Solvent-Polarity-Induced Active Layer Morphology Control in Crystalline Diketopyrrolopyrrole-Based Low Band Gap Polymer Photovoltaics

NASA Astrophysics Data System (ADS)

Ferdous, Sunzida; Liu, Feng; Wang, Dong; Russell, Thomas

2014-03-01

The effects of various processing solvents on the morphology of diketopyrrolopyrrole (DPP)-based low band gap polymer (PDPPBT) and phenyl-C71-butyric acid methyl ester (PC71BM) blends are studied. The quality of the processing solvents was varied systematically using a mixture of a non-aromatic polar primary solvent with high boiling point secondary solvents of increasing polarities. An unfavorable solvent-PC71BM interaction affects the growth process of polymer crystallites inside the blend. When non-aromatic polar solvent was used, large PC71BM aggregates were formed that increase in size with the addition of non-polar secondary solvents. When polar solvents were instead used as the secondary solvents, the size scales of the aggregates decrease markedly, creating a percolated fibrillar network. Power conversion efficiencies of 0.03% to 5% are obtained, depending on the solvent system used.

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

NASA Astrophysics Data System (ADS)

Krishnan, Karthik; Aono, Masakazu; Tsuruoka, Tohru

2016-07-01

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

GAP Peptide Synthesis via Design of New GAP Protecting Group: An Fmoc/tBu Synthesis of Thymopentin Free from Polymers, Chromatography and Recrystallization

PubMed Central

Seifert, Cole W.; Paniagua, Armando; White, Gabrielle A.; Cai, Lucy

2016-01-01

A novel method for Fmoc/tBu solution-phase peptide synthesis and the development of a new benzyl-type GAP protecting group is reported. This new GAP protecting group is utilized in place of a polymer support, facilitating C→N Fmoc peptide synthesis without chromatography, recrystallization, or polymer supports. The GAP group can be added and removed in high yield, and was used to synthesize over 1 gram of the immunostimulant, thymopentin, in high overall yield (83%) and purity (99%). PMID:28663711

Theoretical study of geometrical and electronic structures of various thiophene-based tricyclic polymers

NASA Astrophysics Data System (ADS)

Hong, Sung Y.; Song, Jung M.

1997-12-01

A theoretical study of a variety of tricyclic polymers [-(C8H2X2Y)n-] with two different types of bridging groups was performed, X=S and Y=CH2, SiH2, C=O, C=S, or C=CH2 for the fused bithiophene system and vice versa for the thieno-bicyclic system. These two types of the bridging groups are different from each other in that S favors the aromatic form of a cyclic polymer and the other groups prefer the quinonoid form. Geometrical structures of the polymers were obtained from semiempirical self-consistent-field (SCF) band calculations and the electronic properties from the modified extended Hückel band calculations. It is found that the ground-state geometrical structures of the tricyclic polymers are determined by the bridging groups in the outer rings. That is, the fused bithiophene system is aromatic in the ground state and the thieno-bicyclic system is quinonoid. The ground-state band gaps (which correspond to the absorption peaks of π-π* band transition) of the polymers were estimated to be in the range of 0.7-2.0 eV. The band gaps were analyzed in terms of the bond-length alternation along the conjugated carbon backbone, the C1-C4 interactions, and the electronic effect of the bridging groups. We also investigated the geometrical and electronic structures of polydicyanomethylene-cyclopenta-dicyclopentadiene (PDICNCY). Unlike the theoretical predictions of Toussaint and Bredas [Synth. Met. 69, 637 (1995)], PDICNCY in the ground state was estimated to be of the quinonoid form and to possess a large band gap (2.55 eV) comparable with the gap of polythiophene.

Development of a Microelectromechanical System for Small Satellite Thermal Control

DTIC Science & Technology

2004-05-06

polymer frame or post over a silicon substrate. The membrane should be coated with a high emissivity material. This design was based on the principle...allowing heat conduction to the silicon. While the device was off, both the poor thermal conductivity of the polymer and the gap between membrane and...EnergyThermally Isolating Vacuum and Polymer Heat Conduction (a) (b) Figure 4. Heat conduction and radiation in the on and off states

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

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

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

2014-09-16

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

Fused dithienogermolodithiophene low band gap polymers for high-performance organic solar cells without processing additives.

PubMed

Zhong, Hongliang; Li, Zhe; Deledalle, Florent; Fregoso, Elisa Collado; Shahid, Munazza; Fei, Zhuping; Nielsen, Christian B; Yaacobi-Gross, Nir; Rossbauer, Stephan; Anthopoulos, Thomas D; Durrant, James R; Heeney, Martin

2013-02-13

We report the synthesis of a novel ladder-type fused ring donor, dithienogermolodithiophene, in which two thieno[3,2-b]thiophene units are held coplanar by a bridging dialkyl germanium. Polymerization of this extended monomer with N-octylthienopyrrolodione by Stille polycondensation afforded a polymer, pDTTG-TPD, with an optical band gap of 1.75 eV combined with a high ionization potential. Bulk heterojunction solar cells based upon pDTTG-TPD:PC(71)BM blends afforded efficiencies up to 7.2% without the need for thermal annealing or processing additives.

Structural and optical characterization of PVA:KMnO4 based solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Abdullah, Omed Gh.; Aziz, Shujahadeen B.; Rasheed, Mariwan A.

Solid polymer electrolyte films of polyvinyl alcohol (PVA) doped with a different weight percent of potassium permanganate (KMnO4) were prepared by standard solution cast method. XRD and FTIR techniques were performed for structural study. Complex formation between the PVA polymer and KMnO4 salt was confirmed by Fourier transform infrared (FTIR) spectroscopy. The description of crystalline nature of the solid polymer electrolyte films has been confirmed by XRD analysis. The UV-Visible absorption spectra were analyzed in terms of absorption formula for non-crystalline materials. The fundamental optical parameters such as optical band gap energy, refractive index, optical conductivity, and dielectric constants have been investigated and showed a clear dependence on the KMnO4 concentration. The observed value of optical band gap energy for pure PVA is about 6.27 eV and decreases to a value 3.12 eV for the film sample formed with 4 wt% KMnO4 salt. The calculated values of refractive index and the dielectric constants of the polymer electrolyte films increase with increasing KMnO4 content.

Naphthodipyrrolidone (NDP) based conjugated polymers with high electron mobility and ambipolar transport properties

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

Zhang, Haichang; Zhang, Shuo; Mao, Yifan

Two novel donor–acceptor π-conjugated polymers based on naphthodipyrrolidone (NDP) were synthesized and characterized. The polymers possess low band gaps and suitable molecular orbital levels as ambipolar semiconductors. The thin film organic field effect transistor of NDP polymers exhibited ambipolar transport properties with a high electron mobility up to 0.67 cm 2 V –1 s –1. The grazing-incidence wide-angle X-ray scattering (GIWAXS) studies demonstrated that the polymer molecules pack into a long-range-ordered lamellar structure with isotropically oriented crystalline domains. Thermal annealing promoted edge-on lamellar stacking as evidenced by the increased diffraction intensity along the out-of-plane direction. In conclusion, the polymer withmore » NDP and bithiophene units achieved the best edge-on lamellar stacking after thermal annealing, which yielded the best electron transport performance in this work.« less

Naphthodipyrrolidone (NDP) based conjugated polymers with high electron mobility and ambipolar transport properties

DOE PAGES

Zhang, Haichang; Zhang, Shuo; Mao, Yifan; ...

2017-05-12

Two novel donor–acceptor π-conjugated polymers based on naphthodipyrrolidone (NDP) were synthesized and characterized. The polymers possess low band gaps and suitable molecular orbital levels as ambipolar semiconductors. The thin film organic field effect transistor of NDP polymers exhibited ambipolar transport properties with a high electron mobility up to 0.67 cm 2 V –1 s –1. The grazing-incidence wide-angle X-ray scattering (GIWAXS) studies demonstrated that the polymer molecules pack into a long-range-ordered lamellar structure with isotropically oriented crystalline domains. Thermal annealing promoted edge-on lamellar stacking as evidenced by the increased diffraction intensity along the out-of-plane direction. In conclusion, the polymer withmore » NDP and bithiophene units achieved the best edge-on lamellar stacking after thermal annealing, which yielded the best electron transport performance in this work.« less

High-efficiency hybrid solar cells based on polymer/PbSx Se1-x nanocrystals benefiting from vertical phase segregation.

PubMed

Liu, Zeke; Sun, Yaxiang; Yuan, Jianyu; Wei, Huaixin; Huang, Xiaodong; Han, Lu; Wang, Weiwei; Wang, Haiqiao; Ma, Wanli

2013-10-25

Solution-processed hybrid solar cells employing a low band-gap polymer and PbSx Se1-x alloy nanocrystals, achieving a record high PCE of 5.50% and an optimal FF of 67% are presented. The remarkable device efficiency can be attributed to the high-performance active materials, the optimal polymer/NCs ratio and, more importantly, the vertical donor/(donor:acceptor)/acceptor structure which benefits charge dissociation and transport. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design and synthesis of chlorinated benzothiadiazole-based polymers for efficient solar energy conversion

DOE PAGES

Hu, Zhiming; Chen, Hui; Qu, Jianfei; ...

2017-03-10

Here, chlorinated benzothiadiazide based polymers with multiple chlorine atoms has been designed and synthesized for polymer solar cells with enhanced open circuit voltage up to 0.85 V. The chlorine substitution is found to significantly adjust the band gap of the polymers, and change polymer’s orientation from random morphology of chlorine free PBT4T-2OD, to mixed face-on packing of one chlorine substituted PCBT4T-2OD, and finally to edge-on of two chlorine substituted PCCBT4T-2OD. The optimized chlorinated polymer, PCBT4T-2OD with only one chlorine atom substituted on BT moiety, has been founded to achieve the highest power conversion efficiency up to 8.20% with PC 71BM,more » which is about 68% higher than that of its non-chlorine analogues.« less

High-crystalline medium-band-gap polymers consisting of benzodithiophene and benzotriazole derivatives for organic photovoltaic cells.

PubMed

Kim, Ji-Hoon; Song, Chang Eun; Shin, Nara; Kang, Hyunbum; Wood, Sebastian; Kang, In-Nam; Kim, Bumjoon J; Kim, Bongsoo; Kim, Ji-Seon; Shin, Won Suk; Hwang, Do-Hoon

2013-12-26

Two semiconducting conjugated polymers were synthesized via Stille polymerization. The structures combined unsubstituted or (triisopropylsilyl)ethynyl (TIPS)-substituted 2,6-bis(trimethylstannyl)benzo[1,2-b:4.5-b']dithiophene (BDT) as a donor unit and benzotriazole with a symmetrically branched alkyl side chain (DTBTz) as an acceptor unit. We investigated the effects of the different BDT moieties on the optical, electrochemical, and photovoltaic properties of the polymers and the film crystallinities and carrier mobilities. The optical-band-gap energies were measured to be 1.97 and 1.95 eV for PBDT-DTBTz and PTIPSBDT-DTBTz, respectively. Bulk heterojunction photovoltaic devices were fabricated and power conversion efficiencies of 5.5% and 2.9% were found for the PTIPSBDT-DTBTz- and PBDT-DTBTz-based devices, respectively. This difference was explained by the more optimal morphology and higher carrier mobility in the PTIPSBDT-DTBTz-based devices. This work demonstrates that, under the appropriate processing conditions, TIPS groups can change the molecular ordering and lower the highest occupied molecular orbital level, providing the potential for improved solar cell performance.

Diketopyrrolopyrrole-based Conjugated Polymers Bearing Branched Oligo(Ethylene Glycol) Side Chains for Photovoltaic Devices.

PubMed

Chen, Xingxing; Zhang, Zijian; Ding, Zicheng; Liu, Jun; Wang, Lixiang

2016-08-22

Conjugated polymers are essential for solution-processable organic opto-electronic devices. In contrast to the great efforts on developing new conjugated polymer backbones, research on developing side chains is rare. Herein, we report branched oligo(ethylene glycol) (OEG) as side chains of conjugated polymers. Compared with typical alkyl side chains, branched OEG side chains endowed the resulting conjugated polymers with a smaller π-π stacking distance, higher hole mobility, smaller optical band gap, higher dielectric constant, and larger surface energy. Moreover, the conjugated polymers with branched OEG side chains exhibited outstanding photovoltaic performance in polymer solar cells. A power conversion efficiency of 5.37 % with near-infrared photoresponse was demonstrated and the device performance could be insensitive to the active layer thickness. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance Enhancement of Polymer Solar Cells by Using Two Polymer Donors with Complementary Absorption Spectra.

PubMed

Lu, Heng; Zhang, Xuejuan; Li, Cuihong; Wei, Hedi; Liu, Qian; Li, Weiwei; Bo, Zhishan

2015-07-01

Performance enhancement of polymer solar cells (PSCs) is achieved by expanding the absorption of the active layer of devices. To better match the spectrum of solar radiation, two polymers with different band gaps are used as the donor material to fabricate ternary polymer cells. Ternary blend PSCs exhibit an enhanced short-circuit current density and open-circuit voltage in comparison with the corresponding HD-PDFC-DTBT (HD)- and DT-PDPPTPT (DPP)-based binary polymer solar cells, respectively. Ternary PSCs show a power conversion efficiency (PCE) of 6.71%, surpassing the corresponding binary PSCs. This work demonstrates that the fabrication of ternary PSCs by using two polymers with complementary absorption is an effective way to improve the device performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Planar waveguide microlenses for nonblocking photonic switches and optical interconnects

NASA Astrophysics Data System (ADS)

Glebov, Alexei L.; Huang, Lidu; Lee, Michael; Aoki, Shigenori; Yokouchi, Kishio

2004-09-01

Different types of planar waveguide microlenses are fabricated with PLC technologies from a variety of optical materials such as silica, photo-definable epoxy resins, and a number of other optical polymers. Hybrid microlenses are also fabricated in which the base of the lens, with a double concave gap, is formed from silica and the gap is filled with an optical polymer. The optimized lens structures provide the maximum coupling efficiencies between the input and output channels at distances up to 100 mm with a minimum channel pitch of 0.5-0.7 mm. Experimental and theoretical studies provide results on collimation and focusing properties of single and double microlenses made of silica, polymer, and silica/polymer. The evaluation of the temperature and wavelength effects on the collimation characteristics of the lenses demonstrate that the single lenses are more stable and, thus, more suitable for operations under varying conditions. Examples of the planar waveguide microlens applications are presented. In one application the microlens arrays are integrated in fast electrooptic photonic switching modules. In the other application the microlenses are embedded in the backplanes with nonblocking optical interconnects.

Synthesis and Exciton Dynamics of Donor-Orthogonal Acceptor Conjugated Polymers: Reducing the Singlet-Triplet Energy Gap.

PubMed

Freeman, David M E; Musser, Andrew J; Frost, Jarvist M; Stern, Hannah L; Forster, Alexander K; Fallon, Kealan J; Rapidis, Alexandros G; Cacialli, Franco; McCulloch, Iain; Clarke, Tracey M; Friend, Richard H; Bronstein, Hugo

2017-08-16

The presence of energetically low-lying triplet states is a hallmark of organic semiconductors. Even though they present a wealth of interesting photophysical properties, these optically dark states significantly limit optoelectronic device performance. Recent advances in emissive charge-transfer molecules have pioneered routes to reduce the energy gap between triplets and "bright" singlets, allowing thermal population exchange between them and eliminating a significant loss channel in devices. In conjugated polymers, this gap has proved resistant to modification. Here, we introduce a general approach to reduce the singlet-triplet energy gap in fully conjugated polymers, using a donor-orthogonal acceptor motif to spatially separate electron and hole wave functions. This new generation of conjugated polymers allows for a greatly reduced exchange energy, enhancing triplet formation and enabling thermally activated delayed fluorescence. We find that the mechanisms of both processes are driven by excited-state mixing between π-π*and charge-transfer states, affording new insight into reverse intersystem crossing.

Fabrication of photonic band gap materials

DOEpatents

Constant, Kristen; Subramania, Ganapathi S.; Biswas, Rana; Ho, Kai-Ming

2002-01-15

A method for forming a periodic dielectric structure exhibiting photonic band gap effects includes forming a slurry of a nano-crystalline ceramic dielectric or semiconductor material and monodisperse polymer microspheres, depositing a film of the slurry on a substrate, drying the film, and calcining the film to remove the polymer microspheres therefrom. The film may be cold-pressed after drying and prior to calcining. The ceramic dielectric or semiconductor material may be titania, and the polymer microspheres may be polystyrene microspheres.

Preferential Charge Generation at Aggregate Sites in Narrow Band Gap Infrared Photoresponsive Polymer Semiconductors

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

Sulas, Dana B.; London, Alexander E.; Huang, Lifeng

Infrared organic photodetector materials are investigated using transient absorption spectroscopy, demonstrating that ultrafast charge generation assisted by polymer aggregation is essential to compensate for the energy gap law, which dictates that excited state lifetimes decrease as the band gap narrows. Short sub–picosecond singlet exciton lifetimes are measured in a structurally related series of infrared–absorbing copolymers that consist of alternating cyclopentadithiophene electron–rich “push” units and strong electron–deficient “pull” units, including benzothiadiazole, benzoselenadiazole, pyridalselenadiazole, or thiadiazoloquinoxaline. While the ultrafast lifetimes of excitons localized on individual polymer chains suggest that charge carrier generation will be inefficient, high detectivity for polymer:PC 71BM infrared photodetectorsmore » is measured in the 0.6 < λ < 1.5 µm range. The photophysical processes leading to charge generation are investigated by performing a global analysis on transient absorption data of blended polymer:PC 71BM films. In these blends, charge carriers form primarily at polymer aggregate sites on the ultrafast time scale (within our instrument response), leaving quickly decaying single–chain excitons unquenched. Lastly, the results have important implications for the further development of organic infrared optoelectronic devices, where targeting processes such as excited state delocalization over aggregates may be necessary to mitigate losses to ultrafast exciton decay as materials with even lower band gaps are developed.« less

Preferential Charge Generation at Aggregate Sites in Narrow Band Gap Infrared Photoresponsive Polymer Semiconductors

DOE PAGES

Sulas, Dana B.; London, Alexander E.; Huang, Lifeng; ...

2018-02-13

Infrared organic photodetector materials are investigated using transient absorption spectroscopy, demonstrating that ultrafast charge generation assisted by polymer aggregation is essential to compensate for the energy gap law, which dictates that excited state lifetimes decrease as the band gap narrows. Short sub–picosecond singlet exciton lifetimes are measured in a structurally related series of infrared–absorbing copolymers that consist of alternating cyclopentadithiophene electron–rich “push” units and strong electron–deficient “pull” units, including benzothiadiazole, benzoselenadiazole, pyridalselenadiazole, or thiadiazoloquinoxaline. While the ultrafast lifetimes of excitons localized on individual polymer chains suggest that charge carrier generation will be inefficient, high detectivity for polymer:PC 71BM infrared photodetectorsmore » is measured in the 0.6 < λ < 1.5 µm range. The photophysical processes leading to charge generation are investigated by performing a global analysis on transient absorption data of blended polymer:PC 71BM films. In these blends, charge carriers form primarily at polymer aggregate sites on the ultrafast time scale (within our instrument response), leaving quickly decaying single–chain excitons unquenched. Lastly, the results have important implications for the further development of organic infrared optoelectronic devices, where targeting processes such as excited state delocalization over aggregates may be necessary to mitigate losses to ultrafast exciton decay as materials with even lower band gaps are developed.« less

Tuning the structural and electronic properties of novel thiophene-pyrrole based 1,2,3,4-tetrazine

NASA Astrophysics Data System (ADS)

Dutta, Rakesh; Kalita, Dhruba Jyoti

2017-04-01

Here, we have studied the structural and optoelectronic behaviour of a series of conjugated heterocyclic polymers. The basic monomer unit of the conjugated polymers contains a backbone of novel thiophene and pyrrole based 1,2,3,4-tetrazine. The other oligomers are designed by substituting the basic monomer unit with different electron-donating and electron-withdrawing groups at the nitrogen and the 3rd C-atom of the pyrrole and the thiophene ring respectively. We have calculated dihedral angles, HOMO-LUMO gaps, excitation energies and oscillator strengths by employing TD-DFT method. Our study reveals that compounds having bulky substituents exhibit larger dihedral angles. This in turn renders an increase in the band gaps (ΔH - L). Presence of the electron-withdrawing substituents also increases the ΔH - L values of the oligomers. However, the electron-donating groups decrease the ΔH - L values of the oligomers. Therefore, small electron-donating substituents have an overwhelming effect on the optoelectronic properties of the conjugated polymers which in turn makes them interesting materials with good conduction properties for fabrication of optoelectronic devices such as OLEDs, OFETs and solar cells.

Polymer-based chromophore-catalyst assemblies for solar energy conversion

NASA Astrophysics Data System (ADS)

Leem, Gyu; Sherman, Benjamin D.; Schanze, Kirk S.

2017-12-01

The synthesis of polymer-based assemblies for light harvesting has been motivated by the multi-chromophore antennas that play a role in natural photosynthesis for the potential use in solar conversion technologies. This review describes a general strategy for using polymer-based chromophore-catalyst assemblies for solar-driven water oxidation at a photoanode in a dye-sensitized photoelectrochemical cell (DSPEC). This report begins with a summary of the synthetic methods and fundamental photophysical studies of light harvesting polychormophores in solution which show these materials can transport excited state energy to an acceptor where charge-separation can occur. In addition, studies describing light harvesting polychromophores containing an anchoring moiety (ionic carboxylate) for covalent bounding to wide band gap mesoporous semiconductor surfaces are summarized to understand the photophysical mechanisms of directional energy flow at the interface. Finally, the performance of polychromophore/catalyst assembly-based photoanodes capable of light-driven water splitting to oxygen and hydrogen in a DSPEC are summarized.

Polymer-based chromophore-catalyst assemblies for solar energy conversion.

PubMed

Leem, Gyu; Sherman, Benjamin D; Schanze, Kirk S

2017-01-01

The synthesis of polymer-based assemblies for light harvesting has been motivated by the multi-chromophore antennas that play a role in natural photosynthesis for the potential use in solar conversion technologies. This review describes a general strategy for using polymer-based chromophore-catalyst assemblies for solar-driven water oxidation at a photoanode in a dye-sensitized photoelectrochemical cell (DSPEC). This report begins with a summary of the synthetic methods and fundamental photophysical studies of light harvesting polychormophores in solution which show these materials can transport excited state energy to an acceptor where charge-separation can occur. In addition, studies describing light harvesting polychromophores containing an anchoring moiety (ionic carboxylate) for covalent bounding to wide band gap mesoporous semiconductor surfaces are summarized to understand the photophysical mechanisms of directional energy flow at the interface. Finally, the performance of polychromophore/catalyst assembly-based photoanodes capable of light-driven water splitting to oxygen and hydrogen in a DSPEC are summarized.

para-Azaquinodimethane: A Compact Quinodimethane Variant as an Ambient Stable Building Block for High-Performance Low Band Gap Polymers

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

Liu, Xuncheng; He, Bo; Anderson, Christopher L.

Quinoidal structures incorporating expanded para-quinodimethane (p-QM) units have garnered great interest as functional organic electronic, optical, and magnetic materials. The direct use of the compact p-QM unit as an electronic building block, however, has been inhibited by the high reactivity conveyed by its biradical character. Herein, we introduce a stable p-QM variant, namely p-azaquinodimethane (p-AQM), that incorporates nitrogen atoms in the central ring and alkoxy substituents on the periphery to increase the stability of the quinoidal structure. The succinct synthesis from readily available precursors leads to regio- and stereospecific p-AQMs that can be readily integrated into the backbone of conjugatedmore » polymers. The quinoidal character of the p-AQM unit endows the resulting polymers with narrow band gaps and high carrier transport mobilities. The study of a series of copolymers employing different numbers of thiophene units revealed an unconventional trend in band gaps, which is distinct from the widely adopted donor-acceptor approach to tuning the band gaps of conjugated polymers. Theoretical calculations have shed light on the nature of this trend, which may provide a unique class of conjugated polymers with promising optical and electronic properties.« less

para-Azaquinodimethane: A Compact Quinodimethane Variant as an Ambient Stable Building Block for High-Performance Low Band Gap Polymers

DOE PAGES

Liu, Xuncheng; He, Bo; Anderson, Christopher L.; ...

2017-05-24

Quinoidal structures incorporating expanded para-quinodimethane (p-QM) units have garnered great interest as functional organic electronic, optical, and magnetic materials. The direct use of the compact p-QM unit as an electronic building block, however, has been inhibited by the high reactivity conveyed by its biradical character. Herein, we introduce a stable p-QM variant, namely p-azaquinodimethane (p-AQM), that incorporates nitrogen atoms in the central ring and alkoxy substituents on the periphery to increase the stability of the quinoidal structure. The succinct synthesis from readily available precursors leads to regio- and stereospecific p-AQMs that can be readily integrated into the backbone of conjugatedmore » polymers. The quinoidal character of the p-AQM unit endows the resulting polymers with narrow band gaps and high carrier transport mobilities. The study of a series of copolymers employing different numbers of thiophene units revealed an unconventional trend in band gaps, which is distinct from the widely adopted donor-acceptor approach to tuning the band gaps of conjugated polymers. Theoretical calculations have shed light on the nature of this trend, which may provide a unique class of conjugated polymers with promising optical and electronic properties.« less

Silicon photonic IC embedded optical-PCB for high-speed interconnect application

NASA Astrophysics Data System (ADS)

Kallega, Rakshitha; Nambiar, Siddharth; Kumar, Abhai; Ranganath, Praveen; Selvaraja, Shankar Kumar

2018-02-01

Optical-Printed Circuit Board (PCB) is an emerging optical interconnect technology to bridge the gap between the board edge and the processing module. The technology so far has been used as a broadband transmitter using polymer waveguides in the PCB. In this paper, we report a Silicon Nitride based photonic IC embedded in the PCB along with the polymers as waveguides in the PCB. The motivation for such integration is to bring routing capability and to reduce the power loss due to broadcasting mode.

4-Alkyl-3,5-difluorophenyl-Substituted Benzodithiophene-Based Wide Band Gap Polymers for High-Efficiency Polymer Solar Cells.

