spectroscopies were used to characterize the solid dispersions. Dissolution tests in acetate buffer (pH 5.5) revealed that solid dispersion showed > 200-fold higher concentration of MFA. Supersaturated solution was stable over 1 month and exhibited improved oral bioavailability of MFA in rats, with a 7.8-fold higher area under the plasma concentration-versus-time curve. Solid-state (1)H spin-lattice relaxation time (T(1)) measurement showed that MFA was almost monomolecularly dispersed in the EPO polymer matrix. Intermolecular interaction between MFA and EPO was indicated by solid-state infrared and (13)C-T(1) measurements. Solution-state (1)H-NMR measurement demonstrated that MFA existed in monomolecular state in supersaturated solution. (1)H-T(1) and difference nuclear Overhauser effect measurements indicated that cross relaxation occurred between MFA and EPO due to the small distance between them. The formation and high stability of the supersaturated solution were attributable to the specifically formed intermolecular interactions between MFA and EPO.

Alternative polymer separation technology by centrifugal force in a melted state.

PubMed

Dobrovszky, Károly; Ronkay, Ferenc

2014-11-01

In order to upgrade polymer waste during recycling, separation should take place at high purity. The present research was aimed to develop a novel, alternative separation opportunity, where the polymer fractions were separated by centrifugal force in melted state. The efficiency of the constructed separation equipment was verified by two immiscible plastics (polyethylene terephthalate, PET; low density polyethylene, LDPE), which have a high difference of density, and of which large quantities can also be found in the municipal solid waste. The results show that the developed equipment is suitable not only for separating dry blended mixtures of PET/LDPE into pure components again, but also for separating prefabricated polymer blends. By this process it becomes possible to recover pure polymer substances from multi-component products during the recycling process. The adequacy of results was verified by differential scanning calorimetry (DSC) measurement as well as optical microscopy and Raman spectroscopy. Copyright © 2014 Elsevier Ltd. All rights reserved.

Self-assembled hybrid polymer-TiO2 nanotube array heterojunction solar cells.

PubMed

Shankar, Karthik; Mor, Gopal K; Prakasam, Haripriya E; Varghese, Oomman K; Grimes, Craig A

2007-11-20

Films comprised of 4 microm long titanium dioxide nanotube arrays were fabricated by anodizing Ti foils in an ethylene glycol based electrolyte. A carboxylated polythiophene derivative was self-assembled onto the TiO2 nanotube arrays by immersing them in a solution of the polymer. The binding sites of the carboxylate moiety along the polymer chain provide multiple anchoring sites to the substrate, making for a stable rugged film. Backside illuminated liquid junction solar cells based on TiO2 nanotube films sensitized by the self-assembled polymeric layer showed a short-circuit current density of 5.5 mA cm-2, a 0.7 V open circuit potential, and a 0.55 fill factor yielding power conversion efficiencies of 2.1% under AM 1.5 sun. A backside illuminated single heterojunction solid state solar cell using the same self-assembled polymer was demonstrated and yielded a photocurrent density as high as 2.0 mA cm-2. When a double heterojunction was formed by infiltrating a blend of poly(3-hexylthiophene) (P3HT) and C60-methanofullerene into the self-assembled polymer coated nanotube arrays, a photocurrent as high as 6.5 mA cm-2 was obtained under AM 1.5 sun with a corresponding efficiency of 1%. The photocurrent action spectra showed a maximum incident photon-to-electron conversion efficiency (IPCE) of 53% for the liquid junction cells and 25% for the single heterojunction solid state solar cells.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends

DOEpatents

Skotheim, T.

A polymer blend is disclosed of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Cytocompatibility and response of osteoblastic-like cells to starch-based polymers: effect of several additives and processing conditions.

PubMed

Gomes, M E; Reis, R L; Cunha, A M; Blitterswijk, C A; de Bruijn, J D

2001-07-01

This work reports on the biocompatibility evaluation of new biodegradable starch-based polymers that are under consideration for use in orthopaedic temporary applications and as tissue engineering scaffolds. It has been shown in previous works that by using these polymers it is both possible to produce polymer/hydroxyapatite (HA) composites (with or without the use of coupling agents) with mechanical properties matching those of the human bone, and to obtain 3D structures generated by solid blowing agents, that are suitable for tissue engineering applications. This study was focused on establishing the influence of several additives (ceramic fillers, blowing agents and coupling agents) and processing methods/conditions on the biocompatibility of the materials described above. The cytotoxicity of the materials was evaluated using cell culture methods, according to ISO/EN 109935 guidelines. A cell suspension of human osteosarcoma cells (HOS) was also seeded on a blend of corn starch with ethylene vinyl alcohol (SEVA-C) and on SEVA-C/HA composites, in order to have a preliminary indication on cell adhesion and proliferation on the materials surface. In general, the obtained results show that all the different materials based on SEVA-C, (which are being investigated for use in several biomedical applications), as well as all the additives (including the novel coupling agents) and different processing methods required to obtain the different properties/products, can be used without inducing a cytotoxic behaviour to the developed biomaterials.

Fluorescent Polystyrene Microbeads as Invisible Security Ink and Optical Vapor Sensor for 4-Nitrotoluene.

PubMed

Sonawane, Swapnil L; Asha, S K

2016-04-27

Color-tunable solid-state emitting polystyrene (PS) microbeads were developed by dispersion polymerization, which showed excellent fluorescent security ink characteristics along with sensitive detection of vapors of nitro aromatics like 4-nitro toluene (4-NT). The fluorophores pyrene and perylenebisimide were incorporated into the PS backbone as acrylate monomer and acrylate cross-linker, respectively. Solid state quantum yields of 94 and 20% were observed for the pyrene and perylenebisimide, respectively, in the PS/Py and PS/PBI polymers. The morphology and solid state fluorescence was measured by SEM, fluorescence microscopy, and absorbance and fluorescence spectroscopy techniques. The ethanol dispersion of the polymer could be used directly as a fluorescent security "invisible" ink, which became visible only under ultraviolet light. The color of the ink could be tuned depending on the amounts of the pyrene and perylenebisimide incorporated with blue and orange-green for pyrene alone or perylenebisimide alone beads respectively and various shades in between including pure white for beads incorporating both the fluorophores. More than 80% quenching of pyrene emission was observed upon exposure of the polymer in the form of powder or as spin-coated films to the vapors of 4-NT while the emission of perylenebisimide was unaffected. The limit of detection was estimated at 10(-5) moles (2.7 ppm) of 4-NT vapors. The ease of synthesis of the material along with its invisible ink characteristics and nitro aromatic vapor detection opens up new opportunities for exploring the application of these PS-based materials as optical sensors and fluorescent ink for security purposes.

Enhanced Electrical Conductivity of Molecularly p-Doped Poly(3-hexylthiophene) through Understanding the Correlation with Solid-State Order

PubMed Central

2017-01-01

Molecular p-doping of the conjugated polymer poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) is a widely studied model system. Underlying structure–property relationships are poorly understood because processing and doping are often carried out simultaneously. Here, we exploit doping from the vapor phase, which allows us to disentangle the influence of processing and doping. Through this approach, we are able to establish how the electrical conductivity varies with regard to a series of predefined structural parameters. We demonstrate that improving the degree of solid-state order, which we control through the choice of processing solvent and regioregularity, strongly increases the electrical conductivity. As a result, we achieve a value of up to 12.7 S cm–1 for P3HT:F4TCNQ. We determine the F4TCNQ anion concentration and find that the number of (bound + mobile) charge carriers of about 10–4 mol cm–3 is not influenced by the degree of solid-state order. Thus, the observed increase in electrical conductivity by almost 2 orders of magnitude can be attributed to an increase in charge-carrier mobility to more than 10–1 cm2 V–1 s–1. Surprisingly, in contrast to charge transport in undoped P3HT, we find that the molecular weight of the polymer does not strongly influence the electrical conductivity, which highlights the need for studies that elucidate structure–property relationships of strongly doped conjugated polymers. PMID:29093606

Hyperbranched polyglycerols at the biointerface

NASA Astrophysics Data System (ADS)

Moore, Eli; Thissen, Helmut; Voelcker, Nicolas H.

2013-08-01

The control over biointerfacial interactions is the key to a broad range of biomedical applications, ranging from implantable devices to drug delivery and nanomedicine. In many of these applications, coatings are required that reduce or prevent non-specific interactions with the biological environment, while at the same time presenting specific bioactive signals. Whilst surface coatings based on polymers such as poly(ethylene glycol) (PEG) have been used successfully, many limitations persist in regard to the biocompatibility, stability and functionality of state-of-the-art polymer coatings. Most of these limitations are related to the fact that, typically, linear polymers are used with associated limited chemical functionality. Here, we examine the development of hyperbranched polyglycerols (HPGs) as promising candidates for the replacement of traditional linear polymers, such as the chemically analogous PEG, for the control of biointerfacial interactions. HPGs are highly branched globular molecules that exhibit a high valency, allow easy access to a variety of functionalities and can present biologically active signals. In this review, a comprehensive overview is provided with respect to the history, synthetic strategies, modifications and applications of HPGs.

Dynamics of Surface Reorganization of Poly(methyl methacrylate) in Contact with Water

NASA Astrophysics Data System (ADS)

Horinouchi, Ayanobu; Atarashi, Hironori; Fujii, Yoshihisa; Tanaka, Keiji

2013-03-01

New tools for tailor-made diagnostics, such as DNA arrays and tips for micro-total-analysis systems, are generally made from polymers. In these applications, the polymer surface is in contact with a water phase. However, despite the importance of detailed knowledge of the fundamental interactions of polymer interfaces with liquids, such studies are very limited. As an initial benchmark for designing and constructing specialized biomedical surfaces containing polymer, aggregation states and dynamics of chains at the water interface should be systematically examined. We here apply time-resolved contact angle measurement to study the dynamics of the surface reorganization of poly(methyl methacrylate) (PMMA) in contact with water. By doing the measurements at various temperatures, it is possible to discuss the surface dynamics of PMMA based on the apparent activation energy. Also, sum-frequency generation spectroscopy revealed that the surface reorganization involves the conformational changes in the main chain part as well as the side chains. Hence, the dynamics observed here may reflect the segmental motion at the outermost region of the PMMA film, in which water plays as a plasticizer.

In vitro characterization of a novel polymeric system for preparation of amorphous solid drug dispersions.

PubMed

Mahmoudi, Zahra N; Upadhye, Sampada B; Ferrizzi, David; Rajabi-Siahboomi, Ali R

2014-07-01

Preparation of amorphous solid dispersions using polymers is a commonly used formulation strategy for enhancing the solubility of poorly water-soluble drugs. However, often a single polymer may not bring about a significant enhancement in solubility or amorphous stability of a poorly water-soluble drug. This study describes application of a unique and novel binary polymeric blend in preparation of solid dispersions. The objective of this study was to investigate amorphous solid dispersions of glipizide, a BCS class II model drug, in a binary polymeric system of polyvinyl acetate phthalate (PVAP) and hypromellose (hydroxypropyl methylcellulose, HPMC). The solid dispersions were prepared using two different solvent methods: rotary evaporation (rotavap) and fluid bed drug layering on sugar spheres. The performance and physical stability of the dispersions were evaluated with non-sink dissolution testing, powder X-ray diffraction (PXRD), and modulated differential scanning calorimetry (mDSC). PXRD analysis demonstrated an amorphous state for glipizide, and mDSC showed no evidence of phase separation. Non-sink dissolution testing in pH 7.5 phosphate buffer indicated more than twofold increase in apparent solubility of the drug with PVAP-HPMC system. The glipizide solid dispersions demonstrated a high glass transition temperature (Tg) and acceptable chemical and physical stability during the stability period irrespective of the manufacturing process. In conclusion, the polymeric blend of PVAP-HPMC offers a unique formulation approach for developing amorphous solid dispersions with the flexibility towards the use of these polymers in different ratios and combined quantities depending on drug properties.

A Quasi-Solid-State Li-Ion Capacitor Based on Porous TiO2 Hollow Microspheres Wrapped with Graphene Nanosheets.

PubMed

Wang, Faxing; Wang, Chun; Zhao, Yujuan; Liu, Zaichun; Chang, Zheng; Fu, Lijun; Zhu, Yusong; Wu, Yuping; Zhao, Dongyuan

2016-12-01

The quasi-solid-state Li-ion capacitor is demonstrated with graphene nanosheets prepared by an electrochemical exfoliation as the positive electrode and the porous TiO 2 hollow microspheres wrapped with the same graphene nanosheets as the negative electrode, using a Li-ion conducting gel polymer electrolyte. This device may be the key to bridging the gap between conventional lithium-ion batteries and supercapacitors, meanwhile meeting the safety demands of electronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion-Selective Electrodes.

ERIC Educational Resources Information Center

Arnold, Mark A.; Meyerhoff, Mark E.

1984-01-01

Literature on ion-selective electrodes (ISEs) is reviewed in seven sections: books, conferences, reviews; potentiometric membrane electrodes; glass and solid-state membrane electrodes; liquid and polymer membrane ISEs; coated wire electrodes, ion-selective field effect transistors, and microelectrodes; gas sensors and selective bioelectrode…

Recent advances in degradable lactide-based shape-memory polymers.

PubMed

Balk, Maria; Behl, Marc; Wischke, Christian; Zotzmann, Jörg; Lendlein, Andreas

2016-12-15

Biodegradable polymers are versatile polymeric materials that have a high potential in biomedical applications avoiding subsequent surgeries to remove, for example, an implanted device. In the past decade, significant advances have been achieved with poly(lactide acid) (PLA)-based materials, as they can be equipped with an additional functionality, that is, a shape-memory effect (SME). Shape-memory polymers (SMPs) can switch their shape in a predefined manner upon application of a specific external stimulus. Accordingly, SMPs have a high potential for applications ranging from electronic engineering, textiles, aerospace, and energy to biomedical and drug delivery fields based on the perspectives of new capabilities arising with such materials in biomedicine. This study summarizes the progress in SMPs with a particular focus on PLA, illustrates the design of suitable homo- and copolymer structures as well as the link between the (co)polymer structure and switching functionality, and describes recent advantages in the implementation of novel switching phenomena into SMP technology. Copyright © 2016 Elsevier B.V. All rights reserved.

Transcap: A new integrated hybrid supercapacitor and electrolyte-gated transistor device (Presentation Recording)

NASA Astrophysics Data System (ADS)

Santato, Clara

2015-10-01

The boom in multifunctional, flexible, and portable electronics and the increasing need of low-energy cost and autonomy for applications ranging from wireless sensor networks for smart environments to biomedical applications are triggering research efforts towards the development of self-powered sustainable electronic devices. Within this context, the coupling of electronic devices (e.g. sensors, transistors) with small size energy storage systems (e.g. micro-batteries or micro-supercapacitors) is actively pursued. Micro-electrochemical supercapacitors are attracting much attention in electronics for their capability of delivering short power pulses with high stability over repeated charge/discharge cycling. For their high specific pseudocapacitance, electronically conducting polymers are well known as positive materials for hybrid supercapacitors featuring high surface carbon negative electrodes. The processability of both polymer and carbon is of great relevance for the development of flexible miniaturised devices. Electronically conducting polymers are even well known to feature an electronic conductivity that depends on their oxidation (p-doped state) and that it is modulated by the polymer potential. This property and the related pseudocapacitive response make polymer very attracting channel materials for electrolyte-gated (EG) transistors. Here, we propose a novel concept of "Trans-capacitor", an integrated device that exhibits the storage properties of a polymer/carbon hybrid supercapacitor and the low-voltage operation of an electrolyte-gated transistor.

Extreme Activity of Drug Nanocrystals Coated with A Layer of Non-Covalent Polymers from Self-Assembled Boric Acid

NASA Astrophysics Data System (ADS)

Zhan, Honglei; Liang, Jun F.

2016-12-01

Non-covalent polymers have remarkable advantages over synthetic polymers for wide biomedical applications. In this study, non-covalent polymers from self-assembled boric acid were used as the capping reagent to replace synthetic polymers in drug crystallization. Under acidic pH, boric acid self-assembled on the surface of drug nanocrystals to form polymers with network-like structures held together by hydrogen bonds. Coating driven by boric acid self-assembly had negligible effects on drug crystallinity and structure but resulted in drug nanocrystals with excellent dispersion properties that aided in the formation of a more stable suspension. Boric acid coating improved drug stability dramatically by preventing drug molecules from undergoing water hydrolysis in a neutral environment. More importantly, the specific reactivity of orthoboric groups to diols in cell glycocalyx facilitated a rapid cross-membrane translocation of drug nanocrystals, leading to efficient intracellular drug delivery, especially on cancer cells with highly expressed sialic acids. Boric acid coated nanocrystals of camptothecin, an anticancer drug with poor aqueous solubility and stability, demonstrated extreme cytotoxic activity (IC50 < 5.0 μg/mL) to cancer cells compared to synthetic polymer coated CPT nanocrystals and free CPT. Surface coating using non-covalent polymers from self-assembled boric acid will have wide biomedical applications especially in biomaterials and drug delivery field.

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

PubMed

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

2017-01-01

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. © 2016 Nordic Association for the Publication of BCPT (former Nordic Pharmacological Society).

Extreme Activity of Drug Nanocrystals Coated with A Layer of Non-Covalent Polymers from Self-Assembled Boric Acid.

PubMed

Zhan, Honglei; Liang, Jun F

2016-12-09

Non-covalent polymers have remarkable advantages over synthetic polymers for wide biomedical applications. In this study, non-covalent polymers from self-assembled boric acid were used as the capping reagent to replace synthetic polymers in drug crystallization. Under acidic pH, boric acid self-assembled on the surface of drug nanocrystals to form polymers with network-like structures held together by hydrogen bonds. Coating driven by boric acid self-assembly had negligible effects on drug crystallinity and structure but resulted in drug nanocrystals with excellent dispersion properties that aided in the formation of a more stable suspension. Boric acid coating improved drug stability dramatically by preventing drug molecules from undergoing water hydrolysis in a neutral environment. More importantly, the specific reactivity of orthoboric groups to diols in cell glycocalyx facilitated a rapid cross-membrane translocation of drug nanocrystals, leading to efficient intracellular drug delivery, especially on cancer cells with highly expressed sialic acids. Boric acid coated nanocrystals of camptothecin, an anticancer drug with poor aqueous solubility and stability, demonstrated extreme cytotoxic activity (IC 50  < 5.0 μg/mL) to cancer cells compared to synthetic polymer coated CPT nanocrystals and free CPT. Surface coating using non-covalent polymers from self-assembled boric acid will have wide biomedical applications especially in biomaterials and drug delivery field.

Extreme Activity of Drug Nanocrystals Coated with A Layer of Non-Covalent Polymers from Self-Assembled Boric Acid

PubMed Central

Zhan, Honglei; Liang, Jun F.

2016-01-01

Non-covalent polymers have remarkable advantages over synthetic polymers for wide biomedical applications. In this study, non-covalent polymers from self-assembled boric acid were used as the capping reagent to replace synthetic polymers in drug crystallization. Under acidic pH, boric acid self-assembled on the surface of drug nanocrystals to form polymers with network-like structures held together by hydrogen bonds. Coating driven by boric acid self-assembly had negligible effects on drug crystallinity and structure but resulted in drug nanocrystals with excellent dispersion properties that aided in the formation of a more stable suspension. Boric acid coating improved drug stability dramatically by preventing drug molecules from undergoing water hydrolysis in a neutral environment. More importantly, the specific reactivity of orthoboric groups to diols in cell glycocalyx facilitated a rapid cross-membrane translocation of drug nanocrystals, leading to efficient intracellular drug delivery, especially on cancer cells with highly expressed sialic acids. Boric acid coated nanocrystals of camptothecin, an anticancer drug with poor aqueous solubility and stability, demonstrated extreme cytotoxic activity (IC50 < 5.0 μg/mL) to cancer cells compared to synthetic polymer coated CPT nanocrystals and free CPT. Surface coating using non-covalent polymers from self-assembled boric acid will have wide biomedical applications especially in biomaterials and drug delivery field. PMID:27934922

Structuring of Hydrogels across Multiple Length Scales for Biomedical Applications.

PubMed

Cooke, Megan E; Jones, Simon W; Ter Horst, Britt; Moiemen, Naiem; Snow, Martyn; Chouhan, Gurpreet; Hill, Lisa J; Esmaeli, Maryam; Moakes, Richard J A; Holton, James; Nandra, Rajpal; Williams, Richard L; Smith, Alan M; Grover, Liam M

2018-04-01

The development of new materials for clinical use is limited by an onerous regulatory framework, which means that taking a completely new material into the clinic can make translation economically unfeasible. One way to get around this issue is to structure materials that are already approved by the regulator, such that they exhibit very distinct physical properties and can be used in a broader range of clinical applications. Here, the focus is on the structuring of soft materials at multiple length scales by modifying processing conditions. By applying shear to newly forming materials, it is possible to trigger molecular reorganization of polymer chains, such that they aggregate to form particles and ribbon-like structures. These structures then weakly interact at zero shear forming a solid-like material. The resulting self-healing network is of particular use for a range of different biomedical applications. How these materials are used to allow the delivery of therapeutic entities (cells and proteins) and as a support for additive layer manufacturing of larger-scale tissue constructs is discussed. This technology enables the development of a range of novel materials and structures for tissue augmentation and regeneration. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends

DOEpatents

Skotheim, Terje

1984-01-01

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Variations of structures and solid-state conductivity of isomeric silver(I) coordination polymers having linear and V-shaped thiophene-centered ditriazole ligands

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

Hu, Bin; School of Environmental and Chemical Engineering, Nanchang Hangkong University, Nanchang, 330063; Geng, Jiao

2014-07-01

A pair of new linear and V-shaped acceptor–donor–acceptor (A−D−A) thiophene-centered ditriazole structural isomers, i.e., 2,5-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 1}) and 3,4-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 2}), has been synthesized and characterized. They are used as μ{sub 2}-bridging ligands to prepare a pair of silver(I) coordination polymers formulated as [Ag(L{sup 1})(NO{sub 3})]{sub n} (1) and [Ag(L{sup 2})(NO{sub 3})]{sub n} (2), which are also structural isomers at the supramolecular level. X-ray single-crystal diffraction analyses for 1 and 2 reveal that they exhibit the same one-dimensional (1D) coordination polymers but different structural architectures because of the distinguishable shape and configuration of isomeric ligands (L{sup 1} and L{sup 2})more » and the alterations of the coordination numbers. More interestingly, compared with the free ligands, 1D silver(I) polymeric isomers 1 and 2 show significant enhancement of solid-state conductivity to different extents (1.42×10{sup 4} and 2.17×10{sup 3} times), where 6.96 times' enhancement of solid-state conductivity from 1 to 2 has been observed. The formation of Ag–N coordinative bonds and the configurational discrepancy of L{sup 1} and L{sup 2} are believed to play important roles in facilitating the electron transport between molecules, which can also be supported by Density Function Theory calculations of their band gaps. - Graphical abstract: A pair of linear and V-shaped isomeric thiophene-centered ditriazole ligands (L{sup 1}) and L{sup 2} are used to prepare a pair of silver(I) polymeric isomers (1 and 2), where significant enhancement of solid-state conductivity to different extents are observed originating from the distinguishable shape and configuration of isomeric ligands. - Highlights: • A pair of linear and V-shaped thiophene-centered ditriazole structural isomers is prepared. • They are used as µ{sub 2}-bridging ligands to prepare a pair of silver(I) polymeric isomers. • Significant enhancement of solid-state conductivity is observed for each polymeric isomer.« less

Microwave generated solid dispersions containing Ibuprofen.

PubMed

Moneghini, Mariarosa; Bellich, Barbara; Baxa, Pietro; Princivalle, Francesco

2008-09-01

The purpose of this study was to apply the attractive technique of the microwaves irradiation (MW) for the preparation of solvent-free solid dispersions (SD). In particular, the microwave technology has been considered in order to prepare an enhanced release dosage form for the poorly soluble drug Ibuprofen (IBU), employing PVP/VA 60/40 (PVP/VA 64) and hydroxypropyl-beta-cyclodextrin (HP-beta-CD) as hydrophilic carriers. Their physico-chemical characteristics and dissolution properties were compared to the corresponding physical mixtures and the drug alone. The results of physico-chemical characterization attested a correspondence of the solid state of the drug before and after irradiation treatment and that an amorphous form of the drug was obtained. This result, together with the presence of the hydrophilic polymers determined a remarkable enhancement of the in vitro dissolution rate of the drug suggesting that the microwave technique could be considered as a new and interesting method to prepare drug-polymer systems.