PubMed

Li, Guangwu; Gong, Xue; Zhang, Jicheng; Liu, Yahui; Feng, Shiyu; Li, Cuihong; Bo, Zhishan

2016-02-17

Two novel polymers PTFBDT-BZS and PTFBDT-BZO with 4-alkyl-3,5-difluorophenyl substituted benzodithiophene as the donor unit, benzothiadiazole or benzooxadiazole as the acceptor unit, and thiophene as the spacer have been synthesized and used as donor materials for polymer solar cells (PSCs). These two polymers exhibited wide optical band gaps of about 1.8 eV. PSCs with the blend of PTFBDT-BZS:PC71BM (1:2, by weight) as the active layer fabricated without using any processing additive and any postannealing treatment showed power conversion efficiency (PCE) of 8.24% with an open circuit voltage (Voc) of 0.89 V, a short circuit current (Jsc) of 12.67 mA/cm(2), and a fill factor (FF) of 0.73 under AM 1.5G illumination, indicating that PTFBDT-BZS is a very promising donor polymer for PSCs. The blend of PTFBDT-BZO:PC71BM showed a lower PCE of 5.67% with a Voc of 0.96 V, a Jsc of 9.24 mA/cm(2), and an FF of 0.64. One reason for the lower PCE is probably due to that PTFBDT-BZO has a smaller LUMO offset with PC71BM, which cannot provide enough driving force for charge separation. And another reason is probably due to that PTFBDT-BZO has a lower hole mobility in comparison with PTFBDT-BZS.

A Wide Band Gap Polymer with a Deep Highest Occupied Molecular Orbital Level Enables 14.2% Efficiency in Polymer Solar Cells.

PubMed

Li, Sunsun; Ye, Long; Zhao, Wenchao; Yan, Hongping; Yang, Bei; Liu, Delong; Li, Wanning; Ade, Harald; Hou, Jianhui

2018-05-21

To simultaneously achieve low photon energy loss ( E loss ) and broad spectral response, the molecular design of the wide band gap (WBG) donor polymer with a deep HOMO level is of critical importance in fullerene-free polymer solar cells (PSCs). Herein, we developed a new benzodithiophene unit, i.e., DTBDT-EF, and conducted systematic investigations on a WBG DTBDT-EF-based donor polymer, namely, PDTB-EF-T. Due to the synergistic electron-withdrawing effect of the fluorine atom and ester group, PDTB-EF-T exhibits a higher oxidation potential, i.e., a deeper HOMO level (ca. -5.5 eV) than most well-known donor polymers. Hence, a high open-circuit voltage of 0.90 V was obtained when paired with a fluorinated small molecule acceptor (IT-4F), corresponding to a low E loss of 0.62 eV. Furthermore, side-chain engineering demonstrated that subtle side-chain modulation of the ester greatly influences the aggregation effects and molecular packing of polymer PDTB-EF-T. With the benefits of the stronger interchain π-π interaction, the improved ordering structure, and thus the highest hole mobility, the most symmetric charge transport and reduced recombination are achieved for the linear decyl-substituted PDTB-EF-T (P2)-based PSCs, leading to the highest short-circuit current density and fill factor (FF). Due to the high Flory-Huggins interaction parameter (χ), surface-directed phase separation occurs in the P2:IT-4F blend, which is supported by X-ray photoemission spectroscopy results and cross-sectional transmission electron microscope images. By taking advantage of the vertical phase distribution of the P2:IT-4F blend, a high power conversion efficiency (PCE) of 14.2% with an outstanding FF of 0.76 was recorded for inverted devices. These results demonstrate the great potential of the DTBDT-EF unit for future organic photovoltaic applications.

Preparation and characterization of a poly (1, 4-phenylenevinylene) derivative-based hybrid thin film nanocomposites with enhanced performance

NASA Astrophysics Data System (ADS)

Belhaj, Marwa; Jemmeli, Dhouha; Dridi, Cherif; Ben Salem, Balkiss; Jaballah, Najmeddine; Majdoub, Mustapha; Yatskiv, Roman; Grym, Jan

2018-05-01

In this study, a poly (1, 4-phenylenevinylene) derivative (PPV-C6) was synthesized via Gilch polycondensation, and its electrochemical and optical characteristics were determined by cyclic voltammetry analysis, ultraviolet-visible, and photoluminescence spectroscopy. The polymer exhibited semiconductor behavior with an optical band gap of about 2.02 eV. Thin-film hybrid nanocomposites were prepared based on PPV-C6 with a large range of concentrations of sol-gel synthesized surfactant-free ZnO nanoparticles (n-ZnO). We investigated the photophysical properties of nanocomposites with different weight ratios of n-ZnO. The optical absorption spectra of PPV-C6: n-ZnO nanocomposites exhibited moderate variation in terms of the optical band gap energy with respect to the pristine polymer. Photoluminescence spectra indicated that the optimum n-ZnO concentration was about 50 wt% to achieve photoluminescence quenching, which corresponded to the most homogeneous surface and efficient charge transfer due to optimal exciton dissociation. We established good correlations between the investigated properties.

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

Hu, Zhiming; Chen, Hui; Qu, Jianfei

Here, chlorinated benzothiadiazide based polymers with multiple chlorine atoms has been designed and synthesized for polymer solar cells with enhanced open circuit voltage up to 0.85 V. The chlorine substitution is found to significantly adjust the band gap of the polymers, and change polymer’s orientation from random morphology of chlorine free PBT4T-2OD, to mixed face-on packing of one chlorine substituted PCBT4T-2OD, and finally to edge-on of two chlorine substituted PCCBT4T-2OD. The optimized chlorinated polymer, PCBT4T-2OD with only one chlorine atom substituted on BT moiety, has been founded to achieve the highest power conversion efficiency up to 8.20% with PC 71BM,more » which is about 68% higher than that of its non-chlorine analogues.« less

Graphene Calisthenics: Modeling the Polymer-induced Graphene Stretching for Next Generation Electronics

NASA Astrophysics Data System (ADS)

Huo, Mandy; Meaker, Kacey; Chong, Su-Ann; Crommie, Michael

2014-03-01

Graphene is one atomic layer of graphite. It is stronger than steel yet very elastic. Although graphene is a semiconductor with no band gap, we can introduce a gap using various methods in order to make it useful in next-generation electronics. One way to do this is to strain graphene. While we can easily strain graphene uniaxially, this type of strain does not produce appreciable band gaps until relatively high strain percentages close to the fracture point of graphene. However, with a special strain geometry we can produce band gaps well before reaching the breaking point of graphene. This has been done experimentally, but not in a controlled manner. From previous research, strain percentages around 10 percent produce appreciable band gaps. Increasing the strain will increase the size of these gaps, but graphene breaks at around 20 percent strain. We propose to control the amount by which we strain graphene by placing it on a special polymer which expands when light is shone on it. In this project we use COMSOL, a finite element analysis software, to estimate the strain resulting in graphene due to stretching it with a given polymer geometry to find the shapes which will produce the specified strain.

Effects of Surface Roughness and Mechanical Properties of Cover-Layer on Near-Field Optical Recording

NASA Astrophysics Data System (ADS)

Kim, Jin-Hong; Lee, Jun-Seok; Lim, Jungshik; Seo, Jung-Kyo

2009-03-01

Narrow gap distance in cover-layer incident near-field recording (NFR) configuration causes a collision problem in the interface between a solid immersion lens and a disk surface. A polymer cover-layer with smooth surface results in a stable gap servo while a nanocomposite cover-layer with high refractive index shows a collision problem during the gap servo test. Even though a dielectric cover-layer, in which the surface is rougher than the polymer, supplements the mechanical properties, an unclear eye pattern due to an unstable gap servo can be obtained after a chemical mechanical polishing. Not only smooth surface but also good mechanical properties of cover-layer are required for the stable gap servo in the NFR.

Recombination in polymer-fullerene bulk heterojunction solar cells

NASA Astrophysics Data System (ADS)

Cowan, Sarah R.; Roy, Anshuman; Heeger, Alan J.

2010-12-01

Recombination of photogenerated charge carriers in polymer bulk heterojunction (BHJ) solar cells reduces the short circuit current (Jsc) and the fill factor (FF). Identifying the mechanism of recombination is, therefore, fundamentally important for increasing the power conversion efficiency. Light intensity and temperature-dependent current-voltage measurements on polymer BHJ cells made from a variety of different semiconducting polymers and fullerenes show that the recombination kinetics are voltage dependent and evolve from first-order recombination at short circuit to bimolecular recombination at open circuit as a result of increasing the voltage-dependent charge carrier density in the cell. The “missing 0.3 V” inferred from comparison of the band gaps of the bulk heterojunction materials and the measured open-circuit voltage at room-temperature results from the temperature dependence of the quasi-Fermi levels in the polymer and fullerene domains—a conclusion based on the fundamental statistics of fermions.

Approaching Intra- and Interchain Charge Transport of Conjugated Polymers Facilely by Topochemical Polymerized Single Crystals.

PubMed

Yao, Yifan; Dong, Huanli; Liu, Feng; Russell, Thomas P; Hu, Wenping

2017-08-01

Charge transport of small molecules is measured well with scanning tunneling microscopy, conducting atomic force microscopy, break junction, nanopore, and covalently bridging gaps. However, the manipulation and measurement of polymer chains remain a long-standing fundamental issue in conjugated polymers and full of challenge since conjugated polymers are naturally disordered materials. Here, a fundamental breakthrough in generating high-quality conjugated-polymer nanocrystals with extended conjugation and exceptionally high degrees of order using a surface-supported topochemical polymerization method is demonstrated. In the crystal the conjugated-polymer chains are extended along the long axis of the crystal with the side chains perpendicular to the long axis. Devices with conducting channels along the polymer chains show efficient charge transport, nearly two orders of magnitude greater than the interchain charge transport along the π-π stacking direction. This is the first example to clarify intra- and interchain charge transport based on an individual single crystal of conjugated polymers, and demonstrate the importance of intrachain charge transport in plastic electronics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Specific Consideration on Superior Performance and Evaluation Methods of Polymer-housed Surge Arresters

NASA Astrophysics Data System (ADS)

Ishizaki, Yoshihiro; Kobayashi, Misao; Suzuki, Hironori; Futagami, Koichi

It is very suitable to select the polymer materials for the housings of surge arresters (SAs), because the polymer materials are generally soft and light weight. Therefore, many kinds of polymer-housed SAs using various polymer materials have been developed, and expanding into many countries. Considering these backgrounds, the JEC technical report (JEC-TR) 23002-2008; polymer-housed surge arrester(1) has been established based on the existent relevant standards of arresters, such as JEC-2371-2003; Insulator-housed surge arresters(2) and IEC 60099-4 Edition 2.2, Metal-oxide surge arresters (MOSAs) without gaps for a.c. systems(3) in order to introduce the technology and provide a common guide for testing of polymer-housed SAs. According as the JEC-TR, the various new applications of the polymer-housed SAs, which are caused by superior advantages such as compact, light weight, safe failure mode, anti-seismic performance, anti-pollution performance and cost efficiency design, have been realized recently in Japan. Therefore, this paper gives specific consideration on the superior performance of the polymer-housed SAs and the evaluation methods of the polymer-housed SAs, because there are some issues in the existent standards to be solved.

Synthesis, Characterization and TFT Characteristics of Diketopyrrolopyrrole Based Copolymer.

PubMed

Bathula, Chinna; Jeong, Seunghoon; Chung, Jeyon; Kang, Youngjong

2016-03-01

A novel diketopyrrolopyrrole (DPP) based low band gap polymer, poly[4,8-bis(triisopropylsilylethynyl) benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-[2,5-di-hexyl-3,6-dithiophen-2-ylpyrrolo[3,4-c]pyrrole-1,4-dione] (PTIPSBDT-DPP) is synthesized by Stille polymerization for use in thin film transistor (TFTs). The new polymer contain extended aromatic π-conjugated segments alternating with the DPP units and are designed to increase the free energy for charge generation to overcome current limitations in photocurrent generation. In this study we describe the synthesis, thermal stability, optical, electrochemical properties and TFT characteristics.

Equation of State and Damage in Polyethylene

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

Coe, Joshua Damon; Brown, Eric; Cady, Carl Mcelhinney

The dynamic response of polymers differs significantly from those of metals, upon which many of the National Laboratories' deformation, damage, and failure models are based. Their moduli, yield strength, and damage characteristics are highly strain rate-, temperature-, and phase-dependent, requiring models that encompass a wide range of phenomena including some not in equilibrium. Recently, Los Alamos developed the Glassy Amorphous Polymer (GAP) 1 model [1] to address limitations in existing models of polymer deformation. GAP captures both volumetric (equation of state) and deviatoric (shear) response, including a non-equilibrium component to the former (a feature determined to be crucial in capturingmore » the low-pressure, viscoelastic response to impact loading). GAP has already been applied to polymers such as PMMA, PTFE, epoxy, and Kel-F 800, but with an emphasis on impact response as opposed to damage or failure. The current effort was launched to address this gap in predictive capability. For reasons that will be made clear, semi-crystalline polyethylene (PE) was chosen to serve as a model system for parameterization and validation. PE (-C 2H 4-)n is one of the most widely used polymers in industrial and engineering contexts, chiey due to the versatility of its mechanical response. This response can be tuned through network and chain structure, degree of crystallinity, and molecular weight. PE is found in several forms including low density (LDPE), high density (HDPE), and ultra-high molecular weight (UHMWPE). The focus here was on HDPE and UHMWPE, of pedigree described in the following section. Materials were well-characterized prior to study and are representative of semi-crystalline polymers of interest to DOE and DoD. Semi-crystalline PE undergoes a glass transition at low temperature (-35°C) and melts across a range of moderate temperatures (~80-180°C), depending on its structure. It is typically inert chemically, has low strength and high ductility, and the high strength and anisotropy of UHMWPE ber, in particular, have driven its use in engineering, impact, and armor applications. Surprisingly little is known, however, about the influence of PE's crystalline structure and associated phase transitions (including melt) on its response to dynamic compression. A broad suite of experiments was used to calibrate the GAP model for HDPE and UHMWPE. Section IV examines the effects of tensile strain on the structure and integrity of PE crystalline domains. These data were used to inform the preliminary damage model described in Section XII, whose roots lie in statistical physics and network theory. The viscoelastic and plastic components of GAP rely heavily on the stress-strain data of Section VI, which also include dynamic extrusion and Taylor anvil experiments used to validate the damage model. The thermal data of Section X provide crucial inputs to the equilibrium EOS in GAP, as well as the much broader range SESAME EOS whose construction is outlined in Section XI. Section VII details plate impact experiments characterizing the low-pressure shock locus and failure (spall) using in situ electromagnetic gauges. A previously reported \\cusp" in the principal Hugoniot near 0.5 kbar was confirmed, and a multi-wave structure was observed over a limited input stress range above the cusp. This cusp is believed due to solid-solid phase transitions associated with the crystalline domains of the polymer.« less

Flow induced migration in polymer melts – Theory and simulation

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

Dorgan, John Robert, E-mail: jdorgan@mines.edu; Rorrer, Nicholas Andrew, E-mail: nrorrer@mines.edu

2015-04-28

Flow induced migration, whereby polymer melts are fractionated by molecular weight across a flow field, represents a significant complication in the processing of polymer melts. Despite its long history, such phenomena remain relatively poorly understood. Here a simple analytical theory is presented which predicts the phenomena based on well-established principles of non-equilibrium thermodynamics. It is unambiguously shown that for purely viscous materials, a gradient in shear rate is needed to drive migration; for purely viscometric flows no migration is expected. Molecular scale simulations of flow migration effects in dense polymer melts are also presented. In shear flow the melts exhibitmore » similar behavior as the quiescent case; a constant shear rate across the gap does not induce chain length based migration. In comparison, parabolic flow causes profound migration for both unentangled and entangled melts. These findings are consistent with the analytical theory. The picture that emerges is consistent with flow induced migration mechanisms predominating over competing chain degradation mechanisms.« less

Influence of heteroatoms on photovoltaic performance of donor–acceptor copolymers based on 2,6-di(thiophen-2-yl)benzo[1,2-b:4,5-b']difurans and diketopyrrolopyrrole

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

Kobilka, Brandon M.; Hale, Benjamin J.; Ewan, Monique D.

2013-01-01

Donor–acceptor conjugated polymers based on the novel donor 3,7-didodecyl-2,6-di(thiophen-2-yl)benzo[1,2-b:4,5-b']difuran, and 1,4-diketopyrrolo[3,4-c]pyrrole as the acceptor were synthesized via the Stille cross-coupling reaction. The alkyl chains on the diketopyrrolopyrrole monomers were varied to engineer the solubility and morphology of the materials. Thiophene and furan moieties were used to flank the DPP group and the impact of these heterocycles on the polymers' properties evaluated. All of the polymers have similar optoelectronic properties with optical band-gaps of 1.3–1.4 eV, LUMO levels of -3.7 to -3.8 eV and HOMO levels of -5.5 to -5.6 eV. The furan-containing polymers have better solubility than the all-thiophene polymers,more » as significantly higher molecular weight materials of the former were readily dissolved. When the polymers were used as donor materials along with PC71BM as the electron-acceptor in bulk-heterojunction photovoltaic cells, power conversion efficiencies of up to 2.9% were obtained, with the furan-containing polymers giving the best results.« less

Relating nanoindentation to macroindentation of wood

Treesearch

Robert J. Moon; Joseph E. Jakes; Jim F. Beecher; Charles R. Frihart; Donald S. Stone

2009-01-01

Wood has several levels of hierarchical structure, spanning from the configuration of growth-rings down to the configuration of the base polymers (cellulose, hemicellulose, and lignin). The bulk properties of wood result from the culmination of interactions over all length scales. Gaps presently exist in the fundamental knowledge relating the contribution of wood...

Strong Photonic-Band-Gap Effect on the Spontaneous Emission in 3D Lead Halide Perovskite Photonic Crystals.

PubMed

Zhou, Xue; Li, Mingzhu; Wang, Kang; Li, Huizeng; Li, Yanan; Li, Chang; Yan, Yongli; Zhao, Yongsheng; Song, Yanlin

2018-03-25

Stimulated emission in perovskite-embedded polymer opal structures is investigated. A polymer opal structure is filled with a perovskite, and perovskite photonic crystals are prepared. The spontaneous emission of the perovskite embedded in the polymer opal structures exhibits clear signatures of amplified spontaneous emission (ASE) via gain modulation. The difference in refractive-index contrast between the perovskite and the polymer opal is large enough for retaining photonic-crystals properties. The photonic band gap has a strong effect on the fluorescence emission intensity and lifetime. The stimulated emission spectrum exhibits a narrow ASE rather than a wide fluorescence peak in the thin film. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorinated arene, imide and unsaturated pyrrolidinone based donor acceptor conjugated polymers: Synthesis, structure-property and device studies

NASA Astrophysics Data System (ADS)

Liyanage, Arawwawala Don Thilanga

After the discovery of doped polyacetylene, organic semiconductor materials are widely studied as high impending active components in consumer electronics. They have received substantial consideration due to their potential for structural tailoring, low cost, large area and mechanically flexible alternatives to common inorganic semiconductors. To acquire maximum use of these materials, it is essential to get a strong idea about their chemical and physical nature. Material chemist has an enormous role to play in this novel area, including development of efficient synthetic methodologies and control the molecular self-assembly and (opto)-electronic properties. The body of this thesis mainly focuses on the substituent effects: how different substituents affect the (opto)-electronic properties of the donor-acceptor (D-A) conjugated polymers. The main priority goes to understand, how different alkyl substituent effect to the polymer solubility, crystallinity, thermal properties (e.g.: glass transition temperature) and morphological order. Three classes of D-A systems were extensively studied in this work. The second chapter mainly focuses on the synthesis and structure-property study of fluorinated arene (TFB) base polymers. Here we used commercially available 1,4-dibromo-2,3,5,6-tetrafluorobenzene (TFB) as the acceptor material and prepare several polymers using 3,3'-dialkyl(3,3'-R2T2) or 3,3'-dialkoxy bithiophene (3,3'-RO2T2) units as electron donors. A detail study was done using 3,3'-bithiophene donor units incorporating branched alkoxy-functionalities by systematic variation of branching position and chain length. The study allowed disentangling the branching effects on (i) aggregation tendency, intermolecular arrangement, (iii) solid state optical energy gaps, and (iv) electronic properties in an overall consistent picture, which might guide future polymer synthesis towards optimized materials for opto-electronic applications. The third chapter mainly focused on the structure-property study of imide functionalized D-A polymers. Here we used thiophene-imide (TPD) as the acceptor moiety and prepare several D-A polymers by varying the donor units. When selecting the donor units, more priority goes to the fused ring systems. One main reason to use imide functionality is due to the, open position of the imide nitrogen, which provides an attaching position to alkyl substituent. Through this we can easily manipulate solubility and solid state packing arrangement. Also these imide acceptors have low-lying LUMOs due to their electron deficient nature and this will allow tuning the optical energy gap by careful choice of donor materials with different electron donating ability. The fourth chapter mainly contribute to the synthesis and structure property study of a completely novel electron acceptor moiety consist of a unsaturated pyrrolidinone unit known as Pechmann dye (PD) core. Pechmann dyes are closely related to the Indigo family. This can refer as 3-butenolide dimer connected via an alkene bridge, containing a benzene ring at the 5 and 5' positions of the lactone rings. We have prepared several D-A polymers using this PD system with benzodithiophene (BDT) as the donor unit. Different to common D-A polymers the HOMO and LUMO of the PD acceptor moiety are energetically located within the gap of the BDT, so that the electronic and optical properties (HOMO-LUMO transition) are dictated by the PD properties. The promising electronic properties, band gaps, high absorption coefficients and broad absorption suggest this new D-A polymers as an interesting donor material for organic solar cell (OSC) applications. KEY WORDS: Organic semiconductor materials, Self assembly, (opto)-electronic properties, Donor-Acceptor conjugated polymers, Fluorinated arene, 3,3'-bithiophene donors, Thiophene-imide (TPD), Pechmann dye, benzodithiophene, organic solar cell.

Tuning the electronic and optical properties of NDT-based conjugated polymers by adopting fused heterocycles as acceptor units: a theoretical study.

PubMed

Cheng, Na; Zhang, Changqiao; Liu, Yongjun

2017-08-01

Donor-acceptor conjugated polymers have been successfully applied in bulk heterojunction solar cell devices. Tuning their donor and acceptor units allows the design of new polymers with desired electronic and optical properties. Here, to screen new candidate polymers based on a newly synthesized donor unit, dithieo[2,3-d:2',3'-d']naphtho[1,2-b:3,4-b']dithiophene (NDT), a series of model polymers with different acceptor units were designed and denoted NDT-A 0 to NDT-A 12 , and the structures and optical properties of those polymers were investigated using DFT and TDDFT calculations. The results of the calculations revealed that the electronic and optical properties of these polymers depend on the acceptor unit present; specifically, their HOMO energies ranged from -4.89 to -5.38 eV, their HOMO-LUMO gaps ranged from 1.30 to 2.80 eV, and their wavelengths of maximum absorption ranged from 538 to 1212 nm. The absorption spectra of NDT-A 1 to NDT-A 6 , NDT-A 8 , NDT-A 9 , and NDT-A 12 occur within the visible region (<900 nm), indicating that these polymers are potential candidates for use in solar cells. On the other hand, the absorption spectra of NDT-A 7 , NDT-A 10 , and NDT-A 11 extend much further into the near-infrared region, implying that they absorb near-infrared light. These polymers could meet the requirements of donor units for use in tandem and ternary solar cells. Graphical abstract Theoretical calculations by TD-DFT reveal that the optical properties of NDT-based conjugated polymers can be well tuned by adopting different acceptor units, and these ploymers are potential donor materials for tandem and ternary solar cells.

Vaporizable Scaffolds for Fabricating Thermoelectric Modules

NASA Technical Reports Server (NTRS)

Sakamoto, Jeffrey; Yen, Shiao-pin; Fleurial, Jean-Pierre; Paik, Jong-Ah

2006-01-01

A process for fabricating thermoelectric modules with vacuum gaps separating the thermoelectric legs has been conceived, and the feasibility of some essential parts of the process has been demonstrated. The vacuum gaps are needed to electrically insulate the legs from each other. The process involves the use of scaffolding in the form of sheets of a polymer to temporarily separate the legs by the desired distance, which is typically about 0.5 mm. During a bonding subprocess that would take place in a partial vacuum at an elevated temperature, the polymer would be vaporized, thereby creating the vacuum gaps.

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

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

Orbitals, Occupation Numbers, and Band Structure of Short One-Dimensional Cadmium Telluride Polymers.

PubMed

Valentine, Andrew J S; Talapin, Dmitri V; Mazziotti, David A

2017-04-27

Recent work found that soldering CdTe quantum dots together with a molecular CdTe polymer yielded field-effect transistors with much greater electron mobility than quantum dots alone. We present a computational study of the CdTe polymer using the active-space variational two-electron reduced density matrix (2-RDM) method. While analogous complete active-space self-consistent field (CASSCF) methods scale exponentially with the number of active orbitals, the active-space variational 2-RDM method exhibits polynomial scaling. A CASSCF calculation using the (48o,64e) active space studied in this paper requires 10 24 determinants and is therefore intractable, while the variational 2-RDM method in the same active space requires only 2.1 × 10 7 variables. Natural orbitals, natural-orbital occupations, charge gaps, and Mulliken charges are reported as a function of polymer length. The polymer, we find, is strongly correlated, despite possessing a simple sp 3 -hybridized bonding scheme. Calculations reveal the formation of a nearly saturated valence band as the polymer grows and a charge gap that decreases sharply with polymer length.

Current progress and technical challenges of flexible liquid crystal displays

NASA Astrophysics Data System (ADS)

Fujikake, Hideo; Sato, Hiroto

2009-02-01

We focused on several technical approaches to flexible liquid crystal (LC) display in this report. We have been developing flexible displays using plastic film substrates based on polymer-dispersed LC technology with molecular alignment control. In our representative devices, molecular-aligned polymer walls keep plastic-substrate gap constant without LC alignment disorder, and aligned polymer networks create monostable switching of fast-response ferroelectric LC (FLC) for grayscale capability. In the fabrication process, a high-viscosity FLC/monomer solution was printed, sandwiched and pressed between plastic substrates. Then the polymer walls and networks were sequentially formed based on photo-polymerization-induced phase separation in the nematic phase by two exposure processes of patterned and uniform ultraviolet light. The two flexible backlight films of direct illumination and light-guide methods using small three-primary-color light-emitting diodes were fabricated to obtain high-visibility display images. The fabricated flexible FLC panels were driven by external transistor arrays, internal organic thin film transistor (TFT) arrays, and poly-Si TFT arrays. We achieved full-color moving-image displays using the flexible FLC panel and the flexible backlight film based on field-sequential-color driving technique. Otherwise, for backlight-free flexible LC displays, flexible reflective devices of twisted guest-host nematic LC and cholesteric LC were discussed with molecular-aligned polymer walls. Singlesubstrate device structure and fabrication method using self-standing polymer-stabilized nematic LC film and polymer ceiling layer were also proposed for obtaining LC devices with excellent flexibility.