Biomedical research of novel biodegradable copoly(amino acid)s based on 6-aminocaproic acid and L-proline.

PubMed

Zhang, Weipeng; Shao, Jianmin

2010-08-01

The biomedical properties of novel biodegradable copoly(amino acid)s based on 6-aminocaproic acid and L-proline were analyzed in this article. The cytotoxicity of the copolymer films was tested in vitro using human embryonic kidney (HEK) 293 cells. The cell proliferation, cell cycle, cell apoptosis, and hemolysis of the polymers were also investigated. No significant cytotoxic response was detected statistically by cytotoxicity assay, and the results of cell apoptosis and cell cycle showed that there were no statistically significant differences in them. Generally, the cells spread and grew well on polymer film. Meanwhile, the extent of hemolysis on the polymers was acceptable. Evaluation of cytotoxicity by cell cycle and apoptosis as a supplementary assay is correspondingly discussed in this article. (c) 2010 Wiley Periodicals, Inc.

Solid electrolytes

DOEpatents

Abraham, Kuzhikalail M.; Alamgir, Mohamed

1993-06-15

This invention pertains to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized (encapsulated) in a solid organic polymer matrix. In particular, this invention relates to solid polymer electrolytes derived by immobilizing complexes (solvates) formed between a Li salt such as LiAsF.sub.6, LiCF.sub.3 SO.sub.3 or LiClO.sub.4 and a mixture of aprotic organic solvents having high dielectric constants such as ethylene carbonate (EC) (dielectric constant=89.6) and propylene carbonate (PC) (dielectric constant=64.4) in a polymer matrix such as polyacrylonitrile, poly(tetraethylene glycol diacrylate), or poly(vinyl pyrrolidinone).

Comparison of spray drying, electroblowing and electrospinning for preparation of Eudragit E and itraconazole solid dispersions.

PubMed

Sóti, Péter Lajos; Bocz, Katalin; Pataki, Hajnalka; Eke, Zsuzsanna; Farkas, Attila; Verreck, Geert; Kiss, Éva; Fekete, Pál; Vigh, Tamás; Wagner, István; Nagy, Zsombor K; Marosi, György

2015-10-15

Three solvent based methods: spray drying (SD), electrospinning (ES) and air-assisted electrospinning (electroblowing; EB) were used to prepare solid dispersions of itraconazole and Eudragit E. Samples with the same API/polymer ratios were prepared in order to make the three technologies comparable. The structure and morphology of solid dispersions were identified by scanning electron microscopy and solid phase analytical methods such as, X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC) and Raman chemical mapping. Moreover, the residual organic solvents of the solid products were determined by static headspace-gas chromatography/mass spectroscopy measurements and the wettability of samples was characterized by contact angle measurement. The pharmaceutical performance of the three dispersion type, evaluated by dissolution tests, proved to be very similar. According to XRPD and DSC analyses, made after the production, all the solid dispersions were free of any API crystal clusters but about 10 wt% drug crystallinity was observed after three months of storage in the case of the SD samples in contrast to the samples produced by ES and EB in which the polymer matrix preserved the API in amorphous state. Copyright © 2015 Elsevier B.V. All rights reserved.

A novel gel based on an ionic complex from a dendronized polymer and ciprofloxacin: Evaluation of its use for controlled topical drug release.

PubMed

García, Mónica C; Cuggino, Julio C; Rosset, Clarisa I; Páez, Paulina L; Strumia, Miriam C; Manzo, Ruben H; Alovero, Fabiana L; Alvarez Igarzabal, Cecilia I; Jimenez-Kairuz, Alvaro F

2016-12-01

The development and characterization of a novel, gel-type material based on a dendronized polymer (DP) loaded with ciprofloxacin (CIP), and the evaluation of its possible use for controlled drug release, are presented in this work. DP showed biocompatible and non-toxic behaviors in cultured cells, both of which are considered optimal properties for the design of a final material for biomedical applications. These results were encouraging for the use of the polymer loaded with CIP (as a drug model), under gel form, in the development of a new controlled-release system to be evaluated for topical administration. First, DP-CIP ionic complexes were obtained by an acid-base reaction using the high density of carboxylic acid groups of the DP and the amine groups of the CIP. The complexes obtained in the solid state were broadly characterized using FTIR spectroscopy, XRP diffraction, DSC-TG analysis and optical microscopy techniques. Gels based on the DP-CIP complexes were easily prepared and presented excellent mechanical behaviors. In addition, optimal properties for application on mucosal membranes and skin were achieved due to their high biocompatibility and acute skin non-irritation. Slow and sustained release of CIP toward simulated physiological fluids was observed in the assays (in vitro), attributed to ion exchange phenomenon and to the drug reservoir effect. An in vitro bacterial growth inhibition assay showed significant CIP activity, corresponding to 38 and 58% of that exhibited by a CIP hydrochloride solution at similar CIP concentrations, against Staphylococcus aureus and Pseudomonas aeruginosa, respectively. However, CIP delivery was appropriate, both in terms of magnitude and velocity to allow for a bactericidal effect. In conclusion, the final product showed promising behavior, which could be exploited for the treatment of topical and mucosal opportunistic infections in human or veterinary applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Detection of ethanol in alcoholic beverages or vapor phase using fluorescent molecules embedded in a nanofibrous polymer.

PubMed

Akamatsu, Masaaki; Mori, Taizo; Okamoto, Ken; Komatsu, Hirokazu; Kumagai, Ken; Shiratori, Seimei; Yamamura, Masaki; Nabeshima, Tatsuya; Sakai, Hideki; Abe, Masahiko; Hill, Jonathan P; Ariga, Katsuhiko

2015-03-25

An alcohol sensor was developed using the solid-state fluorescence emission of terphenyl-ol (TPhOH) derivatives. Admixtures of TPhOH and sodium carbonate exhibited bright sky-blue fluorescence in the solid state upon addition of small quantities of ethanol. A series of terphenol derivatives was synthesized, and the effects of solvent polarities and the structures of these π-conjugated systems on their fluorescence were systematically investigated by using fluorescence spectroscopy. In particular, π-extended TPhOHs and TPhOHs containing electron-withdrawing groups exhibited significant solvatochromism, and fluorescence colors varied from blue to red. Detection of ethanol contents in alcohol beverages (detection limit ∼ 5 v/v %) was demonstrated using different TPhOHs revealing the effect of molecular structure on sensing properties. Ethanol contents in alcoholic beverages could be estimated from the intensity of the fluorescence elicited from the TPhOHs. Moreover, when terphenol and Na2CO3 were combined with a water-absorbent polymer, ethanol could be detected at lower concentrations. Detection of ethanol vapor (8 v/v % in air) was also accomplished using a nanofibrous polymer scaffold as the immobilized sensing film.

Free-Standing Conducting Polymer Films for High-Performance Energy Devices.

PubMed

Li, Zaifang; Ma, Guoqiang; Ge, Ru; Qin, Fei; Dong, Xinyun; Meng, Wei; Liu, Tiefeng; Tong, Jinhui; Jiang, Fangyuan; Zhou, Yifeng; Li, Ke; Min, Xue; Huo, Kaifu; Zhou, Yinhua

2016-01-18

Thick, uniform, easily processed, highly conductive polymer films are desirable as electrodes for solar cells as well as polymer capacitors. Here, a novel scalable strategy is developed to prepare highly conductive thick poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (HCT-PEDOT:PSS) films with layered structure that display a conductivity of 1400 S cm(-1) and a low sheet resistance of 0.59 ohm sq(-1). Organic solar cells with laminated HCT-PEDOT:PSS exhibit a performance comparable to the reference devices with vacuum-deposited Ag top electrodes. More importantly, the HCT-PEDOT:PSS film delivers a specific capacitance of 120 F g(-1) at a current density of 0.4 A g(-1). All-solid-state flexible symmetric supercapacitors with the HCT-PEDOT:PSS films display a high volumetric energy density of 6.80 mWh cm(-3) at a power density of 100 mW cm(-3) and 3.15 mWh cm(-3) at a very high power density of 16160 mW cm(-3) that outperforms previous reported solid-state supercapacitors based on PEDOT materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Strong Photo-Amplification Effects in Flexible Organic Capacitors with Small Molecular Solid-State Electrolyte Layers Sandwiched between Photo-Sensitive Conjugated Polymer Nanolayers

PubMed Central

Lee, Hyena; Kim, Jungnam; Kim, Hwajeong; Kim, Youngkyoo

2016-01-01

We demonstrate strong photo-amplification effects in flexible organic capacitors which consist of small molecular solid-state electrolyte layers sandwiched between light-sensitive conjugated polymer nanolayers. The small molecular electrolyte layers were prepared from aqueous solutions of tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (ALQSA3), while poly(3-hexylthiophene) (P3HT) was employed as the light-sensitive polymer nanolayer that is spin-coated on the indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film substrates. The resulting capacitors feature a multilayer device structure of PET/ITO/P3HT/ALQSA3/P3HT/ITO/PET, which were mechanically robust due to good adhesion between the ALQSA3 layers and the P3HT nanolayers. Results showed that the specific capacitance was increased by ca. 3-fold when a white light was illuminated to the flexible organic multilayer capacitors. In particular, the capacity of charge storage was remarkably (ca. 250-fold) enhanced by a white light illumination in the potentiostatic charge/discharge operation, and the photo-amplification functions were well maintained even after bending for 300 times at a bending angle of 180o. PMID:26846891

Strong Photo-Amplification Effects in Flexible Organic Capacitors with Small Molecular Solid-State Electrolyte Layers Sandwiched between Photo-Sensitive Conjugated Polymer Nanolayers.

PubMed

Lee, Hyena; Kim, Jungnam; Kim, Hwajeong; Kim, Youngkyoo

2016-02-05

We demonstrate strong photo-amplification effects in flexible organic capacitors which consist of small molecular solid-state electrolyte layers sandwiched between light-sensitive conjugated polymer nanolayers. The small molecular electrolyte layers were prepared from aqueous solutions of tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (ALQSA3), while poly(3-hexylthiophene) (P3HT) was employed as the light-sensitive polymer nanolayer that is spin-coated on the indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film substrates. The resulting capacitors feature a multilayer device structure of PET/ITO/P3HT/ALQSA3/P3HT/ITO/PET, which were mechanically robust due to good adhesion between the ALQSA3 layers and the P3HT nanolayers. Results showed that the specific capacitance was increased by ca. 3-fold when a white light was illuminated to the flexible organic multilayer capacitors. In particular, the capacity of charge storage was remarkably (ca. 250-fold) enhanced by a white light illumination in the potentiostatic charge/discharge operation, and the photo-amplification functions were well maintained even after bending for 300 times at a bending angle of 180(°).

Oxidation reaction of polyether-based material and its suppression in lithium rechargeable battery using 4 V class cathode, LiNi1/3Mn1/3Co1/3O2.

PubMed

Kobayashi, Takeshi; Kobayashi, Yo; Tabuchi, Masato; Shono, Kumi; Ohno, Yasutaka; Mita, Yuichi; Miyashiro, Hajime

2013-12-11

The all solid-state lithium battery with polyether-based solid polymer electrolyte (SPE) is regarded as one of next-generation lithium batteries, and has potential for sufficient safety because of the flammable-electrolyte-free system. It has been believed that polyether-based SPE is oxidized at the polymer/electrode interface with 4 V class cathodes. Therefore, it has been used for electric devices such as organic transistor, and lithium battery under 3 V. We estimated decomposition reaction of polyether used as SPE of all solid-state lithium battery. We first identified the decomposed parts of polyether-based SPE and the conservation of most main chain framework, considering the results of SPE analysis after long cycle operations. The oxidation reaction was found to occur slightly at the ether bond in the main chain with the branched side chain. Moreover, we resolved the issue by introducing a self-sacrificing buffer layer at the interface. The introduction of sodium carboxymethyl cellulose (CMC) to the 4 V class cathode surface led to the suppression of SPE decomposition at the interface as a result of the preformation of a buffer layer from CMC, which was confirmed by the irreversible exothermic reaction during the first charge, using electrochemical calorimetry. The attained 1500 cycle operation is 1 order of magnitude longer than those of previously reported polymer systems, and compatible with those of reported commercial liquid systems. The above results indicate to proceed to an intensive research toward the realization of 4 V class "safe" lithium polymer batteries without flammable liquid electrolyte.

Use of Tween Polymer To Enhance the Compatibility of the Li/Electrolyte Interface for the High-Performance and High-Safety Quasi-Solid-State Lithium-Sulfur Battery.

PubMed

Liu, Jie; Qian, Tao; Wang, Mengfan; Zhou, Jinqiu; Xu, Na; Yan, Chenglin

2018-06-07

Lithium metal batteries have attracted increasing attention recently due to their particular advantages in energy density. However, as for their practical application, the development of solid-state lithium metal batteries is restricted because of the poor Li/electrolyte interface, low Li-ion conductivity, and irregular growth of Li dendrites. To address the above issues, we herein report a high Li-ion conductivity and compatible polymeric interfacial layer by grafting tween-20 on active lithium metal. Sequential oxyethylene groups in tween-grafted Li (TG-Li) improve the ion conductivity and the compatibility of the Li/electrolyte interface, which enables low overpotentials and stable performance over 1000 cycles. Consequently, the poly(ethylene oxide)-based solid-state lithium-sulfur battery with TG-Li exhibits a high reversible capacity of 1051.2 mA h g -1 at 0.2 C (1 C = 1675 mA h g -1 ) and excellent stability for 500 cycles at 2 C. The decreasing concentration of the sulfur atom with increasing Ar + sputtering depth indicates that the polymer interfacial layer works well in suppressing polysulfide reduction to Li 2 S/Li 2 S 2 on the metallic Li surface even after long-term cycling.

A Self-Referenced Optical Intensity Sensor Network Using POFBGs for Biomedical Applications

PubMed Central

Moraleda, Alberto Tapetado; Montero, David Sánchez; Webb, David J.; García, Carmen Vázquez

2014-01-01

This work bridges the gap between the remote interrogation of multiple optical sensors and the advantages of using inherently biocompatible low-cost polymer optical fiber (POF)-based photonic sensing. A novel hybrid sensor network combining both silica fiber Bragg gratings (FBG) and polymer FBGs (POFBG) is analyzed. The topology is compatible with WDM networks so multiple remote sensors can be addressed providing high scalability. A central monitoring unit with virtual data processing is implemented, which could be remotely located up to units of km away. The feasibility of the proposed solution for potential medical environments and biomedical applications is shown. PMID:25615736

A self-referenced optical intensity sensor network using POFBGs for biomedical applications.

PubMed

Tapetado Moraleda, Alberto; Sánchez Montero, David; Webb, David J; Vázquez García, Carmen

2014-12-12

This work bridges the gap between the remote interrogation of multiple optical sensors and the advantages of using inherently biocompatible low-cost polymer optical fiber (POF)-based photonic sensing. A novel hybrid sensor network combining both silica fiber Bragg gratings (FBG) and polymer FBGs (POFBG) is analyzed. The topology is compatible with WDM networks so multiple remote sensors can be addressed providing high scalability. A central monitoring unit with virtual data processing is implemented, which could be remotely located up to units of km away. The feasibility of the proposed solution for potential medical environments and biomedical applications is shown.

Lipid-polymer hybrid nanoparticle-mediated therapeutics delivery: advances and challenges.

PubMed

Bose, Rajendran J C; Ravikumar, Rramaswamy; Karuppagounder, Vengadeshprabu; Bennet, Devasier; Rangasamy, Sabarinathan; Thandavarayan, Rajarajan A

2017-08-01

With rapid advances in nanomedicine, lipid-polymer hybrid nanoparticles (LPHNPs) have emerged as promising nanocarriers for several biomedical applications, including therapeutics delivery and biomedical imaging. Significant research has been dedicated to biomimetic or targeting functionalization, as well as controlled and image-guided drug-release capabilities. Despite this research, the clinical translation of LPHNP-mediated therapeutics delivery has progressed incrementally. In this review, we discuss the recent advances in and challenges to the development and application of LPHNPs, present examples to demonstrate the advantages of LPHNPs in therapeutics delivery and imaging applications, and discuss the translational obstacles to LPHNP technology. Copyright © 2017. Published by Elsevier Ltd.

Study of Crystal Formation and Nitric Oxide (NO) Release Mechanism from S-Nitroso-N-acetylpenicillamine (SNAP)-Doped CarboSil Polymer Composites for Potential Antimicrobial Applications.

PubMed

Wo, Yaqi; Li, Zi; Colletta, Alessandro; Wu, Jianfeng; Xi, Chuanwu; Matzger, Adam J; Brisbois, Elizabeth J; Bartlett, Robert H; Meyerhoff, Mark E

2017-07-15

Stable and long-term nitric oxide (NO) releasing polymeric materials have many potential biomedical applications. Herein, we report the real-time observation of the crystallization process of the NO donor, S -nitroso- N -acetylpenicillamine (SNAP), within a thermoplastic silicone-polycarbonate-urethane biomedical polymer, CarboSil 20 80A. It is demonstrated that the NO release rate from this composite material is directly correlated with the surface area that the CarboSil polymer film is exposed to when in contact with aqueous solution. The decomposition of SNAP in solution (e.g. PBS, ethanol, THF, etc.) is a pseudo-first-order reaction proportional to the SNAP concentration. Further, catheters fabricated with this novel NO releasing composite material are shown to exhibit significant effects on preventing biofilm formation on catheter surface by Pseudomonas aeruginosa and Proteus mirabilis grown in CDC bioreactor over 14 days, with a 2 and 3 log-unit reduction in number of live bacteria on their surfaces, respectively. Therefore, the SNAP-CarboSil composite is a promising new material to develop antimicrobial catheters, as well as other biomedical devices.

Solid-state radioluminescent zeolite-containing composition and light sources

DOEpatents

Clough, Roger L.; Gill, John T.; Hawkins, Daniel B.; Renschler, Clifford L.; Shepodd, Timothy J.; Smith, Henry M.

1992-01-01

A new type of RL light source consisting of a zeolite crystalline material, the intralattice spaces of which a tritiated compound and a luminophore are sorbed, and which material is optionally further dispersed in a refractive index-matched polymer matrix.

Fabrication of Solid-State Multilayer Glass Capacitors

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

Wilke, Rudeger H. T.; Brown-Shaklee, Harlan James; Casias, Adrian L.

Alkali-free glasses show immense promise for the development of high-energy density capacitors. The high breakdown strengths on single-layer sheets of glass suggest the potential for improved energy densities over existing state-of-the art polymer capacitors. In this paper, we demonstrate the ability to package thin glass to make solid-state capacitors. Individual layers are bonded using epoxy, leading to capacitors that exhibit stable operation over the temperature range -55 °C to +65 °C. Here, this fabrication approach is scalable and allows for proof testing individual layers prior to incorporation of the stack, providing a blueprint for the fabrication of high-energy density capacitors.

Fabrication of Solid-State Multilayer Glass Capacitors

DOE PAGES

Wilke, Rudeger H. T.; Brown-Shaklee, Harlan James; Casias, Adrian L.; ...

2017-07-31

Alkali-free glasses show immense promise for the development of high-energy density capacitors. The high breakdown strengths on single-layer sheets of glass suggest the potential for improved energy densities over existing state-of-the art polymer capacitors. In this paper, we demonstrate the ability to package thin glass to make solid-state capacitors. Individual layers are bonded using epoxy, leading to capacitors that exhibit stable operation over the temperature range -55 °C to +65 °C. Here, this fabrication approach is scalable and allows for proof testing individual layers prior to incorporation of the stack, providing a blueprint for the fabrication of high-energy density capacitors.

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

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

Szymusiak, Magdalena; Kalkowski, Joseph; Luo, Hanying

2017-08-31

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

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

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

Szymusiak, Magdalena; Kalkowski, Joseph; Luo, Hanying

2017-08-16

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

Perspectives on Strategies Using Swellable Polymers in Solid Dispersions for Controlled Drug Release.

PubMed

Tran, Thao T D; Tran, Phuong H L

2017-01-01

Poorly water-soluble drugs, which commonly face the issue of poor absorption and low bioavailability, have been under ongoing research of many formulation scientists for the past few decades. Solid dispersion is one of the most effective strategies in concerns for improving bioavailability of poorly water-soluble drugs. Either application of solid dispersions in dissolution enhancement of poorly water-soluble drugs or the use of swellable polymers in controlled drug release has been reported in pharmaceutical designs widely. However, a review of strategies of using swellable polymers in solid dispersion to take a full advantage of these polymers as a current perspective in facilitating drug bioavailability enhancement is still missing. In this review, we aim to provide a summary of techniques used to formulate a swellable polymer in solid dispersion especially a description of a suitable fabrication method in design of a controlled release solid dispersion. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Synthesis and characterization of poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole: investigation on backbone/pendant interactions in a conducting redox polymer.

PubMed

Huang, Hao; Karlsson, Christoffer; Strømme, Maria; Gogoll, Adolf; Sjödin, Martin

2017-04-19

We herein report the synthesis and electrochemical characterization of poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole, consisting of a polypyrrole backbone derivatized at the beta position by a vinyl-hydroquinone pendant group. The structure of the polymer was characterized by solid state NMR spectroscopy. The interactions between the polypyrrole backbone and the oxidized quinone or reduced hydroquinone pendant groups are probed by several in situ methods. In situ attenuated total reflectance-Fourier transform infrared spectroscopy shows a spectroscopic response from both the doping of the polymer backbone and the redox activity of the pendant groups. Using an in situ Electrochemical Quartz Crystal Microbalance we reveal that the polymer doping is unaffected by the pendant group redox chemistry, as opposed to previous reports. Despite the continuous doping the electrochemical conversion from the hydroquinone state to the quinone state results in a significant conductance drop, as observed by in situ conductivity measurements using an Interdigitated Array electrode set-up. Twisting of the conducting polymer backbone as a result of a decreased separation between pendant groups due to π-π stacking in the oxidized state is suggested as the cause of this conductance drop.

Multilayer white lighting polymer light-emitting diodes

NASA Astrophysics Data System (ADS)

Gong, Xiong; Wang, Shu; Heeger, Alan J.

2006-08-01

Organic and polymer light-emitting diodes (OLEDs/PLEDs) that emit white light are of interest and potential importance for use in active matrix displays (with color filters) and because they might eventually be used for solid-state lighting. In such applications, large-area devices and low-cost of manufacturing will be major issues. We demonstrated that high performance multilayer white emitting PLEDs can be fabricated by using a blend of luminescent semiconducting polymers and organometallic complexes as the emission layer, and water-soluble (or ethanol-soluble) polymers/small molecules (for example, PVK-SO 3Li) as the hole injection/transport layer (HIL/HTL) and water-soluble (or ethanol-soluble) polymers/small molecules (for example, t-Bu-PBD-SO 3Na) as the electron injection/transport layer (EIL/HTL). Each layer is spin-cast sequentially from solutions. Illumination quality light is obtained with stable Commission Internationale d'Eclairage coordinates, stable color temperatures, and stable high color rendering indices, all close to those of "pure" white. The multilayer white-emitting PLEDs exhibit luminous efficiency of 21 cd/A, power efficiency of 6 lm/W at a current density of 23 mA/cm2 with luminance of 5.5 x 10 4 cd/m2 at 16 V. By using water-soluble (ethanol-soluble) polymers/small molecules as HIL/HTL and polymers/small molecules as EIL/ETL, the interfacial mixing problem is solved (the emissive polymer layer is soluble in organic solvents, but not in water/ ethanol). As a result, this device architecture and process technology can potentially be used for printing large-area multiplayer light sources and for other applications in "plastic" electronics. More important, the promise of producing large areas of high quality white light with low-cost manufacturing technology makes the white multilayer white-emitting PLEDs attractive for the development of solid state light sources.

Ultraflexible and tailorable all-solid-state supercapacitors using polyacrylamide-based hydrogel electrolyte with high ionic conductivity.