Damage healing ability of a shape-memory-polymer-based particulate composite with small thermoplastic contents

NASA Astrophysics Data System (ADS)

Nji, Jones; Li, Guoqiang

2012-02-01

The purpose of this study is to investigate the potential of a shape-memory-polymer (SMP)-based particulate composite to heal structural-length scale damage with small thermoplastic additive contents through a close-then-heal (CTH) self-healing scheme that was introduced in a previous study (Li and Uppu 2010 Comput. Sci. Technol. 70 1419-27). The idea is to achieve reasonable healing efficiencies with minimal sacrifice in structural load capacity. By first closing cracks, the gap between two crack surfaces is narrowed and a lesser amount of thermoplastic particles is required to achieve healing. The particulate composite was fabricated by dispersing copolyester thermoplastic particles in a shape memory polymer matrix. It is found that, for small thermoplastic contents of less than 10%, the CTH scheme followed in this study heals structural-length scale damage in the SMP particulate composite to a meaningful extent and with less sacrifice of structural capacity.

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

PubMed

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

2017-01-25

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

Incorporating perylene moiety into poly(phenothiazine-co-bithiophene) backbone for higher charge transport.

PubMed

Tang, Weihua; Ke, Lin; Chen, Zhi-Kuan

2008-03-27

Low band gap pi-conjugated polymers composed of phenothiazine, bithiophene, and perylene moieties were prepared in high yields by using a palladium-catalyzed Suzuki coupling reaction. The polymers were characterized by NMR, gel permeation chromatography, and elemental analysis. The characterizations revealed that high-molecular weight (weight-average molecular weight up to 42,400 g/mol) polymers were thermally stable with a decomposition temperature in the region of 338-354 degrees C and their glass transition temperatures (Tg) ranging from 124 to 136 degrees C. All polymers demonstrated broad optical absorption in the region of 300-550 nm with efficient blue-green light emission. The absorption was broadened further (for ca. 50 nm) when the perylene moiety was incorporated. Cyclic voltammograms displayed that the p- and n-doping processes of all the polymers were partially reversible and that electrochemical band gaps were as low as -2.30 eV with the incorporation of a perylene moiety. The hole mobility of polymers was evaluated by using the space-charge-limited current model with a device structure of ITO/PEDOT:PSS/polymer/Ca. The results show that the incorporation of perylene is beneficial for improving the hole mobility of the conjugated polymers.

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

McLeod, John A., E-mail: jmcleod@suda.edu.cn; Pitman, Amy L.; Moewes, Alexander

The electronic structure of [6,6]-phenyl C{sub 61} butyric acid methyl ester (PCBM), poly(3-hexylthiophene) (P3HT), and P3HT/PCBM blends is studied using soft X-ray emission and absorption spectroscopy and density functional theory calculations. We find that annealing reduces the HOMO-LUMO gap of P3HT and P3HT/PCBM blends, whereas annealing has little effect on the HOMO-LUMO gap of PCBM. We propose a model connecting torsional disorder in a P3HT polymer to the HOMO-LUMO gap, which suggests that annealing helps to decrease the torsional disorder in the P3HT polymers. Our model is used to predict the characteristic length scales of the flat P3TH polymer segmentsmore » in P3HT and P3HT/PCBM blends before and after annealing. Our approach may prove useful in characterizing organic photovoltaic devices in situ or even in operando.« less

Novel donor-acceptor polymer containing 4,7-bis(thiophen-2-yl)benzo[c][1,2,5]thiadiazole for polymer solar cells with power conversion efficiency of 6.21%.

PubMed

Han, Liangliang; Bao, Xichang; Hu, Tong; Du, Zhengkun; Chen, Weichao; Zhu, Dangqiang; Liu, Qian; Sun, Mingliang; Yang, Renqiang

2014-06-01

In order to improve the solution processability of 4,7-bis(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (DTBT)-based polymers, novel donor-acceptor polymer PTOBDTDTBT containing DTBT and benzo[1,2-b:4,5-b']dithiophene (BDT) with conjugated side chain is designed and synthesized with narrow band gap 1.67 eV and low lying HOMO energy level -5.4 eV. The blend film of PTOBDTDTBT and PC71 BM exhibits uniform and smooth film with root-mean-square (RMS) surface roughness 1.15 nm because of the excellent solubility of PTOBDTDTBT when six octyloxy side chains are introduced. The hole mobility of the blend film is measured to be 4.4 × 10(-5) cm(2) V(-1) s(-1) by the space-charge-limited current (SCLC) model. The optimized polymer solar cells (PSCs) based on PTOBDTDTBT/PC71 BM exhibits an improved PCE of 6.21% with Voc = 0.80 V, Jsc = 11.94 mA cm(-2) and FF = 65.10%, one of the highest PCE in DTBT containing polymers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-dimensionally ordered array of air bubbles in a polymer film

NASA Technical Reports Server (NTRS)

Srinivasarao, M.; Collings, D.; Philips, A.; Patel, S.; Brown, C. S. (Principal Investigator)

2001-01-01

We report the formation of a three-dimensionally ordered array of air bubbles of monodisperse pore size in a polymer film through a templating mechanism based on thermocapillary convection. Dilute solutions of a simple, coil-like polymer in a volatile solvent are cast on a glass slide in the presence of moist air flowing across the surface. Evaporative cooling and the generation of an ordered array of breath figures leads to the formation of multilayers of hexagonally packed water droplets that are preserved in the final, solid polymer film as spherical air bubbles. The dimensions of these bubbles can be controlled simply by changing the velocity of the airflow across the surface. When these three-dimensionally ordered macroporous materials have pore dimensions comparable to the wavelength of visible light, they are of interest as photonic band gaps and optical stop-bands.

Molecular-level architectural design using benzothiadiazole-based polymers for photovoltaic applications

PubMed Central

Viswanathan, Vinila N; Rao, Arun D; Pandey, Upendra K; Kesavan, Arul Varman

2017-01-01

A series of low band gap, planar conjugated polymers, P1 (PFDTBT), P2 (PFDTDFBT) and P3 (PFDTTBT), based on fluorene and benzothiadiazole, was synthesized. The effect of fluorine substitution and fused aromatic spacers on the optoelectronic and photovoltaic performance was studied. The polymer, derived from dithienylated benzothiodiazole and fluorene, P1, exhibited a highest occupied molecular orbital (HOMO) energy level at −5.48 eV. Density functional theory (DFT) studies as well as experimental measurements suggested that upon substitution of the acceptor with fluorine, both the HOMO and lowest unoccupied molecular orbital (LUMO) energy levels of the resulting polymer, P2, were lowered, leading to a higher open circuit voltage and short circuit current with an overall improvement of more than 110% for the photovoltaic devices. Moreover, a decrease in the torsion angle between the units was also observed for the fluorinated polymer P2 due to the enhanced electrostatic interaction between the fluorine substituents and sulfur atoms, leading to a high hole mobility. The use of a fused π-bridge in polymer P3 for the enhancement of the planarity as compared to the P1 backbone was also studied. This enhanced planarity led to the highest observed mobility among the reported three polymers as well as to an improvement in the device efficiency by more than 40% for P3. PMID:28546844

GAP/CL-20-Based Compound Explosive: A New Booster Formulation Used in a Small-Sized Initiation Network

NASA Astrophysics Data System (ADS)

Yanju, Wei; Jingyu, Wang; Chongwei, An; Hequn, Li; Xiaomu, Wen; Binshuo, Yu

2017-01-01

With ε-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and glycidyl azide polymer (GAP) as the solid filler and binder, respectively, GAP/CL-20-based compound explosives were designed and prepared. Using micro injection charge technology, the compound explosives were packed into small grooves to explore their application in a small-sized initiation network. The detonation reliability, detonation velocity, mechanical sensitivity, shock sensitivity, and brisance of the explosive were measured and analyzed. The results show that when the solid content of CL-20 is 82 wt%, the explosive charged in the groove has a smooth surface from a macroscopic view. From a microscopic view, a coarse surface is bonded with many CL-20 particles by GAP binder. The GAP/CL-20-based explosive charge successfully generates detonation waves in a groove larger than 0.6 mm × 0.6 mm. When the charge density in the groove is 1.68 g.cm-3 (90% theoretical maximum density), the detonation velocity reaches 7,290 m.s-1. Moreover, this kind of explosive is characterized by low impact and shock sensitivity.

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

PubMed

Voortman, Thomas P; Chiechi, Ryan C

2015-12-30

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

Memory Device and Nanofabrication Techniques Using Electrically Configurable Materials

NASA Astrophysics Data System (ADS)

Ascenso Simões, Bruno

Development of novel nanofabrication techniques and single-walled carbon nanotubes field configurable transistor (SWCNT-FCT) memory devices using electrically configurable materials is presented. A novel lithographic technique, electric lithography (EL), that uses electric field for pattern generation has been demonstrated. It can be used for patterning of biomolecules on a polymer surface and patterning of resist as well. Using electrical resist composed of a polymer having Boc protected amine group and iodonium salt, Boc group on the surface of polymer was modified to free amine by applying an electric field. On the modified surface of the polymer, Streptavidin pattern was fabricated with a sub-micron scale. Also patterning of polymer resin composed of epoxy monomers and diaryl iodonium salt by EL has been demonstrated. Reaction mechanism for electric resist configuration is believed to be induced by an acid generation via electrochemical reduction in the resist. We show a novel field configurable transistor (FCT) based on single-walled carbon nanotube network field-effect transistors in which poly (ethylene glycol) crosslinked by electron-beam is incorporated into the gate. The device conductance can be configured to arbitrary states reversibly and repeatedly by applying external gate voltages. Raman spectroscopy revealed that evolution of the ratio of D- to G-band intensity in the SWCNTs of the FCT progressively increases as the device is configured to lower conductance states. Electron transport studies at low temperatures showed a strong temperature dependence of the resistance. Band gap widening of CNTs up to ˜ 4 eV has been observed by examining the differential conductance-gate voltage-bias voltage relationship. The switching mechanism of the FCT is attributed a structural transformation of CNTs via reversible hydrogenation and dehydrogenations induced by gate voltages, which tunes the CNT bandgap continuously and reversibly to non-volatile analog values. The CNT transistors with field tunable band gaps would facilitate field programmable circuits based on the self-organized CNTs, and might also lead to novel analog memory, neuromorphic, and photonic devices.

Studies of Luminescence Performance on Carbazole Donor and Quinoline Acceptor Based Conjugated Polymer.

PubMed

Upadhyay, Anjali; S, Karpagam

2016-03-01

We report on the synthesis of conjugated polymer (CV-QP) containing carbazole (donor) and quinoline (acceptor) using Wittig methodology. The structural, optical and thermal properties of the polymer were investigated by FT-IR, NMR, GPC, UV, PL, cyclic voltammetry, atomic force microscopy (AFM) and thermogravimetric analysis (TGA). The polymer exhibits thermal stability upto 200 °C and shows good solubility in common organic solvents. The polymer has optical absorption band in a thin film at 360 nm and emission band formed at 473 nm. The optical energy band gap was found to be 2.69 eV as calculated from the onset absorption edge. Fluorescence quenching of the polymer CV-QP was found by using DMA (electron donor) and DMTP (electron acceptor). AFM image indicated that triangular shaped particles were observed and the particle size was found as 1.1 μm. The electrochemical studies of CV-QP reveal that, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the CV-QP are 6.35 and 3.70 eV, which indicated that the polymers are expected to provide charge transporting properties for the development of polymer light-emitting diodes (PLEDs).

Tuning the thermal conductivity of solar cell polymers through side chain engineering.

PubMed

Guo, Zhi; Lee, Doyun; Liu, Yi; Sun, Fangyuan; Sliwinski, Anna; Gao, Haifeng; Burns, Peter C; Huang, Libai; Luo, Tengfei

2014-05-07

Thermal transport is critical to the performance and reliability of polymer-based energy devices, ranging from solar cells to thermoelectrics. This work shows that the thermal conductivity of a low band gap conjugated polymer, poly(4,8-bis-alkyloxybenzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-(alkylthieno[3,4-b]thiophene-2-carboxylate)-2,6-diyl) (PBDTTT), for photovoltaic applications can be actively tuned through side chain engineering. Compared to the original polymer modified with short branched side chains, the engineered polymer using all linear and long side chains shows a 160% increase in thermal conductivity. The thermal conductivity of the polymer exhibits a good correlation with the side chain lengths as well as the crystallinity of the polymer characterized using small-angle X-ray scattering (SAXS) experiments. Molecular dynamics simulations and atomic force microscopy are used to further probe the molecular level local order of different polymers. It is found that the linear side chain modified polymer can facilitate the formation of more ordered structures, as compared to the branched side chain modified ones. The effective medium theory modelling also reveals that the long linear side chain enables a larger heat carrier propagation length and the crystalline phase in the bulk polymer increases the overall thermal conductivity. It is concluded that both the length of the side chains and the induced polymer crystallization are important for thermal transport. These results offer important guidance for actively tuning the thermal conductivity of conjugated polymers through molecular level design.

Characterization of pi-Conjugated Polymers for Transistor and Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Paulsen, Bryan D.

pi-Conjugated polymers represent a unique class of optoelectronic materials. Being polymers, they are solution processable and inherently "soft" materials. This makes them attractive candidates for the production of roll-to-roll printed electronic devices on flexible substrates. The optical and electronic properties of pi-conjugated polymers are synthetically tunable allowing material sets to be tailored to specific applications. Two of the most heavily researched applications are the thin film transistor, the building block of electronic circuits, and the bulk heterojunction solar cell, which holds great potential as a renewable energy source. Key to developing commercially feasible pi-conjugated polymer devices is a thorough understanding of the electronic structure and charge transport behavior of these materials in relationship with polymer structure. Here this structure property relationship has been investigated through electrical and electrochemical means in concert with a variety of other characterization techniques and device test beds. The tunability of polymer optical band gap and frontier molecular orbital energy level was investigated in systems of vinyl incorporating statistical copolymers. Energy levels and band gaps are crucial parameters in developing efficient photovoltaic devices, with control of these parameters being highly desirable. Additionally, charge transport and density of electronic states were investigated in pi-conjugated polymers at extremely high electrochemically induced charge density. Finally, the effects of molecular weight on pi-conjugated polymer optical properties, energy levels, charge transport, morphology, and photovoltaic device performance was examined.

Deformation and flexural properties of denture base polymer reinforced with glass fiber sheet.

PubMed

Kanie, Takahito; Arikawa, Hiroyuki; Fujii, Koichi; Ban, Seiji

2005-09-01

The purpose of this study was to investigate the deformation and flexural properties of acrylic and urethane polymers reinforced with glass fiber sheet. Four types of specimen--self-curing resin plate (R), light-curing oligomer plate containing a reinforcement (GO), and self-curing resin plate containing a reinforcement on one (GR) or both (GRG) sides--were prepared with three thicknesses: 1.5, 2.4, and 3.0 mm. Gaps between polymerized test specimen and a standard metal plate were measured at the corner (C), middle of the long sides (LS), and middle of the short sides (SS). The gaps for R were 0-2.0 microm. GO and GR markedly deformed at Points C, LS, and SS, and the degree of deformation increased as GO became thinner. Flexural strength was significantly increased by the reinforcement (p < 0.05). The flexural moduli of 3.0-mm thick R, GO, and GR were significantly smaller than that of 1.5-mm thick specimens.

Diketopyrrolopyrrole Polymers for Organic Solar Cells.

PubMed

Li, Weiwei; Hendriks, Koen H; Wienk, Martijn M; Janssen, René A J

2016-01-19

Conjugated polymers have been extensively studied for application in organic solar cells. In designing new polymers, particular attention has been given to tuning the absorption spectrum, molecular energy levels, crystallinity, and charge carrier mobility to enhance performance. As a result, the power conversion efficiencies (PCEs) of solar cells based on conjugated polymers as electron donor and fullerene derivatives as electron acceptor have exceeded 10% in single-junction and 11% in multijunction devices. Despite these efforts, it is notoriously difficult to establish thorough structure-property relationships that will be required to further optimize existing high-performance polymers to their intrinsic limits. In this Account, we highlight progress on the development and our understanding of diketopyrrolopyrrole (DPP) based conjugated polymers for polymer solar cells. The DPP moiety is strongly electron withdrawing and its polar nature enhances the tendency of DPP-based polymers to crystallize. As a result, DPP-based conjugated polymers often exhibit an advantageously broad and tunable optical absorption, up to 1000 nm, and high mobilities for holes and electrons, which can result in high photocurrents and good fill factors in solar cells. Here we focus on the structural modifications applied to DPP polymers and rationalize and explain the relationships between chemical structure and organic photovoltaic performance. The DPP polymers can be tuned via their aromatic substituents, their alkyl side chains, and the nature of the π-conjugated segment linking the units along the polymer chain. We show that these building blocks work together in determining the molecular conformation, the optical properties, the charge carrier mobility, and the solubility of the polymer. We identify the latter as a decisive parameter for DPP-based organic solar cells because it regulates the diameter of the semicrystalline DPP polymer fibers that form in the photovoltaic blends with fullerenes via solution processing. The width of these fibers and the photon energy loss, defined as the energy difference between optical band gap and open-circuit voltage, together govern to a large extent the quantum efficiency for charge generation in these blends and thereby the power conversion efficiency of the photovoltaic devices. Lowering the photon energy loss and maintaining a high quantum yield for charge generation is identified as a major pathway to enhance the performance of organic solar cells. This can be achieved by controlling the structural purity of the materials and further control over morphology formation. We hope that this Account contributes to improved design strategies of DPP polymers that are required to realize new breakthroughs in organic solar cell performance in the future.

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.

Switching of the electrical conductivity of plasticized PVC films under uniaxial pressure

NASA Astrophysics Data System (ADS)

Vlasov, D. V.; Apresyan, L. A.; Vlasova, T. V.; Kryshtob, V. I.

2011-11-01

The jumplike switching of the electrical conductivity in wide-band-gap polymer (antistatic plasticized polyvinylchloride) films under uniaxial pressure is studied. In various plasticized PVC materials, the uniaxial pressure inducing a conductivity jump by four orders of magnitude or higher changes from several to several hundreds of bars, and this effect is retained at a film thickness of several hundred microns, which is two orders of magnitude larger than the critical film thicknesses known for other wide-band-gap polymers. In addition to the earlier interpretation of the conductivity anomalies in plasticized PVC, we proposed a phenomenological electron-molecular dynamic nanotrap model, in which local charge transfer is provided by mobile molecule segments in a plasticized polymer.

Polymer photonic crystal slab waveguides

NASA Astrophysics Data System (ADS)

Liguda, C.; Böttger, G.; Kuligk, A.; Blum, R.; Eich, M.; Roth, H.; Kunert, J.; Morgenroth, W.; Elsner, H.; Meyer, H. G.

2001-04-01

We present details of the fabrication, calculations, and transmission measurements for finite two-dimensional (2D) polymer photonic crystal (PC) slab waveguides, which were fabricated from a benzocyclobutene polymer on a low refractive index substrate from Teflon. A square air hole lattice (500 nm lattice constant, 300 nm hole diameter) was realized by electron beam lithography and reactive ion etching. Polarization and wavelength dependent transmission results show TE-like and TM-like stop gaps at 1.3 μm excitation wavelengths and are in good agreement with the calculated data obtained by 2D and three-dimensional finite difference time domain methods. Transmission was suppressed by 15 dB in the center of the TE-like stop gap for a PC length of ten lattice constants.

Synthesis of diketopyrrolopyrrole containing copolymers: a study of their optical and photovoltaic properties.

PubMed

Kanimozhi, Catherine; Balraju, P; Sharma, G D; Patil, Satish

2010-03-11

The diketopyrrolopyrrole-based copolymers PDPP-BBT and TDPP-BBT were synthesized and used as a donor for bulk heterojunction photovoltaic devices. The photophysical properties of these polymers showed absorption in the range 500-600 nm with a maximum peak around 563 nm, while TDPP-BBT showed broadband absorption in the range 620-800 nm with a peak around 656 nm. The power conversion efficiencies (PCE) of the polymer solar cells based on these copolymers and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) were 0.68% (as cast PDPP-BBT:PCBM), 1.51% (annealed PDPP-BBT:PCBM), 1.57% (as cast TDPP-BBT:PCBM), and 2.78% (annealed TDPP-BBT:PCBM), under illumination of AM 1.5 (100 mW/cm(2)). The higher PCE for TDPP-BBT-based polymer solar cells has been attributed to the low band gap of this copolymer as compared to PDPP-BBT, which increases the numbers of photogenerated excitons and corresponding photocurrent of the device. These results indicate that PDPP-BBT and TDPP-BBT act as excellent electron donors for bulk heterojunction devices.

Fast response liquid crystal devices

NASA Astrophysics Data System (ADS)

Wu, Yung-Hsun

Liquid crystal (LC) has been widely used for displays, spatial light modulators, variable optical attenuators (VOAs) and other tunable photonic devices. The response time of these devices is mainly determined by the employed liquid crystal material. The response time of a LC device depends on the visco-elastic coefficient (gamma1/K11), LC cell gap (d), and applied voltage. Hence, low visco-elastic coefficient LC materials and thinner cell gap are favorable for reducing the response time. However, low visco-elastic coefficient LCs are usually associated with a low birefringence because of shorter molecular conjugation. For display applications, such as LCD TVs, low birefringence (Deltan<0.1) LCs are commonly used. However, for optical communications at 1550 nm, low birefringence requires to a thick cell gap which, in turn, increases the response time. How to obtain fast response for the LC devices is a fundamentally important and technically challenging task. In this dissertation, we investigate several methods to improve liquid crystal response time, for examples, using dual-frequency liquid crystals, polymer stabilized liquid crystals, and sheared polymer network liquid crystals. We discover a new class of material, denoted as sheared polymer network liquid crystal (SPNLC) which exhibits a submillisecond response time. Moreover, this response time is insensitive to the LC cell gap. This is the first LC device exhibiting such an interesting property. Chapters 1 and 2 describe the motivation and background of this dissertation. From chapter 3 to chapter 6, dual-frequency liquid crystals and polymer network methods are demonstrated as examples for the variable optical attenuators. Variable optical attenuator (VOA) is a key component in optical communications. Especially, the sheared PNLC VOA shows the best result; its dynamic range reaches 43 dB while the response time is in the submillisecond range at 1550 nm wavelength, which is 50 times faster than the commercial LC-based VOA. In Chapter 7, we report a new device called axially-symmetric sheared polymer network liquid crystals (AS-SPNLC) and use it as LC devices. Through analyzing the structure of this axially-symmetric SPNLC, we construct a 3-D model to explain the observed phenomena. An axially-symmetric sheared polymer network liquid crystal has several attractive features: (1) it is polarization independent, (2) it has gradient phase change, and (3) its response time is fast. It can be used for polarization converter and divergent LC lens. In addition, a new method for simultaneously measuring the phase retardation and optic axis of a compensation film is demonstrated using an axially-symmetric sheared polymer network liquid crystal. By overlaying a tested compensation film with a calibrated SPNLC cell between crossed polarizers, the optic axis and phase retardation value of the compensation film can be determined. This simple technique can be used for simultaneously measuring the optic axis and phase retardations of both A- and C-plates. These compensation films have been used extensively in wide-view LCD industry. Therefore, this method will make an important impact to the LCD industry.

Marked Consequences of Systematic Oligothiophene Catenation in Thieno[3,4-c]pyrrole-4,6-dione and Bithiopheneimide Photovoltaic Copolymers

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

Zhou, Nanjia; Guo, Xugang; Ponce Ortiz, Rocio

As effective building blocks for high-mobility transistor polymers, oligothiophenes are receiving attention for polymer solar cells (PSCs) because the resulting polymers can effectively suppress charge recombination. Here we investigate two series of in-chain donor-acceptor copolymers, PTPDnT and PBTInT, based on thieno[3,4-c]pyrrole-4,6-dione (TPD) or bithiopheneimide (BTI) as electron acceptor units, respectively, and oligothiophenes (nTs) as donor counits, for high-performance PSCs. Intramolecular S···O interaction leads to more planar TPD polymer backbones, however backbone torsion yields greater open-circuit voltages for BTI polymers. Thiophene addition progressively raises polymer HOMOs but marginally affects their band gaps. FT-Raman spectra indicate that PTPDnT and PBTInT conjugation lengthsmore » scale with nT catenation up to n = 3 and then saturate for longer oligomer. Furthermore, the effects of oligothiophene alkylation position are explored, revealing that the alkylation pattern greatly affects film morphology and PSC performance. The 3T with “outward” alkylation in PTPD3T and PBTI3T affords optimal π-conjugation, close stacking, long-range order, and high hole mobilities (0.1 cm 2/(V s)). These characteristics contribute to the exceptional ~80% fill factors for PTPD3T-based PSCs with PCE = 7.7%. The results demonstrate that 3T is the optimal donor unit among nTs (n = 1-4) for photovoltaic polymers. Grazing incidence wide-angle X-ray scattering, transmission electron microscopy, and time-resolved microwave conductivity measurements reveal that the terthiophene-based PTPD3T blend maintains high crystallinity with appreciable local mobility and long charge carrier lifetime. These results provide fundamental materials structure-device performance correlations and suggest guidelines for designing oligothiophene-based polymers with optimal thiophene catenation and appropriate alkylation pattern to maximize PSC performance.« less

Photoexcitation and Photochemical Stability of Organic Photovoltaic Materials from First Principles

NASA Astrophysics Data System (ADS)

Sai, Na; Leung, Kevin

2013-03-01

The development of high efficiency organic photovoltaics (OPV) has recently become enabled by the synthesis of new conjugated polymers with low band gap that allow light absorption over a broader range of the spectrum. Stability of these new polymers, a key requirement for commercialization, has not yet received sufficient attention. Here, we report first-principles theoretical modeling of photo-induced degradation of OPV polymers carried out using ab-initio density functional theory (DFT). We report photooxidation routes and reaction products for reactive species including superoxide oxygen anions and hydroxyl groups interacting with the standard workhorse OPV polymer, poly(3-hexyl-thiophene) (P3HT). We discuss theoretical issues and challenges affecting the modeling such reactions in OPV polymers. We also discuss the application of theoretical methods to low-band-gap polymers, and in particular, the effect of the chemical substitution on the photoexcitation properties of these new polymers. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Deparment of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This work is supported by the Energy Frontier Research Center funded by the U.S. DOE Office of Basic Energy Sciences under Award number DE-SC0001091.

Tandem Solar Cells from Accessible Low Band-Gap Polymers Using an Efficient Interconnecting Layer.

PubMed

Bag, Santanu; Patel, Romesh J; Bunha, Ajaykumar; Grand, Caroline; Berrigan, J Daniel; Dalton, Matthew J; Leever, Benjamin J; Reynolds, John R; Durstock, Michael F

2016-01-13

Tandem solar cell architectures are designed to improve device photoresponse by enabling the capture of wider range of solar spectrum as compared to single-junction device. However, the practical realization of this concept in bulk-heterojunction polymer systems requires the judicious design of a transparent interconnecting layer compatible with both polymers. Moreover, the polymers selected should be readily synthesized at large scale (>1 kg) and high performance. In this work, we demonstrate a novel tandem polymer solar cell that combines low band gap poly isoindigo [P(T3-iI)-2], which is easily synthesized in kilogram quantities, with a novel Cr/MoO3 interconnecting layer. Cr/MoO3 is shown to be greater than 80% transparent above 375 nm and an efficient interconnecting layer for P(T3-iI)-2 and PCDTBT, leading to 6% power conversion efficiencies under AM 1.5G illumination. These results serve to extend the range of interconnecting layer materials for tandem cell fabrication by establishing, for the first time, that a thin, evaporated layer of Cr/MoO3 can work as an effective interconnecting layer in a tandem polymer solar cells made with scalable photoactive materials.

Coarse-grained simulation of polymer-filler blends

NASA Astrophysics Data System (ADS)

Legters, Gregg; Kuppa, Vikram; Beaucage, Gregory; Univ of Dayton Collaboration; Univ of Cincinnati Collaboration

The practical use of polymers often relies on additives that improve the property of the mixture. Examples of such complex blends include tires, pigments, blowing agents and other reactive additives in thermoplastics, and recycled polymers. Such systems usually exhibit a complex partitioning of the components. Most prior work has either focused on fine-grained details such as molecular modeling of chains at interfaces, or on coarse, heuristic, trial-and-error approaches to compounding (eg: tire industry). Thus, there is a significant gap in our understanding of how complex hierarchical structure (across several decades in length) develops in these multicomponent systems. This research employs dissipative particle thermodynamics in conjunction with a pseudo-thermodynamic parameter derived from scattering experiments to represent polymer-filler interactions. DPD simulations will probe how filler dispersion and hierarchical morphology develops in these complex blends, and are validated against experimental (scattering) data. The outcome of our approach is a practical solution to compounding issues, based on a mutually validating experimental and simulation methodology. Support from the NSF (CMMI-1636036/1635865) is gratefully acknowledged.

Graphene-induced band gap renormalization in polythiophene: a many-body perturbation study

NASA Astrophysics Data System (ADS)

Marsusi, F.; Fedorov, I. A.; Gerivani, S.

2018-01-01

Density functional theory and many-body perturbation theory at the G0W0 level are employed to study the electronic properties of polythiophene (PT) adsorbed on the graphene surface. Analysis of the charge density difference shows that substrate-adsorbate interaction leads to a strong physisorption and interfacial electric dipole moment formation. The electrostatic potential displays a  -0.19 eV shift in the graphene work function from its initial value of 4.53 eV, as the result of the interaction. The LDA band gap of the polymer does not show any change. However, the band structure exhibits weak orbital hybridizations resulting from slight overlapping between the polymer and graphene states wave functions. The interfacial polarization effects on the band gap and levels alignment are investigated at the G0W0 level and show a notable reduction of PT band gap compared to that of the isolated chain.

Reducing the efficiency-stability-cost gap of organic photovoltaics with highly efficient and stable small molecule acceptor ternary solar cells

NASA Astrophysics Data System (ADS)

Baran, Derya; Ashraf, Raja Shahid; Hanifi, David A.; Abdelsamie, Maged; Gasparini, Nicola; Röhr, Jason A.; Holliday, Sarah; Wadsworth, Andrew; Lockett, Sarah; Neophytou, Marios; Emmott, Christopher J. M.; Nelson, Jenny; Brabec, Christoph J.; Amassian, Aram; Salleo, Alberto; Kirchartz, Thomas; Durrant, James R.; McCulloch, Iain

2017-03-01

Technological deployment of organic photovoltaic modules requires improvements in device light-conversion efficiency and stability while keeping material costs low. Here we demonstrate highly efficient and stable solar cells using a ternary approach, wherein two non-fullerene acceptors are combined with both a scalable and affordable donor polymer, poly(3-hexylthiophene) (P3HT), and a high-efficiency, low-bandgap polymer in a single-layer bulk-heterojunction device. The addition of a strongly absorbing small molecule acceptor into a P3HT-based non-fullerene blend increases the device efficiency up to 7.7 +/- 0.1% without any solvent additives. The improvement is assigned to changes in microstructure that reduce charge recombination and increase the photovoltage, and to improved light harvesting across the visible region. The stability of P3HT-based devices in ambient conditions is also significantly improved relative to polymer:fullerene devices. Combined with a low-bandgap donor polymer (PBDTTT-EFT, also known as PCE10), the two mixed acceptors also lead to solar cells with 11.0 +/- 0.4% efficiency and a high open-circuit voltage of 1.03 +/- 0.01 V.

Micro-resonators based on integrated polymer technology for optical sensing

NASA Astrophysics Data System (ADS)

Girault, Pauline; Lemaitre, Jonathan; Guendouz, Mohammed; Lorrain, Nathalie; Poffo, Luiz; Gadonna, Michel; Bosc, Dominique

2014-05-01

Research on sensors has experienced a noticeable development over the last decades especially in label free optical biosensors. However, compact sensors without markers for rapid, reliable and inexpensive detection of various substances induce a significant research of new technological solutions. The context of this work is the development of a sensor based on easily integrated and inexpensive micro-resonator (MR) component in integrated optics, highly sensitive and selective mainly in the areas of health and food. In this work, we take advantage of our previous studies on filters based on micro-resonators (MR) to experiment a new couple of polymers in the objective to use MR as a sensing function. MRs have been fabricated by processing SU8 polymer as core and PMATRIFE polymer as cladding layer of the waveguide. The refractive index contrast reaches 0.16 @ 1550 nm. Sub-micronic ring waveguides gaps from 0.5 to 1 μm have been successfully achieved with UV (i-line) photolithography. This work confirms our forecasts, published earlier, about the resolution that can be achieved. First results show a good extinction coefficient of ~17 dB, a quality factor around 104 and a finesse of 12. These results are in concordance with the theoretical study and they allow us to validate our technology with this couple of polymers. Work is going on with others lower cladding materials that will be used to further increase refractive index contrast for sensing applications.

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

Ultrafast optical pulse convertor caused by oscillations of the energy level structure in the conjugated polymer poly(p-phenylenevinylene).

PubMed

Zhang, Yusong; Chen, Weikang; Lin, Zhe; Li, Sheng; George, Thomas F

2017-08-21

For a conjugated polymer irradiated by two optical pulses, the whole process of excitation, involving lattice oscillations, oscillations of the energy level structure, and evolution of the electron cloud, is investigated. Localization of the electron cloud appears in the first 100 fs of irradiation, which in turn induces vibrations of lattice of the polymer chain as well as oscillations of the band gap. These oscillations filter the absorption of the external optical field inversely and convert the original optical field to an ultrafast light field whose intensity varies with a certain period. Based on the mechanism, oscillations of the energy level structure, induced by the external excitation, can be designed as an ultrafast response optical convertor that is able to change the external optical pulse into a new effective light field with a certain oscillation period. This helps provide new insight into designing nanostructures for polymeric optoelectronics.

Tailored donor-acceptor polymers with an A-D1-A-D2 structure: controlling intermolecular interactions to enable enhanced polymer photovoltaic devices.

PubMed

Qin, Tianshi; Zajaczkowski, Wojciech; Pisula, Wojciech; Baumgarten, Martin; Chen, Ming; Gao, Mei; Wilson, Gerry; Easton, Christopher D; Müllen, Klaus; Watkins, Scott E

2014-04-23

Extensive efforts have been made to develop novel conjugated polymers that give improved performance in organic photovoltaic devices. The use of polymers based on alternating electron-donating and electron-accepting units not only allows the frontier molecular orbitals to be tuned to maximize the open-circuit voltage of the devices but also controls the optical band gap to increase the number of photons absorbed and thus modifies the other critical device parameter-the short circuit current. In fact, varying the nonchromophoric components of a polymer is often secondary to the efforts to adjust the intermolecular aggregates and improve the charge-carrier mobility. Here, we introduce an approach to polymer synthesis that facilitates simultaneous control over both the structural and electronic properties of the polymers. Through the use of a tailored multicomponent acceptor-donor-acceptor (A-D-A) intermediate, polymers with the unique structure A-D1-A-D2 can be prepared. This approach enables variations in the donor fragment substituents such that control over both the polymer regiochemistry and solubility is possible. This control results in improved intermolecular π-stacking interactions and therefore enhanced charge-carrier mobility. Solar cells using the A-D1-A-D2 structural polymer show short-circuit current densities that are twice that of the simple, random analogue while still maintaining an identical open-circuit voltage. The key finding of this work is that polymers with an A-D1-A-D2 structure offer significant performance benefits over both regioregular and random A-D polymers. The chemical synthesis approach that enables the preparation of A-D1-A-D2 polymers therefore represents a promising new route to materials for high-efficiency organic photovoltaic devices.

Dilute and Semidilute Solutions of a Nonionic, Rigid, Water-soluble Polymer

NASA Astrophysics Data System (ADS)

Russo, Paul; Huberty, Wayne; Zhang, Donghui; Water-Soluble Rodlike Polymer Team Collaboration

2014-03-01

The solution physics of random polymer chains was established largely on the behavior of commercial polymers such as polystyrene for organic solvents or nonionic poly(ethyleneoxide) for aqueous solvents. Not only are these materials widely available for industrial use, they can be synthesized to be essentially monodisperse. When it comes to stiff polymers, good choices are few and less prone to be used in industrial applications. Much was learned from polypeptides such as poly(benzylglutamate) or poly(stearylglutamate) in polar organic solvents and nonpolar organic solvents, respectively, but aqueous systems generally require charge. Poly(Nɛ-2-[2-(2-Methoxyethoxy) ethoxy]acetyl-L-Lysine) a.k.a. PEGL was pioneered by Deming and coworkers. In principle, PEGL provides a convenient platform from which to study stiff polymer behavior--phase relations, dynamics, liquid crystal formation and gelation--all with good molecular weight control and uniformity and without electrical charge. Still, a large gap in knowledge exists between PEGL and traditional rodlike polymer systems. To narrow this gap, dynamic and static scattering, circular dichroism, and viscosity measurements have been made in dilute and semidilute solutions as necessary preliminaries for lyotropic liquid crystalline and gel phases. Supported by NSF DMR 1306262. Department of Chemistry and Macromolecular Studies Group. Current address: Georgia Institute of Technology, School of Materials Science and Engineering.

Experimental simulation of radiation damage of polymers in space applications by cosmic-ray-type high energy heavy ions and the resulting changes in optical properties

NASA Astrophysics Data System (ADS)

Hossain, U. H.; Ensinger, W.

2015-12-01

Devices operating in space, e.g. in satellites, are being hit by cosmic rays. These include so-called HZE-ions, with High mass (Z) and energy (E). These highly energetic heavy ions penetrate deeply into the materials and deposit a large amount of energy, typically several keV per nm range. Serious damage is created. In space vehicles, polymers are used which are degraded under ion bombardment. HZE ion irradiation can experimentally be simulated in large scale accelerators. In the present study, the radiation damage of aliphatic vinyl- and fluoro-polymers by heavy ions with energies in the GeV range is described. The ions cause bond scission and create volatile small molecular species, leading to considerable mass loss of the polymers. Since hydrogen, oxygen and fluorine-containing molecules are created and these elements are depleted, the remaining material is carbon-richer than the original polymers and contains conjugated CC double bonds. This process is investigated by measuring the optical band gap with UV-Vis absorption spectrometry as a function of ion fluence. The results show how the optical band gaps shift from the UV into the Vis region upon ion irradiation for the different polymers.

Rational material, interface, and device engineering for high-performance polymer and perovskite solar cells (Presentation Recording)

NASA Astrophysics Data System (ADS)

Jen, Alex K.

2015-10-01

The performance of polymer and hybrid solar cells is also strongly dependent on their efficiency in harvesting light, exciton dissociation, charge transport, and charge collection at the metal/organic/metal oxide or the metal/perovskite/metal oxide interfaces. Our laboratory employs a molecular engineering approach to develop processible low band-gap polymers with high charge carrier mobility that can enhance power conversion efficiency of the single junction solar cells to values as high as ~11%. We have also developed several innovative strategies to modify the interface of bulk-heterojunction devices and create new device architectures to fully explore their potential for solar applications. In this talk, the integrated approach of combining material design, interface, and device engineering to significantly improve the performance of polymer and hybrid perovskite photovoltaic cells will be discussed. Specific emphasis will be placed on the development of low band-gap polymers with reduced reorganizational energy and proper energy levels, formation of optimized morphology of active layer, and minimized interfacial energy barriers using functional conductive surfactants. At the end, several new device architectures and optical engineering strategies to make tandem cells and semitransparent solar cells will be discussed to explore the full promise of polymer and perovskite hybrid solar cells.

One-step synthesis and patterning of aligned polymer nanowires on a substrate

DOEpatents

Wang, Zhong L [Marietta, GA; Wang, Xudong [Atlanta, GA; Morber, Jenny R [Atlanta, GA; Liu, Jin [Danbury, CT

2011-11-08

In a method of making a polymer structure on a substrate a layer of a first polymer, having a horizontal top surface, is applied to a surface of the substrate. An area of the top surface of the polymer is manipulated to create an uneven feature that is plasma etched to remove a first portion from the layer of the first polymer thereby leaving the polymer structure extending therefrom. A light emitting structure includes a conductive substrate from which an elongated nanostructure of a first polymer extends. A second polymer coating is disposed about the nanostructure and includes a second polymer, which includes a material such that a band gap exists between the second polymer coating and the elongated nanostructure. A conductive material coats the second polymer coating. The light emitting structure emits light when a voltage is applied between the conductive substrate and the conductive coating.

Modifications in the optical and thermal properties of a CR-39 polymeric detector induced by high doses of γ-radiation

NASA Astrophysics Data System (ADS)

Saad, A. F.; Ibraheim, Mona H.; Nwara, Aya M.; Kandil, S. A.

2018-04-01

Effects of γ-radiation on the optical and thermal properties of a poly allyl diglycol carbonate (PADC), a form of CR-39, polymer have been investigated. CR-39 detectors were exposed to γ-rays at very high doses ranging from 5.0 × 105 to 3.0 × 106 Gy. The induced changes were analyzed using ultraviolet-visible spectroscopy (UV-VIS) in absorbance mode, and thermogravimetric analysis (TGA). The UV-visible spectra of the virgin and γ-irradiated CR-39 polymer detectors displayed a significant decreasing trend in their optical energy band gaps for indirect transitions, whereas for the direct ones showed a little change. This drop in the energy band gap with increasing dose is discussed on the basis of the gamma irradiation induced modifications in the CR-39 polymeric detector. The TGA thermograms show that the weight loss rate increased with increase in dose, which may be due to the disordered system via scission followed by crosslinking in the irradiated polymer detector. The TGA thermograms also indicated that the CR-39 detector decomposed in three/four stages for the virgin and irradiated samples. The activation energy for thermal decomposition was determined using a type of Arrhenius equation based on the TGA experimental results. These experimental results so obtained can be well used in radiation dosimetry.

Bloch oscillations in organic and inorganic polymers

NASA Astrophysics Data System (ADS)

Ribeiro, Luiz Antonio; Ferreira da Cunha, Wiliam; de Almeida Fonseca, Antonio Luciano; e Silva, Geraldo Magela

2017-04-01

The transport of polarons above the mobility threshold in organic and inorganic polymers is theoretically investigated in the framework of a one-dimensional tight-binding model that includes lattice relaxation. The computational approach is based on parameters for which the model Hamiltonian suitably describes different polymer lattices in the presence of external electric fields. Our findings show that, above critical field strengths, a dissociated polaron moves through the polymer lattice as a free electron performing Bloch oscillations. These critical electric fields are considerably smaller for inorganic lattices in comparison to organic polymers. Interestingly, for inorganic lattices, the free electron propagates preserving charge and spin densities' localization which is a characteristic of a static polaron. Moreover, in the turning points of the spatial Bloch oscillations, transient polaron levels are formed inside the band gap, thus generating a fully characterized polaron structure. For the organic case, on the other hand, no polaron signature is observed: neither in the shape of the distortion—those polaron profile signatures are absent—nor in the energy levels—as no such polaron levels are formed during the simulation. These results solve controversial aspects concerning Bloch oscillations recently reported in the literature and may enlighten the understanding about the charge transport mechanism in polymers above their mobility edge.

Mutual Photoluminescence Quenching and Photovoltaic Effect in Large-Area Single-Layer MoS2-Polymer Heterojunctions.

PubMed

Shastry, Tejas A; Balla, Itamar; Bergeron, Hadallia; Amsterdam, Samuel H; Marks, Tobin J; Hersam, Mark C

2016-11-22

Two-dimensional transition metal dichalcogenides (TMDCs) have recently attracted attention due to their superlative optical and electronic properties. In particular, their extraordinary optical absorption and semiconducting band gap have enabled demonstrations of photovoltaic response from heterostructures composed of TMDCs and other organic or inorganic materials. However, these early studies were limited to devices at the micrometer scale and/or failed to exploit the unique optical absorption properties of single-layer TMDCs. Here we present an experimental realization of a large-area type-II photovoltaic heterojunction using single-layer molybdenum disulfide (MoS 2 ) as the primary absorber, by coupling it to the organic π-donor polymer PTB7. This TMDC-polymer heterojunction exhibits photoluminescence intensity that is tunable as a function of the thickness of the polymer layer, ultimately enabling complete quenching of the TMDC photoluminescence. The strong optical absorption in the TMDC-polymer heterojunction produces an internal quantum efficiency exceeding 40% for an overall cell thickness of less than 20 nm, resulting in exceptional current density per absorbing thickness in comparison to other organic and inorganic solar cells. Furthermore, this work provides insight into the recombination processes in type-II TMDC-polymer heterojunctions and thus provides quantitative guidance to ongoing efforts to realize efficient TMDC-based solar cells.

Retention of Antibacterial Activity in Geranium Plasma Polymer Thin Films

PubMed Central

Al-Jumaili, Ahmed; Bazaka, Kateryna

2017-01-01

Bacterial colonisation of biomedical devices demands novel antibacterial coatings. Plasma-enabled treatment is an established technique for selective modification of physicochemical characteristics of the surface and deposition of polymer thin films. We investigated the retention of inherent antibacterial activity in geranium based plasma polymer thin films. Attachment and biofilm formation by Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli was significantly reduced on the surfaces of samples fabricated at 10 W radio frequency (RF) power, compared to that of control or films fabricated at higher input power. This was attributed to lower contact angle and retention of original chemical functionality in the polymer films fabricated under low input power conditions. The topography of all surfaces was uniform and smooth, with surface roughness of 0.18 and 0.69 nm for films fabricated at 10 W and 100 W, respectively. Hardness and elastic modules of films increased with input power. Independent of input power, films were optically transparent within the visible wavelength range, with the main absorption at ~290 nm and optical band gap of ~3.6 eV. These results suggest that geranium extract-derived polymers may potentially be used as antibacterial coatings for contact lenses. PMID:28902134

A Multi-Objective Optimization Technique to Model the Pareto Front of Organic Dielectric Polymers

NASA Astrophysics Data System (ADS)

Gubernatis, J. E.; Mannodi-Kanakkithodi, A.; Ramprasad, R.; Pilania, G.; Lookman, T.

Multi-objective optimization is an area of decision making that is concerned with mathematical optimization problems involving more than one objective simultaneously. Here we describe two new Monte Carlo methods for this type of optimization in the context of their application to the problem of designing polymers with more desirable dielectric and optical properties. We present results of applying these Monte Carlo methods to a two-objective problem (maximizing the total static band dielectric constant and energy gap) and a three objective problem (maximizing the ionic and electronic contributions to the static band dielectric constant and energy gap) of a 6-block organic polymer. Our objective functions were constructed from high throughput DFT calculations of 4-block polymers, following the method of Sharma et al., Nature Communications 5, 4845 (2014) and Mannodi-Kanakkithodi et al., Scientific Reports, submitted. Our high throughput and Monte Carlo methods of analysis extend to general N-block organic polymers. This work was supported in part by the LDRD DR program of the Los Alamos National Laboratory and in part by a Multidisciplinary University Research Initiative (MURI) Grant from the Office of Naval Research.

Bay-annulated indigo (BAI) as an excellent electron accepting building block for high performance organic semiconductors

DOEpatents

Liu, Yi; He, Bo; Pun, Andrew

2015-11-24

A novel electron acceptor based on bay-annulated indigo (BAI) was synthesized and used for the preparation of a series of high performance donor-acceptor small molecules and polymers. The resulting materials possess low-lying LUMO energy level and small HOMO-LUMO gaps, while their films exhibited high crystallinity upon thermal treatment, commensurate with high field effect mobilities and ambipolar transfer characteristics.

Bay-annulated indigo (BAI) as an excellent electron accepting building block for high performance organic semiconductors

DOEpatents

Liu, Yi; He, Bo; Pun, Andrew

2016-04-19

A novel electron acceptor based on bay-annulated indigo (BAI) was synthesized and used for the preparation of a series of high performance donor-acceptor small molecules and polymers. The resulting materials possess low-lying LUMO energy level and small HOMO-LUMO gaps, while their films exhibited high crystallinity upon thermal treatment, commensurate with high field effect mobilities and ambipolar transfer characteristics.

Enhanced performance of polymer solar cells by employing a ternary cascade energy structure.

PubMed

An, Qiaoshi; Zhang, Fujun; Li, Lingliang; Zhuo, Zuliang; Zhang, Jian; Tang, Weihua; Teng, Feng

2014-08-14

We present a route to successfully tackle the two main limitations, low open circuit voltage (Voc) and limited short circuit-density (Jsc), of polymer solar cells (PSCs) based on poly(3-hexylthiophene) (P3HT) as an electron-donor. The indene-C60 bisadduct (ICBA) was selected as an electron acceptor to improve the open circuit voltage (Voc). The narrow band gap polymer poly[(4,8-bis-(2-ethylhexyloxy)-benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-thieno[3,4-b]thiophene)-2,6-diyl] (PBDTTT-C), as a complementary electron-donor material, was doped into the host system of P3HT:ICBA to form ternary cascade energy structured PSCs with increased Jsc. The power conversion efficiency (PCE) of P3HT:ICBA-based cells was improved from 3.32% to 4.38% by doping with 3 wt% PBDTTT-C with 1 min 150 °C annealing treatment. The 4.38% PCE of ternary PSCs is still larger than the 3.79% PCE of PSCs based on P3HT:ICBA with 10 minutes 150 °C annealing treatment.

Reversible Lifting of Surface Supported Lipid Bilayers with a Membrane-Spanning Nonionic Triblock Copolymer

DOE PAGES

Hayden, Steven C.; Junghans, Ann; Majewski, Jaroslaw; ...

2017-02-22

Neutron reflectometry was used to monitor structural variations in surface supported DMPC bilayers induced by the addition of Triton X-100, a surfactant commonly used to aid solubilization of membrane proteins, and the co-addition of a membrane spanning non-ionic amphiphilic triblock copolymer, (PEO 117-PPO 47-PE O117, Pluronic F98). Surfactant addition causes slight compression of the bilayer thickness and the creation of a distinct EO layer that increases the hydrophilic layer proximal to the supporting substrate (i.e., a water and EO gap between the lipid bilayer and quartz) to 6.8 ± 0.4 Å. Addition of the triblock copolymer into the DMPC: Tritonmore » X-100 bilayer increases the complexity (broadens) the lipid phase transition, further compresses the bilayer, and continues to expand the proximal hydrophilic layer thickness. The observed structural changes are temperature dependent with transmembrane polymer insertion achieved at 37 °C leading to a compressed membrane thickness of 39.2 ± 0.2 Å and proximal gap of 45.2 ± 0.2 Å. Temperature driven exclusion of the polymer at 15 °C causes partitioning of the polymer into the proximal space generating a large hydrogel cushion 162 ± 16 Å thick. An intermediate gap width (10 – 27 Å) is achieved at room temperature (22 – 25 °C). The temperature-driven changes in the proximal hydrophilic gap dimensions are shown to be reversible but thermal history causes variation in magnitude. Temperature-driven changes in polymer association with a supported lipid bilayer offer a facile means to reversibly control both the membrane characteristics as well as the separation between membrane and solid substrate.« less

Reversible Lifting of Surface Supported Lipid Bilayers with a Membrane-Spanning Nonionic Triblock Copolymer

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

Hayden, Steven C.; Junghans, Ann; Majewski, Jaroslaw

Neutron reflectometry was used to monitor structural variations in surface supported DMPC bilayers induced by the addition of Triton X-100, a surfactant commonly used to aid solubilization of membrane proteins, and the co-addition of a membrane spanning non-ionic amphiphilic triblock copolymer, (PEO 117-PPO 47-PE O117, Pluronic F98). Surfactant addition causes slight compression of the bilayer thickness and the creation of a distinct EO layer that increases the hydrophilic layer proximal to the supporting substrate (i.e., a water and EO gap between the lipid bilayer and quartz) to 6.8 ± 0.4 Å. Addition of the triblock copolymer into the DMPC: Tritonmore » X-100 bilayer increases the complexity (broadens) the lipid phase transition, further compresses the bilayer, and continues to expand the proximal hydrophilic layer thickness. The observed structural changes are temperature dependent with transmembrane polymer insertion achieved at 37 °C leading to a compressed membrane thickness of 39.2 ± 0.2 Å and proximal gap of 45.2 ± 0.2 Å. Temperature driven exclusion of the polymer at 15 °C causes partitioning of the polymer into the proximal space generating a large hydrogel cushion 162 ± 16 Å thick. An intermediate gap width (10 – 27 Å) is achieved at room temperature (22 – 25 °C). The temperature-driven changes in the proximal hydrophilic gap dimensions are shown to be reversible but thermal history causes variation in magnitude. Temperature-driven changes in polymer association with a supported lipid bilayer offer a facile means to reversibly control both the membrane characteristics as well as the separation between membrane and solid substrate.« less

Chain-Growth Methods for the Synthesis of High Molecular Weight Conducting and Semiconducting Polymers

DTIC Science & Technology

2013-08-25

to produce the desired polymerization in analogy to the well-known “super glue ” anionic polymerization. Although there are abundant examples of...light (a) and UV light (b). 5 are further functionalized and block polymers formed with polynorborene have elastomeric properties. The...top) and UV (bottom) light show the evolution of the band gap of the polymer with increasing molecular weight. The plot on the right shows the

A state of the art review on reinforced concrete beams with openings retrofitted with FRP

NASA Astrophysics Data System (ADS)

Osman, Bashir H.; Wu, Erjun; Ji, Bohai; S Abdelgader, Abdeldime M.