PubMed

Li, Huili; Lv, Tian; Li, Ning; Yao, Yao; Liu, Kai; Chen, Tao

2017-11-30

Hydrogels with high ionic conductivity consisting of a cross-linked polymer network swollen in water are very promising to be used as an electrolyte for all-solid-state supercapacitors. However, there are rather few flexible supercapacitors using ionic conducting hydrogel electrolytes reported to date. In this work, highly flexible and ionic conducting polyacrylamide hydrogels were synthesized through a simple approach. On using the ionic hydrogels as the electrolyte, the resulting supercapacitors not only exhibited a high specific capacitance but also showed a long self-discharge time (over 10 hours to the half of original open-circuit voltage) and a low leakage current. These newly-developed all-solid-state supercapacitors can be bent, knot, and kneaded for 5000 cycles without performance decay, suggesting excellent flexibility and mechanical stability. These all-solid-state supercapacitors can also be easily tailored into strip-like supercapacitors without a short circuit, which provides an efficient approach to fabricate wearable energy storage devices.

Composite solid polymer electrolyte membranes

DOEpatents

Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

2001-06-19

The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

Composite solid polymer electrolyte membranes

DOEpatents

Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

2006-05-30

The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

All-solid-state reduced graphene oxide supercapacitor with large volumetric capacitance and ultralong stability prepared by electrophoretic deposition method.

PubMed

Wang, Mei; Duong, Le Dai; Mai, Nguyen Thi; Kim, Sanghoon; Kim, Youngjun; Seo, Heewon; Kim, Ye Chan; Jang, Woojin; Lee, Youngkwan; Suhr, Jonghwan; Nam, Jae-Do

2015-01-21

Portable energy storage devices have gained special attention due to the growing demand for portable electronics. Herein, an all-solid-state supercapacitor is successfully fabricated based on a poly(vinyl alcohol)-H3PO4 (PVA-H3PO4) polymer electrolyte and a reduced graphene oxide (RGO) membrane electrode prepared by electrophoretic deposition (EPD). The RGO electrode fabricated by EPD contains an in-plane layer-by-layer alignment and a moderate porosity that accommodate the electrolyte ions. The all-solid-state RGO supercapacitor is thoroughly tested to give high specific volumetric capacitance (108 F cm(-3)) and excellent energy and power densities (7.5 Wh cm(-3) and 2.9 W cm(-3), respectively). In addition, the all-solid-state RGO supercapacitor exhibits an ultralong lifetime for as long as 180 days (335 000 cycles), which is an ultrahigh cycling capability for a solid-state supercapacitor. The RGO is also tested for being used as a transparent supercapacitor electrode demonstrating its possible use in various transparent optoelectronic devices. Due to the facile scale-up capability of the EPD process and RGO dispersion, the developed all-solid-state supercapacitor is highly applicable to large-area portable energy storage devices.

High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self-Catalyzed Strategy toward Facile Synthesis.

PubMed

Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Liu, Zhihong; Cui, Guanglei; Feng, Jiwen

2017-11-01

It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self-catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte (C-PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li + and considerable ionic conductivity of 8.9 × 10 -5 S cm -1 at ambient temperature. Moreover, the LiFePO 4 /C-PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self-catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes.

Aqueous Processing for Printed Organic Electronics: Conjugated Polymers with Multistage Cleavable Side Chains.

PubMed

Schmatz, Brian; Yuan, Zhibo; Lang, Augustus W; Hernandez, Jeff L; Reichmanis, Elsa; Reynolds, John R

2017-09-27

The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer's side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics.

Composition and method of preparation of solid state dye laser rods

DOEpatents

Hermes, Robert E.

1992-01-01

The present invention includes solid polymeric-host laser rods prepared using bulk polymerization of acrylic acid ester comonomers which, when admixed with dye(s) capable of supporting laser oscillation and polymerized with a free radical initiator under mild thermal conditions, produce a solid product having the preferred properties for efficient lasing. Unsaturated polymerizable laser dyes can also be employed as one of the comonomers. Additionally, a method is disclosed which alleviates induced optical stress without having to anneal the polymers at elevated temperatures (>85.degree. C.).

The Effects of Polymer Carrier, Hot Melt Extrusion Process and Downstream Processing Parameters on the Moisture Sorption Properties of Amorphous Solid Dispersions

PubMed Central

Feng, Xin; Vo, Anh; Patil, Hemlata; Tiwari, Roshan V.; Alshetaili, Abdullah S.; Pimparade, Manjeet B.; Repka, Michael A.

2017-01-01

Objective The aim of this study was to evaluate the effect of polymer carrier, hot melt extrusion (HME) and downstream processing parameters on the water uptake properties of amorphous solid dispersions. Methods Three polymers and a model drug were used to prepare amorphous solid dispersions utilizing HME technology. The sorption-desorption isotherms of solid dispersions and their physical mixtures were measured by the Dynamic Vapor Sorption system, and the effect of polymer hydrophobicity, hygroscopicity, molecular weight and the HME process were investigated. FTIR imaging was performed to understand the phase separation driven by the moisture. Key findings Solid dispersions with polymeric carriers with lower hydrophilicity, hygroscopicity, and higher molecular weight could sorb less moisture under the high RH conditions. The water uptake ability of polymer-drug solid dispersion systems were decreased compared to the physical mixture after HME, which might be due to the decreased surface area and porosity. The FTIR imaging indicated the homogeneity of the drug molecularly dispersed within the polymer matrix was changed after exposure to high RH. Conclusion Understanding the effect of formulation and processing on the moisture sorption properties of solid dispersions is essential for the development of drug products with desired physical and chemical stability. PMID:26589107

Thermoresponsive Polymers for Nuclear Medicine: Which Polymer Is the Best?

PubMed

Sedláček, Ondřej; Černoch, Peter; Kučka, Jan; Konefal, Rafał; Štěpánek, Petr; Vetrík, Miroslav; Lodge, Timothy P; Hrubý, Martin

2016-06-21

Thermoresponsive polymers showing cloud point temperatures (CPT) in aqueous solutions are very promising for the construction of various systems in biomedical field. In many of these applications these polymers get in contact with ionizing radiation, e.g., if they are used as carriers for radiopharmaceuticals or during radiation sterilization. Despite this fact, radiosensitivity of these polymers is largely overlooked to date. In this work, we describe the effect of electron beam ionizing radiation on the physicochemical and phase separation properties of selected thermoresponsive polymers with CPT between room and body temperature. Stability of the polymers to radiation (doses 0-20 kGy) in aqueous solutions increased in the order poly(N-vinylcaprolactam) (PVCL, the least stable) ≪ poly[N-(2,2-difluoroethyl)acrylamide] (DFP) < poly(N-isopropylacrylamide) (PNIPAM) ≪ poly(2-isopropyl-2-oxazoline-co-2-n-butyl-2-oxazoline) (POX). Even low doses of β radiation (1 kGy), which are highly relevant to the storage of polymer radiotherapeutics and sterilization of biomedical systems, cause significant increase in molecular weight due to cross-linking (except for POX, where this effect is weak). In the case of PVCL irradiated with low doses, the increase in molecular weight induced an increase in the CPT of the polymer. For PNIPAM and DFP, there is strong chain hydrophilization leading to an increase in CPT. From this perspective, POX is the most suitable polymer for the construction of delivery systems that experience exposure to radiation, while PVCL is the least suitable and PNIPAM and DFP are suitable only for low radiation demands.

Carbon Nanotubes Reinforced Composites for Biomedical Applications

PubMed Central

Wang, Wei; Zhu, Yuhe; Liao, Susan; Li, Jiajia

2014-01-01

This review paper reported carbon nanotubes reinforced composites for biomedical applications. Several studies have found enhancement in the mechanical properties of CNTs-based reinforced composites by the addition of CNTs. CNTs reinforced composites have been intensively investigated for many aspects of life, especially being made for biomedical applications. The review introduced fabrication of CNTs reinforced composites (CNTs reinforced metal matrix composites, CNTs reinforced polymer matrix composites, and CNTs reinforced ceramic matrix composites), their mechanical properties, cell experiments in vitro, and biocompatibility tests in vivo. PMID:24707488

Carbon nanotubes reinforced composites for biomedical applications.

PubMed

Wang, Wei; Zhu, Yuhe; Liao, Susan; Li, Jiajia

2014-01-01

This review paper reported carbon nanotubes reinforced composites for biomedical applications. Several studies have found enhancement in the mechanical properties of CNTs-based reinforced composites by the addition of CNTs. CNTs reinforced composites have been intensively investigated for many aspects of life, especially being made for biomedical applications. The review introduced fabrication of CNTs reinforced composites (CNTs reinforced metal matrix composites, CNTs reinforced polymer matrix composites, and CNTs reinforced ceramic matrix composites), their mechanical properties, cell experiments in vitro, and biocompatibility tests in vivo.

Flexible poly(ethylene carbonate)/garnet composite solid electrolyte reinforced by poly(vinylidene fluoride-hexafluoropropylene) for lithium metal batteries

NASA Astrophysics Data System (ADS)

He, Zijian; Chen, Long; Zhang, Bochen; Liu, Yongchang; Fan, Li-Zhen

2018-07-01

Solid-state electrolytes with high ionic conductivities, great flexibility, and easy processability are needed for high-performance solid-state rechargeable lithium batteries. In this work, we synthesize nanosized cubic Li6.25Al0.25La3Zr2O12 (LLZO) by solution combustion method and develop a flexible garnet-based composite solid electrolyte composed of LLZO, poly(ethylene carbonate) (PEC), poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP) and lithium bis(fluorosulfonyl)imide (LiFSI)). In the flexible composite solid electrolytes, LLZO nanoparticles, as ceramic matrix, have a positive effect on ionic conductivities and lithium ion transference number (tLi+). PEC, as a fast ion-conducting polymer, possesses high tLi+ inherently. P(VdF-HFP), as a binder, can strengthen mechanical properties. Consequently, the as-prepared composite solid electrolyte demonstrates high tLi+ (0.82) and superb thermal stability (remaining LLZO matrix after burning). All-solid-state LiFePO4|Li cells assembled with the flexible composite solid electrolyte deliver a high initial discharge specific capacity of 121.4 mAh g-1 and good cycling stability at 55 °C.

Fuel cells with solid polymer electrolyte and their application on vehicles

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

Fateev, V.

1996-04-01

In Russia, solid polymer electrolyte MF-4-SK has been developed for fuel cells. This electrolyte is based on perfluorinated polymer with functional sulfogroups. Investigations on electrolyte properties and electrocatalysts have been carried out.

Investigation of process temperature and screw speed on properties of a pharmaceutical solid dispersion using corotating and counter-rotating twin-screw extruders.

PubMed

Keen, Justin M; Martin, Charlie; Machado, Augie; Sandhu, Harpreet; McGinity, James W; DiNunzio, James C

2014-02-01

The use of corotating twin screw hot-melt extruders to prepare amorphous drug/polymer systems has become commonplace. As small molecule drug candidates exiting discovery pipelines trend towards higher MW and become more structurally complicated, the acceptable operating space shifts below the drug melting point. The objective of this research is to investigate the extrusion process space, which should be selected to ensure that the drug is solubilized in the polymer with minimal thermal exposure, is critical in ensuring the performance, stability and purity of the solid dispersion. The properties of a model solid dispersion were investigated using both corotating and counter-rotating hot-melt twin-screw extruders operated at various temperatures and screw speeds. The solid state and dissolution performance of the resulting solid dispersions was investigated and evaluated in context of thermodynamic predictions from Flory-Huggins Theory. In addition, the residence time distributions were measured using a tracer, modelled and characterized. The amorphous content in the resulting solid dispersions was dependent on the combination of screw speed, temperature and operating mode. The counter-rotating extruder was observed to form amorphous solid dispersions at a slightly lower temperature and with a narrower residence time distribution, which also exhibited a more desirable shape. © 2013 Royal Pharmaceutical Society.

Advances in polymeric systems for tissue engineering and biomedical applications.

PubMed

Ravichandran, Rajeswari; Sundarrajan, Subramanian; Venugopal, Jayarama Reddy; Mukherjee, Shayanti; Ramakrishna, Seeram

2012-03-01

The characteristics of tissue engineered scaffolds are major concerns in the quest to fabricate ideal scaffolds for tissue engineering applications. The polymer scaffolds employed for tissue engineering applications should possess multifunctional properties such as biocompatibility, biodegradability and favorable mechanical properties as it comes in direct contact with the body fluids in vivo. Additionally, the polymer system should also possess biomimetic architecture and should support stem cell adhesion, proliferation and differentiation. As the progress in polymer technology continues, polymeric biomaterials have taken characteristics more closely related to that desired for tissue engineering and clinical needs. Stimuli responsive polymers also termed as smart biomaterials respond to stimuli such as pH, temperature, enzyme, antigen, glucose and electrical stimuli that are inherently present in living systems. This review highlights the exciting advancements in these polymeric systems that relate to biological and tissue engineering applications. Additionally, several aspects of technology namely scaffold fabrication methods and surface modifications to confer biological functionality to the polymers have also been discussed. The ultimate objective is to emphasize on these underutilized adaptive behaviors of the polymers so that novel applications and new generations of smart polymeric materials can be realized for biomedical and tissue engineering applications. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of polymer carriers with regard to the bioavailability enhancement of bifendate solid dispersions prepared by hot-melt extrusion.

PubMed

Feng, Jia; Xu, Lishuang; Gao, Renchao; Luo, Yanfei; Tang, Xing

2012-06-01

The aim of this study was to evaluate several polymer carriers with regard to the bioavailability enhancement of bifendate solid dispersions (SD) prepared by hot-melt extrusion (HME) and select the most appropriate polymer carrier. Solid dispersions containing bifendate in different polymers, including Plasdone(®) S-630, Eudragit(®) EPO and Kollidon(®) VA 64 were prepared by hot-melt extrusion. Differential scanning calorimetry (DSC), Powder X-ray diffraction (XRD) and dissolution testing were used to characterize the systems. Then, the thermal degradation during the HME process and the storage stability of tablets consisting of bifendate-Kollidon(®) VA 64 SD were investigated. Finally, the oral bioavailability of bifendate dosage forms with bifendate-Plasdone(®) S-630 (1/9), bifendate-Eudragit(®) EPO (1/4) and bifendate-Kollidon(®) VA 64 (1/9) SD in beagle dogs was compared with that of commercially available benfidate pills. DSC and XDR analysis showed the dispersion of the drug in the polymer on a molecular basis or in the amorphous state. The drug release from both bifendate-Plasdone(®) S-630 SD and bifendate-Eudragit(®) EPO SD was up to more than 90% with the pH 1.2 simulated gastric fluid as the dissolution medium, while the relative bioavailability was just 87.8 ± 51.8% and 110 ± 62% compared with commercial pills, respectively. The directly compressed tablets with bifendate-Kollidon(®) VA 64 SD were found to dissolve rapidly over 95% within 30 min and the relative bioavailability was 145.0 ± 35.2%. The bioavailability of water-insoluble bifendate was markedly enhanced by dispersing the drug in the polymer carrier Kollidon(®) VA 64 employing HME technology.

Taichi-inspired rigid-flexible coupling cellulose-supported solid polymer electrolyte for high-performance lithium batteries

PubMed Central

Zhang, Jianjun; Yue, Liping; Hu, Pu; Liu, Zhihong; Qin, Bingsheng; Zhang, Bo; Wang, Qingfu; Ding, Guoliang; Zhang, Chuanjian; Zhou, Xinhong; Yao, Jianhua; Cui, Guanglei; Chen, Liquan

2014-01-01

Inspired by Taichi, we proposed rigid-flexible coupling concept and herein developed a highly promising solid polymer electrolyte comprised of poly (ethylene oxide), poly (cyano acrylate), lithium bis(oxalate)borate and robust cellulose nonwoven. Our investigation revealed that this new class solid polymer electrolyte possessed comprehensive properties in high mechanical integrity strength, sufficient ionic conductivity (3 × 10−4 S cm−1) at 60°C and improved dimensional thermostability (up to 160°C). In addition, the lithium iron phosphate (LiFePO4)/lithium (Li) cell using such solid polymer electrolyte displayed superior rate capacity (up to 6 C) and stable cycle performance at 80°C. Furthermore, the LiFePO4/Li battery could also operate very well even at an elevated temperature of 160°C, thus improving enhanced safety performance of lithium batteries. The use of this solid polymer electrolyte mitigates the safety risk and widens the operation temperature range of lithium batteries. Thus, this fascinating study demonstrates a proof of concept of the use of rigid-flexible coupling solid polymer electrolyte toward practical lithium battery applications with improved reliability and safety. PMID:25183416

Interfacial stability and electrochemical behavior of Li/LiFePO4 batteries using novel soft and weakly adhesive photo-ionogel electrolytes

NASA Astrophysics Data System (ADS)

Aidoud, D.; Etiemble, A.; Guy-Bouyssou, D.; Maire, E.; Le Bideau, J.; Guyomard, D.; Lestriez, B.

2016-10-01

We have developed flexible polymer-gel electrolytes based on a polyacrylate cross-linked matrix that confines an ionic liquid doped with a lithium salt. Free-standing solid electrolyte membrane is obtained after UV photo-polymerization of acrylic monomers dissolved inside the ionic liquid/lithium salt mixture. The liquid precursor of the photo-ionogel may also be directly deposited onto porous composite electrode, which results in all-solid state electrode/electrolyte stacking after UV illumination. Minor variations in the polymer component of the electrolyte formulation significantly affect the electrochemical behavior in LiFePO4/lithium and lithium/lithium cells. The rate performance increases with an increase of the ionic conductivity, which decreases with the polymer content and decreases with increasing oxygen content in the polyacrylate matrix. Their fairly low modulus endow them weak and beneficial pressure-sensitive-adhesive character. X-Rays Tomography shows that the solid-state photo-ionogel electrolytes keep their integrity upon cycling and that their surface remains smooth. The coulombic efficiency of LiFePO4/lithium cells increases with an increase of the adhesive strength of the photo-ionogel, suggesting a relationship between the contact intimacy at the lithium/photo-ionogel interface and the efficiency of the lithium striping/plating. In lithium/lithium cells, only the photo-ionogels with the higher adhesion strength are able to allow the reversible striping/plating of lithium.

Imidazolium-based Block Copolymers as Solid-State Separators for Alkaline Fuel Cells and Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Nykaza, Jacob Richard

In this study, polymerized ionic liquid (PIL) diblock copolymers were explored as solid-state polymer separators as an anion exchange membrane (AEM) for alkaline fuel cells AFCs and as a solid polymer electrolyte (SPE) for lithium-ion batteries. Polymerized ionic liquid (PIL) block copolymers are a distinct set of block copolymers that combine the properties of both ionic liquids (e.g., high conductivity, high electrochemical stability) and block copolymers (e.g., self-assembly into various nanostructures), which provides the opportunity to design highly conductive robust solid-state electrolytes that can be tuned for various applications including AFCs and lithium-ion batteries via simple anion exchange. A series of bromide conducting PIL diblock copolymers with an undecyl alkyl side chain between the polymer backbone and the imidazolium moiety were first synthesized at various compositions comprising of a PIL component and a non-ionic component. Synthesis was achieved by post-functionalization from its non-ionic precursor PIL diblock copolymer, which was synthesized via the reverse addition fragmentation chain transfer (RAFT) technique. This PIL diblock copolymer with long alkyl side chains resulted in flexible, transparent films with high mechanical strength and high bromide ion conductivity. The conductivity of the PIL diblock copolymer was three times higher than its analogous PIL homopolymer and an order of magnitude higher than a similar PIL diblock copolymer with shorter alkyl side chain length, which was due to the microphase separated morphology, more specifically, water/ion clusters within the PIL microdomains in the hydrated state. Due to the high conductivity and mechanical robustness of this novel PIL block copolymer, its application as both the ionomer and AEM in an AFC was investigated via anion exchange to hydroxide (OH-), where a maximum power density of 29.3 mW cm-1 (60 °C with H2/O2 at 25 psig (172 kPa) backpressure) was achieved. Rotating disk electrode (RDE) experiments determined the interfacial resistance imposed during cell assembly between the AEM, catalyst, and ionomer was a factor in fuel cell performance. Further RDE studies investigated the electrochemical stability of the PIL block copolymer ionomer under applied potentials, where it was determined that potential cycling increased the degradation compared to constant voltage or open circuit voltage studies. The PIL diblock copolymer was then anion exchanged to the bis(trifluoromethane)sulfonamide (TFSI-) anion form and imbibed with a lithium salt and ionic liquid solution for use as a SPE in lithium-ion batteries resulting in a maximum discharge capacity of 112 mAh g-1 at 0.1 C with a Coulombic efficiency greater than 94% over 100 cycles. PIL block copolymers have promising mechanical properties and transport properties (i.e., ion conductivity) in both the hydrated (hydrophilic anions; Br-, OH-) and dry (hydrophobic anions; TFSI-) states resulting in highly conductive, chemically/thermally stable, and mechanically robust solid-state polymer separators for use as AEMs in AFCs and as SPEs in lithium-ion batteries.

PHOTOSENSITIVE 2,5-DISTYRYLPYRAZINE PARTICLES PRODUCED FROM RAPID EXPANSION OF SUPERCRITICAL SOLUTIONS. (R826648)

EPA Science Inventory

Solvent-free, photoreactive particles of 2,5-distyrylpyrazine (DSP) monomer were developed by rapid precipitation from an expanding supercritical chlorodifluoromethane solution. DSP polymer particles were produced by solid-state photopolymerization. DSP particles below a criti...

75 FR 32418 - Notice of Intent To Grant Partially Exclusive License of the United States Patent Application No...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-08

... biologically natural material can be produced in bioreactors and transformed for use as a dry solid. The resulting biopolymer material can be used in place of synthetic, petroleum-based polymers for soil amendment...

Stiffness, strength and adhesion characterization of electrochemically deposited conjugated polymer films

PubMed Central

Qu, Jing; Ouyang, Liangqi; Kuo, Chin-chen; Martin, David C.

2015-01-01

Conjugated polymers such as poly(3,4-ethylenedioxythiphene) (PEDOT) are of interest for a variety of applications including interfaces between electronic biomedical devices and living tissue. The mechanical properties, strength, and adhesion of these materials to solid substrates are all vital for long-term applications. We have been developing methods to quantify the mechanical properties of conjugated polymer thin films. In this study the stiffness, strength and the interfacial shear strength (adhesion) of electrochemically deposited PEDOT and PEDOT-co-1,3,5-tri[2-(3,4-ethylene dioxythienyl)]-benzene (EPh) were studied. The estimated Young’s modulus of the PEDOT films was 2.6 ± 1.4 GPa, and the strain to failure was around 2%. The tensile strength was measured to be 56 ± 27 MPa. The effective interfacial shear strength was estimated with a shear-lag model by measuring the crack spacing as a function of film thickness. For PEDOT on gold/palladium-coated hydrocarbon film substrates an interfacial shear strength of 0.7 ± 0.3 MPa was determined. The addition of 5 mole% of a tri-functional EDOT crosslinker (EPh) increased the tensile strength of the films to 283 ± 67 MPa, while the strain to failure remained about the same (2%). The effective interfacial shear strength was increased to 2.4 ± 0.6 MPa. PMID:26607768

Synergistic effect of polyaniline coverage and surface microstructure on the inhibition of Pseudomonas aeruginosa biofilm formation.

PubMed

Gallarato, L A; Mulko, L E; Dardanelli, M S; Barbero, C A; Acevedo, D F; Yslas, E I

2017-02-01

Biofilm Formation is a survival strategy for microorganisms to adapt to their environment. Microbial cells in biofilm become tolerant and resistant to antibiotics and immune responses, increasing the difficulties for the clinical treatment of microbial infections. The surface chemistry and the micro/nano-topography of solid interfaces play a major role in mediating microorganism activity and adhesion. The effect of the surface chemical composition and topography on the adhesion and viability of Pseudomonas aeruginosa was studied. Polymeric (polyethylene terephthalate) surfaces were covered with a conducting polymer (polyaniline, PANI) film by in-situ polymerization and microstructured by Direct Laser Interference Patterning (DLIP). The viability of Pseudomonas aeruginosa on the different surfaces was investigated. The physicochemical properties of the surfaces were characterized by water contact angle measurements, scanning electron microscopy and atomic force microscopy. Bacterial biofilms were imaged by atomic force and scanning electron microscopies. The bacterial viability decreased on PANI compared with the substrate (polyethylene terephthalate) and it decreased even more upon micro-structuring the PANI films. In addition, the biofilm reduction could be improved using polymers with different chemical composition and/or the same polymer with different topographies. Both methods presented diminish the bacterial attachment and biofilm formation. These findings present a high impact related to materials for biomedical engineer applications regarding medical devices, as prostheses or catheters. Copyright © 2016 Elsevier B.V. All rights reserved.