2016-09-01

The use of externally bonded fiber reinforced polymer (FRP) sheets, strips or steel plates is a modern and convenient way for strengthening of reinforced concrete (RC) beams. Several researches have been carried out on reinforced concrete beams with web openings that strengthened using fiber reinforced polymer composite. Majority of researches focused on shear strengthening compared with flexural strengthening, while others studied the effect of openings on shear and flexural separately with various loading. This paper investigates the impact of more than sixty articles on opening reinforced concrete beams with and without strengthening by fiber reinforcement polymers FRP. Moreover, important practical issues, which are contributed in shear strengthening of beams with different strengthening techniques, such as steel plate and FRP laminate, and detailed with various design approaches are discussed. Furthermore, a simple technique of applying fiber reinforced polymer contributed with steel plate for strengthening the RC beams with openings under different load application is concluded. Directions for future research based on the existing gaps of the present works are presented.

Functional Polymer Opals and Porous Materials by Shear-Induced Assembly of Tailor-Made Particles.

PubMed

Gallei, Markus

2018-02-01

Photonic band-gap materials attract enormous attention as potential candidates for a steadily increasing variety of applications. Based on the preparation of easily scalable monodisperse colloids, such optically attractive photonic materials can be prepared by an inexpensive and convenient bottom-up process. Artificial polymer opals can be prepared by shear-induced assembly of core/shell particles, yielding reversibly stretch-tunable materials with intriguing structural colors. This feature article highlights recent developments of core/shell particle design and shear-induced opal formation with focus on the combination of hard and soft materials as well as crosslinking strategies. Structure formation of opal materials relies on both the tailored core/shell architecture and the parameters for polymer processing. The emphasis of this feature article is on elucidating the particle design and incorporation of addressable moieties, i.e., stimuli-responsive polymers as well as elaborated crosslinking strategies for the preparation of smart (inverse) opal films, inorganic/organic opals, and ceramic precursors by shear-induced ordering. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superficial and Inner Examination of a Microwave-Irradiated Dental Acrylic Resin and Its Metal-Polymer Interface.

PubMed

Popescu, Marian C; Bita, Bogdan I; Tucureanu, Vasilica; Vasilache, Dan; Banu, Melania A; Avram, Andrei M; Giurescu-Dumitrescu, Raluca A

2018-02-01

The aim of this study is to conduct an extended surface and cross-section characterization of a denture base acrylic resin subjected to 500, 650, and 750 W microwave irradiation for 2, 3, and 5 min to assess its morphological modifications. A commercial heat-cured powder was polymerized according to the manufacturer's specifications and distributed into 20 circular samples. A stainless-steel wire was partially embedded in half of the discs, in order to investigate the metal-polymer interface. High-resolution scanning electron microscopy (SEM) imaging, white light interferometry, roughness measurements and Fourier transform infrared spectrometry were employed for morphological and structural evaluation of the irradiated polymer. Superficial adaptation was discovered after 5 min exposure at 500 W, 650 W, and 750 W, revealing significant roughness correction for 750 W. SEM characterization revealed the inner alteration of the resin for the 750 W protocol and a metal-polymer gap developed regardless of the irradiation conditions. The considerable temperature fluctuations that the samples were subject to during the experiments did not essentially change the poly(methyl-methacrylate) bond structure.

Physico-chemical properties of PMMA/ZnO nanocomposite capped with 1-chloro-9,10-bis (phenyl ethynyl) anthracene

NASA Astrophysics Data System (ADS)

Anandalli, Mallikarjun; Kanakaraj, T. M.; Hebbar, Vidyashree; Naik, Jagadish; Bhajantri, R. F.

2018-05-01

The nanocomposite films of polymethyl methacrylate (PMMA)/zinc oxide (ZnO) capped with different weight (0.25wt%,1wt%) percentage of fluorescence dye 1-chlor-9,10-bis (phenyl ethynyl anthracene (C30H17Cl) were prepared using solution casting method. ZnO powder dispersed in the polymer matrix uniformly, enhance the optical and physical properties of nanocomposite. Interaction of fluorescence dye and ZnO with polymer matrix gives the emerging applications, due to the fact that the dye C30H17Cl emits yellow light and it has wide band gap, hole transporting material. The prepared samples have been studied using the experimental techniques such as FTIR, UV-Visible (indirect energy gap plots), XRD, AFM. The FTIR used to confirm the peaks of ZnO nanoparticles dispersed in polymer matrix and interaction of the dye. From the UV-Visible technique, the optical band gap of the nanocomposites has been investigated, and the obtained optical band gap reduces with increase in weight % of dye in PMMA/ZnO. The AFM results show the surface morphology and smoothness of the nanocomposite films. The crystallinity of the PMMA/ZnO:C30H17Cl nanocomposite has been estimated using powder XRD patterns. The prepared nanocomposites films useful for the wide range of applications.

Polymer Assisted Functional Ceramic Nanofibrous Structures for Potential Optoelectronic and Photocatalytic Applications

NASA Astrophysics Data System (ADS)

Aykut, Yakup

The use of fossil fuels adversely effects the environment and hence increases global warming. On the other hand the lack of fuel reservoirs triggers people to find environmentally friendly new energy sources. Solar cell technology is one of the developing energy production technologies in green productions. Currently, many solar cells are made of highly purified silicon crystals. However silicon based solar cells have high energy conversion efficiency, they are highly brittle, expensive, and time consuming during the fabrication process. Organic and metal oxide based photovoltaic materials are a more cost-effective alternative to silicon based solar cells. In ceramic materials, Titanium dioxide (TiO2), zinc oxide (ZnO) and magnesium zinc oxide (MgxZn 1-xO) have intensive research interest owing to their optoelectronic and photocatalytic properties, and they have been used in dye sensitized solar cells as electron acceptor layer due to their high band gap properties and having low conduction band levels than electron donor dye molecules or quantum dots. On the other hand, energy band levels of the ceramic materials are considerable affected by their crystal microstructures, shapes and doping materials. Because of their high surface to volume ratio, nanofibers are suitable as active energy conversions layers in organic and dye sensitized solar cells. Using nanofibrous ceramic structure instead of film provides higher energy conversion efficiency since the high surface areas of the electrospun mats may accommodate a greater concentration of dye molecules or quantum dots, which could result in greater efficiency of electron transfer within the material, as compared to traditional film-based technologies. Also, the continuous structure of nanofibers may allow for effective electron transfer as a result of the direct conduction pathway of the photoelectrons along the fibers. Moreover, 3D structures of nanofibrous mat allow scattering and absorbing the photons multiple times. Sol-Gel electrospinning procedure has been widely used to obtain ceramic nanofibers. Briefly, at sol-gel electrospinning procedure, a carrier polymer and ceramic precursor is dissolved in an appropriate solvent, and polymer/ceramic precursor composite nanofibers are produced with a following electrospinning process. Then, as spun nanofibers are calcined at high temperatures to remove polymer and other organic residues from the fibers and convert ceramic precursor into ceramic nanofibers. We investigate temperature dependent crystal phase transformations of electrospun TiO2 nanofibers regardless of other parameters and observed their microstructures and optical properties due to different calcination temperatures. Quantum dots are semi conductive metallic nanocrystals with very wide light absorption range in UV, visible and even in near-infrared regions depending on the size of the quantum dots. On the other hand, TiO2 is a high band gap semiconductor material and absorbs the light in UV range that limits its photovoltaic applications. In order to extend its light absorption through visible region, we sensitized and incorporated low band gap CdSe quantum dot on electrospun TiO2 nanofibers. Zinc oxide (ZnO) is another high band gap ceramic materials with promising optical properties have been used for photonic applications. Intrinsic lattice defects in ZnO are one of the main limitation factors that affect the device performance tremendously and could be controlled due to fabrication process. We investigated the effect of different type of surfactants with different charge groups on fiber morphology, microstructure and optical properties of sol-gel electrospun ZnO nanofibers. Finally, in order to tune band gap energy level of ZnO nanofibers to higher values, we doped Mg2+ into ZnO nanofibers. Because Zn2+ and Mg2+ have similar atomic radii, some of Zn2+ ions are replaced with Mg 2+ ions in the structure to produce different "x" value of MgxZn1-xO due to amount of Mg content. We produced tuned band gap MgxZn1-xO nanofibers via sol-gel electrospinning.

Structural and optical band gap of PEO/PVP polymer blend

NASA Astrophysics Data System (ADS)

Basappa, M.; Yesappa, L.; Niranjana, M.; Ashokkumar, S. P.; Vandana, M.; Vijeth, H.; Devendrappa, H.

2018-05-01

The PEO/PVP polymers blend film at different wt % of PVP is prepared by solution casting method using methanol as a solvent. The blend was characterized by FT-IR to confirm the blend and the peak observed in the region 1230-980 cm-1 corresponds to C-O-C symmetric and asymmetric stretching. The UV-visible absorption shows red shift from 190 to 220 nm in the ultra violet region is attributed to π→π* transition. The direct and indirect optical band gaps were determined and found decreases from 4.99 to 4.62 eV with increased PVP wt % to 50:50.

Evaluation of structural and optical properties of Ce3+ ions doped (PVA/PVP) composite films for new organic semiconductors

NASA Astrophysics Data System (ADS)

Ali, F. M.; Kershi, R. M.; Sayed, M. A.; AbouDeif, Y. M.

2018-06-01

Polymer blend films based on Polyvinyl alcohol (PVA)/Poly(vinylpyrrolidone) (PVP) doped with different concentration of cerium ions [(PVA/PVP)-x wt.% Ce3+] (x = 3%, 5%, 10% and 15%) were prepared by the conventional solution casting technique. The characteristics of the prepared polymer composite films were studied using X-ray diffraction (XRD), FT-IR and UV-Vis. spectroscopy. The XRD patterns of the investigated samples revealed a clear reduction on the structural parameters such as crystallinity degree and cluster size D of the doped PVA/PVP blend films compared with the virgin one whereas there is no big difference in the d spacing of the product composite films. Significant changes in FT-IR spectra are observed which reveal an interactions between the cerium ions and PVA/PVP blends. The absorption spectra in the ultraviolet-visible region showed a wide red shift in the fundamental absorption edge of (PVA/PVP)-x wt. % Ce3+ composites. The optical gap Eg gradually decreased from 4.54 eV for the undoped PVA/PVP film to 3.10 eV by increasing Ce3+ ions content. The optical dispersion parameters have been analyzed according to Wemple-Didomenico single oscillator model. The dispersion energy Ed, the single oscillator energy Eo, the average inter-band oscillator wavelength λo and the static refractive index no are strongly affected by cerium ions doping. Cerium ions incorporation in PVA/PVP blend films leads to a significant increase in the refractive index and decrease in the optical gap. These results are likely of great important in varieties of applications including polymer waveguides, organic semiconductors, polymer solar cells and optoelectronics devices.

Structural and optical properties of self-assembled chains of plasmonic nanocubes

DOE PAGES

Klinkova, Anna; Gang, Oleg; Therien-Aubin, Heloise; ...

2014-10-10

Solution-based linear self-assembly of metal nanoparticles offers a powerful strategy for creating plasmonic polymers, which, so far, have been formed from spherical nanoparticles and nanorods. Here, we report linear solution-based self-assembly of metal nanocubes (NCs), examine the structural characteristics of the NC chains and demonstrate their advanced optical characteristics. Predominant face-to-face assembly of large NCs coated with short polymer ligands led to a larger volume of hot spots in the chains, a nearly uniform E-field enhancement in the gaps between co-linear NCs and a new coupling mode for NC chains, in comparison with chains of nanospheres with similar dimensions, compositionmore » and surface chemistry. The NC chains exhibited a stronger surface enhanced Raman scattering (SERS) signal, in comparison with linear assemblies of nanospheres. The experimental results were in agreement with finite difference time domain (FDTD) simulations.« less

A generic interface to reduce the efficiency-stability-cost gap of perovskite solar cells

NASA Astrophysics Data System (ADS)

Hou, Yi; Du, Xiaoyan; Scheiner, Simon; McMeekin, David P.; Wang, Zhiping; Li, Ning; Killian, Manuela S.; Chen, Haiwei; Richter, Moses; Levchuk, Ievgen; Schrenker, Nadine; Spiecker, Erdmann; Stubhan, Tobias; Luechinger, Norman A.; Hirsch, Andreas; Schmuki, Patrik; Steinrück, Hans-Peter; Fink, Rainer H.; Halik, Marcus; Snaith, Henry J.; Brabec, Christoph J.

2017-12-01

A major bottleneck delaying the further commercialization of thin-film solar cells based on hybrid organohalide lead perovskites is interface loss in state-of-the-art devices. We present a generic interface architecture that combines solution-processed, reliable, and cost-efficient hole-transporting materials without compromising efficiency, stability, or scalability of perovskite solar cells. Tantalum-doped tungsten oxide (Ta-WOx)/conjugated polymer multilayers offer a surprisingly small interface barrier and form quasi-ohmic contacts universally with various scalable conjugated polymers. In a simple device with regular planar architecture and a self-assembled monolayer, Ta-WOx-doped interface-based perovskite solar cells achieve maximum efficiencies of 21.2% and offer more than 1000 hours of light stability. By eliminating additional ionic dopants, these findings open up the entire class of organics as scalable hole-transporting materials for perovskite solar cells.

Synthesis of metal-polymer nanocomposites for fuel applications

NASA Astrophysics Data System (ADS)

Pontes Lima, Ricardo Jose

Metal particles have long been of interest as fuel and fuel additives for propellants and explosives because their high-density energy. In general, their volumetric energy density is higher as compared to conventional hydrocarbon-based fuel. This advantage is clearly beneficial for volume-limited rocket propulsion systems, in which the most important parameter is the density-based specific impulse. It is widely known that the reactivity of metal particles increases when particle size decreases. Significant improvements in combustion behaviors of propellant have been attributed to the use of nanosize metal particles, for example faster burning rates and shorter ignition delay time. For this reason the application of nanosize particles as fuel could be preferable than large particles. However, several difficulties limit the use of ultrafine particles in fuel applications and propellants. Most of them are attributed to the oxide layer formation on the particles that prevents good combustion performance. In boron applications, practical difficulties such as poor ignition and combustion performance, have so far limited extensive use of boron for fuel applications. Indications are that application of non-oxide coatings on particles protects them against premature oxidation and enhances their combustion properties. A number of methods have been proposed to coat metal particles with a variety of organic compounds or other metals. Common applications provides coatings of saturated hydrocarbons or fatty acids, such as oleic acid as a means to passivation the particles. Recently, high-energy ball milling, in combination with chemical reactions, was applied to fabricate nanostructured metal particles coated with organic compounds. One of the advantages of this technique is that the passivation be integrated into the production of particles as a single step. For example, the reactive milling of boron in oleic acid solution showed an improved reactivity of as-milled powders. However, the versatility of the mechanical milling technique suggests that a vast range of organic compounds could be applied to the capping of particles. Thus, developing a new method to obtain metal nanosized particles coated with chemical substances that can further improve the properties of particles is a great challenge. The first contribution of this work is to investigate the reactive milling process of metal powders, such as boron and aluminum, to better understand the experimental methodology as a means to obtain energetic-capped metal particles. To this end, a comparative experimental study was performed to evaluate two variations of the mechanical milling. In a typical procedure, metal powders and the reagents are poured into the mill vial at the start of milling. The organic reactions occur simultaneously in the milling process. In the alternative procedure, the powders are milled prior the addition of the organic reagent, thus a stepwise process is done. For both methods, an organic functionalized compound was grafted onto the particles, followed by their incorporation into an energetic polymer matrix to create a metal-polymer composite. The results highlight the differences in shape in size of particles, identifying some drawbacks for both applications, as well as analyzing the effects on combustion properties of the organic-capped powders and the binder composites. The analysis of the first results of the reactive milling showed that this way might lead to by-products and self-polymerization of organic coatings. That is the main drawback for the simultaneous milling process, preventing a better performance of as-milled powders. Considering this problem, it was necessary to modify the milling procedure to further improve the capping of metal particle. Thus, the second part of experiments applies an energetic polymer direct grafted onto particles as a means to further improvements in the energetic properties of powders. Glycidyl azide polymer (GAP) was chosen as candidate to coat the particles because of its good energetic properties. Since the mixture viscosity increases as the size of particles decreases, low-viscosity reagents are recommended to avoid very high viscosity. The molecular weight of GAP can range from 700 to 5500 and the number of hydroxyl end groups from 0 (GAP plasticizer) to 3. Among these polymers, the GAP plasticizer (700 g mol-1, low viscosity) has good properties to be applied in reactive milling. However, some functionalized groups are necessary to graft the polymer onto metal particles and the GAP plasticizer does not carry telechelic hydroxyl groups. To achieve a better reactivity of this polymer and the fresh metal surface, the GAP plasticizer was chemically modified to make some additional acid-functionalized branches in the main chain of the polymer. The direct method for coating the metal particles with the modified GAP was more effective in forming the energetic layer, which has influenced the dispersion of powders into polymers and increased the total energy release by the combustion of metal-polymer composites. The last phase of this research addressed the production of boron-polymer composites for combustion purposes. Boron has a very high gravimetric (58 kJ/g) and volumetric (136 kJ/cc) heating value. This clearly exceeds other metal or other conventional hydrocarbon fuels in both mass and volumetric energy production. Despite of this great potential energy, boron has rarely achieved its potential in propulsion systems, whereas the aluminum is the most common metal employed in the preparation of composite solid propellants. A number of studies addressed to the boron combustion attribute its reduced performance to a certain combustion property of the metal. The boron oxide (B2O3) layer, normally found on the particles is highly stable and leads to long ignition delay times. Therefore, the elemental boron ignites in a two-stage process. The first stage corresponds to the burning of boron covered with an oxide layer, and the second stage involves the completion of the combustion of the bare boron particle. The use of light metals, such as magnesium and aluminum as additives in boron formulations, has been indicated as a means to enhance its combustion efficiency. Recently, improvements of the combustion efficiency of boron were associated with the use of magnesium and aluminum as additives. The mechanism proposed for these improvements was boron oxide removal by reaction with aluminum and the additional heat release by the easy ignition of magnesium. In this work, it was proposed to apply of a layer of energetic polymer on the boron particles, which, in addition to releasing a significant amount of energy, brings other benefits in terms of the final application of the particles as fuel (i.e., the dispersion of particles into a polymer binder).

(QC Themes) Type-Two Quantum Computing in PBG-Based Cavities for Efficient Simulation of Lattice Gas Dynamics

DTIC Science & Technology

2008-04-26

substrate Si3N4 Diameter : 540 nm Pitch : 760 nm Diamond Holes in Diamond (HID) Pillars of Diamond (POD) POD with Electrooptic Polymer at Center 3D ...Diamond film : 2 um Si- substrate Al : 0.2 um PMMA : 0.5um 1. Deposit UNCD film 2. Deposit Al metal 3. Deposit PMMA on Al 4. E-beam Lithography 5...band-gap (PBG) based cavities. The cavities are etched directly on to the diamond substrate . The set of coupled qubits in each spot represents an

Theoretical study of the design dye-sensitivity for usage in the solar cell device

NASA Astrophysics Data System (ADS)

Alrikabi, Alaa

There are many applications in the polymer chemistry, pharmaceutical, agricultural and industrial fields of the thiadiazole molecule and their derivatives. Allowance of the energy gap of the polymer conjugated is an object of great interesting debit for the possible removal of a doping in the preparation of highly conductivity polymers. Thiadiazoles derivatives are structural foundation of the polymer materials. In this present work, the electronic properties of graphene nanoflakes (GNFs)-phenanthrene-1,3,4-thiadiazoles oligomers are studied and discussed. Where thiadiazoles is expanded from one to 9 unit's molecules at the structure. The energy gap, HOMO, LUMO distribution, total energy, Fermi level energy, work function, maximum wavelength absorption, vertical absorption energies, and oscillator strengths are calculated for each molecule. All calculations are carry out by usage density function theory (DFT) and depended time density function theory (TD-DFT) with the B3LYP/6-31G model in the Gaussian 09W software packages. Results show that increasing the number of monomeric units lead to great enhance in the electronic properties, which caused it decreased the band gap from 3.17 eV in the system with one unit of thiadiazole just to 1.35 eV in the system with 9 units of thiadiazole. This case is raised the value of maximum absorption wavelengths to >500 nm to give the better performance in optoelectronic and solar cell, as these structures have prime absorption bands within the solar spectrum.

Electroluminescence property of organic light emitting diode (OLED)

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

Özdemir, Orhan; Kavak, Pelin; Saatci, A. Evrim

2013-12-16

Transport properties of electrons and holes were investigated not only in a anthracene-containing poly(p-phenylene-ethynylene)- alt - poly(p-phenylene-vinylene) (PPE-PPV) polymer (AnE-PVstat) light emitting diodes (OLED) but also in an ITO/Ag/polymer/Ag electron and ITO/PEDOT:PSS/polymer/Au hole only devices. Mobility of injected carriers followed the Poole-Frenkel type conduction mechanism and distinguished in the frequency range due to the difference of transit times in admittance measurement. Beginning of light output took place at the turn-on voltage (or flat band voltage), 1.8 V, which was the difference of energy band gap of polymer and two barrier offsets between metals and polymer.

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.

On-chip free beam optics on a polymer-based photonic integration platform.

PubMed

Happach, M; de Felipe, D; Conradi, H; Friedhoff, V N; Schwartz, E; Kleinert, M; Brinker, W; Zawadzki, C; Keil, N; Hofmann, W; Schell, M

2017-10-30

This paper presents on-chip free beam optics on polymer-based photonic components. Due to the circumstance that waveguide-based optics allows no direct beam access we use Gradient index (GRIN) lenses assembled into the chip to collimate the beam from the waveguides. This enables low loss power transmission over a length of 1432 µm. Even though the beam propagates through air it is possible to create a resonator with a wavelength shift of 0.002 nm/°C, hence the allowed deviations from the ITU-T grid (100 GHz) are met for ± 20 °C. In order to guarantee reliable laser stability, it is necessary to implement optical isolators at the output of the laser. This requires the insertion of bulk material into the chip and is realized by a 1050 µm thick coated glass. Due to the large gap of the free-space section, it is possible to combine different resonators together. This demonstrates the feasibility of an integrated wavelength-meter.

Density Functional Study on A-Units Based on Thieno[3,4- c]pyrrole-4,6-dione for Organic Solar Cells

NASA Astrophysics Data System (ADS)

Tang, Xiaoqin; Shen, Wei; Fu, Zhiyong; Liu, Xiaorui; Li, Ming

2017-08-01

The use of polymer donor materials has allowed great progress in organic solar cells. To search for potential donor materials, we have designed a series of donor-acceptor (D-A)-type alternating polymers composed of dithieno[3,2- b:2',3'- d]pyrrole (DTP) electron-rich units and thieno[3,4- c]pyrrole-4,6-dione (TPD) electron-deficient units. Their electronic and optical properties have been investigated using density functional theory and Marcus theory. The calculation results demonstrate that introduction of cyclic compounds (furyl, thienyl, and phenyl) into electron-deficient units of the molecules can result in lower highest occupied molecular orbital (HOMO) levels and reorganization energies compared with the experimental molecule ( X 0 ). To investigate the effects of electron-withdrawing units, three electron-withdrawing substituents (-OCH3, -F, and -CN) were introduced into the thienyl. The results indicated that the polymer X 2-3 will show the best performance among the designed polymers, offering low-lying HOMO energy level (-5.47 eV), narrow energy gap (1.97 eV), and high hole mobility (7.45 × 10-2 cm2 V-1 s-1). This work may provide a guideline for the design of efficient D-A polymers for organic solar cells with enhanced performance.

Influence of Water on Tribological Properties of Wood-Polymer Composites

NASA Astrophysics Data System (ADS)

Mysiukiewicz, Olga; Sterzyński, Tomasz

2017-08-01

Utilization of ecological materials for appliances and products is one of the ways to achieve the goal of sustainability.Wood-polymer composites as a cheap, lightweight, durable and esthetic material has gained attention of scientists, engineers and consumers alike. Different kinds of polymeric matrices, plants used as the fillers, chemical of physical modifiers and processing technologies have already been widely studied. Nonetheless, surprisingly few information on Wood-Polymer Composites' tribology can be found. This paper is an attempt to fill this gap. Polypropylene-and poly(lactic acid)-based composites with varying wood flour content have been analyzed. The Brinell's hardness and coefficient of friction of the samples have been determined. In order to evaluate the influence of the moisture content on the tribological and mechanical properties of the composites, the samples have also been aged in water. The investigation revealed that polymeric composites filled with wood flour can present favorable coefficient of friction, compared to the neat resins. The results of our study can establish a good starting point for further investigation.

High-quality photonic crystals with a nearly complete band gap obtained by direct inversion of woodpile templates with titanium dioxide.

PubMed

Marichy, Catherine; Muller, Nicolas; Froufe-Pérez, Luis S; Scheffold, Frank

2016-02-25

Photonic crystal materials are based on a periodic modulation of the dielectric constant on length scales comparable to the wavelength of light. These materials can exhibit photonic band gaps; frequency regions for which the propagation of electromagnetic radiation is forbidden due to the depletion of the density of states. In order to exhibit a full band gap, 3D PCs must present a threshold refractive index contrast that depends on the crystal structure. In the case of the so-called woodpile photonic crystals this threshold is comparably low, approximately 1.9 for the direct structure. Therefore direct or inverted woodpiles made of high refractive index materials like silicon, germanium or titanium dioxide are sought after. Here we show that, by combining multiphoton lithography and atomic layer deposition, we can achieve a direct inversion of polymer templates into TiO2 based photonic crystals. The obtained structures show remarkable optical properties in the near-infrared region with almost perfect specular reflectance, a transmission dip close to the detection limit and a Bragg length comparable to the lattice constant.

Optical and electrical effects of plasmonic nanoparticles in high-efficiency hybrid solar cells.