3-V Solid-State Flexible Supercapacitors with Ionic-Liquid-Based Polymer Gel Electrolyte for AC Line Filtering.

PubMed

Kang, Yu Jin; Yoo, Yongju; Kim, Woong

2016-06-08

State-of-the-art solid-state flexible supercapacitors with sufficiently fast response speed for AC line filtering application suffer from limited energy density. One of the main causes of the low energy density is the low cell voltage (1 V), which is limited by aqueous-solution-based gel electrolytes. In this work, we demonstrate for the first time a 3-V flexible supercapacitor for AC line filtering based on an ionic-liquid-based polymer gel electrolyte and carbon nanotube electrode material. The flexible supercapacitor exhibits an areal energy density that is more than 20 times higher than that of the previously demonstrated 1-V flexible supercapacitor (0.66 vs 0.03 μWh/cm(2)) while maintaining excellent capacitive behavior at 120 Hz. The supercapacitor shows a maximum areal power density of 1.5 W/cm(2) and a time constant of 1 ms. The improvement of the cell voltage while maintaining the fast-response capability greatly improves the potential of supercapacitors for high-frequency applications in wearable and/or portable electronics.

Nanocellulose in Polymer Composites and Biomedical: Research and Applications

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

Lu, Yuan; Tekinalp, Halil L; Peter, William H

Nanocellulose materials are nano-sized cellulose fibers or crystals that are produced by bacteria or derived from plants. These materials exhibit exceptional strength characteristics, light weight, transparency, and excellent biocompatibility. Compared to some other nanomaterials, nanocellulose is renewable and less expensive to produce. As such, a wide range of applications for nanocellulose has been envisioned. Most extensively studied areas include polymer composites and biomedical applications. Cellulose nanofibrils and nanocrystals have been used to reinforce both thermoplastic and thermoset polymers. Given the hydrophilic nature of these materials, the interfacial properties with most polymers are often poor. Various surface modification procedures have thusmore » been adopted to improve the interaction between polymer matrix and cellulose nanofibrils or nanocrystals. In addition, the applications of nanocellulose as biomaterials have been explored including wound dressing, tissue repair, and medical implants. Nanocellulose materials for wound healing and periodontal tissue recovery have become commercially available, demonstrating the great potential of nanocellulose as a new generation of biomaterials. In this review, we highlight the applications of nanocellulose as reinforcing fillers for composites and the effect of surface modification on the mechanical properties as well as the application as biomaterials.« less

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

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

PubMed

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

2017-08-07

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

Polysaccharide-Coated Magnetic Nanoparticles for Imaging and Gene Therapy

PubMed Central

Uthaman, Saji; Cherukula, Kondareddy; Cho, Chong-Su; Park, In-Kyu

2015-01-01

Today, nanotechnology plays a vital role in biomedical applications, especially for the diagnosis and treatment of various diseases. Among the many different types of fabricated nanoparticles, magnetic metal oxide nanoparticles stand out as unique and useful tools for biomedical applications, because of their imaging characteristics and therapeutic properties such as drug and gene carriers. Polymer-coated magnetic particles are currently of particular interest to investigators in the fields of nanobiomedicine and fundamental biomaterials. Theranostic magnetic nanoparticles that are encapsulated or coated with polymers not only exhibit imaging properties in response to stimuli, but also can efficiently deliver various drugs and therapeutic genes. Even though a large number of polymer-coated magnetic nanoparticles have been fabricated over the last decade, most of these have only been used for imaging purposes. The focus of this review is on polysaccharide-coated magnetic nanoparticles used for imaging and gene delivery. PMID:26078971

Effects of drug-carrier interactions on drug dissolution from binary and ternary matrices

NASA Astrophysics Data System (ADS)

Iqbal, Zafar

For nearly five decades, pharmaceutical researchers have studied solid solutions of drugs in polymers as a potential means to enhance the dissolution of drugs with poor aqueous solubility. This has become of greater importance in recent years because most new potential drug compounds (new chemical entities) exhibit poor water solubility and present great challenges to scientists who must design dosage forms from which the drugs are bioavailable. During the formulation of a solid solution, the drug undergoes physical but not chemical alterations that increase its chemical potential in the formulation relative to that of the pure drug in its stable form. This increased chemical potential is responsible for enhanced dissolution as well as physical instabilities, such as amorphous to crystalline conversions and precipitation within the solid state. The chemical potential is derived from the Gibbs free energy, so it is reasonable to explain the behavior of solid solution systems in terms of thermodynamics. Solid solutions and dispersions have been extensively studied by pharmaceutical scientists, both with regard to manufacturing aspects and the proposal of various models in attempts to explain the physical bases for how these systems work. Recently, Dave and Bellantone proposed a model based on the thermodynamic changes resulting from the formulation of binary solid solutions of a drug in the polymer PVP. Their model introduced a modification of the F-H theory, which was used to quantify the drug-polymer interaction energies and calculate the entropy of mixing of the drug and polymer. In this work, the model of Dave and Bellantone was extended to include three-component systems, consisting of one drug mixed in a carrier matrix consisting of mixture of two polymers or a polymer and a surfactant. For this research, solid solutions were formed using various drug weight fractions in the formulations. The study focused on the following points: (1) Prepare solid solution formulations and perform appropriate physical characterizations. (2) Characterize the increase in drug dissolution rates resulting from solid solution formulations. (3) Relate the initial dissolution rates to the drug solubility. (4) Explain the solubility enhancement from solid solution dosage in terms of the drug polymer interactions using the extended thermodynamic model. Two poorly water soluble drugs, levonorgestrel (LEVO) and ethinyl estradiol (EE) were formulated in seven solid solution preparations comprised of four carrier systems. Materials used as carriers included various combinations of the polymers PVP K-30, Copovidone (COP), Poloxamer 182, and the surfactant TweenRTM 20. Additionally, ibuprofen (IBU) was used in three formulations consisting of various combinations of PVP K-30, Copovidone and TweenRTM 20. Formulations with various drug weight fractions (0.5%--30%) were prepared using the solvent evaporation technique. Each formulation was tested for dissolution using intrinsic dissolution apparatus (USP). The solid solutions were compressed into tablets into the sample die that maintained a constant surface area during the dissolution process. DSC, XRD and NIRS scans identified that the crystalline peaks of the drug disappeared with the addition of the polymer for all ratios of EE, indicating the formation of solid solutions (to within the limits of detection of the equipment). This was also observed for the LEVO dispersions up to 10% drug loading. At higher drug loading, solutions were formed but some small degree crystallinity was also present. For each experiment, the initial dissolution rates were obtained from the slope of the mass dissolved vs. time plots taken at early times, and volume normalized initial dissolution rates RV were calculated by dividing the initial dissolution rate by the volume fraction of the drug in the formulation. Comparison of the RV values for the various formulations with a reference RV (typically that of the pure drug or of the formulation with the highest polymer content) allowed calculation of relative volume normalized dissolution rates (RNV). The various RNV were used in the thermodynamic model for data analyses and to determine the interactions between the drug and carrier molecules. It was generally seen that RNV increased with decreased drug fraction, and was adequately modeled by the equations derived from the extended thermodynamic model. It was concluded that the model proposed for the binary and ternary systems successfully represented the mechanism of drug-polymer interaction and the energy changes taken place within the dispersion systems. The dissolution data analysis and subsequent understanding of physical modifications in the dispersion systems characterized by XRD, NIRS and DSC further substantiated the findings. The understanding of the fundamental physical might help scientists to predict the effects of mixing various drugs and polymers, and the effects of varying ratios.

Highly Flexible and Planar Supercapacitors Using Graphite Flakes/Polypyrrole in Polymer Lapping Film.

PubMed

Raj, C Justin; Kim, Byung Chul; Cho, Won-Je; Lee, Won-gil; Jung, Sang-Don; Kim, Yong Hee; Park, Sang Yeop; Yu, Kook Hyun

2015-06-24

Flexible supercapacitor electrodes have been fabricated by simple fabrication technique using graphite nanoflakes on polymer lapping films as flexible substrate. An additional thin layer of conducting polymer polypyrrole over the electrode improved the surface conductivity and exhibited excellent electrochemical performances. Such capacitor films showed better energy density and power density with a maximum capacitance value of 37 mF cm(-2) in a half cell configuration using 1 M H2SO4 electrolyte, 23 mF cm(-2) in full cell, and 6 mF cm(-2) as planar cell configuration using poly(vinyl alcohol) (PVA)/phosphoric acid (H3PO4) solid state electrolyte. Moreover, the graphite nanoflakes/polypyrrole over polymer lapping film demonstrated good flexibility and cyclic stability.

Investigation of structure-property relationships in systematic series of novel polymers

NASA Technical Reports Server (NTRS)

Gillham, J. K.

1976-01-01

Solid state transitions in polymeric materials was associated with the onset of sub-molecular motions of the polymer chains. Although these were considered to be intramolecular in general, the local environment of the polymer molecule exerts a strong influence through, for example, the effects of crystallinity, polarity and diluents. The manner of specimen preparation and previous history also affect transitions. The transitions are considered to arise when sufficient free volume is available to permit the occurrence of these side chain and backbone reorientations. The glass transition is the principal transition of amorphous polymeric materials and is associated with the onset of long range segmental motion of the polymer backbone. The various types of shorter range motion occurring below the glass transition have been catalogued.

Application of Fused Deposition Modelling (FDM) Method of 3D Printing in Drug Delivery.

PubMed

Long, Jingjunjiao; Gholizadeh, Hamideh; Lu, Jun; Bunt, Craig; Seyfoddin, Ali

2017-01-01

Three-dimensional (3D) printing is an emerging manufacturing technology for biomedical and pharmaceutical applications. Fused deposition modelling (FDM) is a low cost extrusion-based 3D printing technique that can deposit materials layer-by-layer to create solid geometries. This review article aims to provide an overview of FDM based 3D printing application in developing new drug delivery systems. The principle methodology, suitable polymers and important parameters in FDM technology and its applications in fabrication of personalised tablets and drug delivery devices are discussed in this review. FDM based 3D printing is a novel and versatile manufacturing technique for creating customised drug delivery devices that contain accurate dose of medicine( s) and provide controlled drug released profiles. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Ultrafast fiber lasers: practical applications

NASA Astrophysics Data System (ADS)

Pastirk, Igor; Sell, Alexander; Herda, Robert; Brodschelm, Andreas; Zach, Armin

2015-05-01

Over past three decades ultrafast lasers have come a long way from the bulky, demanding and very sensitive scientific research projects to widely available commercial products. For the majority of this period the titanium-sapphire-based ultrafast systems were the workhorse for scientific and emerging industrial and biomedical applications. However the complexity and intrinsic bulkiness of solid state lasers have prevented even larger penetration into wider array of practical applications. With emergence of femtosecond fiber lasers, based primarily on Er-doped and Yb-doped fibers that provide compact, inexpensive and dependable fs and ps pulses, new practical applications have become a reality. The overview of current state of the art ultrafast fiber sources, their basic principles and most prominent applications will be presented, including micromachining and biomedical implementations (ophthalmology) on one end of the pulse energy spectrum and 3D lithography and THz applications on the other.

Air Force Phillips Laboratory Battery Program overview

NASA Technical Reports Server (NTRS)

House, Shaun

1992-01-01

Battery development and testing efforts at Phillips Laboratory fall into three main categories: nickel hydrogen, sodium sulfur, and solid state batteries. Nickel hydrogen work is broken down into a Low Earth Orbit (LEO) Life Test Program, a LEO Pulse Test Program, and a Hydrogen Embrittlement Investigation. Sodium sulfur work is broken down into a Geosynchronous Earth Orbit (GEO) Battery Flight Test and a Hot Launch Evaluation. Solid state polymer battery work consists of a GEO Battery Development Program, a Pulse Power Battery Small Business Innovation Research (SBIR), and an in-house evaluation of current generation laboratory cells. An overview of the program is presented.

Special Issue on Powering the Future Force: New Power & Energy Technologies for the Warfighter (AMMTIAC Quarterly, Volume 4, Number 1 / WSTIAC Quarterly, Volume 9, Number 1)

DTIC Science & Technology

2009-04-27

an aromatic acidic polymer such as SPEEK or SPSf. Figure 5 shows four basic polymers in which benzimidazole (BIm), amino- benzimidazole (ABIm...Z., A. Manthiram, and M. D. Guiver, “Blend Membranes Based on Sulfonated Polyetheretherketone and Polysulfone Bearing Benzimidazole Side Groups for...Sulfonated Poly(ether ether ketone) and Polysulfone Bearing Benzimidazole Side Groups for Direct Methanol Fuel Cells,” Electrochemical and Solid State Letters

Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide

NASA Astrophysics Data System (ADS)

Jin, Jun-Cheng; Tong, Wen-Quan; Fu, Ai-Yun; Xie, Cheng-Gen; Chang, Wen-Gui; Wu, Ju; Xu, Guang-Nian; Zhang, Ya-Nan; Li, Jun; Li, Yong; Yang, Peng-Qi

2015-05-01

Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1-3 contain four types of 21 helical chains. While the Nd(III) ions are bridged through μ2-HIDC2- and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature.

Synthesis, characterization and solid state electrical properties of 1-D coordination polymer of the type [CuxNi1-x(dadb)·yH2O]n

NASA Astrophysics Data System (ADS)

Prasad, R. L.; Kushwaha, A.; Shrivastava, O. N.

2012-12-01

New heterobimetallic complexes [CuxNi1-x(dadb)·yH2O]n {where dadb=2,5-Diamino-3,6-dichloro-1,4-benzoquinone (1); x=1 (2), 0.5 (4), 0.25 (5), 0.125 (6), 0.0625 (7) and 0 (3); y=2; n=degree of polymerization} were synthesized and characterized. Heterobimetallic complexes show normal magnetic moments, whereas, monometallic complexes exhibit magnetic moments less than the value due to spin only. Thermo-gravimetric analysis shows that degradation of the ligand dadb moiety is being controlled by the electronic environment of the Cu(II) ions in preference over Ni(II) in heterobimetallic complexes. Existence of the mixed valency/non-integral oxidation states of copper and nickel metal ions in the complex 4 has been attributed from magnetic moment and ESR spectral results. Solid state dc electrical conductivity of all the complexes was investigated. Monometallic complexes were found to be semiconductors, whereas heterobimetallic coordination polymer 4 was found to exhibit metallic behaviour. Existence of mixed valency/ non-integral oxidation state of metal ions seems to be responsible for the metallic behaviour.

Facile modification of nanodiamonds with hyperbranched polymers based on supramolecular chemistry and their potential for drug delivery.

PubMed

Huang, Hongye; Liu, Meiying; Jiang, Ruming; Chen, Junyu; Mao, Liucheng; Wen, Yuanqing; Tian, Jianwen; Zhou, Naigen; Zhang, Xiaoyong; Wei, Yen

2018-03-01

Due to their excellent chemical stability and remarkable biocompatibility, nanodiamonds (NDs) have received widespread research attention by the biomedical field. The excellent water dispersibility of NDs has significant importance for biomedical applications. Therefore, surface modification of NDs with hydrophilic polymers has been extensively investigated over the past few decades. In this study, we synthesize β-CD containing hyperbranched polymer functionalized ND (ND-β-CD-HPG) composites with high water dispersibility via supramolecular chemistry based on the host-guest interactions between β-Cyclodextrin (β-CD) and adamantine (Ad). The hydroxyl groups of NDs first reacted with 1, 1-adamantanecarbonyl chloride to obtain ND-Ad, which was further functionalized with β-CD containing hyperbranched polymers to form the final ND-β-CD-HPG composites. The successful preparation of ND-β-CD-HPG composites was confirmed by several characterization techniques. Furthermore, the loading and release of the anticancer agent doxorubicin hydrochloride (DOX) on ND-β-CD-HPG composites was also examined to explore its potential in drug delivery. When compared with traditional methods of surface modification of NDs, this method was convenient, fast and efficient. We demonstrated that ND-β-CD-HPG composites have great water dispersibility, low toxicity, high drug-loading capacity and controlled drug-release behavior. Based on these characteristics, ND-β-CD-HPG composites are expected to have high potential for biomedical applications. Copyright © 2017 Elsevier Inc. All rights reserved.

Dip-pen nanopatterning of photosensitive conducting polymer using a monomer ink

NASA Astrophysics Data System (ADS)

Su, Ming; Aslam, Mohammed; Fu, Lei; Wu, Nianqiang; Dravid, Vinayak P.

2004-05-01

Controlled patterning of conducting polymers at a micro- or nanoscale is the first step towards the fabrication of miniaturized functional devices. Here, we introduce an approach for the nanopatterning of conducting polymers using an improved monomer "ink" in dip-pen nanolithography (DPN). The nominal monomer "ink" is converted, in situ, to its conducting solid-state polymeric form after patterned. Proof-of-concept experiments have been performed with acid-promoted polymerization of pyrrole in a less reactive environment (tetrahydrofuran). The ratios of reactants are optimized to give an appropriate rate to match the operation of DPN. A similar synthesis process for the same polymer in its bulk form shows a high conductance and crystalline structure. The miniaturized conducting polymer sensors with light detection ability are fabricated by DPN using the improved ink formula, and exhibit excellent response, recovery, and sensitivity parameters.

Solid-state NMR characterization of cross-linking in EPDM/PP blends from 1H-13C polarization transfer dynamics.

PubMed

Aluas, Mihaela; Filip, Claudiu

2005-05-01

A novel approach for solid-state NMR characterization of cross-linking in polymer blends from the analysis of (1)H-(13)C polarization transfer dynamics is introduced. It extends the model of residual dipolar couplings under permanent cross-linking, typically used to describe (1)H transverse relaxation techniques, by considering a more realistic distribution of the order parameter along a polymer chain in rubbers. Based on a systematic numerical analysis, the extended model was shown to accurately reproduce all the characteristic features of the cross-polarization curves measured on such materials. This is particularly important for investigating blends of great technological potential, like thermoplastic elastomers, where (13)C high-resolution techniques, such as CP-MAS, are indispensable to selectively investigate structural and dynamical properties of the desired component. The validity of the new approach was demonstrated using the example of the CP build-up curves measured on a well resolved EPDM resonance line in a series of EPDM/PP blends.

Multifunctional Fluorescent-Magnetic Polymeric Colloidal Particles: Preparations and Bioanalytical Applications.

PubMed

Kaewsaneha, Chariya; Tangboriboonrat, Pramuan; Polpanich, Duangporn; Elaissari, Abdelhamid

2015-10-28

Fluorescent-magnetic particles (FMPs) play important roles in modern materials, especially as nanoscale devices in the biomedical field. The interesting features of FMPs are attributed to their dual detection ability, i.e., fluorescent and magnetic modes. Functionalization of FMPs can be performed using several types of polymers, allowing their use in various applications. The synergistic potentials for unique multifunctional, multilevel targeting nanoscale devices as well as combination therapies make them particularly attractive for biomedical applications. However, the synthesis of FMPs is challenging and must be further developed. In this review article, we summarized the most recent representative works on polymer-based FMP systems that have been applied particularly in the bioanalytical field.

Cyclodextrins Based Electrochemical Sensors for Biomedical and Pharmaceutical Analysis.

PubMed

Lenik, Joanna

2017-01-01

Electrochemical sensors are very convenient devices, as they may be used in a lot of fields starting from the food industry to environmental monitoring and medical diagnostics. They offer the values of simple design, reversible and reproducible measurements, as well as ensuring precise and accurate analytical information. Compared with other methods, electrochemical sensors are relatively simple as well as having low costs, which has led to intensive development, especially in the field of medicine and pharmaceuticals within the last decade. Recently, the number of publications covering the determination of aminoacids, dopamine, cholesterol, uric acid, biomarkers, vitamins and other pharmaceutical and biological compounds has significantly increased. Many possible types of such sensors and biosensors have been proposed: owing to the kind of the detection-potentiometric voltametric, amperometry, and the materials that can be used for, e.g. designing molecular architecture of the electrode/solution interface, carbon paste, carbon nanotubes, glass carbon, graphite, graphene, PVC, conductive polymers and/or nanoparticles. The active compounds which provide the complex formation with analyte (in the case of non-current techniques) or activate biomolecules electrochemically by particle recognition and selective preconcentration of analyte on the electrode surface (in the case of current techniques) are the most recently used cyclodextrins. These macrocyclic compounds have the ability to interact with a large diversity of guest particles to form complexes of the type of guest host, for example, with particles from drugs, biomolecules, through their hydrophilic outer surface and lipophilic inner cavities. Cyclodextrins have been the subject of frequent electrochemical studies that focused mostly on both their interactions in a solid state and in solution. The process of preparing of CDs modified electrodes would, consequently, open new avenues for new electrochemical sensors and, therefore, widen their use in biomedical and drug analysis. This review presents information on manufacturing techniques and performances of these sensors and biosensors. The opportunities for these sensors to carry out biomedical and pharmaceutical researches are demonstrated. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Synthesis and characterization of a new photo-crosslinkable glycol chitosan thermogel for biomedical applications.

PubMed

Cho, Ik Sung; Cho, Myeong Ok; Li, Zhengzheng; Nurunnabi, Md; Park, Sung Young; Kang, Sun-Woong; Huh, Kang Moo

2016-06-25

The major limitations of typical thermogelling polymers for practical applications are low gel stability and weak mechanical properties under physiological conditions. In this study, we have synthesized a new polysaccharide-based thermogelling polymer that can be photo-crosslinked by UV irradiation to form a mechanically resilient and elastic hydrogel. Methacrylated hexanoyl glycol chitosan (M-HGC), was synthesized by a series of chemical modifications, N-hexanoylation and N-methacrylation, of glycol chitosan (GC). Various M-HGC polymers with different methacryl group contents were synthesized and their thermogelling and photo-crosslinkable properties were evaluated. The M-HGCs demonstrated a thermo-reversible sol-gel transition behavior in aqueous solutions. The thermally-induced hydrogels could be chemically crosslinked by UV-triggered photo-crosslinking. From the cytotoxicity studies using MTT and the live/dead assay, the M-HGC hydrogels showed non-cytotoxicity. These photo-crosslinkable thermogelling M-HGC polymers may hold great promises for various biomedical applications, such as an injectable delivery system and 3D cell culture. Copyright © 2016 Elsevier Ltd. All rights reserved.

Molecular implications of drug-polymer solubility in understanding the destabilization of solid dispersions by milling.

PubMed

Yang, Ziyi; Nollenberger, Kathrin; Albers, Jessica; Qi, Sheng

2014-07-07

The solubility of drugs in polymer matrixes has been recognized as one of the key factors governing the physical stability of solid dispersions. This study has explored the implications of drug solubility on the destabilization that occurs on milling, which is often used as an additional process for hot melt extruded (HME) solid dispersions. The theoretical drug solubility in the polymer was first predicted using various theoretical and experimental approaches. The destabilization effects of high-energy mechanical milling on the solid dispersions with drug loadings below and above the predicted solubility were then investigated using a range of thermal, microscopic, and spectroscopic techniques. Four model drug-polymer combinations were studied. The HME formulations with drug loading below the predicted solid solubility (undersaturated and true molecular dispersion) showed good stability against milling. In contrast, milling destabilized supersaturated HME dispersions via increasing molecular mobility and creating phase-separated, amorphous, drug-rich domains. However, these additional amorphous drug-rich domains created by milling show good stability under ambient conditions, though crystallization can be accelerated by additional heating. These results highlighted that the processing method used to prepare the solid dispersions may play a role in facilitating the stabilization of amorphous drug in supersaturated solid dispersions. The degree of supersaturation of the drug in the polymer showed significant impact on the destabilization behavior of milling on solid dispersions. An improved understanding of the destabilization behavior of solid dispersions upon milling can provide new insights into the processing related apparent solubility of drugs in polymers.

The effects of polymer carrier, hot melt extrusion process and downstream processing parameters on the moisture sorption properties of amorphous solid dispersions.