PubMed

Fu, Wei-Fei; Chen, Xiaoqiang; Yang, Xi; Wang, Ling; Shi, Ye; Shi, Minmin; Li, Han-Ying; Jen, Alex K-Y; Chen, Jun-Wu; Cao, Yong; Chen, Hong-Zheng

2013-10-28

Plasmonics have been proven to be an effective way to harness more incident light to achieve high efficiency in photovoltaic devices. Herein, we explore the possibility that plasmonics can be utilized to enhance light trapping and power conversion efficiency (PCE) for polymer-quantum dot (QD) hybrid solar cells (HSCs). Based on a low band-gap polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and a CdSe QD bulk-heterojunction (BHJ) system, gold nanoparticles were doped at different locations of the devices. Successfully, an improved PCE of 3.20 ± 0.22% and 3.16 ± 0.15% was achieved by doping the hole transporting layer and the active layer, respectively, which are among the highest values reported for CdSe QD based HSCs. A detailed study of processing, characterization, microscopy, and device fabrication is conducted to understand the underlying mechanism for the enhanced device performance. The success of this work provides a simple and generally applicable approach to enhance light harnessing of polymer-QD hybrid solar cells.

Synthesis of ZnO nanorods and observation of resistive switching memory in ZnO based polymer nanocomposites

NASA Astrophysics Data System (ADS)

Nair, Manjula G.; Malakar, Meenakshi; Mohapatra, Saumya R.; Chowdhury, Avijit

2018-05-01

This research reports the observation of bipolar resistive switching memory in ZnO nanorod based polymer nanocomposites. We synthesized ZnO nanorods by wet-chemical method and characterized them using XRD, UV-VIS spectroscopy and SEM. The synthesized materials have hexagonal ZnO phase with grain size of 24 nm and having strong orientation along (101) direction as observed from XRD. The SEM micrograph confirms the formation of ZnO nanorods with diameter in the range of 10 to 20 nm and length of the order of 1 µm. From optical absorption spectra the band gap is estimated to be 2.42 eV. ZnO nanorods were dispersed in PVDF-HFP polymer matrix to prepare the nanocomposite. This nanocomposite was used as active layer in the devices having sandwich structure of ITO/PVDF-HFP+ZnO nanorods/Al. Bipolar non-volatile memory was observed with ON-OFF resistance ratio of the order of 103 and with a wide voltage window of 2.3V. The switching mechanism could be due to the trapping and de-trapping of electrons by the ZnO nanorods in the nanocomposite during ON and OFF states respectively.

Nanophotonics: Energy Transfer towards Enhanced Luminescent Chemosensing

PubMed Central

Aad, Roy; Couteau, Christophe; Lérondel, Gilles

2015-01-01

We discuss a recently proposed novel photonic approach for enhancing the fluorescence of extremely thin chemosensing polymer layers. We present theoretical and experimental results demonstrating the concept of gain-assisted waveguided energy transfer (G-WET) on a very thin polymer nanolayer spincoated on an active ZnO thin film. The G-WET approach is shown to result in an 8-fold increase in polymer fluorescence. We then extend the G-WET concept to nanostructured media. The benefits of using active nanostructured substrates on the sensitivity and fluorescence of chemosensing polymers are discussed. Preliminary theoretical results on enlarged sensing surface and photonic band-gap are presented. PMID:28788025

Displacement of polarons by vibrational modes in doped conjugated polymers

NASA Astrophysics Data System (ADS)

Anderson, M.; Ramanan, C.; Fontanesi, C.; Frick, A.; Surana, S.; Cheyns, D.; Furno, M.; Keller, T.; Allard, S.; Scherf, U.; Beljonne, D.; D'Avino, G.; von Hauff, E.; Da Como, E.

2017-10-01

Organic pi-conjugated polymers are deemed to be soft materials with strong electron-phonon coupling, which results in the formation of polarons, i.e., charge carriers dressed by self-localized distortion of the nuclei. Universal signatures for polarons are optical resonances below the band gap and intense vibrational modes (IVMs), both found in the infrared (IR) spectral region. Here, we study p -doped conjugated homo- and copolymers by combining first-principles modelling and optical spectroscopy from the far-IR to the visible. Polaronic IVMs are found to feature absorption intensities comparable to purely electronic transitions and, most remarkably, show only loose resemblance to the Raman or IR-active modes of the neutral polymer. The IVM frequency is dramatically scaled down (up to 50%) compared to the backbone carbon-stretching modes in the pristine polymers. The very large intensity of IVMs is associated with displacement of the excess positive charge along the backbone driven by specific vibrational modes. We propose a quantitative picture for the identification of these polaron shifting modes that solely based on structural information, directly correlates with their IR intensity. This finding finally discloses the elusive microscopic mechanism behind the huge IR intensity of IVMs in doped polymeric semiconductors.

Photonic Microresonators from Charge Transfer in Polymer Particles: Toward Enhanced and Tunable Two-Photon Emission.

PubMed

Vattikunta, Radhika; Venkatakrishnarao, Dasari; Sahoo, Chakradhar; Naraharisetty, Sri Ram Gopal; Narayana Rao, Desai; Müllen, Klaus; Chandrasekar, Rajadurai

2018-05-16

Novel photonic microresonators with enhanced nonlinear optical (NLO) intensity are fabricated from polymer particles. As an additional advantage, they offer band gap tunability from the visible to near-infrared regions. A special protocol including (i) copolymerization of 4-(1-pyrenyl)-styrene, styrene, and 1,4-divinylbenzene, (ii) extraction of a dispersible and partly dissolvable, lightly cross-linked polymer network (PN), and (iii) treatment of the blue-emitting PN with electron acceptor (A) molecules such as 1,2,4,5-tetracyanobenzene (TCNB) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) furnishes orange- and red-emitting D-A charge-transfer (CT) complexes with the pendant pyrene units. These complexes, here named PN-TCNB and PN-TCNQ, respectively, precipitate as microparticles upon the addition of water and subsequent ultrasonication. Upon electronic excitation, these spherical microparticles act as whispering-gallery-mode resonators by displaying optical resonances in the photoluminescence (PL) spectra because of light confinement. Further, the trapped incident light increases the light-matter interaction and thereby enhances the PL intensity, including the two-photon luminescence. The described protocol for polymer-based CT microresonators with tunable NLO emissions holds promise for a myriad of photonic applications.

Visible-light active conducting polymer nanostructures with superior photocatalytic activity

NASA Astrophysics Data System (ADS)

Ghosh, Srabanti; Kouame, Natalie Amoin; Remita, Samy; Ramos, Laurence; Goubard, Fabrice; Aubert, Pierre-Henri; Dazzi, Alexandre; Deniset-Besseau, Ariane; Remita, Hynd

2015-12-01

The development of visible-light responsive photocatalysts would permit more efficient use of solar energy, and thus would bring sustainable solutions to many environmental issues. Conductive polymers appear as a new class of very active photocatalysts under visible light. Among them poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the most promising conjugated polymer with a wide range of applications. PEDOT nanostructures synthesized in soft templates via chemical oxidative polymerization demonstrate unprecedented photocatalytic activities for water treatment without the assistance of sacrificial reagents or noble metal co-catalysts and turn out to be better than TiO2 as benchmark catalyst. The PEDOT nanostructures exhibit a narrow band gap (E = 1.69 eV) and are characterized by excellent ability to absorb light in visible and near infrared region. The novel PEDOT-based photocatalysts are very stable with cycling and can be reused without appreciable loss of activity. Interestingly, hollow micrometric vesicular structures of PEDOT are not effective photocatalysts as compared to nanometric spindles suggesting size and shape dependent photocatalytic properties. The visible-light active photocatalytic properties of the polymer nanostructures present promising applications in solar light harvesting and broader fields.

Controlling the optical properties of polyaniline doped by boric acid particles by changing their doping agent and initiator concentration

NASA Astrophysics Data System (ADS)

Cabuk, Mehmet; Gündüz, Bayram

2017-12-01

In this study, polyaniline doped by boric acid (PAni:BA) conducting polymers were chemically synthesized by oxidative polymerization method using (NH4)2S208 (APS) as initiator. Pani:BA conducting polymers were synthesized by using two different APS/aniline molar ratios as 1:1 and 2:1. Their results were compared with PAni doped by HCl (PAni) conducting polymer. Structural properties of the PAni, PAni:BA (1:1) and PAni:BA (2:1) conducting polymers were characterized by using FTIR, SEM, TGA, particle size and apparent density measurements. Effects of doping agents and initiator concentrations on optical properties were investigated in detail. The optoelectronic parameters such as absorption band edge, molar extinction coefficient, direct allowed band gap, refractive index, optical conductance and electrical conductance of the PAni, PAni:BA (1:1) and PAni:BA (2:1) were determined. The absorption band edge and direct allowed band gap of PAni were decreased with doping BA and increasing APS ratio. Also, the refractive index values of the materials were calculated from experimental results and compared with obtained results from Moss, Ravindra, Herve-Vandamme, Reddy and Kumar-Singh relations.

Theoretical studies of optics and charge transport in organic conducting oligomers and polymers: Rational design of improved transparent and conducting polymers

NASA Astrophysics Data System (ADS)

Hutchison, Geoffrey Rogers

Theoretical studies on a variety of oligo- and polyheterocycles elucidate their optical and charge transport properties, suggesting new, improved transparent conductive polymers. First-principles calculations provide accurate methodologies for predicting both optical band gaps of neutral and cationic oligomers and intrinsic charge transfer rates. Multidimensional analysis reveals important motifs in chemical tailorability of oligoheterocycle optical and charge transport properties. The results suggest new directions for design of novel materials. Using both finite oligomer and infinite polymer calculations, the optical band gaps in polyheterocycles follow a modified particle-in-a-box formalism, scaling approximately as 1/N (where N is the number of monomer units) in short chains, saturating for long chains. Calculations demonstrate that band structure changes upon heteroatom substitution, (e.g., from polythiophene to polypyrrole) derive from heteroatom electron affinity. Further investigation of chemical variability in substituted oligoheterocycles using multidimensional statistics reveals the interplay between heteroatom and substituent in correlations between structure and redox/optical properties of neutral and cationic species. A linear correlation between band gaps of neutral and cationic species upon oxidation of conjugated oligomers, shows redshifts of optical absorption for most species and blueshifts for small band gap species. Interstrand charge-transport studies focus on two contributors to hopping-style charge transfer rates: internal reorganization energy and the electronic coupling matrix element. Statistical analysis of chemical variability of reorganization energies in oligoheterocycles proves the importance of reorganization energy in determining intrinsic charge transfer rates (e.g., charge mobility in unsubstituted oligothiophenes). Computed bandwidths across several oligothiophene crystal packing motifs show similar electron and hole bandwidths, and show that well-known tilted and herringbone motifs in oligothiophenes are driven by electrostatic repulsion. Tilted stacks exhibit intrinsic charge-transfer rates smaller than cofacial stacks, but with lower packing energy. Given similar electron and hole bandwidths, a charge injection model explains substitution-modulated majority carrier changes in n- and p-type oligothiophene field-effect transistors.

GPU based 3D feature profile simulation of high-aspect ratio contact hole etch process under fluorocarbon plasmas

NASA Astrophysics Data System (ADS)

Chun, Poo-Reum; Lee, Se-Ah; Yook, Yeong-Geun; Choi, Kwang-Sung; Cho, Deog-Geun; Yu, Dong-Hun; Chang, Won-Seok; Kwon, Deuk-Chul; Im, Yeon-Ho

2013-09-01

Although plasma etch profile simulation has been attracted much interest for developing reliable plasma etching, there still exist big gaps between current research status and predictable modeling due to the inherent complexity of plasma process. As an effort to address this issue, we present 3D feature profile simulation coupled with well-defined plasma-surface kinetic model for silicon dioxide etching process under fluorocarbon plasmas. To capture the realistic plasma surface reaction behaviors, a polymer layer based surface kinetic model was proposed to consider the simultaneous polymer deposition and oxide etching. Finally, the realistic plasma surface model was used for calculation of speed function for 3D topology simulation, which consists of multiple level set based moving algorithm, and ballistic transport module. In addition, the time consumable computations in the ballistic transport calculation were improved drastically by GPU based numerical computation, leading to the real time computation. Finally, we demonstrated that the surface kinetic model could be coupled successfully for 3D etch profile simulations in high-aspect ratio contact hole plasma etching.

Interface Energetics and Chemical Doping of Organic Electronic Materials

NASA Astrophysics Data System (ADS)

Kahn, Antoine

2014-03-01

The energetics of organic semiconductors and their interfaces are central to the performance of organic thin film devices. The relative positions of charge transport states across the many interfaces of multi-layer OLEDs, OPV cells and OFETs determine in great part the efficiency and lifetime of these devices. New experiments are presented here, that look in detail at the position of these transport states and associated gap states and electronic traps that tail into the energy gap of organic molecular (e.g. pentacene) or polymer (P3HT, PBDTTT-C) semiconductors, and which directly affect carrier mobility in these materials. Disorder, sometime caused by simple exposure to an inert gas, impurities and defects are at the origin of these electronic gap states. Recent efforts in chemical doping in organic semiconductors aimed at mitigating the impact of electronic gap states are described. An overview of the reducing or oxidizing power of several n- and p-type dopants for vacuum- or solution-processed films, and their effect on the electronic structure and conductivity of both vacuum- and solution-processed organic semiconductor films is given. Finally, the filling (compensation) of active gap states via doping is investigated on the electron-transport materials C60 and P(NDI2OD-T2) , and the hole-transport polymer PBDTTT-C.

Impact of the Crystallite Orientation Distribution on Exciton Transport in Donor-Acceptor Conjugated Polymers.

PubMed

Ayzner, Alexander L; Mei, Jianguo; Appleton, Anthony; DeLongchamp, Dean; Nardes, Alexandre; Benight, Stephanie; Kopidakis, Nikos; Toney, Michael F; Bao, Zhenan

2015-12-30

Conjugated polymers are widely used materials in organic photovoltaic devices. Owing to their extended electronic wave functions, they often form semicrystalline thin films. In this work, we aim to understand whether distribution of crystallographic orientations affects exciton diffusion using a low-band-gap polymer backbone motif that is representative of the donor/acceptor copolymer class. Using the fact that the polymer side chain can tune the dominant crystallographic orientation in the thin film, we have measured the quenching of polymer photoluminescence, and thus the extent of exciton dissociation, as a function of crystal orientation with respect to a quenching substrate. We find that the crystallite orientation distribution has little effect on the average exciton diffusion length. We suggest several possibilities for the lack of correlation between crystallographic texture and exciton transport in semicrystalline conjugated polymer films.

Etude, par principes premiers, des effets de la correlation entre electrons sur les proprietes electroniques et magnetiques de polymeres pontes et de supraconducteurs a haute temperature critique

NASA Astrophysics Data System (ADS)

Pesant, Simon

Description of complex systems by Density functional theory is treated in this thesis. First, the Density functional theory and a few functionals used to simulate cristals are presented. Specifically, the LDA and GGA functionnals are described and their limits are exposed. Furthermore, the Hubbard model as well as the LDA+U functionnal are addressed in this chapter. These methods enable the study of highly correlated materials. Then, results obtained on polymers are summarized in two articles. The first one treats the band gap variation of ladder-type polymers compared to non ladder type ones. The second article considers small band gap polymers. In this case, it will be shown that an hybrid functional, which contains exact exchange, is required to describe the electronic properties of the polymers under study. Finally, the last chapter address the study of cuprates superconductors. The LDA+U can account for the localization of electrons in copper orbitals. Consequently, a study of the impact of this functionnal on electronic properties of cuprates is conducted. The chapter is ended by an article treating magnetic orders in doped La 2CuO4. Supplementary materials of the second article and a description of the theory of superconductivity of Bardeen, Cooper and Schrieffer are put in annex. Keywords : Electronic correlation, DFT, LDA+U, cuprates, polymers, magnetic orders

Activity and Safety of Synthetic Lectins Based on Benzoboroxole-Functionalized Polymers for Inhibition of HIV Entry

PubMed Central

Mahalingam, Alamelu; Geonnotti, Anthony R.; Balzarini, Jan; Kiser, Patrick F.

2011-01-01

Lectins derived from plant and microbial sources constitute a vital class of entry inhibitors that target the oligomannose residues on the HIV envelope gp120. Despite their potency and specificity, success of lectin-based entry inhibitors may be impeded by issues in regards to economical production, formulation and potential mitogenicity. Therefore, there exists a gap in the HIV therapeutics pipeline that underscores the need for mass producible, synthetic, broad-spectrum, and biocomptabile inhibitors of HIV entry. Here, we present the development of a polymeric synthetic lectin, based on benzoboroxole (BzB), which exhibits weak affinity (~25 M−1) for non-reducing sugars, similar to those found on the HIV envelope. High molecular weight BzB-functionalized polymers demonstrated antiviral activity that increased with an increase in ligand density and molecular weight of the polymer construct; revealing that polyvalency improves activity. Polymers showed significant increase in activity from 25 to 75 mol% BzB functionalization with EC50 of 15 μM and 15 nM, respectively. A further increase in mole functionalization to 90% resulted in an increase of the EC50 (59 ± 5 nM), likely due to the elongated rigid structure of the polymer chain compelled by electrostatic repulsion between the boronic acid groups. An increase in molecular weight of the polymer at 50 mol% BzB functionalization showed a gradual but significant increase in antiviral activity, with the highest activity seen with the 382 kDa polymer (EC50 of 1.1 ± 0.5 nM in CEM cells and 11 ± 3 nM in TZM-bl cells). Supplementing the polymer backbone with 10 mol% sulfonic acid not only increased the aqueous solubility of the polymers by at least 50-fold, but also demonstrated a synergistic increase in anti-HIV activity (4.0 ± 1.5 nM in TZM-bl cells), possibly due to electrostatic interactions between the negatively charged polymer backbone and the positively charged V3-loop in the gp120. The benzoboroxole-sulfonic acid copolymers showed no decrease in activity in the presence of a seminal concentration of fructose (p > 0.05). Additionally, the co-polymers exhibit minimal, if any effect on the cellular viability, barrier properties, or cytokine levels in human reconstructed ecto-cervical tissue after 3 days of repeated exposure and did not show pronounced activity against a variety of other RNA and DNA viruses. PMID:21879735

Conjugated ladder polymers by a cyclopentannulation polymerization

DOE PAGES

Bheemireddy, Sambasiva R.; Hautzinger, Matthew P.; Li, Tao; ...

2017-04-03

Here, we report a nontraditional synthesis of cyclopentafused-polycyclic aromatic hydrocarbon embedded ladder polymers using a palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction. Donor–acceptor type polymers containing a cyclopenta[hi]aceanthrylene acceptor groups can be synthesized by a palladium catalyzed copolymerization between 9,10-dibromoanthracene and a variety of bis(arylethynyl)arenes to give polymers with molecular weights (Mn) of 9–22 kDa. The bis(arylethynyl)arenes were composed of benzene, thiophene, or thieno[3,2- b]thiophene moieties, which provided access to a series of four donor–acceptor copolymers. The polymers were subjected to cyclodehydrogenation with FeCl 3 to access rigid ladder type polymers with the conversion investigated by 13C NMRmore » of isotopically labeled polymers. As a result, the ladder polymers possess broad UV–Vis absorptions and narrow optical band gaps of 1.17–1.29 eV and are p-type semiconductors in organic field effect transistors.« less

Conjugated ladder polymers by a cyclopentannulation polymerization

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

Bheemireddy, Sambasiva R.; Hautzinger, Matthew P.; Li, Tao

Here, we report a nontraditional synthesis of cyclopentafused-polycyclic aromatic hydrocarbon embedded ladder polymers using a palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction. Donor–acceptor type polymers containing a cyclopenta[hi]aceanthrylene acceptor groups can be synthesized by a palladium catalyzed copolymerization between 9,10-dibromoanthracene and a variety of bis(arylethynyl)arenes to give polymers with molecular weights (Mn) of 9–22 kDa. The bis(arylethynyl)arenes were composed of benzene, thiophene, or thieno[3,2- b]thiophene moieties, which provided access to a series of four donor–acceptor copolymers. The polymers were subjected to cyclodehydrogenation with FeCl 3 to access rigid ladder type polymers with the conversion investigated by 13C NMRmore » of isotopically labeled polymers. As a result, the ladder polymers possess broad UV–Vis absorptions and narrow optical band gaps of 1.17–1.29 eV and are p-type semiconductors in organic field effect transistors.« less

Bridging the Resolution Gap in Structural Modeling of 3D Genome Organization

PubMed Central

Marti-Renom, Marc A.; Mirny, Leonid A.

2011-01-01

Over the last decade, and especially after the advent of fluorescent in situ hybridization imaging and chromosome conformation capture methods, the availability of experimental data on genome three-dimensional organization has dramatically increased. We now have access to unprecedented details of how genomes organize within the interphase nucleus. Development of new computational approaches to leverage this data has already resulted in the first three-dimensional structures of genomic domains and genomes. Such approaches expand our knowledge of the chromatin folding principles, which has been classically studied using polymer physics and molecular simulations. Our outlook describes computational approaches for integrating experimental data with polymer physics, thereby bridging the resolution gap for structural determination of genomes and genomic domains. PMID:21779160

Preliminary Results on the Corrosion Behaviour of a New Biodegradable Metallic Material Based on Zinc

NASA Astrophysics Data System (ADS)

Dobriţa, S.; Istrate, B.; Cimpoeşu, N.; Stanciu, S.; Apostol, V.; Cimpoeşu, R.; Ioniţă, I.; Paraschiv, P.

2018-06-01

The class of biomaterials (metallic, polymer or ceramics) has applications as implants with a temporary function. Among magnezium (high corrosion rate) and iron (slow corrosion rate) based biodegradable alloys a new class based on zinc try to fullfill the gap between the first two alloy systems concerning the degradation rate. The role of these alloys is to provide some specific characteristics for a limited period of time. In this article preliminary results based on microstructural and chemical characteristics of a Zn-Mg alloy are presented. The results were obtained using optical and electronic microscopy (MO and SEM) and dispersive energy spectroscpy (EDS) and X-ray difraction (XRD).

Recent advances in the chemical modification of unsaturated polymers

NASA Technical Reports Server (NTRS)

Schulz, D. N.; Turner, S. R.; Golub, M. A.

1982-01-01

The present discussion has the objective to update the most comprehensive reviews on the considered subject and to fill in the gaps of less complete, but more modern treatments. Only simple chemical functionalization or structural modification of unsaturated polymers are covered, and the literature of diene polymer modification since 1974 is emphasized. Attention is given to hydrogenation, halogenation and hydrohalogenation, cyclization, cis-trans isomerization, epoxidation, ene and other cycloaddition reactions, sulfonation, carboxylation, phosphonylation, sulfenyl chloride addition, carbene addition, metalation, and silylation. It is pointed out that modern synthetic reagents and catalysts have been advantageously employed to improve process and/or product quality. Synthetic techniques have been refined to allow the selective modification of specific polymer microstructures or blocks.

A Donor-Acceptor Conjugated Polymer with Alternating Isoindigo Derivative and Bithiophene Units for Near-Infrared Modulated Cancer Thermo-Chemotherapy.

PubMed

Li, Dong-Dong; Wang, Jun-Xia; Ma, Yan; Qian, Hai-Sheng; Wang, Dong; Wang, Li; Zhang, Guobing; Qiu, Longzhen; Wang, Yu-Cai; Yang, Xian-Zhu

2016-08-03

Conjugated polymers containing alternating donor/acceptor units have strong and sharp absorbance peaks in near-infrared (NIR) region, which could be suitable for photothermal therapy. However, these polymers as photothermal transducers are rarely reported because of their water insolubility, which limits their applications for cancer therapy. Herein, we report the donor-acceptor conjugated polymer PBIBDF-BT with alternating isoindigo derivative (BIBDF) and bithiophene (BT) units as a novel photothermal transducer, which exhibited strong near-infrared (NIR) absorbance due to its low band gap (1.52 eV). To stabilize the conjugated polymer physiological environments, we utilized an amphiphilic copolymer, poly(ethylene glycol)-block-poly(hexyl ethylene phosphate) (mPEG-b-PHEP), to stabilize PBIBDF-BT-based nanoparticles (PBIBDF-BT@NPPPE) through a single emulsion method. The obtained nanoparticles PBIBDF-BT@NPPPE showed great stability in physiological environments and excellent photostability. Moreover, the PBIBDF-BT@NPPPE exhibited high photothermal conversion efficiency, reaching 46.7%, which is relatively high compared with those of commonly used materials for photothermal therapy. Accordingly, in vivo and in vitro experiments demonstrated that PBIBDF-BT@NPPPE exhibits efficient photothermal anticancer efficacy. More importantly, PBIBDF-BT@NPPPE could simultaneously encapsulate other types of therapeutic agents though hydrophobic interactions with the PHEP core and achieve NIR-triggered intracellular drug release and a synergistic combination therapy of thermo-chemotherapy for the treatment of cancer.

Use of array of conducting polymers for differentiation of coconut oil products.

PubMed

Rañola, Rey Alfred G; Santiago, Karen S; Sevilla, Fortunato B

2016-01-01

An array of chemiresistors based on conducting polymers was assembled for the differentiation of coconut oil products. The chemiresistor sensors were fabricated through the potentiostatic electrodeposition of polyaniline (PANi), polypyrrole (PPy) and poly(3-methylthiophene) (P-3MTp) on the gap separating two planar gold electrodes set on a Teflon substrate. The change in electrical resistance of the sensors was measured and observed after exposing the array to the headspace of oil samples. The sensor response was found rapid, reversible and reproducible. Different signals were obtained for each coconut oil sample and pattern recognition techniques were employed for the analysis of the data. The developed system was able to distinguish virgin coconut oil (VCO) from refined, bleached & deodorised coconut oil (RBDCO), flavoured VCO, homemade VCO, and rancid VCO. Copyright © 2015 Elsevier B.V. All rights reserved.

The nanofluidic confinement apparatus: studying confinement-dependent nanoparticle behavior and diffusion

PubMed Central

Fringes, Stefan; Holzner, Felix

2018-01-01

The behavior of nanoparticles under nanofluidic confinement depends strongly on their distance to the confining walls; however, a measurement in which the gap distance is varied is challenging. Here, we present a versatile setup for investigating the behavior of nanoparticles as a function of the gap distance, which is controlled to the nanometer. The setup is designed as an open system that operates with a small amount of dispersion of ≈20 μL, permits the use of coated and patterned samples and allows high-numerical-aperture microscopy access. Using the tool, we measure the vertical position (termed height) and the lateral diffusion of 60 nm, charged, Au nanospheres as a function of confinement between a glass surface and a polymer surface. Interferometric scattering detection provides an effective particle illumination time of less than 30 μs, which results in lateral and vertical position detection accuracy ≈10 nm for diffusing particles. We found the height of the particles to be consistently above that of the gap center, corresponding to a higher charge on the polymer substrate. In terms of diffusion, we found a strong monotonic decay of the diffusion constant with decreasing gap distance. This result cannot be explained by hydrodynamic effects, including the asymmetric vertical position of the particles in the gap. Instead we attribute it to an electroviscous effect. For strong confinement of less than 120 nm gap distance, we detect the onset of subdiffusion, which can be correlated to the motion of the particles along high-gap-distance paths. PMID:29441273

Hole Transfer from Low Band Gap Quantum Dots to Conjugated Polymers in Organic/Inorganic Hybrid Photovoltaics.