PubMed

Feng, Xin; Vo, Anh; Patil, Hemlata; Tiwari, Roshan V; Alshetaili, Abdullah S; Pimparade, Manjeet B; Repka, Michael A

2016-05-01

The aim of this study was to evaluate the effect of polymer carrier, hot melt extrusion and downstream processing parameters on the water uptake properties of amorphous solid dispersions. Three polymers and a model drug were used to prepare amorphous solid dispersions utilizing the hot melt extrusion technology. The sorption-desorption isotherms of solid dispersions and their physical mixtures were measured by the dynamic vapour sorption system, and the effects of polymer hydrophobicity, hygroscopicity, molecular weight and the hot melt extrusion process were investigated. Fourier transform infrared (FTIR) imaging was performed to understand the phase separation driven by the moisture. Solid dispersions with polymeric carriers with lower hydrophilicity, hygroscopicity and higher molecular weight could sorb less moisture under the high relative humidity (RH) conditions. The water uptake ability of polymer-drug solid dispersion systems were decreased compared with the physical mixture after hot melt extrusion, which might be due to the decreased surface area and porosity. The FTIR imaging indicated that the homogeneity of the drug molecularly dispersed within the polymer matrix was changed after exposure to high RH. Understanding the effect of formulation and processing on the moisture sorption properties of solid dispersions is essential for the development of drug products with desired physical and chemical stability. © 2015 Royal Pharmaceutical Society.

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

Wang, Hui; Chen, Yan; Hood, Zachary D.

All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na 3SbS 4, a novel Na superionic conductor that needs much lower processing temperature belowmore » 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm -1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.« less

High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self‐Catalyzed Strategy toward Facile Synthesis

PubMed Central

Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Feng, Jiwen

2017-01-01

Abstract It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self‐catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte (C‐PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li+ and considerable ionic conductivity of 8.9 × 10−5 S cm−1 at ambient temperature. Moreover, the LiFePO4/C‐PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self‐catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes. PMID:29201612

Release of engineered nanomaterials from polymer nanocomposites: diffusion, dissolution, and desorption.

PubMed

Duncan, Timothy V; Pillai, Karthik

2015-01-14

Polymer nanocomposites-polymer-based materials that incorporate filler elements possessing at least one dimension in the nanometer range-are increasingly being developed for commercial applications ranging from building infrastructure to food packaging to biomedical devices and implants. Despite a wide range of intended applications, it is also important to understand the potential for exposure to these nanofillers, which could be released during routine use or abuse of these materials, so it can be determined whether they pose a risk to human health or the environment. This article is the first in a series of two that review the state of the science regarding the release of engineered nanomaterials (ENMs) from polymer nanocomposites. Two ENM release paradigms are considered in this series: the release of ENMs via passive diffusion, desorption, and dissolution into external liquid media and release of ENMs assisted by matrix degradation. The present article focuses primarily on the first paradigm and includes (1) an overview of basic interactions between polymers and liquid environments and a brief summary of diffusion physics as they apply to polymeric materials; (2) a summary of both experimental and theoretical methods to assess contaminant release (including ENMs) from polymers by diffusion, dissolution, and desorption; and (3) a thorough, critical review of the associated body of peer-reviewed literature on ENM release by these mechanisms. A short outlook section on knowledge gaps and future research needs is also provided.

Solid state nuclear magnetic resonance investigation of polymer backbone dynamics in poly(ethylene oxide) based lithium and sodium polyether-ester-sulfonate ionomers.

PubMed

Roach, David J; Dou, Shichen; Colby, Ralph H; Mueller, Karl T

2013-05-21

Polymer backbone dynamics of single ion conducting poly(ethylene oxide) (PEO)-based ionomer samples with low glass transition temperatures (T(g)) have been investigated using solid-state nuclear magnetic resonance. Experiments detecting (13)C with (1)H decoupling under magic angle spinning (MAS) conditions identified the different components of the polymer backbone (PEO spacer and isophthalate groups) and their relative mobilities for a suite of lithium- and sodium-containing ionomer samples with varying cation contents. Variable temperature (203-373 K) (1)H-(13)C cross-polarization MAS (CP-MAS) experiments also provided qualitative assessment of the differences in the motions of the polymer backbone components as a function of cation content and identity. Each of the main backbone components exhibit distinct motions, following the trends expected for motional characteristics based on earlier Quasi Elastic Neutron Scattering and (1)H spin-lattice relaxation rate measurements. Previous (1)H and (7)Li spin-lattice relaxation measurements focused on both the polymer backbone and cation motion on the nanosecond timescale. The studies presented here assess the slower timescale motion of the polymer backbone allowing for a more comprehensive understanding of the polymer dynamics. The temperature dependences of (13)C linewidths were used to both qualitatively and quantitatively examine the effects of cation content and identity on PEO spacer mobility. Variable contact time (1)H-(13)C CP-MAS experiments were used to further assess the motions of the polymer backbone on the microsecond timescale. The motion of the PEO spacer, reported via the rate of magnetization transfer from (1)H to (13)C nuclei, becomes similar for T≳1.1 T(g) in all ionic samples, indicating that at similar elevated reduced temperatures the motions of the polymer backbones on the microsecond timescale become insensitive to ion interactions. These results present an improved picture, beyond those of previous findings, for the dependence of backbone dynamics on cation density (and here, cation identity as well) in these amorphous PEO-based ionomer systems.

A constitutive law for degrading bioresorbable polymers.

PubMed

Samami, Hassan; Pan, Jingzhe

2016-06-01

This paper presents a constitutive law that predicts the changes in elastic moduli, Poisson's ratio and ultimate tensile strength of bioresorbable polymers due to biodegradation. During biodegradation, long polymer chains are cleaved by hydrolysis reaction. For semi-crystalline polymers, the chain scissions also lead to crystallisation. Treating each scission as a cavity and each new crystal as a solid inclusion, a degrading semi-crystalline polymer can be modelled as a continuum solid containing randomly distributed cavities and crystal inclusions. The effective elastic properties of a degrading polymer are calculated using existing theories for such solid and the tensile strength of the degrading polymer is predicted using scaling relations that were developed for porous materials. The theoretical model for elastic properties and the scaling law for strength form a complete constitutive relation for the degrading polymers. It is shown that the constitutive law can capture the trend of the experimental data in the literature for a range of biodegradable polymers fairly well. Copyright © 2016 Elsevier Ltd. All rights reserved.

An insight into non-emissive excited states in conjugated polymers

NASA Astrophysics Data System (ADS)

Hu, Zhongjian; Willard, Adam P.; Ono, Robert J.; Bielawski, Christopher W.; Rossky, Peter J.; vanden Bout, David A.

2015-09-01

Conjugated polymers in the solid state usually exhibit low fluorescence quantum yields, which limit their applications in many areas such as light-emitting diodes. Despite considerable research efforts, the underlying mechanism still remains controversial and elusive. Here, the nature and properties of excited states in the archetypal polythiophene are investigated via aggregates suspended in solvents with different dielectric constants (ε). In relatively polar solvents (ε>~ 3), the aggregates exhibit a low fluorescence quantum yield (QY) of 2-5%, similar to bulk films, however, in relatively nonpolar solvents (ε<~ 3) they demonstrate much higher fluorescence QY up to 20-30%. A series of mixed quantum-classical atomistic simulations illustrate that dielectric induced stabilization of nonradiative charge-transfer (CT) type states can lead to similar drastic reduction in fluorescence QY as seen experimentally. Fluorescence lifetime measurement reveals that the CT-type states exist as a competitive channel of the formation of emissive exciton-type states.

Thermodynamic phase behavior of API/polymer solid dispersions.

PubMed

Prudic, Anke; Ji, Yuanhui; Sadowski, Gabriele

2014-07-07

To improve the bioavailability of poorly soluble active pharmaceutical ingredients (APIs), these materials are often integrated into a polymer matrix that acts as a carrier. The resulting mixture is called a solid dispersion. In this work, the phase behaviors of solid dispersions were investigated as a function of the API as well as of the type and molecular weight of the carrier polymer. Specifically, the solubility of artemisinin and indomethacin was measured in different poly(ethylene glycol)s (PEG 400, PEG 6000, and PEG 35000). The measured solubility data and the solubility of sulfonamides in poly(vinylpyrrolidone) (PVP) K10 and PEG 35000 were modeled using the perturbed-chain statistical associating fluid theory (PC-SAFT). The results show that PC-SAFT predictions are in a good accordance with the experimental data, and PC-SAFT can be used to predict the whole phase diagram of an API/polymer solid dispersion as a function of the kind of API and polymer and of the polymer's molecular weight. This remarkably simplifies the screening process for suitable API/polymer combinations.

Immobilization of organic radioactive and non-radioactive liquid waste in a composite matrix

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

Galkin, Anatoliy; Gelis, Artem V.; Castiglioni, Andrew J.

A method for immobilizing liquid radioactive waste is provided, the method having the steps of mixing waste with polymer to form a non-liquid waste; contacting the non-liquid waste with a solidifying agent to create a mixture, heating the mixture to cause the polymer, waste, and filler to irreversibly bind in a solid phase, and compressing the solid phase into a monolith. The invention also provides a method for immobilizing liquid radioactive waste containing tritium, the method having the steps of mixing liquid waste with polymer to convert the liquid waste to a non-liquid waste, contacting the non-liquid waste with amore » solidifying agent to create a mixture, heating the mixture to form homogeneous, chemically stable solid phase, and compressing the chemically stable solid phase into a final waste form, wherein the polymer comprises approximately a 9:1 weight ratio mixture of styrene block co-polymers and cross linked co-polymers of acrylamides.« less

In-situ preparation of poly(ethylene oxide)/Li3PS4 hybrid polymer electrolyte with good nanofiller distribution for rechargeable solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Chen, Shaojie; Wang, Junye; Zhang, Zhihua; Wu, Linbin; Yao, Lili; Wei, Zhenyao; Deng, Yonghong; Xie, Dongjiu; Yao, Xiayin; Xu, Xiaoxiong

2018-05-01

Nano-sized fillers in a polymer matrix with good distribution can play a positive role in improving polymer electrolytes in the aspects of ionic conductivity, mechanical property and electrochemical performance of Li-ion cells. Herein, polyethylene oxide (PEO)/Li3PS4 hybrid polymer electrolyte is prepared via a new in-situ approach. The ionic conductivities of the novel hybrid electrolytes with variable proportions are measured, and the optimal electrolyte of PEO-2%vol Li3PS4 presents a considerable ionic conductivity of 8.01 × 10-4 S cm-1 at 60 °C and an electrochemical window up to 5.1 V. The tests of DSC and EDXS reveal that the Li3PS4 nanoparticles with better distribution, as active fillers scattering in the PEO, exhibit a positive effect on the transference of lithium ion and electrochemical interfacial stabilities. Finally, the assembled solid-state LiFePO4/Li battery presents a decent cycling performance (80.9% retention rate after 325 cycles at 60 °C) and excellent rate capacities with 153, 143, 139 and 127 mAh g-1 at the discharging rate of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C. It is fully proved that it is an advanced strategy to preparing the new organic/inorganic hybrid electrolytes for lithium-ion batteries applications.

A two-dimensional layered Cd(II) coordination polymer with a three-dimensional supramolecular architecture incorporating mixed multidentate N- and O-donor ligands.

PubMed

Huang, Qiu-Ying; Su, Ming-Yang; Meng, Xiang-Ru

2015-06-01

The combination of N-heterocyclic and multicarboxylate ligands is a good choice for the construction of metal-organic frameworks. In the title coordination polymer, poly[bis{μ2-1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole-κ(2)N(3):N(4)}(μ4-butanedioato-κ(4)O(1):O(1'):O(4):O(4'))(μ2-butanedioato-κ(2)O(1):O(4))dicadmium], [Cd(C4H4O4)(C9H8N6)]n, each Cd(II) ion exhibits an irregular octahedral CdO4N2 coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole (bimt) ligands. Cd(II) ions are connected by two kinds of crystallographically independent succinate ligands to generate a two-dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three-dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.

Efficient and Stable Photovoltaic Characteristics of Quasi-Solid State DSSC using Polymer Gel Electrolyte Based on Ionic Liquid in Organosiloxane Polymer Gels

NASA Astrophysics Data System (ADS)

Pujiarti, H.; Arsyad, W. S.; Shobih; Muliani, L.; Hidayat, R.

2018-04-01

Dye-Sensitized Solar Cell (DSSC) is still one of the promising solar cell types among the third generation of solar cells because of easiness of fabrication and variety of available materials. In this type of solar cell, the electrolyte is one of the important components for regenerating excited dyes and transporting electric charge carriers to the counter electrode. Indeed, the power conversion efficiency of DSSC can be then significantly affected by the chemical and physical properties of the electrolyte. The simplest electrolyte system of an I-/I3 - redox couple in an organic solvent, however, has some drawbacks due to corrosive properties, volatile and leakage problem. Use of solid phase or gel phase electrolyte may overcome those problems, but it is often considered to suppress the efficiency due to low ion diffusion. Here, we report the photovoltaic characteristics of DSSC using polymer gel electrolyte (PGE), which is composed of ionic liquid and an organosiloxane polymer gel. The better cell performance with power conversion efficiency of about 6% has been obtained by optimizing the mesoporous size of the TiO2 layer and the PGE viscosity.

Spectroscopic optimization of all-solid-state electrochromic devices using PANI

NASA Astrophysics Data System (ADS)

Hugot-Le Goff, Anne; Bernard, Marie-Claude; Bich, Vu T.; Binh, Nguyen T.; Zeng, Wen

1997-12-01

The interesting optical properties of polyaniline (PANI) allowed its utilization in all solid-state electrochromic devices. Using a sulfonic acid polymer as solid electrolyte gave to PANI an unusual optical behavior leading to electrochromic properties very superior to the properties that it has in any liquid inorganic electrolyte. The improved conductivity of PANI doped with AMP-sulfonate is displayed by the presence of a free-carriers tail even at pH as high as 4.5. The free-carriers tail is studied using UV/vis/near IR spectroscopy, and the kinetics of coloration/bleaching are studied using Optical Multichannel Analysis in the 1.5 - 3 eV range. The modifications of the PANI optical features by solid-state doping are examined. The possibility to still improve the performances of these devices--in particular their rate of color change--by using `secondarily doped' PANI is investigated, which requires a preliminary spectrochemical analysis of PANI films doped with camphorsulfonic acid and treated in m-cresol during their electrochemical polarization.

Alginate: properties and biomedical applications

PubMed Central

Lee, Kuen Yong; Mooney, David J.

2011-01-01

Alginate is a biomaterial that has found numerous applications in biomedical science and engineering due to its favorable properties, including biocompatibility and ease of gelation. Alginate hydrogels have been particularly attractive in wound healing, drug delivery, and tissue engineering applications to date, as these gels retain structural similarity to the extracellular matrices in tissues and can be manipulated to play several critical roles. This review will provide a comprehensive overview of general properties of alginate and its hydrogels, their biomedical applications, and suggest new perspectives for future studies with these polymers. PMID:22125349

Analysis of a nanocrystalline polymer dispersion of ebselen using solid-state NMR, Raman microscopy, and powder X-ray diffraction.

PubMed

Vogt, Frederick G; Williams, Glenn R

2012-07-01

Nanocrystalline drug-polymer dispersions are of significant interest in pharmaceutical delivery. The purpose of this work is to demonstrate the applicability of methods based on two-dimensional (2D) and multinuclear solid-state NMR (SSNMR) to a novel nanocrystalline pharmaceutical dispersion of ebselen with polyvinylpyrrolidone-vinyl acetate (PVP-VA), after initial characterization with other techniques. A nanocrystalline dispersion of ebselen with PVP-VA was prepared and characterized by powder X-ray diffraction (PXRD), confocal Raman microscopy and mapping, and differential scanning calorimetry (DSC), and then subjected to detailed 1D and 2D SSNMR analysis involving ¹H, ¹³C, and ⁷⁷Se isotopes and ¹H spin diffusion. PXRD was used to show that dispersion contains nanocrystalline ebselen in the 35-60 nm size range. Confocal Raman microscopy and spectral mapping were able to detect regions where short-range interactions may occur between ebselen and PVP-VA. Spin diffusion effects were analyzed using 2D SSNMR experiments and are able to directly detect interactions between ebselen and the surrounding PVP-VA. The methods used here, particularly the 2D SSNMR methods based on spin diffusion, provided detailed structural information about a nanocrystalline polymer dispersion of ebselen, and should be useful in other studies of these types of materials.

Alternative polymer separation technology by centrifugal force in a melted state

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

Dobrovszky, Károly; Ronkay, Ferenc, E-mail: ronkay@pt.bme.hu

2014-11-15

Highlights: • Waste separation should take place at high purity. • Developed a novel, alternative separation method, where the separation occurred in a melted state by centrifugal forces. • Possibility of separation two different plastics into neat fractions. • High purity fractions were established at granulates and also at prefabricated blend. • Results were verified by DSC, optical microscopy and Raman spectroscopy. - Abstract: In order to upgrade polymer waste during recycling, separation should take place at high purity. The present research was aimed to develop a novel, alternative separation opportunity, where the polymer fractions were separated by centrifugal forcemore » in melted state. The efficiency of the constructed separation equipment was verified by two immiscible plastics (polyethylene terephthalate, PET; low density polyethylene, LDPE), which have a high difference of density, and of which large quantities can also be found in the municipal solid waste. The results show that the developed equipment is suitable not only for separating dry blended mixtures of PET/LDPE into pure components again, but also for separating prefabricated polymer blends. By this process it becomes possible to recover pure polymer substances from multi-component products during the recycling process. The adequacy of results was verified by differential scanning calorimetry (DSC) measurement as well as optical microscopy and Raman spectroscopy.« less

Ionic Borate-Based Covalent Organic Frameworks: Lightweight Porous Materials for Lithium-Stable Solid State Electrolytes

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

Black, Hayden T.; Harrison, Katharine Lee

2016-10-01

The synthesis and characterization of the first polyelectrolyte of intrinsic microporosity (PEIM) is described. The novel material was synthesized via reaction between the nitrile group in the polymer backbone and n-butyl lithium, effectively anchoring an imine anion to the porous framework while introducing a mobile lithium counterion. The PEIM was characterized by 13C, 1H, and 7Li NMR experiments, revealing quantitative conversion of the nitrile functionality to the anionic imine. Variable temperature 7Li NMR analysis of the dry PEIM and the electrolyteswollen PEIM revealed that lithium ion transport within the dry PEIM was largely due to interchain hopping of the Limore » + ions, and that the mobility of polymer associated Li + was reduced after swelling in electrolyte solution. Meanwhile, the swollen PEIM supported efficient transport of dissolved Li + within the expanded pores. These results are discussed in the context of developing novel solid or solid-like lithium ion electrolytes using the new PEIM material.« less

Solid dispersion of efavirenz in PVP K-30 by conventional solvent and kneading methods.

PubMed

Alves, Lariza Darlene Santos; de La Roca Soares, Mônica Felts; de Albuquerque, Camila Tavares; da Silva, Elica Rodrigues; Vieira, Alexandre Couto Carneiro; Fontes, Danilo Augusto Ferreira; Figueirêdo, Camila Bezerra Melo; Soares Sobrinho, José Lamartine; Rolim Neto, Pedro José

2014-04-15

Efavirenz (EFV) used as a part of the treatment of first choice in antiretroviral therapy for AIDS has low aqueous solubility and presents problems of absorption. We thus initially present a phase solubility diagram with carriers of different classes. With a view to obtaining a solid dispersion (SD) with suitable consistency to that of a solid formulation, we chose to use PVP K-30, since polymers present some of the best results. The kneading (KN) and solvent evaporation (EV) methods were thus used at different rates. These were characterized by the way of DSC, FT-IR, SEM, DR-X and dissolution. SD EV proved unsatisfactory, resulting in a decreased dissolution rate, despite the amorphous state of the samples, while the SD KN 4:1 (EFV:polymer) and physical mixtures (PM) had a higher rate of dissolution. SD KN and PM 4:1 were also evaluated for stability after storage, with benefits being observed in relation to EFV. Copyright © 2014. Published by Elsevier Ltd.

Oil and fat absorbing polymers

NASA Technical Reports Server (NTRS)

Marsh, H. E., Jr. (Inventor)

1977-01-01

A method is described for forming a solid network polymer having a minimal amount of crosslinking for use in absorbing fats and oils. The polymer remains solid at a swelling ratio in oil or fat of at least ten and provides an oil absorption greater than 900 weight percent.

Ohm's Law, Batteries, and the Clean Energy Landscape

NASA Astrophysics Data System (ADS)

Balsara, Nitash

The need for creating safe electrolytes for lithium batteries is significant given the continued safety problems associated with current lithium-ion batteries. Nonflammable polymer electrolytes offer a possible solution but the rate of lithium ion transport is too low for practical applications. In this talk, I will discuss some of the fundamental factors that limit ion transport in polymers. Polymer electrolytes obey Ohm's Law, i.e. in the limit of small applied potentials, the current generated at steady state is proportional to the applied potential. Factors that determine the current generated will be determined using the continuum theory of Newman. Independent measurements of ion diffusion by pulsed-field gradient NMR will also be presented. The talk will end with a discussion of the possibility of commercializing all-solid batteries with polymer electrolytes.

Role of salt concentration in blend polymer for energy storage conversion devices

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

Arya, Anil; Sharma, A. L., E-mail: alsharmaiitkgp@gmail.com; Sadiq, M.

2016-05-06

Solid Polymer Electrolytes (SPE) are materials of considerable interest worldwide, which serves dual purpose of electrolyte and separator between electrode compartments in renewable energy conversion/storage devices such as; high energy density batteries, electrochromic display devices, and supercapacitors. Polymer blend electrolytes are prepared for various concentration of salt (Ö/Li) with the constant ratio (0.5 gm) of each PEO and PAN polymers (blend polymer) using solution casting technique. Solid polymeric ionic conductor as a separator is the ultimate substitute to eliminate the drawback related to liquid and gel polymer ionic conductors. In the present work, solid polymer electrolyte film consisting of PEO,more » PAN and LiPF{sub 6} are examined for various concentration of lithium salt by keeping PEO/PAN blend ratio as a constant with a view to optimize the dominant salt concentration which could give the maximum conductivity at ambient temperature.« less

A Green Method for Processing Polymers using Dense Gas Technology

PubMed Central

Yoganathan, Roshan B.; Mammucari, Raffaella; Foster, Neil R.

2010-01-01

Dense CO2 can be used as an environmentally-benign polymer processing medium because of its liquid-like densities and gas-like mass transfer properties.In this work, polymer bio-blends of polycarbonate (PC), a biocompatible polymer, and polycaprolactone (PCL), a biodegradable polymer were prepared. Dense CO2 was used as a reaction medium for the melt-phase PC polymerization in the presence of dense CO2-swollen PCL particles and this method was used to prepare porous PC/PCL blends. To extend the applicability of dense CO2 to the biomedical industry and polymer blend processing, the impregnation of ibuprofen into the blend was conducted and subsequent dissolution characteristics were observed.

Nanoporous adsorption effect on altering Li+ diffusion pathway by a highly ordered porous electrolyte additive for high rate all-solid-state lithium metal batteries.

PubMed

Li, Wenwen; Zhang, Sanpei; Wang, Bangrun; Gu, Sui; Xu, Dong; Wang, Jianing; Chen, Chunhua; Wen, Zhaoyin

2018-06-19

Solid polymer electrolytes (SPEs) have shown extraordinary promise for all-solid-state lithium metal batteries with high energy density and flexibility but are mainly limited by the low ionic conductivity and their poor stability with lithium metal anode. In this work, we propose a highly ordered porous electrolyte additive derived from SSZ-13 for high-rate all-solid-state lithium metal batteries. The nanoporous adsorption effect provided by the highly ordered porous nanoparticles in the poly (ethylene oxide) (PEO) electrolyte are found to significantly improve the Li + conductivity (1.91×10 -3 S cm -1 at 60°C, 4.43×10 -5 S cm -1 at 20°C) and widen the electrochemical stability window to 4.7 V vs Li + /Li. Meanwhile, the designed PEO-based electrolyte demonstrates enhanced stability with the lithium metal anode. Through systematically increasing Li + diffusion, widening the electrochemical stability window and enhancing the stability of the SSZ-CPE electrolyte, the LiFePO4/SSZ-CPE/Li cell is optimized to deliver high-rate capability and stable cycling performance, which demonstrates great potential for all-solid-state energy storage application.