PubMed

Colbert, Adam E; Janke, Eric M; Hsieh, Stephen T; Subramaniyan, Selvam; Schlenker, Cody W; Jenekhe, Samson A; Ginger, David S

2013-01-17

We use photoinduced absorption (PIA) spectroscopy to investigate pathways for photocurrent generation in hybrid organic/inorganic quantum dot bulk heterojunction solar cells. We study blends of the conjugated polymer poly(2,3-bis(2-(hexyldecyl)quinoxaline-5,8-diyl-alt-N-(2-hexyldecyl)dithieno[3,2-b:2',3'-d]pyrrole) (PDTPQx-HD) with PbS quantum dots and find that positively charged polarons are formed on the conjugated polymer following selective photoexcitation of the PbS quantum dots. This result provides a direct spectroscopic fingerprint demonstrating that photoinduced hole transfer occurs from the photoexcited quantum dots to the host polymer. We compute the relative yields of long-lived holes following photoexcitation of both the polymer and quantum dot phases and estimate that more long-lived polarons are produced per photon absorbed by the polymer phase than by the quantum dot phase.

Highly ductile UV-shielding polymer composites with boron nitride nanospheres as fillers.

PubMed

Fu, Yuqiao; Huang, Yan; Meng, Wenjun; Wang, Zifeng; Bando, Yoshio; Golberg, Dmitri; Tang, Chengchun; Zhi, Chunyi

2015-03-20

Polymer composites with enhanced mechanical, thermal or optical performance usually suffer from poor ductility induced by confined mobility of polymer chains. Herein, highly ductile UV-shielding polymer composites are successfully fabricated. Boron nitride (BN) materials, with a wide band gap of around ∼6.0 eV, are used as fillers to achieve the remarkably improved UV-shielding performance of a polymer matrix. In addition, it is found that spherical morphology BN as a filler can keep the excellent ductility of the composites. For a comparison, it is demonstrated that traditional fillers, including conventional BN powders can achieve the similar UV-shielding performance but dramatically decrease the composite ductility. The mechanism behind this phenomenon is believed to be lubricant effects of BN nanospheres for sliding of polymer chains, which is in consistent with the thermal analyses. This study provides a new design to fabricate UV-shielding composite films with well-preserved ductility.

Polymer/Polymer Blend Solar Cells Using Tetraazabenzodifluoranthene Diimide Conjugated Polymers as Electron Acceptors

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

Li, Haiyan; Hwang, Ye-Jin; Earmme, Taeshik

2015-03-02

Two n-type semiconducting polymers with alternating arylene (thiophene or selenophene)–tetraazabenzodifluoranthene diimide (BFI) donor–acceptor architecture have been investigated as new electron acceptors in polymer/polymer blend solar cells. The new selenophene-linked polymer, PBFI-S, has a significantly smaller optical band gap (1.13 eV) than the thiophene-linked PBFI-T (1.38 eV); however, both polymers have similar HOMO/LUMO energy levels determined from cyclic voltammetry. Blends of PBFI-T with the thiazolothiazole–dithienylsilole donor polymer (PSEHTT) gave a 2.60% power conversion efficiency (PCE) with a 7.34 mA/cm2 short-circuit current. In contrast, PBFI-S:PSEHTT blends had a 0.75% PCE with similarly reduced photocurrent and external quantum efficiency. Reduced free energy formore » charge transfer and reduced bulk electron mobility in PBFI-S:PSEHTT blends compared to PBFI-T:PSEHTT blends as well as significant differences in bulk film morphology are among the reasons for the large loss in efficiency in PBFI-S:PSEHTT blend solar cells.« less

An Alkylated Indacenodithieno[3,2-b]thiophene-Based Nonfullerene Acceptor with High Crystallinity Exhibiting Single Junction Solar Cell Efficiencies Greater than 13% with Low Voltage Losses.

PubMed

Fei, Zhuping; Eisner, Flurin D; Jiao, Xuechen; Azzouzi, Mohammed; Röhr, Jason A; Han, Yang; Shahid, Munazza; Chesman, Anthony S R; Easton, Christopher D; McNeill, Christopher R; Anthopoulos, Thomas D; Nelson, Jenny; Heeney, Martin

2018-02-01

A new synthetic route, to prepare an alkylated indacenodithieno[3,2-b]thiophene-based nonfullerene acceptor (C8-ITIC), is reported. Compared to the reported ITIC with phenylalkyl side chains, the new acceptor C8-ITIC exhibits a reduction in the optical band gap, higher absorptivity, and an increased propensity to crystallize. Accordingly, blends with the donor polymer PBDB-T exhibit a power conversion efficiency (PCE) up to 12.4%. Further improvements in efficiency are found upon backbone fluorination of the donor polymer to afford the novel material PFBDB-T. The resulting blend with C8-ITIC shows an impressive PCE up to 13.2% as a result of the higher open-circuit voltage. Electroluminescence studies demonstrate that backbone fluorination reduces the energy loss of the blends, with PFBDB-T/C8-ITIC-based cells exhibiting a small energy loss of 0.6 eV combined with a high J SC of 19.6 mA cm -2 . © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Morphological and Optical Characteristics of Chitosan(1-x):Cuox (4 ≤ x ≤ 12) Based Polymer Nano-Composites: Optical Dielectric Loss as an Alternative Method for Tauc's Model.

PubMed

Aziz, Shujahadeen B

2017-12-13

In this work, copper (Cu) nanoparticles with observable surface plasmonic resonance (SPR) peaks were synthesized by an in-situ method. Chitosan host polymer was used as a reduction medium and a capping agent for the Cu nanoparticles. The surface morphology of the samples was investigated through the use of scanning electron micrograph (SEM) technique. Copper nanoparticles appeared as chains and white specks in the SEM images. The strong peaks due to the Cu element observed in the spectrum of energy dispersive analysis of X-rays. For the nanocomposite samples, obvious peaks due to the SPR phenomena were obtained in the Ultraviolet-visible (UV-vis) spectra. The effect of Cu nanoparticles on the host band gap was understood from absorption edges shifting of absorption edges to lower photon energy. The optical dielectric loss parameter obtained from the measurable quantities was used as an alternative method to study the band structure of the samples. Quantum mechanical models drawbacks, in the study of band gap, were explained based on the optical dielectric loss. A clear dispersion region was able to be observed in refractive indices spectra of the composite samples. A linear relationship with a regression value of 0.99 was achieved between the refractive index and volume fractions of CuI content. Cu nanoparticles with various sizes and homogenous dispersions were also determined from transmission electron microscope (TEM) images.

Morphological and Optical Characteristics of Chitosan(1−x):Cuox (4 ≤ x ≤ 12) Based Polymer Nano-Composites: Optical Dielectric Loss as an Alternative Method for Tauc’s Model

PubMed Central

2017-01-01

In this work, copper (Cu) nanoparticles with observable surface plasmonic resonance (SPR) peaks were synthesized by an in-situ method. Chitosan host polymer was used as a reduction medium and a capping agent for the Cu nanoparticles. The surface morphology of the samples was investigated through the use of scanning electron micrograph (SEM) technique. Copper nanoparticles appeared as chains and white specks in the SEM images. The strong peaks due to the Cu element observed in the spectrum of energy dispersive analysis of X-rays. For the nanocomposite samples, obvious peaks due to the SPR phenomena were obtained in the Ultraviolet-visible (UV-vis) spectra. The effect of Cu nanoparticles on the host band gap was understood from absorption edges shifting of absorption edges to lower photon energy. The optical dielectric loss parameter obtained from the measurable quantities was used as an alternative method to study the band structure of the samples. Quantum mechanical models drawbacks, in the study of band gap, were explained based on the optical dielectric loss. A clear dispersion region was able to be observed in refractive indices spectra of the composite samples. A linear relationship with a regression value of 0.99 was achieved between the refractive index and volume fractions of CuI content. Cu nanoparticles with various sizes and homogenous dispersions were also determined from transmission electron microscope (TEM) images. PMID:29236074

Water Splitting with Series-Connected Polymer Solar Cells.

PubMed

Esiner, Serkan; van Eersel, Harm; van Pruissen, Gijs W P; Turbiez, Mathieu; Wienk, Martijn M; Janssen, René A J

2016-10-12

We investigate light-driven electrochemical water splitting with series-connected polymer solar cells using a combined experimental and modeling approach. The expected maximum solar-to-hydrogen conversion efficiency (η STH ) for light-driven water splitting is modeled for two, three, and four series-connected polymer solar cells. In the modeling, we assume an electrochemical water splitting potential of 1.50 V and a polymer solar cell for which the external quantum efficiency and fill factor are both 0.65. The minimum photon energy loss (E loss ), defined as the energy difference between the optical band gap (E g ) and the open-circuit voltage (V oc ), is set to 0.8 eV, which we consider a realistic value for polymer solar cells. Within these approximations, two series-connected single junction cells with E g = 1.73 eV or three series-connected cells with E g = 1.44 eV are both expected to give an η STH of 6.9%. For four series-connected cells, the maximum η STH is slightly less at 6.2% at an optimal E g = 1.33 eV. Water splitting was performed with series-connected polymer solar cells using polymers with different band gaps. PTPTIBDT-OD (E g = 1.89 eV), PTB7-Th (E g = 1.56 eV), and PDPP5T-2 (E g = 1.44 eV) were blended with [70]PCBM as absorber layer for two, three, and four series-connected configurations, respectively, and provide η STH values of 4.1, 6.1, and 4.9% when using a retroreflective foil on top of the cell to enhance light absorption. The reasons for deviations with experiments are analyzed and found to be due to differences in E g and E loss . Light-driven electrochemical water splitting was also modeled for multijunction polymer solar cells with vertically stacked photoactive layers. Under identical assumptions, an η STH of 10.0% is predicted for multijunction cells.

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.

Calculation of photonic bandgap for 2D hexagonal and square structure base on hybrid polymer material

NASA Astrophysics Data System (ADS)

Hidayat, S.; Riveli, N.

2018-05-01

We have calculated 2D photonic crystal band gap using plane-wave expansion method. The studied model of structures is hexagonal lattice and square lattice of rod cylinder in air. We have simulated the dispersion relation of it structure using hybrid polymer as rod material. The parameter structures are nrod = 1.5, nhole = 1, and rrod = 0.25a, where a is lattice constant. We found the distributed feedback occurs at the edge of upper band or frequency at 0.66 (a/λ). In our experimental work, we have successfully fabricated the 2D photonic crystal from hybrid polymer incorporated with organic dye laser. The lasing characteristics ware investigated using strip-line excitation light of SHG Nd-YAG laser (λ=532 nm). The lasing wavelengths for hexagonal structure are observed at 606 nm and 621 nm for photonic crystal period of 400 nm and 410 nm, respectively. λ=532 nm). Whereas the square structure, the lasing wavelengths are observed at (588 nm ± 2) and (606 nm ± 2 nm) for grating period of 391 nm and 405 nm.

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

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

Photoelectrochemical electrodes

NASA Technical Reports Server (NTRS)

Williams, R. M.; Rembaum, A. (Inventor)

1983-01-01

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

Modification of fluorescence and optical properties of Rhodamine B dye doped PVA/Chitosan polymer blend films

NASA Astrophysics Data System (ADS)

Padmakumari, R.; Ravindrachary, V.; Mahantesha, B. K.; Sagar, Rohan N.; Sahanakumari, R.; Bhajantri, R. F.

2018-05-01

Pure and Rhodamine B doped Poly (vinyl alcohol)/Chitosan composite films are prepared using solution casting method. Fourier transforms infrared spectra (FTIR), Ultraviolet-Visible (UV-Vis), fluorescence studies were used to characterize the prepared polymer films. The FT-IR results show that the appearance of new peaks along with shift in peak positions indicates the interaction of Rhodamine B with PVA-CS blend. Optical absorption edge, band gap and activation energy were determined from UV-Visible studies. The optical absorption edge increases, band gap decreases and activation energy increases with dopant concentration respectively. The corresponding emission spectra were studied using fluorescence spectroscopy. From the fluorescence study the quenching phenomena are observed in emission wavelength range of 607nm-613nm upon excitation with absorption maxima 443nm.

Electrical tuning of three-dimensional photonic crystals using polymer dispersed liquid crystals

NASA Astrophysics Data System (ADS)

McPhail, Dennis; Straub, Martin; Gu, Min

2005-01-01

Electrically tunable three-dimensional photonic crystals with a tunable wavelength range of over 70nm of stop gaps between 3 and 4μm have been generated in a liquid crystal-polymer composite. The photonic crystals were fabricated by femtosecond-laser direct writing of void channels in an inverse woodpile configuration with 20 layers providing an extinction of infrared light transmission of 70% in the stacking direction. Stable structures could be manufactured up to a liquid crystal concentration of 24%. Applying a direct voltage of several hundred volts in the stacking direction of the photonic crystal changes the alignment of the liquid crystal directors and hence the average refractive index of the structure. This mechanism permits the direct tuning of the photonic stop gap.

Light-Directed Tuning of Plasmon Resonances via Plasmon-Induced Polymerization Using Hot Electrons

PubMed Central

2017-01-01

The precise morphology of nanoscale gaps between noble-metal nanostructures controls their resonant wavelengths. Here we show photocatalytic plasmon-induced polymerization can locally enlarge the gap size and tune the plasmon resonances. We demonstrate light-directed programmable tuning of plasmons can be self-limiting. Selective control of polymer growth around individual plasmonic nanoparticles is achieved, with simultaneous real-time monitoring of the polymerization process in situ using dark-field spectroscopy. Even without initiators present, we show light-triggered chain growth of various monomers, implying plasmon initiation of free radicals via hot-electron transfer to monomers at the Au surface. This concept not only provides a programmable way to fine-tune plasmons for many applications but also provides a window on polymer chemistry at the sub-nanoscale. PMID:28670601

Structural symmetry breaking of silicon containing polymers and their relation with electrical conductivity and Raman active vibrations

NASA Astrophysics Data System (ADS)

Cabrera, Alejandro; González, Carmen; Tagle, Luis; Terraza, Claudio; Volkmann, Ulrich; Barriga, Andrés; Ramos, Esteban; Pavez, Maximiliano

2011-03-01

The incorporation of silicon into the polymeric main chain or side groups can provide an enhancement in chemical, physical and mechanical properties. We report an efficient method for the synthesis of polymers containing silicon in the main chain, from the polycondensation reactions of four optically active carboxylic diacid. The solubility of the polymers, the molecular weight, the glass transition and the thermal stability were studied by standard techniques. Raman spectroscopy was used to probe the conformation of stretching modes as function of the temperature. The conductivity measurements indicated that the alignment of the molecules is a crucial parameter for electrical performance. When the polymers were exposed to iodine, charge transfer increased their mobility and decreased their optical band gaps. These novel properties highlight the possibility to generate alternative active opto-electronics polymers.

Graphene Calisthenics: Straintronics of Graphene with Light-Reactive Azobenzene Polymer

NASA Astrophysics Data System (ADS)

Meaker, Kacey; Cao, Peigen; Huo, Mandy; Crommie, Michael

2014-03-01

Although a promising target for next-generation electronics, graphene's lack of a band gap is a severe hindrance. There are many ways of opening a gap, and one controllable way is through application of specific non-uniform strains which can produce extremely large pseudomagnetic fields. This effect was predicted and verified experimentally, but so far there have been few methods developed that reliably control the size, location, separation and amount of strain in graphene. We have used a layer of light-reactive azobenzene polymer beneath the graphene to produce strained monolayer graphene with light exposure. Using Raman spectroscopy, we have measured a shift of up to 20 cm-1 in the 2D peak when the graphene and polymer sample was exposed to 532 nm laser illumination indicating that the graphene is undergoing a strain from deformation of the azobenzene layer below. AFM topographic measurements and COMSOL simulations were used to verify this assertion. Use of polymeric materials to reliably strain graphene in non-uniform ways could result in controllable production of large pseudomagnetic fields in graphene and more control over graphene's low-energy charge carriers.

A Technique for Estimating the Surface Conductivity of Single Molecules

NASA Astrophysics Data System (ADS)

Bau, Haim; Arsenault, Mark; Zhao, Hui; Purohit, Prashant; Goldman, Yale

2007-11-01

When an AC electric field at 2MHz was applied across a small gap between two metal electrodes elevated above a surface, rhodamine-phalloidin-labeled actin filaments were attracted to the gap and became suspended between the two electrodes. The variance of each filament's horizontal, lateral displacement was measured as a function of electric field intensity and position along the filament. The variance significantly decreased as the electric field intensity increased. Hypothesizing that the electric field induces electroosmotic flow around the filament that, in turn, induces drag on the filament, which appears as effective tension, we estimated the tension using a linear, Brownian dynamic model. Based on the tension, we estimated the filament's surface conductivity. Our experimental method provides a novel means for trapping and manipulating biological filaments and for probing the surface conductance and mechanical properties of single polymers.

A combined semiempirical-DFT study of oligomers within the finite-chain approximation, evolution from oligomers to polymers.

PubMed

Derosa, Pedro A

2009-06-01

A computationally cheap approach combining time-independent density functional theory (TIDFT) and semiempirical methods with an appropriate extrapolation procedure is proposed to accurately estimate geometrical and electronic properties of conjugated polymers using just a small set of oligomers. The highest occupied molecular orbital-lowest unoccupied molecular orbital gap (HLG) obtained at a TIDFT level (B3PW91) for two polymers, trans-polyacetylene--the simplest conjugated polymer, and a much larger poly(2-methoxy-5-(2,9-ethyl-hexyloxy)-1,4-phenylenevinylene (MEH-PPV) polymer converge to virtually the same asymptotic value than the excitation energy obtained with time-dependent DFT (TDDFT) calculations using the same functional. For TIDFT geometries, the HLG is found to converge to a value within the experimentally accepted range for the band gap of these polymers, when an exponential extrapolation is used; however if semiempirical geometries are used, a linear fit of the HLG versus 1/n is found to produce the best results. Geometrical parameters are observed to reach a saturation value in good agreement with experimental information, within the length of oligomers calculated here and no extrapolation was considered necessary. Finally, the performance of three different semiempirical methods (AM1, PM3, and MNDO) and for the TIDFT calculations, the performance of 7 different full electron basis sets (6-311+G**, 6-31+ +G**, 6-311+ +G**, 6-31+G**, 6-31G**, 6-31+G*, and 6-31G) is compared and it is determined that the choice of semiempirical method or the basis set does not significantly affect the results. 2008 Wiley Periodicals, Inc.

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.

Coplanar asymmetrical reduced graphene oxide-titanium electrodes for polymer photodetectors.

PubMed

Pang, Shuping; Yang, Shubin; Feng, Xinliang; Müllen, Klaus

2012-03-22

Narrow gaps and a "built-in" potential originating from the different work functions of reduced graphene oxide (RGO) and titanium electrodes are used to explain the improved photosensitivity of the poly(3-hexylthiophene) photodetectors with asymmetrical RGO-Ti electrodes presented here compared to those based on symmetrical electrodes. Easy processing, high photosensitivity, high on/off ratio, and low energy consumption contribute to the promising potential of coplanar asymmetrical electrodes in the field of photoelectric devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methodological comparison on hybrid nano organic solar cell fabrication

NASA Astrophysics Data System (ADS)

Vairavan, Rajendaran; Hambali, Nor Azura Malini Ahmad; Wahid, Mohamad Halim Abd; Retnasamy, Vithyacharan; Shahimin, Mukhzeer Mohamad

2018-02-01

The development of low cost solar cells has been the main focus in recent years. This has lead to the generation of photovoltaic cells based on hybrid of nanoparticle-organic polymer materials. This type of hybrid photovoltaic cells can overcome the problem of polymeric devices having low optical absorption and carrier mobilities. The hybrid cell has the potential of bridging the efficiency gap, which in present in organic and inorganic semiconductor materials. This project focuses on obtaining an hybrid active layer consisting of nanoparticles and organic polymer, to understand the parameter involved in obtaining this active layer and finally to investigate if the addition of nano particles in to the active layer could enhance the output of the hybrid solar cell. The hybrid active layer have will be deposited using the spin coating technique by using CdTe, CdS nano particles mixed with poly (2-methoxy,5-(2-ethyl-hexyloxy)-p-phenylvinylene)MEH-PPV.

Variable Gap Conjugated Polymers

DTIC Science & Technology

2005-12-01

conducting gold interfacial layer interjected between the ITO glass electrode and the PEDOT/PSS hole transport layer . A family of low band gap, and near IR...which can be used as both electrochromics and as the hole transport layers in light emitting diodes. Hybrid electrochromic and electroluminescent (EC...MEH-PPV, P3HT, etc.) in order to blanket the solar spectrum. Initial device results on these multi-component blends are promising. In addition, we

Synthesis of crumpled nanosheets of polymeric carbon nitride from melamine cyanurate

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

Dante, Roberto C., E-mail: rcdante@yahoo.com; Martín-Ramos, Pablo; Sánchez-Arévalo, F.M.

2013-05-01

Polymeric carbon nitride was synthesized by pyrolysis in nitrogen flux at different temperatures between 450 and 700 °C using melamine cyanurate as a reagent and sulfuric acid as a catalyst. The obtained carbon nitride consisted of curled nanosheets (650 °C), and globular particles (700 °C) with formula C₆N₇NHNH₂. The reaction yield of the catalyzed reaction was around the 15% for the sample treated at 700 °C, in a tapped crucible. The optical band gap of the polymer obtained at 700 °C is around 2.9 eV. The gap to the Fermi level is around 2 eV, considerably above the half ofmore » the band gap (due to electrons trapped in the gap), indicating that the polymer is probably a n-type semiconductor. - Graphical abstract: Transition from amorphous to crystalline carbon nitride, which is composed of globular particles and is a n-type wide band semiconductor. Highlights: • We synthetized carbon nitride using melamine cyanurate. • The reaction of carbon nitride formation is catalyzed by sulfuric acid. • The carbon nitride obtained at 700 °C is composed of globular particles. • The material obtained at 700 °C is a n-type semiconductor.« less

Development and characterization of amorphous acrylate networks for use as switchable adhesives inspired from shapememory behavior

NASA Astrophysics Data System (ADS)

Lakhera, Nishant

Several types of insects and animals such as spiders and geckos are inherently able to climb along vertical walls and ceilings. This remarkable switchable adhesive behavior has been attributed to the fibrillar structures on their feet, with size ranging from few nanometers to a few micrometers depending on the species. Several studies have attempted to create synthetic micro-patterned surfaces trying to imitate this adhesive behavior seen in nature. The experimental procedures are scattered, with sole purpose of trying to increase adhesion, thereby making direct comparison between studies very difficult. There is a lack of fundamental understanding on adhesion of patterned surfaces. The influence of critical parameters like material modulus, glass transition temperature, viscoelastic effects, temperature and water absorption on adhesion is not fully explored and characterized. These parameters are expected to have a decisive influence on adhesion behavior of the polymer. Previous studies have utilized conventional "off-the-shelf" materials like epoxy, polyurethanes etc. It is however, impossible to change the material modulus, glass transition temperature etc. of these polymer systems without changing the base constituents itself, thereby explaining the gaps in the current research landscape. The purpose of this study was to use acrylate shape-memory polymers (SMPs) for their ability to be tailored to specific mechanical properties by control of polymer chemistry, without changing the base constituents. Polymer networks with tailorable glass transition, material modulus, water absorption etc. were developed and adhesion studies were performed to investigate the influence of temperature, viscoelastic effects, material modulus on the adhesion behavior of flat acrylate polymer surfaces. The knowledge base gained from these studies was utilized to better understand the fundamental mechanisms associated with adhesion behavior of patterned acrylate surfaces. Thermally induced switchable adhesion and water induced switchable adhesion of patterned acrylate surfaces was investigated. The viscoelastic energy dissipation occurring during the detachment phase was shown to dramatically increase adhesion under both thermally induced and water induced conditions. This effect was most pre-dominant at the glass transition temperature of the material. Increase in pre-load force and unloading velocity were also shown to increase the adhesive capability of the patterned acrylate SMPs.

Multi-wavelength laser from dye-doped cholesteric polymer films.

PubMed

Huang, Yuhua; Wu, Shin-Tson

2010-12-20

A multi-wavelength laser is demonstrated using a dye-doped cholesteric polymer film whose reflection bandwidth is broadened with several oscillations. Due to the abrupt change of the density of state between oscillation peak and valley, each oscillation functions as a photonic band gap for generating a laser wavelength under the excitation of a pumping laser. As a result, a multiple wavelength laser is generated. Results indicate that the dye-doped cholesteric liquid crystal polymer film is a good candidate for fabricating broadband lasers such as white light lasers. Potential applications include experimental testing of laser materials, identification markers, information displays, and inertial confinement laser fusion.

Self Assembly and Interface Engineering of Organic Functional Materials for High Performance Polymer Solar Cells

NASA Astrophysics Data System (ADS)

Jen, Alex

2010-03-01

The performance of polymer solar cells are strongly dependent on the efficiency of light harvesting, exciton dissociation, charge transport, and charge collection at the metal/organic, metal/metal oxide, and organic/metal oxide interfaces. To improve the device performance, two parallel approaches were used: 1) developing novel low band gap conjugated polymers with good charge-transporting properties and 2) modifying the interfaces between the organic/metal oxide and organic/metal layers with functional self-assembling monolayers to tune their energy barriers. Moreover, the molecule engineering approach was also used to tune the energy level, charge mobility, and morphology of organic semiconductors.

Properties, performance and associated hazards of state-of-the-art durable water repellent (DWR) chemistry for textile finishing.