"Cooking the sample": radiofrequency induced heating during solid-state NMR experiments.

PubMed

d'Espinose de Lacaillerie, Jean-Baptiste; Jarry, Benjamin; Pascui, Ovidiu; Reichert, Detlef

2005-09-01

Dissipation of radiofrequency (RF) energy as heat during continuous wave decoupling in solid-state NMR experiment was examined outside the conventional realm of such phenomena. A significant temperature increase could occur while performing dynamic NMR measurements provided the sample contains polar molecules and the sequence calls for relatively long applications of RF power. It was shown that the methyl flip motion in dimethylsulfone (DMS) is activated by the decoupling RF energy conversion to heat during a CODEX pulse sequence. This introduced a significant bias in the correlation time-temperature dependency measurement used to obtain the activation energy of the motion. By investigating the dependency of the temperature increase in hydrated lead nitrate on experimental parameters during high-power decoupling one-pulse experiments, the mechanisms for the RF energy deposition was identified. The samples were heated due to dissipation of the energy absorbed by dielectric losses, a phenomenon commonly known as "microwave" heating. It was thus established that during solid-state NMR experiments at moderate B0 fields, RF heating could lead to the heating of samples containing polar molecules such as hydrated polymers and inorganic solids. In particular, this could result in systematic errors for slow dynamics measurements by solid-state NMR.

Crystallization Kinetics of Indomethacin/Polyethylene Glycol Dispersions Containing High Drug Loadings.

PubMed

Duong, Tu Van; Van Humbeeck, Jan; Van den Mooter, Guy

2015-07-06

The reproducibility and consistency of physicochemical properties and pharmaceutical performance are major concerns during preparation of solid dispersions. The crystallization kinetics of drug/polyethylene glycol solid dispersions, an important factor that is governed by the properties of both drug and polymer has not been adequately explored, especially in systems containing high drug loadings. In this paper, by using standard and modulated differential scanning calorimetry and X-ray powder diffraction, we describe the influence of drug loading on crystallization behavior of dispersions made up of indomethacin and polyethylene glycol 6000. Higher drug loading increases the amorphicity of the polymer and inhibits the crystallization of PEG. At 52% drug loading, polyethylene glycol was completely transformed to the amorphous state. To the best of our knowledge, this is the first detailed investigation of the solubilization effect of a low molecular weight drug on a semicrystalline polymer in their dispersions. In mixtures containing up to 55% indomethacin, the dispersions exhibited distinct glass transition events resulting from amorphous-amorphous phase separation which generates polymer-rich and drug-rich domains upon the solidification of supercooled polyethylene glycol, whereas samples containing at least 60% drug showed a single amorphous phase during the period in which crystallization normally occurs. The current study demonstrates a wide range in physicochemical properties of drug/polyethylene glycol solid dispersions as a result of the complex nature in crystallization of this system, which should be taken into account during preparation and storage.

An overview on characterization, utilization and leachate analysis of biomedical waste incinerator ash.

PubMed

Rajor, Anita; Xaxa, Monika; Mehta, Ratika; Kunal

2012-10-15

Solid waste management is one of the major global environmental issues, as there is continuous increase in industrial globalization and generation of waste. Solid wastes encompass the heterogeneous mass of throwaways from the urban community as well as the homogeneous accumulations of agricultural, industrial and mineral wastes. Biomedical waste pose a significant impact on health and environment. A proper waste management system should be required to dispose hazardous biomedical waste and incineration should be the best available technology to reduce the volume of this hazardous waste. The incineration process destroys pathogens and reduces the waste volume and weight but leaves a solid material called biomedical waste ash as residue which increases the levels of heavy metals, inorganic salts and organic compounds in the environment. Disposal of biomedical waste ash in landfill may cause contamination of groundwater as metals are not destroyed during incineration. The limited space and the high cost for land disposal led to the development of recycling technologies and the reuse of ash in different systems. In order to minimize leaching of its hazardous components into the environment several studies confirmed the successful utilization of biomedical waste ash in agriculture and construction sector. This paper presents the overview on the beneficial use of ash in agriculture and construction materials and its leachate characteristics. This review also stressed on the need to further evaluate the leachate studies of the ashes and slag for their proper disposal and utilization. Copyright © 2012 Elsevier Ltd. All rights reserved.

Aqueous Processing for Printed Organic Electronics: Conjugated Polymers with Multistage Cleavable Side Chains

PubMed Central

2017-01-01

The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer’s side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics. PMID:28979937

Equilibrium Gold Nanoclusters Quenched with Biodegradable Polymers

PubMed Central

Murthy, Avinash K.; Stover, Robert J.; Borwankar, Ameya U.; Nie, Golay D.; Gourisankar, Sai; Truskett, Thomas M.; Sokolov, Konstantin V.; Johnston, Keith P.

2013-01-01

Although sub-100 nm nanoclusters of metal nanoparticles are of interest in many fields including biomedical imaging, sensors and catalysis, it has been challenging to control their morphologies and chemical properties. Herein, a new concept is presented to assemble equilibrium Au nanoclusters of controlled size by tuning the colloidal interactions with a polymeric stabilizer, PLA(1k)-b-PEG(10k)-b-PLA(1k). The nanoclusters form upon mixing a dispersion of ~5 nm Au nanospheres with a polymer solution followed by partial solvent evaporation. A weakly adsorbed polymer quenches the equilibrium nanocluster size and provides steric stabilization. Nanocluster size is tuned from ~20 nm to ~40 nm by experimentally varying the final Au nanoparticle concentration and the polymer/Au ratio, along with the charge on the initial Au nanoparticle surface. Upon biodegradation of the quencher, the nanoclusters reversibly and fully dissociate to individual ~5 nm primary particles. Equilibrium cluster size is predicted semi-quantitatively with a free energy model that balances short-ranged depletion and van der Waals attractions with longer-ranged electrostatic repulsion, as a function of the Au and polymer concentrations. The close spacings of the Au nanoparticles in the clusters produce strong NIR extinction over a broad range of wavelengths from 650 to 900 nm, which is of practical interest in biomedical imaging. PMID:23230905

Thomas Gennett | NREL

Science.gov Websites

catalysts through ion implantation and sputtering Non-aqueous flow batteries based on organic energy-storage organic radical polymer in the solid state," Journal of Physical Chemistry C (2015) 119(37), 21369 . Braunecker, T.W. Kemper, R.E. Larsen, T. Gennett, "Close packing of nitroxide radicals in stable organic

Polymerization of euphorbia oil in carbon dioxide media

USDA-ARS?s Scientific Manuscript database

Boron trifluoride diethyl etherate (BF3•OEt2), Lewis acid, catalyzed ring-opening polymerization of euphorbia oil (EO), a natural epoxy oil, was conducted in carbon dioxide. The resulting polymers (RPEO) were characterized by FTIR, 1H-NMR, 13C-NMR, solid state 13C-NMR spectroscopies, differential sc...

Coatings Based on Nanodispersed Oxide Materials Produced by the Method of Pneumatic Spraying

NASA Astrophysics Data System (ADS)

Potekaev, A. I.; Lysak, I. A.; Malinovskaya, T. D.; Lysak, G. V.

2018-03-01

New approaches are proposed, relying on which the coatings from nanodispersed oxide materials are formed on polypropylene fibers. It is shown that in the course of the viscous fluid - solid state transition of the polymer its nanoparticles are stabilized on the surface of the formed fibers.

Comparison of HPMC based polymers performance as carriers for manufacture of solid dispersions using the melt extruder.

PubMed

Ghosh, Indrajit; Snyder, Jennifer; Vippagunta, Radha; Alvine, Marilyn; Vakil, Ronak; Tong, Wei-Qin; Vippagunta, Sudha

2011-10-31

Preparation of amorphous solid dispersions using hot-melt extrusion process for poorly water soluble compounds which degrade on melting remains a challenge due to exposure to high temperatures. The aim of this study was to develop a physically and chemically stable amorphous solid dispersion of a poorly water-soluble compound, NVS981, which is highly thermal sensitive and degrades upon melting at 165 °C. Hydroxypropyl Methyl Cellulose (HPMC) based polymers; HPMC 3cps, HPMC phthalate (HPMCP) and HPMC acetyl succinate (HPMCAS) were selected as carriers to prepare solid dispersions using hot melt extrusion because of their relatively low glass transition temperatures. The solid dispersions were compared for their ease of manufacturing, physical stability such as recrystallization potential, phase separation, molecular mobility and enhancement of drug dissolution. Two different drug loads of 20 and 50% (w/w) were studied in each polymer system. It was interesting to note that solid dispersions with 50% (w/w) drug load were easier to process in the melt extruder compared to 20% (w/w) drug load in all three carriers, which was attributed to the plasticizing behavior of the drug substance. Upon storage at accelerated stability conditions, no phase separation was observed in HPMC 3cps and HPMCAS solid dispersions at the lower and higher drug load, whereas for HPMCP, phase separation was observed at higher drug load after 3 months. The pharmaceutical performance of these solid dispersions was evaluated by studying drug dissolution in pH 6.8 phosphate buffer. Drug release from solid dispersion prepared from polymers used for enteric coating, i.e. HPMCP and HPMCAS was faster compared with the water soluble polymer HPMC 3cps. In conclusion, of the 3 polymers studied for preparing solid dispersions of thermally sensitive compound using hot melt extrusion, HPMCAS was found to be the most promising as it was easily processible and provided stable solid dispersions with enhanced dissolution. Copyright © 2011 Elsevier B.V. All rights reserved.

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

PubMed Central

Li, Yutao; Zhou, Weidong; Chen, Xi; Lü, Xujie; Cui, Zhiming; Xin, Sen; Xue, Leigang; Jia, Quanxi; Goodenough, John B.

2016-01-01

A solid electrolyte with a high Li-ion conductivity and a small interfacial resistance against a Li metal anode is a key component in all-solid-state Li metal batteries, but there is no ceramic oxide electrolyte available for this application except the thin-film Li-P oxynitride electrolyte; ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites in a short time. Here, we introduce a solid electrolyte LiZr2(PO4)3 with rhombohedral structure at room temperature that has a bulk Li-ion conductivity σLi = 2 × 10−4 S⋅cm−1 at 25 °C, a high electrochemical stability up to 5.5 V versus Li+/Li, and a small interfacial resistance for Li+ transfer. It reacts with a metallic lithium anode to form a Li+-conducting passivation layer (solid-electrolyte interphase) containing Li3P and Li8ZrO6 that is wet by the lithium anode and also wets the LiZr2(PO4)3 electrolyte. An all-solid-state Li/LiFePO4 cell with a polymer catholyte shows good cyclability and a long cycle life. PMID:27821751

Novel nanofluidic chemical cells based on self-assembled solid-state SiO2 nanotubes.

PubMed

Zhu, Hao; Li, Haitao; Robertson, Joseph W F; Balijepalli, Arvind; Krylyuk, Sergiy; Davydov, Albert V; Kasianowicz, John J; Suehle, John S; Li, Qiliang

2017-10-27

Novel nanofluidic chemical cells based on self-assembled solid-state SiO 2 nanotubes on silicon-on-insulator (SOI) substrate have been successfully fabricated and characterized. The vertical SiO 2 nanotubes with a smooth cavity are built from Si nanowires which were epitaxially grown on the SOI substrate. The nanotubes have rigid, dry-oxidized SiO 2 walls with precisely controlled nanotube inner diameter, which is very attractive for chemical-/bio-sensing applications. No dispersion/aligning procedures were involved in the nanotube fabrication and integration by using this technology, enabling a clean and smooth chemical cell. Such a robust and well-controlled nanotube is an excellent case of developing functional nanomaterials by leveraging the strength of top-down lithography and the unique advantage of bottom-up growth. These solid, smooth, clean SiO 2 nanotubes and nanofluidic devices are very encouraging and attractive in future bio-medical applications, such as single molecule sensing and DNA sequencing.

Novel nanofluidic chemical cells based on self-assembled solid-state SiO2 nanotubes

NASA Astrophysics Data System (ADS)

Zhu, Hao; Li, Haitao; Robertson, Joseph W. F.; Balijepalli, Arvind; Krylyuk, Sergiy; Davydov, Albert V.; Kasianowicz, John J.; Suehle, John S.; Li, Qiliang

2017-10-01

Novel nanofluidic chemical cells based on self-assembled solid-state SiO2 nanotubes on silicon-on-insulator (SOI) substrate have been successfully fabricated and characterized. The vertical SiO2 nanotubes with a smooth cavity are built from Si nanowires which were epitaxially grown on the SOI substrate. The nanotubes have rigid, dry-oxidized SiO2 walls with precisely controlled nanotube inner diameter, which is very attractive for chemical-/bio-sensing applications. No dispersion/aligning procedures were involved in the nanotube fabrication and integration by using this technology, enabling a clean and smooth chemical cell. Such a robust and well-controlled nanotube is an excellent case of developing functional nanomaterials by leveraging the strength of top-down lithography and the unique advantage of bottom-up growth. These solid, smooth, clean SiO2 nanotubes and nanofluidic devices are very encouraging and attractive in future bio-medical applications, such as single molecule sensing and DNA sequencing.

Characterization of Hydrophobic Interactions of Polymers with Water and Phospholipid Membranes Using Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Drenscko, Mihaela

Polymers and lipid membranes are both essential soft materials. The structure and hydrophobicity/hydrophilicity of polymers, as well as the solvent they are embedded in, ultimately determines their size and shape. Understating the variation of shape of the polymer as well as its interactions with model biological membranes can assist in understanding the biocompatibility of the polymer itself. Computer simulations, in particular molecular dynamics, can aid in characterization of the interaction of polymers with solvent, as well as polymers with model membranes. In this thesis, molecular dynamics serve to describe polymer interactions with a solvent (water) and with a lipid membrane. To begin with, we characterize the hydrophobic collapse of single polystyrene chains in water using molecular dynamics simulations. Specifically, we calculate the potential of mean force for the collapse of a single polystyrene chain in water using metadynamics, comparing the results between all atomistic with coarse-grained molecular simulation. We next explore the scaling behavior of the collapsed globular shape at the minimum energy configuration, characterized by the radius of gyration, as a function of chain length. The exponent is close to one third, consistent with that predicted for a polymer chain in bad solvent. We also explore the scaling behavior of the Solvent Accessible Surface Area (SASA) as a function of chain length, finding a similar exponent for both all-atomistic and coarse-grained simulations. Furthermore, calculation of the local water density as a function of chain length near the minimum energy configuration suggests that intermediate chain lengths are more likely to form dewetted states, as compared to shorter or longer chain lengths. Next, in order to investigate the molecular interactions between single hydrophobic polymer chains and lipids in biological membranes and at lipid membrane/solvent interface, we perform a series of molecular dynamics simulations of small membranes using all atomistic and coarse-grained methods. The molecular interaction between common polymer chains used in biomedical applications and the cell membrane is unknown. This interaction may affect the biocompatibility of the polymer chains. Molecular dynamics simulations offer an emerging tool to characterize the interaction between common degradable polymer chains used in biomedical applications, such as polycaprolactone, and model cell membranes. We systematically characterize with long-time all-atomistic molecular dynamics simulations the interaction between single polycaprolactone chains of varying chain lengths with a model phospholipid membrane. We find that the length of polymer chain greatly affects the nature of interaction with the membrane, as well as the membrane properties. Furthermore, we next utilize advanced sampling techniques in molecular dynamics to characterize the two-dimensional free energy surface for the interaction of varying polymer chain lengths (short, intermediate, and long) with model cell membranes. We find that the free energy minimum shifts from the membrane-water interface to the hydrophobic core of the phospholipid membrane as a function of chain length. These results can be used to design polymer chain lengths and chemistries to optimize their interaction with cell membranes at the molecular level.

Use of Atomic Oxygen for Increased Water Contact Angles of Various Polymers for Biomedical Applications

NASA Technical Reports Server (NTRS)

deGroh, Kim; Berger, Lauren; Roberts, Lily

2009-01-01

The purpose of this study was to determine the effect of atomic oxygen (AO) exposure on the hydrophilicity of nine different polymers for biomedical applications. Atomic oxygen treatment can alter the chemistry and morphology of polymer surfaces, which may increase the adhesion and spreading of cells on Petri dishes and enhance implant growth. Therefore, nine different polymers were exposed to atomic oxygen and water-contact angle, or hydrophilicity, was measured after exposure. To determine whether hydrophilicity remains static after initial atomic oxygen exposure, or changes with higher fluence exposures, the contact angles between the polymer and water droplet placed on the polymer s surface were measured versus AO fluence. The polymers were exposed to atomic oxygen in a 100-W, 13.56-MHz radio frequency (RF) plasma asher, and the treatment was found to significantly alter the hydrophilicity of non-fluorinated polymers. Pristine samples were compared with samples that had been exposed to AO at various fluence levels. Minimum and maximum fluences for the ashing trials were set based on the effective AO erosion of a Kapton witness coupon in the asher. The time intervals for ashing were determined by finding the logarithmic values of the minimum and maximum fluences. The difference of these two values was divided by the desired number of intervals (ideally 10). The initial desired fluence was then multiplied by this result (2.37), as was each subsequent desired fluence. The flux in the asher was determined to be approximately 3.0 x 10(exp 15) atoms/sq cm/sec, and each polymer was exposed to a maximum fluence of 5.16 x 10(exp 20) atoms/sq cm.

Publications in biomedical and environmental sciences programs, 1981

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

Moody, J.B.

1982-07-01

This bibliography contains 698 references to articles in journals, books, and reports published in the subject area of biomedical and environmental sciences during 1981. There are 520 references to articles published in journals and books and 178 references to reports. Staff members in the Biomedical and Environmental Sciences divisions have other publications not included in this bibliography; for example, theses, book reviews, abstracts published in journals or symposia proceedings, pending journal publications and reports such as monthly, bimonthly, and quarterly progress reports, contractor reports, and reports for internal distribution. This document is sorted by the division, and then alphabetically bymore » author. The sorting by divisions separates the references by subject area in a simple way. The divisions represented in the order that they appear in the bibliography are Analytical Chemistry, Biology, Chemical Technology, Information R and D, Health and Safety Research, Instrumentation and Controls, Computer Sciences, Energy, Engineering Technology, Solid State, Central Management, Operations, and Environmental Sciences. Indexes are provided by author, title, and journal reference.« less

Wafer-scale integrated micro-supercapacitors on an ultrathin and highly flexible biomedical platform.

PubMed

Maeng, Jimin; Meng, Chuizhou; Irazoqui, Pedro P

2015-02-01

We present wafer-scale integrated micro-supercapacitors on an ultrathin and highly flexible parylene platform, as progress toward sustainably powering biomedical microsystems suitable for implantable and wearable applications. All-solid-state, low-profile (<30 μm), and high-density (up to ~500 μF/mm(2)) micro-supercapacitors are formed on an ultrathin (~20 μm) freestanding parylene film by a wafer-scale parylene packaging process in combination with a polyaniline (PANI) nanowire growth technique assisted by surface plasma treatment. These micro-supercapacitors are highly flexible and shown to be resilient toward flexural stress. Further, direct integration of micro-supercapacitors into a radio frequency (RF) rectifying circuit is achieved on a single parylene platform, yielding a complete RF energy harvesting microsystem. The system discharging rate is shown to improve by ~17 times in the presence of the integrated micro-supercapacitors. This result suggests that the integrated micro-supercapacitor technology described herein is a promising strategy for sustainably powering biomedical microsystems dedicated to implantable and wearable applications.

Applications of conducting polymers and their issues in biomedical engineering

PubMed Central

Ravichandran, Rajeswari; Sundarrajan, Subramanian; Venugopal, Jayarama Reddy; Mukherjee, Shayanti; Ramakrishna, Seeram

2010-01-01

Conducting polymers (CPs) have attracted much interest as suitable matrices of biomolecules and have been used to enhance the stability, speed and sensitivity of various biomedical devices. Moreover, CPs are inexpensive, easy to synthesize and versatile because their properties can be readily modulated by (i) surface functionalization techniques and (ii) the use of a wide range of molecules that can be entrapped or used as dopants. This paper discusses the various surface modifications of the CP that can be employed in order to impart physico-chemical and biological guidance cues that promote cell adhesion/proliferation at the polymer–tissue interface. This ability of the CP to induce various cellular mechanisms widens its applications in medical fields and bioengineering. PMID:20610422

First Principles Modeling of Structure and Transport in Solid Polymer Electrolytes, Ionic Liquids, and Methanol/Water Mixtures

DTIC Science & Technology

2016-02-10

potential in making high- performance solid state lithium ion batteries [1,2]. Among them, the polyethylene oxide-alkali salts systems PEO6:XPF6 (X = H...electrolytes for magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group...magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group of Prof. Vito Di

Solid polymeric electrolytes for lithium batteries

DOEpatents

Angell, Charles A.; Xu, Wu; Sun, Xiaoguang

2006-03-14

Novel conductive polyanionic polymers and methods for their preparion are provided. The polyanionic polymers comprise repeating units of weakly-coordinating anionic groups chemically linked to polymer chains. The polymer chains in turn comprise repeating spacer groups. Spacer groups can be chosen to be of length and structure to impart desired electrochemical and physical properties to the polymers. Preferred embodiments are prepared from precursor polymers comprising the Lewis acid borate tri-coordinated to a selected ligand and repeating spacer groups to form repeating polymer chain units. These precursor polymers are reacted with a chosen Lewis base to form a polyanionic polymer comprising weakly coordinating anionic groups spaced at chosen intervals along the polymer chain. The polyanionic polymers exhibit high conductivity and physical properties which make them suitable as solid polymeric electrolytes in lithium batteries, especially secondary lithium batteries.

Solid polymer battery electrolyte and reactive metal-water battery

DOEpatents

Harrup, Mason K.; Peterson, Eric S.; Stewart, Frederick F.

2000-01-01

In one implementation, a reactive metal-water battery includes an anode comprising a metal in atomic or alloy form selected from the group consisting of periodic table Group 1A metals, periodic table Group 2A metals and mixtures thereof. The battery includes a cathode comprising water. Such also includes a solid polymer electrolyte comprising a polyphosphazene comprising ligands bonded with a phosphazene polymer backbone. The ligands comprise an aromatic ring containing hydrophobic portion and a metal ion carrier portion. The metal ion carrier portion is bonded at one location with the polymer backbone and at another location with the aromatic ring containing hydrophobic portion. The invention also contemplates such solid polymer electrolytes use in reactive metal/water batteries, and in any other battery.

Design, construction and performance of a portable handheld electrohydrodynamic multi-needle spray gun for biomedical applications.

PubMed

Sofokleous, Panagiotis; Stride, Eleanor; Bonfield, William; Edirisinghe, Mohan

2013-01-01

Electrohydrodynamic (EHD) processing has attracted substantial interest in the technological and pharmaceutical sectors in recent years. Given the complexity of the process, exploring new ideas for EHD electrospraying and electrospinning delivery is a challenge. In this article, the design, construction and testing of a portable handheld EHD multi-needle device are described to produce multifunctional particles and fibers. Solid and encapsulated polymer particles and fibers were generated in order to study the performance of the device. The intrinsic properties of the feed solution/suspension and the processing conditions were adjusted to ensure robustness of the process and give uniform and reproducible products, with diameters ranging from the sub-micrometer scale to a few micrometers. These products have a broad range of applications in many advanced industrial sectors e.g. drug delivery systems, wound dressing patches, low calorie food products and cosmetics. Copyright © 2012 Elsevier B.V. All rights reserved.

Rapid self-assembly of complex biomolecular architectures during mussel byssus biofabrication

PubMed Central

Priemel, Tobias; Degtyar, Elena; Dean, Mason N.; Harrington, Matthew J.

2017-01-01

Protein-based biogenic materials provide important inspiration for the development of high-performance polymers. The fibrous mussel byssus, for instance, exhibits exceptional wet adhesion, abrasion resistance, toughness and self-healing capacity–properties that arise from an intricate hierarchical organization formed in minutes from a fluid secretion of over 10 different protein precursors. However, a poor understanding of this dynamic biofabrication process has hindered effective translation of byssus design principles into synthetic materials. Here, we explore mussel byssus assembly in Mytilus edulis using a synergistic combination of histological staining and confocal Raman microspectroscopy, enabling in situ tracking of specific proteins during induced thread formation from soluble precursors to solid fibres. Our findings reveal critical insights into this complex biological manufacturing process, showing that protein precursors spontaneously self-assemble into complex architectures, while maturation proceeds in subsequent regulated steps. Beyond their biological importance, these findings may guide development of advanced materials with biomedical and industrial relevance. PMID:28262668

Biodegradable ceramic-polymer composites for biomedical applications: A review.

PubMed

Dziadek, Michal; Stodolak-Zych, Ewa; Cholewa-Kowalska, Katarzyna

2017-02-01

The present work focuses on the state-of-the-art of biodegradable ceramic-polymer composites with particular emphasis on influence of various types of ceramic fillers on properties of the composites. First, the general needs to create composite materials for medical applications are briefly introduced. Second, various types of polymeric materials used as matrices of ceramic-containing composites and their properties are reviewed. Third, silica nanocomposites and their material as well as biological characteristics are presented. Fourth, different types of glass fillers including silicate, borate and phosphate glasses and their effect on a number of properties of the composites are described. Fifth, wollastonite as a composite modifier and its effect on composite characteristics are discussed. Sixth, composites containing calcium phosphate ceramics, namely hydroxyapatite, tricalcium phosphate and biphasic calcium phosphate are presented. Finally, general possibilities for control of properties of composite materials are highlighted. Copyright © 2016 Elsevier B.V. All rights reserved.

Conformal Electroplating of Azobenzene-Based Solar Thermal Fuels onto Large-Area and Fiber Geometries.

PubMed

Zhitomirsky, David; Grossman, Jeffrey C

2016-10-05

There is tremendous growth in fields where small functional molecules and colloidal nanomaterials are integrated into thin films for solid-state device applications. Many of these materials are synthesized in solution and there often exists a significant barrier to transition them into the solid state in an efficient manner. Here, we develop a methodology employing an electrodepositable copolymer consisting of small functional molecules for applications in solar energy harvesting and storage. We employ azobenzene solar thermal fuel polymers and functionalize them to enable deposition from low concentration solutions in methanol, resulting in uniform and large-area thin films. This approach enables conformal deposition on a variety of conducting substrates that can be either flat or structured depending on the application. Our approach further enables control over film growth via electrodepsition conditions and results in highly uniform films of hundreds of nanometers to microns in thickness. We demonstrate that this method enables superior retention of solar thermal fuel properties, with energy densities of ∼90 J/g, chargeability in the solid state, and exceptional materials utilization compared to other solid-state processing approaches. This novel approach is applicable to systems such as photon upconversion, photovoltaics, photosensing, light emission, and beyond, where small functional molecules enable solid-state applications.

Relating hydrogen-bonding interactions with the phase behavior of naproxen/PVP K 25 solid dispersions: evaluation of solution-cast and quench-cooled films.

PubMed

Paudel, Amrit; Nies, Erik; Van den Mooter, Guy

2012-11-05

In this work, we investigated the relationship between various intermolecular hydrogen-bonding (H-bonding) interactions and the miscibility of the model hydrophobic drug naproxen with the hydrophilic polymer polyvinylpyrrolidone (PVP) across an entire composition range of solid dispersions prepared by quasi-equilibrium film casting and nonequilibrium melt quench cooling. The binary phase behavior in solid dispersions exhibited substantial processing method dependence. The solid state solubility of crystalline naproxen in PVP to form amorphous solid dispersions was 35% and 70% w/w naproxen in solution-cast films and quench-cooled films, respectively. However, the presence of a single mixed phase glass transition indicated the amorphous miscibility to be 20% w/w naproxen for the films, beyond which amorphous-amorphous and/or crystalline phase separations were apparent. This was further supported by the solution state interactions data such as PVP globular size distribution and solution infrared spectral profiles. The borderline melt composition showed cooling rate dependence of amorphization. The glass transition and melting point depression profiles of the system were treated with the analytical expressions based on Flory-Huggins mixing theory to interpolate the equilibrium solid solubility. FTIR analysis and subsequent spectral deconvolution revealed composition and miscibility dependent variations in the strength of drug-polymer intermolecular H-bonding. Two types of H-bonded populations were evidenced from 25% w/w and 35% w/w naproxen in solution-cast films and quench-cooled films, respectively, with the higher fraction of strongly H-bonded population in the drug rich domains of phase separated amorphous film compositions and highly drug loaded amorphous quench-cooled dispersions.

New metastable form of glibenclamide prepared by redispersion from ternary solid dispersions containing polyvinylpyrrolidone-K30 and sodium lauryl sulfate.

PubMed

Thongnopkoon, Thanu; Puttipipatkhachorn, Satit

2016-01-01

Modification of polymorphic forms of poorly water-soluble drugs is one way to achieve the desirable properties. In this study, glibenclamide (GBM) particles with different polymorphic forms, including a new metastable form, were obtained from redispersion of ternary solid dispersion systems. The ternary solid dispersion systems, consisting of GBM, polyvinylpyrrolidone-K30 (PVP-K30) and sodium lauryl sulfate (SLS), were prepared by solvent evaporation method and subsequently redispersed in deionized water. The precipitated drug particles were then collected at a given time period. The drug particles with different polymorphic forms could be achieved depending on the polymer/surfactant ratio. Amorphous drug nanoparticles could be obtained by using a high polymer/surfactant ratio, whereas two different crystalline forms were obtained from the systems containing low polymer/surfactant ratios. Interestingly, a new metastable form IV of GBM with improved dissolution behavior could be obtained from the system of GBM:PVP-K30:SLS with the weight ratio of 2:2:4. This new polymorphic form IV of GBM was confirmed by differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffractometry (PXRD) and solid state 13 C nuclear magnetic resonance (NMR) spectroscopy. The molecular arrangement of the new polymorphic form IV of GBM was proposed. The GBM particles with polymorphic form IV also showed an improved dissolution behavior. In addition, it was found that the formation of the new polymorphic form IV of GBM by this process was reproducible.

Improved physicochemical characteristics of felodipine solid dispersion particles by supercritical anti-solvent precipitation process.

PubMed

Won, Dong-Han; Kim, Min-Soo; Lee, Sibeum; Park, Jeong-Sook; Hwang, Sung-Joo

2005-09-14

Solid dispersions of felodipine were formulated with HPMC and surfactants by the conventional solvent evaporation (CSE) and supercritical anti-solvent precipitation (SAS) methods. The solid dispersion particles were characterized by particle size, zeta potential, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), powder X-ray diffraction (XRD), solubility and dissolution studies. The effects of the drug/polymer ratio and surfactants on the solubility of felodipine were also studied. The mean particle size of the solid dispersions was 200-250 nm; these had a relatively regular spherical shape with a narrow size distribution. The particle size of the solid dispersions from the CSE method increased at 1 h after dispersed in distilled water. However, the particle sizes of solid dispersions from the SAS process were maintained for 6 h due to the increased solubility of felodipine. The physical state of felodipine changed from crystalline to amorphous during the CSE and SAS processes, confirmed by DSC/XRD data. The equilibrium solubility of the felodipine solid dispersion prepared by the SAS process was 1.5-20 microg/ml, while the maximum solubility was 35-110 microg/ml. Moreover, the solubility of felodipine increased with decreasing drug/polymer ratio or increasing HCO-60 content. The solid dispersions from the SAS process showed a high dissolution rate of over 90% within 2 h. The SAS process system may be used to enhance solubility or to produce oral dosage forms with high dissolution rate.

Enhanced intestinal permeability and oral bioavailability of enalapril maleate upon complexation with the cationic polymethacrylate Eudragit E100.

PubMed

Ramírez-Rigo, María V; Olivera, María E; Rubio, Modesto; Manzo, Ruben H

2014-05-13

The low bioavailability of enalapril maleate associated to its instability in solid state motivated the development of a polyelectrolyte-drug complex between enalapril maleate and the cationic polymethacrylate Eudragit E100. The solid complexes were characterized by DSC-TG, FT-IR and X-ray diffraction. Their aqueous dispersions were evaluated for drug delivery in bicompartimental Franz cells and electrokinetic potentials. Stability in solid state was also evaluated using an HPLC-UV stability indicating method. Absorption of enalapril maleate was assessed thorough the rat everted gut sac model. In addition, urinary recovery after oral administration in rats was used as an indicator of systemic exposition. The solid materials are stable amorphous solids in which both moieties of enalapril maleate are ionically bonded to the polymer. Their aqueous dispersions exhibited controlled release over more than 7h in physiologic saline solution, being ionic exchange the fundamental mechanism that modified the extent and rate of drug release. Intestinal permeation of enalapril maleate was 1.7 times higher in the presence of the cationic polymer. This increase can be related with the capacity to adhere the mucosa due to the positive zeta potential of the complexes. As a consequence bioavailability was significantly improved (1.39 times) after oral administration of the complexes. In addition, no signs of chemical decomposition were observed after a 14months period. The results indicated that the products are new chemical entities that improve unfavorable properties of a useful drug. Copyright © 2014 Elsevier B.V. All rights reserved.

Manipulating Semicrystalline Polymers in Confinement.

PubMed

Shingne, Nitin; Geuss, Markus; Thurn-Albrecht, Thomas; Schmidt, Hans-Werner; Mijangos, Carmen; Steinhart, Martin; Martín, Jaime

2017-08-17

Because final properties of nanoscale polymeric structures are largely determined by the solid-state microstructure of the confined polymer, it is imperative not only to understand how the microstructure of polymers develops under nanoscale confinement but also to establish means to manipulate it. Here we present a series of processing strategies, adapted from methods used in bulk polymer processing, that allow us to control the solidification of polymer nanostructures. First, we show that supramolecular nucleating agents can be readily used to modify the crystallization kinetics of confined poly(vinylidene fluoride) (PVDF). In addition, we demonstrate that microstructural features that are not traditionally affected by nucleating agents, such as the orientation of crystals, can be tuned with the crystallization temperature applied. Interestingly, we also show that high crystallization temperatures and long annealing periods induce the formation of the γ modification of PVDF, hence enabling the simple production of ferro/piezoelectric nanostructures. We anticipate that the approaches presented here can open up a plethora of new possibilities for the processing of polymer-based nanostructures with tailored properties and functionalities.

Structural modifications of polymethacrylates: impact on thermal behavior and release characteristics of glassy solid solutions.

PubMed

Claeys, Bart; De Coen, Ruben; De Geest, Bruno G; de la Rosa, Victor R; Hoogenboom, Richard; Carleer, Robert; Adriaensens, Peter; Remon, Jean Paul; Vervaet, Chris

2013-11-01

Polymethacrylates such as Eudragit® polymers are well established as drug delivery matrix. Here, we synthesize several Eudragit E PO (n-butyl-, dimethylaminoethyl-, methyl-methacrylate-terpolymer) analogues via free radical polymerization. These polymers are processed via hot melt extrusion, followed by injection molding and evaluated as carriers to produce immediate release solid solution tablets. Three chemical modifications increased the glass transition temperature of the polymer: (a) substitution of n-butyl by t-butyl groups, (b) reduction of the dimethylaminoethyl methacrylate (DMAEMA) content, and (c) incorporation of a bulky isobornyl repeating unit. These structural modifications revealed the possibility to increase the mechanical stability of the tablets via altering the polymer Tg without influencing the drug release characteristics and glassy solid solution forming properties. The presence of DMAEMA units proved to be crucial with respect to API/polymer interaction (essential in creating glassy solid solutions) and drug release characteristics. Moreover, these chemical modifications accentuate the need for a more rational design of (methacrylate) polymer matrix excipients for drug formulation via hot melt extrusion and injection molding. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrical conductivity studies on Ammonium bromide incorporated with Zwitterionic polymer blend electrolyte for battery application

NASA Astrophysics Data System (ADS)

Parameswaran, V.; Nallamuthu, N.; Devendran, P.; Nagarajan, E. R.; Manikandan, A.

2017-06-01

Solid polymer blend electrolytes are widely studied due to their extensive applications particularly in electrochemical devices. Blending polymer makes the thermal stability, higher mechanical strength and inorganic salt provide ionic charge carrier to enhance the conductivity. In these studies, 50% polyvinyl alcohol (PVA), 50% poly (N-vinyl pyrrolidone) (PVP) and 2.5% L-Asparagine mixed with different ratio of the Ammonium bromide (NH4Br), have been synthesized using solution casting technique. The prepared PVA/PVP/L-Asparagine/doped-NH4Br polymer blend electrolyte films have been characterized by various analytical methods such as FT-IR, XRD, impedance spectroscopy, TG-DSC and scanning electron microscopy. FT-IR, XRD and TG/DSC analysis revealed the structural and thermal behavior of the complex formation between PVA/PVP/L-Asparagine/doped-NH4Br. The ionic conductivity and the dielectric properties of PVA/PVP/L-Asparagine/doped-NH4Br polymer blend electrolyte films were examined using impedance analysis. The highest ionic conductivity was found to be 2.34×10-4 S cm-1 for the m.wt. composition of 50%PVA:50%PVP:2.5%L-Asparagine:doped 0.15 g NH4Br at ambient temperature. Solid state proton battery is fabricated and the observed open circuit voltage is 1.1 V and its performance has been studied.

Nanocrystal/sol-gel nanocomposites

DOEpatents

Klimov, Victor L.; Petruska, Melissa A.

2010-05-25

The present invention is directed to a process for preparing a solid composite having colloidal nanocrystals dispersed within a sol-gel matrix, the process including admixing colloidal nanocrystals with an amphiphilic polymer including hydrophilic groups selected from the group consisting of --COOH, --OH, --SO.sub.3H, --NH.sub.2, and --PO.sub.3H.sub.2 within a solvent to form an alcohol-soluble colloidal nanocrystal-polymer complex, admixing the alcohol-soluble colloidal nanocrystal-polymer complex and a sol-gel precursor material, and, forming the solid composite from the admixture. The present invention is also directed to the resultant solid composites and to the alcohol-soluble colloidal nanocrystal-polymer complexes.

Solid State Ionics: from Michael Faraday to green energy-the European dimension.

PubMed

Funke, Klaus

2013-08-01

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag 2 S and PbF 2 and coined terms such as cation and anion , electrode and electrolyte . In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an 'evolving scheme of materials science', point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987.

Solid State Ionics: from Michael Faraday to green energy—the European dimension

PubMed Central

Funke, Klaus

2013-01-01

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag2S and PbF2 and coined terms such as cation and anion, electrode and electrolyte. In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an ‘evolving scheme of materials science’, point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987. PMID:27877585

Fabrication and characterization of shape memory polymers at small-scales

NASA Astrophysics Data System (ADS)

Wornyo, Edem

The objective of this research is to thoroughly investigate the shape memory effect in polymers, characterize, and optimize these polymers for applications in information storage systems. Previous research effort in this field concentrated on shape memory metals for biomedical applications such as stents. Minimal work has been done on shape memory polymers; and the available work on shape memory polymers has not characterized the behaviors of this category of polymers fully. Copolymer shape memory materials based on diethylene glycol dimethacrylate (DEGDMA) crosslinker, and tert butyl acrylate (tBA) monomer are designed. The design encompasses a careful control of the backbone chemistry of the materials. Characterization methods such as dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC); and novel nanoscale techniques such as atomic force microscopy (AFM), and nanoindentation are applied to this system of materials. Designed experiments are conducted on the materials to optimize spin coating conditions for thin films. Furthermore, the recovery, a key for the use of these polymeric materials for information storage, is examined in detail with respect to temperature. In sum, the overarching objectives of the proposed research are to: (i) Design shape memory polymers based on polyethylene glycol dimethacrylate (PEGDMA) and diethylene glycol dimethacrylate (DEGDMA) crosslinkers, 2-hydroxyethyl methacrylate (HEMA) and tert-butyl acrylate monomer (tBA). (ii) Utilize dynamic mechanical analysis (DMA) to comprehend the thermomechanical properties of shape memory polymers based on DEGDMA and tBA. (iii) Utilize nanoindentation and atomic force microscopy (AFM) to understand the nanoscale behavior of these SMPs, and explore the strain storage and recovery of the polymers from a deformed state. (iv) Study spin coating conditions on thin film quality with designed experiments. (iv) Apply neural networks and genetic algorithms to optimize these systems.

Solid Polymer Electrolyte (SPE) fuel cell technology program

NASA Technical Reports Server (NTRS)

1979-01-01

The overall objectives of the Phase IV Solid Polymer Electrolyte Fuel Cell Technology Program were to: (1) establish fuel cell life and performance at temperatures, pressures and current densities significantly higher than those previously demonstrated; (2) provide the ground work for a space energy storage system based on the solid polymer electrolyte technology (i.e., regenerative H2/O2 fuel cell); (3) design, fabricate and test evaluate a full-scale single cell unit. During this phase, significant progress was made toward the accomplishment of these objectives.

Synthesis and characterization of citrate-based fluorescent small molecules and biodegradable polymers.

PubMed

Xie, Zhiwei; Kim, Jimin P; Cai, Qing; Zhang, Yi; Guo, Jinshan; Dhami, Ranjodh S; Li, Li; Kong, Bin; Su, Yixue; Schug, Kevin A; Yang, Jian

2017-03-01

Novel citric acid based photoluminescent dyes and biodegradable polymers are synthesized via a facile "one-pot" reaction. A comprehensive understanding of the fluorescence mechanisms of the resulting citric acid-based fluorophores is reported. Two distinct types of fluorophores are identified: a thiozolopyridine family with high quantum yield, long lifetime, and exceptional photostability, and a dioxopyridine family with relatively lower quantum yield, multiple lifetimes, and solvent-dependent band shifting behavior. Applications in molecular labeling and cell imaging were demonstrated. The above discoveries contribute to the field of fluorescence chemistry and have laid a solid foundation for further development of new fluorophores and materials that show promise in a diversity of fluorescence-based applications. Photoluminescent materials are pivotal for fluorescence based imaging, labeling and sensing applications. Understanding their fluorescence mechanism is challenging and imperative. We develop a new class of citric acid-derived fluorescent materials in forms of polymers and small molecular dyes by a one-step solvent free reaction. We discovered two different classes of citric acid-derived fluorophores. A two-ring thiozolopyridine structure demonstrates strong fluorescence and exceptional resistance to photo-bleaching. A one-ring dioxopyridine exhibits relative weak fluorescence but with intriguing excitation and solvent-dependent emission wavelength shifting. Our methodology of synthesizing citric acid-derived fluorophores and the understanding on their luminescence are instrumental to the design and production of a large number of new photoluminescent materials for biological and biomedical applications. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

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

Pearse, Alexander J.; Schmitt, Thomas E.; Fuller, Elliot J.

Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiO tBu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li 2PO 2N between 250 and 300°C. The P/N ratio of the films is always 1, indicative of a particular polymorph ofmore » LiPON which closely resembles a polyphosphazene. Films grown at 300°C have an ionic conductivity of (6.51 ± 0.36)×10 -7 S/cm at 35°C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li +. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO 2 as the cathode and Si as the anode operating at up to 1 mA/cm 2. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<40nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.« less

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

DOE PAGES

Pearse, Alexander J.; Schmitt, Thomas E.; Fuller, Elliot J.; ...

2017-04-10

Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiO tBu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li 2PO 2N between 250 and 300°C. The P/N ratio of the films is always 1, indicative of a particular polymorph ofmore » LiPON which closely resembles a polyphosphazene. Films grown at 300°C have an ionic conductivity of (6.51 ± 0.36)×10 -7 S/cm at 35°C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li +. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO 2 as the cathode and Si as the anode operating at up to 1 mA/cm 2. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<40nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.« less

The competition of hydrogen-like and isotropic interactions on polymer collapse

NASA Astrophysics Data System (ADS)

Krawczyk, J.; Owczarek, A. L.; Prellberg, T.

2007-09-01

We investigate a lattice model of polymers where the nearest neighbour monomer monomer interaction strengths differ according to whether the local configurations have so-called 'hydrogen-like' formations or not. If the interaction strengths are all the same then the classical θ-point collapse transition occurs on lowering the temperature, and the polymer enters the isotropic liquid drop phase known as the collapsed globule. On the other hand, strongly favouring the hydrogen-like interactions gives rise to an anisotropic folded (solid-like) phase on lowering the temperature. We use Monte Carlo simulations up to a length of 256 to map out the phase diagram in the plane of parameters and determine the order of the associated phase transitions. We discuss the connections to semi-flexible polymers and other polymer models. Importantly, we demonstrate that for a range of energy parameters, two phase transitions occur on lowering the temperature, the second being a transition from the globule state to the crystal state. We argue from our data that this globule-to-crystal transition is continuous in two dimensions in accord with field-theory arguments concerning Hamiltonian walks, but is first order in three dimensions.

Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

PubMed

Sun, Che-Nan; Zawodzinski, Thomas A; Tenhaeff, Wyatt E; Ren, Fei; Keum, Jong Kahk; Bi, Sheng; Li, Dawen; Ahn, Suk-Kyun; Hong, Kunlun; Rondinone, Adam J; Carrillo, Jan-Michael Y; Do, Changwoo; Sumpter, Bobby G; Chen, Jihua

2015-03-28

Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

Porous organic polymers with different pore structures for sensitive solid-phase microextraction of environmental organic pollutants.

PubMed

Huang, Zhoubing; Liu, Shuqin; Xu, Jianqiao; Yin, Li; Zheng, Juan; Zhou, Ningbo; Ouyang, Gangfeng

2017-10-09

Adsorption capacity is the major sensitivity-limited factor in solid-phase microextraction. Due to its light-weight properties, large specific surface area and high porosity, especially tunable pore structures, the utilization of porous organic polymers as solid-phase microextraction adsorbents has attracting researchers' attentions. However, these works mostly concentrated on the utilization of specific porous organic polymers for preparing high-performance solid-phase microextraction coatings. The relationship between pore structures and adsorption performance of the porous organic polymers still remain unclear. Herein, three porous organic polymers with similar properties but different pore distributions were prepared by condensation polymerization reaction of phloroglucinol and terephthalaldehyde, which were fabricated as solid-phase microextraction coatings subsequently. The adsorption capacity of the porous organic polymers-coated fibers were evaluated by using benzene and its derivatives (i.e.,benzene, toluene, ethylbenzene and m-xylene) and polycyclic aromatic hydrocarbons as the target analytes. The results showed that the different adsorption performance of these porous organic polymers was mainly caused by their different pore volumes instead of their surface areas or pore sizes. Finally, the proposed method by using the mesoporous organic polymer coating was successfully applied to the determination of benzene and its derivatives in environmental water samples. As for analytical performance, high pre-concentration factors (74-2984), satisfactory relative recoveries (94.5 ± 18.5-116.9 ± 12.5%), intraday precision (2.44-5.34%), inter-day precision (4.62-7.02%), low limit of detections (LODs, 0.10-0.29 ng L -1 ) and limit of quantifications (LOQs, 0.33-0.96 ng L -1 ) were achieved under the optimal conditions. This study provides an important idea in the rational design of porous organic polymers for solid-phase microextraction or other adsorption applications. Copyright © 2017 Elsevier B.V. All rights reserved.

High-Performance Flexible Solid-State Supercapacitor with an Extended Nanoregime Interface through in Situ Polymer Electrolyte Generation.

PubMed

Anothumakkool, Bihag; Torris A T, Arun; Veeliyath, Sajna; Vijayakumar, Vidyanand; Badiger, Manohar V; Kurungot, Sreekumar

2016-01-20

Here, we report an efficient strategy by which a significantly enhanced electrode-electrolyte interface in an electrode for supercapacitor application could be accomplished by allowing in situ polymer gel electrolyte generation inside the nanopores of the electrodes. This unique and highly efficient strategy could be conceived by judiciously maintaining ultraviolet-triggered polymerization of a monomer mixture in the presence of a high-surface-area porous carbon. The method is very simple and scalable, and a prototype, flexible solid-state supercapacitor could even be demonstrated in an encapsulation-free condition by using the commercial-grade electrodes (thickness = 150 μm, area = 12 cm(2), and mass loading = 7.3 mg/cm(2)). This prototype device shows a capacitance of 130 F/g at a substantially reduced internal resistance of 0.5 Ω and a high capacitance retention of 84% after 32000 cycles. The present system is found to be clearly outperforming a similar system derived by using the conventional polymer electrolyte (PVA-H3PO4 as the electrolyte), which could display a capacitance of only 95 F/g, and this value falls to nearly 50% in just 5000 cycles. The superior performance in the present case is credited primarily to the excellent interface formation of the in situ generated polymer electrolyte inside the nanopores of the electrode. Further, the interpenetrated nature of the polymer also helps the device to show a low electron spin resonance and power rate and, most importantly, excellent shelf-life in the unsealed flexible conditions. Because the nature of the electrode-electrolyte interface is the major performance-determining factor in the case of many electrochemical energy storage/conversion systems, along with the supercapacitors, the developed process can also find applications in preparing electrodes for the devices such as lithium-ion batteries, metal-air batteries, polymer electrolyte membrane fuel cells, etc.

Development of thermal energy storage materials for biomedical applications.

PubMed

Shukla, A; Sharma, Atul; Shukla, Manjari; Chen, C R

2015-01-01

The phase change materials (PCMs) have been utilized widely for solar thermal energy storage (TES) devices. The quality of these materials to remain at a particular temperature during solid-liquid, liquid-solid phase transition can also be utilized for many biomedical applications as well and has been explored in recent past already. This study reports some novel PCMs developed by them, along with some existing PCMs, to be used for such biomedical applications. Interestingly, it was observed that the heating/cooling properties of these PCMs enhance the quality of a variety of biomedical applications with many advantages (non-electric, no risk of electric shock, easy to handle, easy to recharge thermally, long life, cheap and easily available, reusable) over existing applications. Results of the present study are quite interesting and exciting, opening a plethora of opportunities for more work on the subject, which require overlapping expertise of material scientists, biochemists and medical experts for broader social benefits.

Mechanical and chemical effects of ion-texturing biomedical polymers

NASA Technical Reports Server (NTRS)

Weigand, A. J.; Cenkus, M. A.

1979-01-01

To determine whether sputter etching may provide substantial polymer surface texturing with insignificant changes in chemical and mechanical properties, an 8 cm beam diameter, electron bombardment, argon ion source was used to sputter etch (ion-texture process) nine biomedical polymers. The materials included silicone rubber, 32% carbon impregnated polyolefin, polyoxymethylene, polytetrafluoroethylene, ultrahigh molecular weight (UHMW) polyethylene, UHMW polyethylene with carbon fibers (10%), and several polyurethanes (bioelectric, segmented, and cross linked). Ion textured microtensile specimens of each material except UHMW polyethylene and UHMW polyethylene with 10% carbon fibers were used to determine the effect of ion texturing on tensile properties. Scanning electron microscopy was used to determine surface morphology changes, and electron spectroscopy for chemical analysis was used to analyze the near surface chemical changes that result from ion texturing. Ion energies of 500 eV with beam current densities ranging from 0.08 to 0.19 mA/sq cm were used to ion texture the various materials. Standard microtensile specimens of seven polymers were exposed to a saline environment for 24 hours prior to and during the tensile testing. The surface chemical changes resulting from sputter etching are minimal in spite of the often significant changes in the surface morphology.

Surface modification of polymers for biocompatibility via exposure to extreme ultraviolet radiation.

PubMed

Inam Ul Ahad; Bartnik, Andrzej; Fiedorowicz, Henryk; Kostecki, Jerzy; Korczyc, Barbara; Ciach, Tomasz; Brabazon, Dermot

2014-09-01

Polymeric biomaterials are being widely used for the treatment of various traumata, diseases and defects in human beings due to ease in their synthesis. As biomaterials have direct interaction with the extracellular environment in the biological world, biocompatibility is a topic of great significance. The introduction or enhancement of biocompatibility in certain polymers is still a challenge to overcome. Polymer biocompatibility can be controlled by surface modification. Various physical and chemical methods (e.g., chemical and plasma treatment, ion implantation, and ultraviolet irradiation etc.) are in use or being developed for the modification of polymer surfaces. However an important limitation in their employment is the alteration of bulk material. Different surface and bulk properties of biomaterials are often desirable for biomedical applications. Because extreme ultraviolet (EUV) radiation penetration is quite limited even in low density mediums, it could be possible to use it for surface modification without influencing the bulk material. This article reviews the degree of biocompatibility of different polymeric biomaterials being currently employed in various biomedical applications, the surface properties required to be modified for biocompatibility control, plasma and laser ablation based surface modification techniques, and research studies indicating possible use of EUV for enhancing biocompatibility. © 2013 Wiley Periodicals, Inc.

Effect of processing on Polymer/Composite structure and properties

NASA Technical Reports Server (NTRS)

1982-01-01

Advances in the vitality and economic health of the field of polymer forecasting are discussed. A consistent and rational point of view which considers processing as a participant in the underlying triad of relationships which comprise materials science and engineering is outlined. This triad includes processing as it influences material structure, and ultimately properties. Methods in processing structure properties, polymer science and engineering, polymer chemistry and synthesis, structure and modification and optimization through processing, and methods of melt flow modeling in processing structure property relations of polymer were developed. Mechanical properties of composites are considered, and biomedical materials research to include polymer processing effects are studied. An analysis of the design technology of advances graphite/epoxy composites is also reported.

Solid State Ionic Materials - Proceedings of the 4th Asian Conference on Solid State Ionics

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Yahaya, M.; Talib, I. A.; Salleh, M. M.

1994-07-01

The Table of Contents for the full book PDF is as follows: * Preface * I. INVITED PAPERS * Diffusion of Cations and Anions in Solid Electrolytes * Silver Ion Conductors in the Crystalline State * NMR Studies of Superionic Conductors * Hall Effect and Thermoelectric Power in High Tc Hg-Ba-Ca-Cu-O Ceramics * Solid Electrolyte Materials Prepared by Sol-Gel Chemistry * Preparation of Proton-Conducting Gel Films and their Application to Electrochromic Devices * Thin Film Fuel Cells * Zirconia based Solid Oxide Ion Conductors in Solid Oxide Fuel Cells * The Influence of Anion Substitution on Some Phosphate-based Ion Conducting Glasses * Lithium Intercalation in Carbon Electrodes and its Relevance in Rocking Chair Batteries * Chemical Sensors using Proton Conducting Ceramics * NMR/NQR Studies of Y-Ba-Cu-O Superconductors * Silver Molybdate Glasses and Battery Systems * New Highly Conducting Polymer Ionics and their Application in Electrochemical Devices * Study of Li Electrokinetics on Oligomeric Electrolytes using Microelectrodes * Calculation of Conductivity for Mixed-Phase Electrolytes PEO-MX-Immiscible Additive by Means of Effective Medium Theory * II. CONTRIBUTED PAPERS * Phase Relationship and Electrical Conductivity of Sr-V-O System with Vanadium Suboxide * Amorphous Li+ Ionic Conductors in Li2SO4-Li2O-P2O5 System * Fast Ion Transport in KCl-Al2O3 Composites * The Effect of the Second Phase Precipitation on the Ionic Conductivity of Zr0.85Mg0.15O1.85 * Conductivity Measurements and Phase Relationships in CaCl2-CaHCl Solid Electrolyte * Relationships Between Crystal Structure and Sodium Ion Conductivity in Na7Fe4(AsO4)6 and Na3Al2(AsO4)3 * Electrical Conductivity and Solubility Limit of Ti4+ Ion in Na1+x TiyZr2-ySixP3-xO12 System * Study on Sodium Fast Ion Conductors of Na1+3xAlxTi2-xSi2xP3-2xO12 System * Influences of Zirconia on the Properties of β''-Alumina Ceramics * Decay of Luminescence from Cr3+ Ions in β-Alumina * Lithium Ion Conductivity in the Li4XO4-Li2SO4 (X=Si, Ge, Ti) Systems * A DSC and Conductivity Study of the Influence of Cesium Ion on the Beta-Alpha Transition in Silver Iodide * Phase Diagrams, Stoichiometries and Properties of Bi4V2O11:M2+ Solid Electrolytes * Physical Properties of Electrodeposited Silver Chromotungstate * Pseudopotential Study of Bonding in the Superionic Material AgI: The Effect of Statistical Distribution of Mobile Ions * Cubic Phase Dominant Region in Submicron BaTiO3 Particles * The Crystallization of CoZr Amorphous Alloys via Electrical Resistivity * Cation Ratio Related Properties of Synthetic Mg/Al Layered Double Hydroxide and it's Nanocomposite * DC Conductivity of Nano-Particles of Silver Iodide * Effect of Anomalous Diffusion on Quasielastic Scattering in Superionic Conductors * Computer Simulation Study of Conductivity Enhancement in Superionic-Insulator Composites * Dynamics of Superionic Silver and Copper Iodide Salt Melts * Influence of Dopant Salt AgI, Glass Modifier Ag2O and Glass Formers (SeO3 + MoO3) on Electrical Conductivity in Quaternary Glassy System * Fast Ion Conductivity in the Presence of Competitive Network Formers * Role of Alkali Ions in Borate Glasses * Inelastic Light Scattering in Cadmium Borate Glasses * Investigation on Transport Properties of Mixed Glass System 0.75 [0.75AgI:0.25AgCl]. 0.25[Ag2O:CrO3] * Conduction Mechanism in Lithium Tellurite Glasses * Optimized Silver Tungstoarsenate Glass Electrolyte * Stabilized Superfine Zirconia Powder Prepared by Sol-Gel Process * Study of New PAN-based Electrolytes * Electrical and Thermal Characterization of PVA based Polymer Electrolytes * Conductive Electroactive Polymers: Versatile Solid State Ionic Materials * The Role of Ag2O Addition on the Superconducting Properties of Y-124 Compound * Absorption Spectra Studies of the C60 Films on Transition Metal Film Substrates * Effect of Alumina Dispersal on the Conductivity and Crystallite Size of Polymer Electrolyte * New Mixed Galss-Polymer Solid Electrolytes * The Sputtered La0.5Sr0.5MnO3-Yttria Stabilized Zirconia Composite Electrode in Solid Oxide Fuel Cells * A Solid Electrochemical Ferro Sensor for Molten Matte * SnO2-based Sensor for H2S Monitoring-Electrical Conductivity Measurements and Device Testing * Humidity Sensor using Potassium Tungsten Bronze Synthesized from Peroxo-Polytungstic Acid * Study on Li/LiClO4/V6O13 Test Cells * Fabrication and Characterisation of Some Solid Electrolyte Cells Containing CuI and Silver Oxysalts * Solid State Battery of Proton Conducting Sodium Thiosulphate Pentahydrate * Low Temperature Synthesis of LiMn2O4 for Secondary Lithium Batteries * Effect of Different Cathode Active Materials on Battery Performance with Silver Molybdate Electrolyte Partially Substituted with Zinc Oxide * Fabrication and Characterization of Electrochemical Cells based on Silver Molybdoarsenate and Silver Tungstoarsenate Glass Electrolytes * Lorentz Force Dependence of Dissipation in a Granular Superconductor * Late Entry (Invited paper) * Simultaneous Voltammetry and Spectroscopy of Polyaniline in Propylene Carbonate * Author Index * Tentative List of Participants

Phase Behaviour and Miscibility Studies of Collagen/Silk Fibroin Macromolecular System in Dilute Solutions and Solid State.

PubMed

Ghaeli, Ima; de Moraes, Mariana A; Beppu, Marisa M; Lewandowska, Katarzyna; Sionkowska, Alina; Ferreira-da-Silva, Frederico; Ferraz, Maria P; Monteiro, Fernando J

2017-08-18

Miscibility is an important issue in biopolymer blends for analysis of the behavior of polymer pairs through the detection of phase separation and improvement of the mechanical and physical properties of the blend. This study presents the formulation of a stable and one-phase mixture of collagen and regenerated silk fibroin (RSF), with the highest miscibility ratio between these two macromolecules, through inducing electrostatic interactions, using salt ions. For this aim, a ternary phase diagram was experimentally built for the mixtures, based on observations of phase behavior of blend solutions with various ratios. The miscibility behavior of the blend solutions in the miscible zones of the phase diagram was confirmed quantitatively by viscosimetric measurements. Assessing the effects of biopolymer mixing ratio and salt ions, before and after dialysis of blend solutions, revealed the importance of ion-specific interactions in the formation of coacervate-based materials containing collagen and RSF blends that can be used in pharmaceutical, drug delivery, and biomedical applications. Moreover, the conformational change of silk fibroin from random coil to beta sheet, in solution and in the final solid films, was detected by circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR), respectively. Scanning electron microscopy (SEM) exhibited alterations of surface morphology for the biocomposite films with different ratios. Surface contact angle measurement illustrated different hydrophobic properties for the blended film surfaces. Differential scanning calorimetry (DSC) showed that the formation of the beta sheet structure of silk fibroin enhances the thermal stability of the final blend films. Therefore, the novel method presented in this study resulted in the formation of biocomposite films whose physico-chemical properties can be tuned by silk fibroin conformational changes by applying different component mixing ratios.

Single lithium-ion conducting solid polymer electrolytes: advances and perspectives.

PubMed

Zhang, Heng; Li, Chunmei; Piszcz, Michal; Coya, Estibaliz; Rojo, Teofilo; Rodriguez-Martinez, Lide M; Armand, Michel; Zhou, Zhibin

2017-02-06

Electrochemical energy storage is one of the main societal challenges to humankind in this century. The performances of classical Li-ion batteries (LIBs) with non-aqueous liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues, and the energy density of the state-of-the-art LIBs cannot satisfy the practical requirement. Therefore, rechargeable lithium metal batteries (LMBs) have been intensively investigated considering the high theoretical capacity of lithium metal and its low negative potential. However, the progress in the field of non-aqueous liquid electrolytes for LMBs has been sluggish, with several seemingly insurmountable barriers, including dendritic Li growth and rapid capacity fading. Solid polymer electrolytes (SPEs) offer a perfect solution to these safety concerns and to the enhancement of energy density. Traditional SPEs are dual-ion conductors, in which both cations and anions are mobile and will cause a concentration polarization thus leading to poor performances of both LIBs and LMBs. Single lithium-ion (Li-ion) conducting solid polymer electrolytes (SLIC-SPEs), which have anions covalently bonded to the polymer, inorganic backbone, or immobilized by anion acceptors, are generally accepted to have advantages over conventional dual-ion conducting SPEs for application in LMBs. A high Li-ion transference number (LTN), the absence of the detrimental effect of anion polarization, and the low rate of Li dendrite growth are examples of benefits of SLIC-SPEs. To date, many types of SLIC-SPEs have been reported, including those based on organic polymers, organic-inorganic hybrid polymers and anion acceptors. In this review, a brief overview of synthetic strategies on how to realize SLIC-SPEs is given. The fundamental physical and electrochemical properties of SLIC-SPEs prepared by different methods are discussed in detail. In particular, special attention is paid to the SLIC-SPEs with high ionic conductivity and high LTN. Finally, perspectives on the main challenges and focus on the future research are also presented.

Self-assembling semiconducting polymers--rods and gels from electronic materials.

PubMed

Clark, Andrew P-Z; Shi, Chenjun; Ng, Benny C; Wilking, James N; Ayzner, Alexander L; Stieg, Adam Z; Schwartz, Benjamin J; Mason, Thomas G; Rubin, Yves; Tolbert, Sarah H

2013-02-26

In an effort to favor the formation of straight polymer chains without crystalline grain boundaries, we have synthesized an amphiphilic conjugated polyelectrolyte, poly(fluorene-alt-thiophene) (PFT), which self-assembles in aqueous solutions to form cylindrical micelles. In contrast to many diblock copolymer assemblies, the semiconducting backbone runs parallel, not perpendicular, to the long axis of the cylindrical micelle. Solution-phase micelle formation is observed by X-ray and visible light scattering. The micelles can be cast as thin films, and the cylindrical morphology is preserved in the solid state. The effects of self-assembly are also observed through spectral shifts in optical absorption and photoluminescence. Solutions of higher-molecular-weight PFT micelles form gel networks at sufficiently high aqueous concentrations. Rheological characterization of the PFT gels reveals solid-like behavior and strain hardening below the yield point, properties similar to those found in entangled gels formed from surfactant-based micelles. Finally, electrical measurements on diode test structures indicate that, despite a complete lack of crystallinity in these self-assembled polymers, they effectively conduct electricity.

Manufacturing Technology of Composite Materials-Principles of Modification of Polymer Composite Materials Technology Based on Polytetrafluoroethylene.

PubMed

Panda, Anton; Dyadyura, Kostiantyn; Valíček, Jan; Harničárová, Marta; Zajac, Jozef; Modrák, Vladimír; Pandová, Iveta; Vrábel, Peter; Nováková-Marcinčínová, Ema; Pavelek, Zdeněk

2017-03-31

The results of the investigations into the technological formation of new wear-resistant polymer composites based on polytetrafluoroethylene (PTFE) filled with disperse synthetic and natural compounds are presented. The efficiency of using PTFE composites reinforced with carbon fibers depends on many factors, which influence the significant improvement of physicomechanical characteristics. The results of this research allow stating that interfacial and surface phenomena of the polymer-solid interface and composition play a decisive role in PTFE composites properties. Fillers hinder the relative movement of the PTFE molecules past one another and, in this way, reduce creep or deformation of the parts, reducing the wear rate of parts used in dynamic applications as well as the coefficient of thermal expansion. The necessary structural parameters of such polymer composites are provided by regimes of process equipment.

Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

PubMed Central

Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

2016-01-01

Here we demonstrate that by regulating the mobility of classic −EO− based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm−1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions. PMID:26791572

Solid electrolyte material manufacturable by polymer processing methods

DOEpatents

Singh, Mohit; Gur, Ilan; Eitouni, Hany Basam; Balsara, Nitash Pervez

2012-09-18

The present invention relates generally to electrolyte materials. According to an embodiment, the present invention provides for a solid polymer electrolyte material that is ionically conductive, mechanically robust, and can be formed into desirable shapes using conventional polymer processing methods. An exemplary polymer electrolyte material has an elastic modulus in excess of 1.times.10.sup.6 Pa at 90 degrees C. and is characterized by an ionic conductivity of at least 1.times.10.sup.-5 Scm-1 at 90 degrees C. An exemplary material can be characterized by a two domain or three domain material system. An exemplary material can include material components made of diblock polymers or triblock polymers. Many uses are contemplated for the solid polymer electrolyte materials. For example, the present invention can be applied to improve Li-based batteries by means of enabling higher energy density, better thermal and environmental stability, lower rates of self-discharge, enhanced safety, lower manufacturing costs, and novel form factors.

Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

NASA Astrophysics Data System (ADS)

Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

2016-01-01

Here we demonstrate that by regulating the mobility of classic -EO- based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm-1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions.

Thermomechanical Properties of Polylactic Acid-Graphene Composites: A State-of-the-Art Review for Biomedical Applications

PubMed Central

2017-01-01

Due to its biodegradable and bioabsorbable characteristics polylactic acid (PLA) has attracted considerable attention for numerous biomedical applications. Moreover, a number of tissue engineering problems for function restoration of impaired tissues have been addressed by using PLA and its copolymers due to their biocompatibility and distinctive mechanical properties. Recent studies on various stereocomplex formation between enantiomeric PLA, poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) indicated that stereocomplexation enhances the mechanical properties as well as the thermal- and hydrolysis-resistance of PLA polymers. On the other hand, biomedical application of graphene is a relatively new front with significant potential. Many recent reports have indicated that understanding of graphene-cell (or tissue, organ) interactions; particularly the cellular uptake mechanisms are still challenging. Therefore, use of graphene or graphene oxide properly embedded in suitable PLA matrices can positively impact and accelerate the growth, differentiation, and proliferation of stem cells, conceivably minimizing concerns over cytotoxicity of graphene. As such, PLA-graphene composites hold great promise in tissue engineering, regenerative medicine, and in other biomedical fields. However, since PLA is classified as a hard bio-polyester prone to hydrolysis, understanding and engineering of thermo-mechanical properties of PLA-graphene composites are very crucial for such cutting-edge applications. Hence, this review aims to present an overview of current advances in the preparation and applications of PLA-graphene composites and their properties with focus on various biomedical uses such as scaffolds, drug delivery, cancer therapy, and biological imaging, together with a brief discussion on the challenges and perspectives for future research in this field. PMID:28773109

Dendrite Suppression by Synergistic Combination of Solid Polymer Electrolyte Crosslinked with Natural Terpenes and Lithium-Powder Anode for Lithium-Metal Batteries.

PubMed

Shim, Jimin; Lee, Jae Won; Bae, Ki Yoon; Kim, Hee Joong; Yoon, Woo Young; Lee, Jong-Chan

2017-05-22

Lithium-metal anode has fundamental problems concerning formation and growth of lithium dendrites, which prevents practical applications of next generation of high-capacity lithium-metal batteries. The synergistic combination of solid polymer electrolyte (SPE) crosslinked with naturally occurring terpenes and lithium-powder anode is promising solution to resolve the dendrite issues by substituting conventional liquid electrolyte/separator and lithium-foil anode system. A series of SPEs based on polysiloxane crosslinked with natural terpenes are prepared by facile thiol-ene click reaction under mild condition and the structural effect of terpene crosslinkers on electrochemical properties is studied. Lithium powder with large surface area is prepared by droplet emulsion technique (DET) and used as anode material. The effect of the physical state of electrolyte (solid/liquid) and morphology of lithium-metal anode (powder/foil) on dendrite growth behavior is systematically studied. The synergistic combination of SPE and lithium-powder anode suggests an effective solution to suppress the dendrite growth owing to the formation of a stable solid-electrolyte interface (SEI) layer and delocalized current density. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Introduction to polymer-based solid-contact ion-selective electrodes-basic concepts, practical considerations, and current research topics.

PubMed

Bieg, Christoph; Fuchsberger, Kai; Stelzle, Martin

2017-01-01

This review aims at providing an introductory overview for researchers new to the field of ion-selective electrodes. Both state of the art technology and novel developments towards solid-contact reference (sc-RE) and solid-contact ion selective electrodes (sc-ISE) are discussed. This technology has potentially widespread and important applications provided certain performance criteria can be met. We present basic concepts, operation principles, and theoretical considerations with regard to their function. Analytical performance and suitability of sc-RE and sc-ISE for a given application depend on critical parameters, which are discussed in this review. Comprehensive evaluation of sensor performance along this set of parameters is considered indispensable to allow for a well-founded comparison of different technologies. Methods and materials employed in the construction of sc-RE and sc-ISE, in particular the solid contact and the polymer membrane composite, are presented and discussed in detail. Operation principles beyond potentiometry are mentioned, which would further extend the field of ISE application. Finally, we conclude by directing the reader to important areas for further scientific research and development work considered particularly critical and promising for advancing this field in sensor R&D. Graphical Abstract ᅟ.

Insight into the Broad Field of Polymer Nanocomposites: From Carbon Nanotubes to Clay Nanoplatelets, via Metal Nanoparticles

PubMed Central

Stefanescu, Eduard A.; Daranga, Codrin; Stefanescu, Cristina

2009-01-01

Highly ordered polymer nanocomposites are complex materials that display a rich morphological behavior owing to variations in composition, structure, and properties on a nanometer length scale. Metal-polymer nanocomposite materials are becoming more popular for applications requiring low cost, high metal surface areas. Catalytic systems seem to be the most prevalent application for a wide range of metals used in polymer nanocomposites, particularly for metals like Pt, Ni, Co, and Au, with known catalytic activities. On the other hand, among the most frequently utilized techniques to prepare polymer/CNT and/or polymer/clay nanocomposites are approaches like melt mixing, solution casting, electrospinning and solid-state shear pulverization. Additionally, some of the current and potential applications of polymer/CNT and/or polymer/clay nanocomposites include photovoltaic devices, optical switches, electromagnetic interference (EMI) shielding, aerospace and automotive materials, packaging, adhesives and coatings. This extensive review covers a broad range of articles, typically from high impact-factor journals, on most of the polymer-nanocomposites known to date: polymer/carbon nanotubes, polymer/metal nanospheres, and polymer/clay nanoplatelets composites. The various types of nanocomposites are described form the preparation stages to performance and applications. Comparisons of the various types of nanocomposites are conducted and conclusions are formulated.

An air-stable Na 3SbS 4 superionic conductor prepared by a rapid and economic synthetic procedure

DOE PAGES

Wang, Hui; Chen, Yan; Hood, Zachary D.; ...

2016-01-01

All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na 3SbS 4, a novel Na superionic conductor that needs much lower processing temperature belowmore » 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm -1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.« less