PubMed

Holmquist, H; Schellenberger, S; van der Veen, I; Peters, G M; Leonards, P E G; Cousins, I T

2016-05-01

Following the phase-out of long-chain per- and polyfluoroalkyl substances (PFASs), the textile industry had to find alternatives for side-chain fluorinated polymer based durable water repellent (DWR) chemistries that incorporated long perfluoroalkyl side chains. This phase-out and subsequent substitution with alternatives has resulted in a market where both fluorinated and non-fluorinated DWRs are available. These DWR alternatives can be divided into four broad groups that reflect their basic chemistry: side-chain fluorinated polymers, silicones, hydrocarbons and other chemistries (includes dendrimer and inorganic nanoparticle chemistries). In this critical review, the alternative DWRs are assessed with regards to their structural properties and connected performance, loss and degradation processes resulting in diffuse environmental emissions, and hazard profiles for selected emitted substances. Our review shows that there are large differences in performance between the alternative DWRs, most importantly the lack of oil repellence of non-fluorinated alternatives. It also shows that for all alternatives, impurities and/or degradation products of the DWR chemistries are diffusively emitted to the environment. Our hazard ranking suggests that hydrocarbon based DWR is the most environmentally benign, followed by silicone and side-chain fluorinated polymer-based DWR chemistries. Industrial commitments to reduce the levels of impurities in silicone based and side-chain fluorinated polymer based DWR formulations will lower the actual risks. There is a lack of information on the hazards associated with DWRs, in particular for the dendrimer and inorganic nanoparticle chemistries, and these data gaps must be filled. Until environmentally safe alternatives, which provide the required performance, are available our recommendation is to choose DWR chemistry on a case-by-case basis, always weighing the benefits connected to increased performance against the risks to the environment and human health. Copyright © 2016 Elsevier Ltd. All rights reserved.

Interface-engineering additives of poly(oxyethylene tridecyl ether) for low-band gap polymer solar cells consisting of PCDTBT:PCBM₇₀ bulk-heterojunction layers.

PubMed

Huh, Yoon Ho; Park, Byoungchoo

2013-01-14

We herein report on the improved photovoltaic (PV) effects of using a polymer bulk-heterojunction (BHJ) layer that consists of a low-band gap electron donor polymer of poly(N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)) (PCDTBT) and an acceptor of [6,6]-phenyl C₇₁ butyric acid methyl ester (PCBM₇₀), doped with an interface-engineering surfactant additive of poly(oxyethylene tridecyl ether) (PTE). The presence of an interface-engineering additive in the PV layer results in excellent performance; the addition of PTE to a PCDTBT:PCBM₇₀ system produces a power conversion efficiency (PCE) of 6.0%, which is much higher than that of a reference device without the additive (4.9%). We attribute this improvement to an increased charge carrier lifetime, which is likely to be the result of the presence of PTE molecules oriented at the interfaces between the BHJ PV layer and the anode and cathode, as well as at the interfaces between the phase-separated BHJ domains. Our results suggest that the incorporation of the PTE interface-engineering additive in the PCDTBT:PCBM₇₀ PV layer results in a functional composite system that shows considerable promise for use in efficient polymer BHJ PV cells.

A review of alternatives to di (2-ethylhexyl) phthalate-containing medical devices in the neonatal intensive care unit

PubMed Central

Van Vliet, EDS; Reitano, EM; Chhabra, JS; Bergen, GP; Whyatt, RM

2012-01-01

Objective To conduct an extensive literature and toxicological database review on substitute compounds and available alternative medical products to replace polyvinyl chloride (PVC) and/or di(2-ethylhexyl) phthalate (DEHP), and conduct a DEHP-medical inventory analysis at a large metropolitan neonatal intensive care unit (NICU). Study Design A systematic search for DEHP-free alternative products was performed using online databases. An informal audit of a large metropolitan NICU was undertaken in 2005 and 2006; 21 products were identified that could potentially contain DEHP. Availability of DEHP-free alternatives was determined through company websites and phone interviews. Result Two alternative approaches are available for replacing DEHP in NICU medical products: (1) replacement by DEHP-free plasticizers; and (2) replacement of PVC entirely through the use of other polymers. Both approaches seem to provide less harmful substitutes to DEHP, but support PVC-free polymers as the preferred alternative. However, significant data gaps exist, particularly for the alternative polymers. In all, 10 out of 21 (48%) products in the NICU audit were DEHP-free; six consisted of alternative polymers and four of alternative plasticizers. Of the remaining 11 products, only three were available without DEHP at the time of the audit. Conclusion Because of significant data gaps, systematic toxicological testing of DEHP-free alternatives is imperative. Continued development of alternative products is also needed. PMID:21311501

Formation of anisotropic hollow-fiber membranes via thermally induced phase separation

NASA Astrophysics Data System (ADS)

Batarseh, Melanie Turkett

The goal of this research project was to study the formation of anisotropic hollow fiber membranes via thermally induced phase separation (TIPS). This objective included developing a fundamental knowledge of the factors that contribute to anisotropy and studying how anisotropy can be controlled via operational parameters in hollow fiber spinning. The objective was met by creating a model to simulate the mass and heat transfer in the fiber wall during spinning and by experimentally varying spinning parameters and observing the affect on the membrane microstructure. The TIPS membrane formation process consists of forming a homogeneous solution of polymer and diluent and extruding the solution through a spinneret to form a hollow fiber. The fiber is cooled in an air gap followed by a quench bath, which results in phase separation of the solution into a diluent-rich phase dispersed in a continuous polymer-rich liquid phase. The diluent-rich domains grow in size until the polymer-rich phase crystallizes. Then the diluent is removed, and the spaces left behind become the pores of the microporous membrane. Therefore, the size of the diluent-rich domains when the polymer solidifies is related to the size of the pores in the finished membrane. Increasing the polymer concentration of the homogeneous solution or increasing the cooling rate of the phase separated solution decreases the domain size, and thus decreases pore size. An anisotropic membrane, which has a gradation of pore size from small pores at the feed-side to large pores at the permeate-side, can be formed by creating a concentration gradient or a cooling rate gradient across the membrane. In hollow fiber spinning, a concentration gradient can be created by allowing diluent to evaporate from the outside wall of the fiber in the air gap, and a cooling rate gradient can be created by quenching the fiber in a liquid bath. The spinning model calculates concentration and temperature profiles across the hollow fiber wall over time. The model results indicate that spinning temperature, air velocity, and air gap length have a significant effect on the concentration profile in the wall, and spinning temperature and quench temperature have a significant effect on the cooling rate profile. Experimental results indicate that increasing the air gap length from 5 to 50 cm. or increasing the quench temperature from 298 to 323 K has a significant effect on the anisotropic structure of the hollow fiber.

Charge injection and transport in regioregular poly(3-hexylthiophene)-based field-effect transistors

NASA Astrophysics Data System (ADS)

Singh, Kumar Abhishek

Organic (semi)conductors are poised as never before to transform the electronics industry towards unprecedented versatility. In this thesis, we have taken an experimental approach to address the effect of nanostructure and the energy-level alignment at the metal/polymer interface on charge injection and transport in regioregular poly(3-hexylthiophene) (rr-P3HT) based field-effect transistors (FETs). We found that the mobility and contact resistance in rr-P3HT based FETs show an inverse relationship, and that both properties were affected by the nanostructure of the polymer proving that that charge injection, in addition to charge transport, is significantly affected by the bulk-transport properties of rr-P3HT. Thereafter we successfully recessed the contacts into the SiO 2 dielectric to minimize the effect of the step between the metal contacts and the dielectric on the polymer nanomorphology. The planarization of the devices resulted in a dramatic improvement of the nanomorphology of rr-P3HT reflected as an improvement in charge injection as evident from the decrease in contact resistance values. Gold contacts were also modified by treating them with self-assembled monolayers (SAMs) of aromatic thiols. Electron-poor (electron-rich) SAMs resulted in an increase (decrease) in the Au work function because of the electron-withdrawing (-donating) tendency of the polar molecules. The change in metal work-function by SAM modification also resulted in a modulation of the contact resistance. While there was a clear effect on charge injection upon modification of the contacts, either by SAMs or planarization, the mobility values improved only in the short-channel devices indicating that at longer channels the OFETs are channel-limited because of grain-boundary limited charge transport. Photoemission spectroscopy was also conducted to investigate the energy level alignment at bottom-contact (polymer-on-metal) and top-contact (metal-on-polymer) geometries for high work function metals (Au, Pt) and rr-P3HT. The Fermi energy level was found to be pinned at the polaronic energy level within the band gap of rr-P3HT resulting in barrier-less interfaces for charge injection. Photoemission spectroscopy studies of the metal-on-polymer configuration also provided insight into the chemical structure of the metal/polymer interface. Platinum was found to react with sulfur from the thiophene ring whereas Au was found to be relatively unreactive.

How Does a Hydrophobic Macromolecule Respond to Mixed Osmolyte Environment?

PubMed

Tah, Indrajit; Mondal, Jagannath

2016-10-04

The role of the protecting osmolyte Trimethyl N-oxide (TMAO) in counteracting the denaturing effect of urea on a protein is quite well established. However, the mechanistic role of osmolytes on the hydrophobic interaction underlying protein folding is a topic of contention and is emerging as a key area of biophysical interest. Although recent experiment and computer simulation have established that individual aqueous solution of TMAO and urea respectively stabilizes and destabilizes the collapsed conformation of a hydrophobic polymer, it remains to be explored how a mixed aqueous solution of protecting and denaturing osmolytes influences the conformations of the polymer. In order to bridge the gap, we have simulated the conformational behavior of both a model hydrophobic polymer and a synthetic polymer polystyrene in an aqueous mixture of TMAO and urea. Intriguingly, our free energy based simulations on both the systems show that even though a pure aqueous solution of TMAO stabilizes the collapsed or globular conformation of the hydrophobic polymer, addition of TMAO to an aqueous solution of urea further destabilizes the collapsed conformation of the hydrophobic polymer. We also observe that the extent of destabilization in a mixed osmolyte solution is relatively higher than that in pure aqueous urea solution. The reinforcement of the denaturation effect of the hydrophobic macromolecule in a mixed osmolyte solution is in stark contrast to the well-known counteracting role of TMAO in proteins under denaturing condition of urea. In both model and realistic systems, our results show that in a mixed aqueous solution, greater number of cosolutes preferentially bind to the extended conformation of the polymer relative to that in the collapsed conformation, thereby complying with Tanford-Wyman preferential solvation theory disfavoring the collapsed conformation. The results are robust across a range of osmolyte concentrations and multiple cosolute forcefields. Our findings unequivocally imply that the action of mixed osmolyte solution on hydrophobic polymer is significantly distinct from that of proteins.

Facile doping of anionic narrow-band-gap conjugated polyelectrolytes during dialysis.

PubMed

Mai, Cheng-Kang; Zhou, Huiqiong; Zhang, Yuan; Henson, Zachary B; Nguyen, Thuc-Quyen; Heeger, Alan J; Bazan, Guillermo C

2013-12-02

PCPDTBTSO3 K, an anionic, narrow-band-gap conjugated polyelectrolyte, was found to be doped after dialysis. The proposed doping mechanism involves protonation of the polymer backbone, followed by electron transfer from a neutral chain, to generate radical cations, which are stabilized by the pendant sulfonate anions. Formation of polarons is supported by spectroscopy and electrical-conductivity measurements. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructure and Properties of Thermally Sprayed Functionally Graded Coatings for Polymeric Substrates

NASA Technical Reports Server (NTRS)

Ivosevic, M.; Knight, R.; Kalidindi, S. R.; Palmese, G. R.; Sutter, J. K.

2003-01-01

The use of polymer matrix composites (PMCs) in the gas flow path of advanced turbine engines offers significant benefits for aircraft engine performance but their useful lifetime is limited by their poor erosion resistance. High velocity oxy-fuel (HVOF) sprayed polymer/cermet functionally graded (FGM) coatings are being investigated as a method to address this technology gap by providing erosion and oxidation protection to polymer matrix composites. The FGM coating structures are based on a polyimide matrix filled with varying volume fractions of WC-Co. The graded coating architecture was produced using a combination of internal and external feedstock injection, via two computer-controlled powder feeders and controlled substrate preheating. Porosity, coating thickness and volume fraction of the WC-Co filler retained in the coatings were determined using standard metallographic techniques and computer image analysis. The pull-off strength (often referred to as the adhesive strength) of the coatings was evaluated according to the ASTM D 4541 standard test method, which measured the greatest normal tensile force that the coating could withstand. Adhesive/cohesive strengths were determined for three different types of coating structures and compared based on the maximum indicated load and the surface area loaded. The nature and locus of the fractures were characterized according to the percent of adhesive and/or cohesive failure, and the tested interfaces and layers involved were analyzed by Scanning Electron Microscopy.

Comparison of self-written waveguide techniques and bulk index matching for low-loss polymer waveguide interconnects

NASA Astrophysics Data System (ADS)

Burrell, Derek; Middlebrook, Christopher

2016-03-01

Polymer waveguides (PWGs) are used within photonic interconnects as inexpensive and versatile substitutes for traditional optical fibers. The PWGs are typically aligned to silica-based optical fibers for coupling. An epoxide elastomer is then applied and cured at the interface for index matching and rigid attachment. Self-written waveguides (SWWs) are proposed as an alternative to further reduce connection insertion loss (IL) and alleviate marginal misalignment issues. Elastomer material is deposited after the initial alignment, and SWWs are formed by injecting ultraviolet (UV) light into the fiber or waveguide. The coupled UV light cures a channel between the two differing structures. A suitable cladding layer can be applied after development. Such factors as longitudinal gap distance, UV cure time, input power level, polymer material selection and choice of solvent affect the resulting SWWs. Experimental data are compared between purely index-matched samples and those with SWWs at the fiber-PWG interface. It is shown that < 1 dB IL per connection can be achieved by either method and results indicate lowest potential losses associated with a fine-tuned self-writing process. Successfully fabricated SWWs reduce overall processing time and enable an effectively continuous low-loss rigid interconnect.

Structural diversification and photocatalytic properties of three Cd(II) coordination polymers decorated with different auxiliary ligands

NASA Astrophysics Data System (ADS)

Yin, Wen-Yu; Zhuang, Guo-Yong; Huang, Zuo-Long; Cheng, Hong-Jian; Zhou, Li; Ma, Man-Hong; Wang, Hao; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin

2016-03-01

Three cadmium coordination polymers, [Cd(bismip)]n (1), {[Cd(bismip)(phen)]·H2O}n (2) and {[Cd2(bismip)2(4,4‧-bipy)]·2H2O}n (3) (H2bismip=5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid, phen=1,10-phenanthroline, 4,4‧-bipy=4,4‧-bipyridine) have been prepared under solvothermal conditions. In 1, the [Cd4(bismip)3] units are jointed by bismip ligands to afford a three-dimensional (3D) architecture. Complex 2 exhibits a 3D supramolecular framework based on the interconnection of 1D chains through hydrogen bonding interactions and π-π packing interactions. 3 is a two-fold interpenetrating 3D architecture with a (4·82)(42·84) Schläfli symbol in which 2D layers are interlinked by 4,4‧-bipy ligands. The diverse structures of compounds 1-3 indicate that the auxiliary ligands have significant effects on the final structures. The photoluminescent properties and photocatalytic properties of these coordination polymers in the solid state were also investigated. Remarkably, 3 shows the wide gap semiconductor nature and exhibit excellent photocatalytic performance.

Predictable Particle Engineering: Programming the Energy Level, Carrier Generation, and Conductivity of Core-Shell Particles.

PubMed

Yuan, Conghui; Wu, Tong; Mao, Jie; Chen, Ting; Li, Yuntong; Li, Min; Xu, Yiting; Zeng, Birong; Luo, Weiang; Yu, Lingke; Zheng, Gaofeng; Dai, Lizong

2018-06-20

Core-shell structures are of particular interest in the development of advanced composite materials as they can efficiently bring different components together at nanoscale. The advantage of this structure greatly relies on the crucial design of both core and shell, thus achieving an intercomponent synergistic effect. In this report, we show that decorating semiconductor nanocrystals with a boronate polymer shell can easily achieve programmable core-shell interactions. Taking ZnO and anatase TiO 2 nanocrystals as inner core examples, the effective core-shell interactions can narrow the band gap of semiconductor nanocrystals, change the HOMO and LUMO levels of boronate polymer shell, and significantly improve the carrier density of core-shell particles. The hole mobility of core-shell particles can be improved by almost 9 orders of magnitude in comparison with net boronate polymer, while the conductivity of core-shell particles is at most 30-fold of nanocrystals. The particle engineering strategy is based on two driving forces: catechol-surface binding and B-N dative bonding and having a high ability to control and predict the shell thickness. Also, this approach is applicable to various inorganic nanoparticles with different components, sizes, and shapes.

Flexible nano-GFO/PVDF piezoelectric-polymer nano-composite films for mechanical energy harvesting

NASA Astrophysics Data System (ADS)

Mishra, Monali; Roy, Amritendu; Dash, Sukalyan; Mukherjee, Somdutta

2018-03-01

Owing to the persistent quest of renewable energy technology, piezoelectric energy harvesters are gathering considerable research interest due to their potential in driving microelectronic devices with small power requirement. Electrical energy (milli to microwatt range) is generated from mechanical counterparts such as vibrations of machines, human motion, flowing water etc. based on the principles of piezoelectricity. Flexible high piezoelectric constant (d33) ceramic/polymer composites are crucial components for fabricating these energy harvesters. The polymer composites composed of gallium ferrite nanoparticles and polyvinylidene fluoride (PVDF) as the matrix have been synthesized by solvent casting method. First, 8 wt. % PVDF was dissolved in DMF and then different compositions of GaFeO3 or GFO (10, 20, 30 wt. %) (with respect to PVDF only) nanocomposites were synthesized. The phase of the synthesized nanocomposites were studied by X- Ray diffraction which shows that with the increase in the GFO concentration, the intensity of diffraction peaks of PVDF steadily decreased and GFO peaks became increasingly sharp. As the concentration of GFO increases in the PVDF polymer matrix, band gap is also increased albeit to a small extent. The maximum measured output voltage and current during mechanical pressing and releasing conditions were found to be ~ 3.5 volt and 4 nA, respectively in 30 wt % GFO-PVDF composite, comparable to the available literature.

Effects of anhydrous AlCl3 dopant on the structural, optical and electrical properties of PVA-PVP polymer composite films

NASA Astrophysics Data System (ADS)

Shanmugam, G.; Krishnakumar, V.

2018-05-01

Polymer composite films based on PVA-PVP with AlCl3 as the dopant at different concentrations were prepared using solution casting technique. XRD patterns reveal the increase in amorphousity of the films with AlCl3 doping. Optical absorption studies exhibit that the values of optical absorption coefficient, direct and indirect optical band gaps are found to decrease with increase in AlCl3 concentration. It confirms the charge transfer in complexes between the polymer and the dopant. The dielectric studies show the increase in dielectric constant at low frequency with increasing AlCl3 concentration and temperature. The ac conductivity and ionic conductivity increase with the AlCl3 content and the maximum value at room temperature is found to be 6.89 × 10-4 and 8.05 × 10-5 S/cm for higher AlCl3 doped PVA-PVP film. The estimated ionic conductivity value is three or four orders of magnitude greater than those obtained in the certain representative polymer-salt complexes as reported earlier. Electrical modulus plots confirm the removal of electrode polarization and the low conductivity relaxation time with Al doping. The activation energy estimated from the temperature dependent dc conductivity plot is agreed well with the migration energy calculated from the temperature dependent electric modulus plot.

Aqueous processing of low-band-gap polymer solar cells using roll-to-roll methods.

PubMed

Andersen, Thomas R; Larsen-Olsen, Thue T; Andreasen, Birgitta; Böttiger, Arvid P L; Carlé, Jon E; Helgesen, Martin; Bundgaard, Eva; Norrman, Kion; Andreasen, Jens W; Jørgensen, Mikkel; Krebs, Frederik C

2011-05-24

Aqueous nanoparticle dispersions of a series of three low-band-gap polymers poly[4,8-bis(2-ethylhexyloxy)benzo(1,2-b:4,5-b')dithiophene-alt-5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)(2,1,3-benzothiadiazole)-5,5'-diyl] (P1), poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] (P2), and poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (P3) were prepared using ultrasonic treatment of a chloroform solution of the polymer and [6,6]-phenyl-C(61)-butyric acid methyl ester ([60]PCBM) mixed with an aqueous solution of sodium dodecylsulphate (SDS). The size of the nanoparticles was established using small-angle X-ray scattering (SAXS) of the aqueous dispersions and by both atomic force microscopy (AFM) and using both grazing incidence SAXS (GISAXS) and grazing incidence wide-angle X-ray scattering (GIWAXS) in the solid state as coated films. The aqueous dispersions were dialyzed to remove excess detergent and concentrated to a solid content of approximately 60 mg mL(-1). The formation of films for solar cells using the aqueous dispersion required the addition of the nonionic detergent FSO-100 at a concentration of 5 mg mL(-1). This enabled slot-die coating of high quality films with a dry thickness of 126 ± 19, 500 ± 25, and 612 ± 22 nm P1, P2, and P3, respectively for polymer solar cells. Large area inverted polymer solar cells were thus prepared based on the aqueous inks. The power conversion efficiency (PCE) reached for each of the materials was 0.07, 0.55, and 0.15% for P1, P2, and P3, respectively. The devices were prepared using coating and printing of all layers including the metal back electrodes. All steps were carried out using roll-to-roll (R2R) slot-die and screen printing methods on flexible substrates. All five layers were processed using environmentally friendly methods and solvents. Two of the layers were processed entirely from water (the electron transport layer and the active layer).

Multi-Scale Simulation of Interfacial Phenomena and Nano-Particle Placement in Polymer Matrix Composites

DTIC Science & Technology

2012-08-01

Molecular Dynamics Simulations Coarse-Grain Particle Dynamics Simulations Local structure; Force field parameterization Extended structure...K) C8H18 C12H26 C16H34 Adhesive forces can cause local density gradients and defects " Pronounced layering of polymer near interfaces...reactive end groups (CnH2n+1S) on Cu Gap SubPc on C60 Pentacene on a-SiO2 Cyclopentene on Au Crystalline CuPc on Al Polyimide on Si

Calculation of longitudinal polarizability and second hyperpolarizability of polyacetylene with the coupled perturbed Hartree-Fock/Kohn-Sham scheme: Where it is shown how finite oligomer chains tend to the infinite periodic polymer

NASA Astrophysics Data System (ADS)

Lacivita, Valentina; Rèrat, Michel; Orlando, Roberto; Ferrero, Mauro; Dovesi, Roberto

2012-03-01

The longitudinal polarizability, αxx, and second hyperpolarizability, γxxxx, of polyacetylene are evaluated by using the coupled perturbed Hartree-Fock/Kohn-Sham (HF/KS) scheme as implemented in the periodic CRYSTAL code and a split valence type basis set. Four different density functionals, namely local density approximation (LDA) (pure local), Perdew-Becke-Ernzerhof (PBE) (gradient corrected), PBE0, and B3LYP (hybrid), and the Hartree-Fock Hamiltonian are compared. It is shown that very tight computational conditions must be used to obtain well converged results, especially for γxxxx, that is, very sensitive to the number of k points in reciprocal space when the band gap is small (as for LDA and PBE), and to the extension of summations of the exact exchange series (HF and hybrids). The band gap in LDA is only 0.01 eV: at least 300 k points are required to obtain well converged total energy and equilibrium geometry, and 1200 for well converged optical properties. Also, the exchange series convergence is related to the band gap. The PBE0 band gap is as small as 1.4 eV and the exchange summation must extend to about 130 Å from the origin cell. Total energy, band gap, equilibrium geometry, polarizability, and second hyperpolarizability of oligomers -(C2H2)m-, with m up to 50 (202 atoms), and of the polymer have been compared. It turns out that oligomers of that length provide an extremely poor representation of the infinite chain polarizability and hyperpolarizability when the gap is smaller than 0.2 eV (that is, for LDA and PBE). Huge differences are observed on αxx and γxxxx of the polymer when different functionals are used, that is in connection to the well-known density functional theory (DFT) overshoot, reported in the literature about short oligomers: for the infinite model the ratio between LDA (or PBE) and HF becomes even more dramatic (about 500 for αxx and 1010 for γxxxx). On the basis of previous systematic comparisons of results obtained with various approaches including DFT, HF, Moller-Plesset (MP2) and coupled cluster for finite chains, we can argue that, for the infinite chain, the present HF results are the most reliable.

Evidence of the charge-density wave state in polypyrrole nanotubes

DOE PAGES

Sarma, Abhisakh; Sanyal, Milan K.; Littlewood, Peter B.

2015-04-13

Here, we present a detailed investigation of the low-frequency dielectric and conductivity properties of conducting polymer nanowires. Our results, obtained by connecting ~10 7 nanowires in parallel, show that these polypyrrole nanowires behave like conventional charge-density wave (CDW) materials, in their nonlinear and dynamic response, together with scaling of relaxation time and conductivity. The observed Arrhenius law for both these quantities gives a CDW gap of 3.5 meV in the regime of temperature (~40 K) in which the CDW state survives. We find good agreement with a theory of weakly pinned CDW, screened by thermally excited carriers across the CDWmore » gap. The identification of polymer nanowires as CDW provides us a model system to investigate charge ordering owing to electrostatic interaction, relevant to a variety of systems from dusty plasma to molecular biology.« less

Tunneling spectroscopy measurements on hydrogen-bonded supramolecular polymers.

PubMed

Vonau, François; Shokri, Roozbeh; Aubel, Dominique; Bouteiller, Laurent; Guskova, Olga; Sommer, Jens-Uwe; Reiter, Günter; Simon, Laurent

2014-07-21

We studied the formation of hydrogen-bonded supramolecular polymers of Ethyl Hexyl Urea Toluene (EHUT) on a gold (111) surface by low temperature scanning tunneling microscopy. Tunneling spectroscopy performed along an individual molecule embedded in a self-assembled layer revealed strong changes in the value of the HOMO-LUMO gap. A variation of the LUMO state is attributed to the effect of space charge accumulation resulting from anisotropic adhesion of the molecule. In addition, for specific tunneling conditions, changes induced through the formation of hydrogen bonds became visible in the differential conductance (dI/dV) maps; isolated molecules, hydrogen bonded dimers and supramolecular polymers of EHUT were distinguishable through their electronic properties.

Tunneling spectroscopy measurements on hydrogen-bonded supramolecular polymers

NASA Astrophysics Data System (ADS)

Vonau, François; Shokri, Roozbeh; Aubel, Dominique; Bouteiller, Laurent; Guskova, Olga; Sommer, Jens-Uwe; Reiter, Günter; Simon, Laurent

2014-06-01

We studied the formation of hydrogen-bonded supramolecular polymers of Ethyl Hexyl Urea Toluene (EHUT) on a gold (111) surface by low temperature scanning tunneling microscopy. Tunneling spectroscopy performed along an individual molecule embedded in a self-assembled layer revealed strong changes in the value of the HOMO-LUMO gap. A variation of the LUMO state is attributed to the effect of space charge accumulation resulting from anisotropic adhesion of the molecule. In addition, for specific tunneling conditions, changes induced through the formation of hydrogen bonds became visible in the differential conductance (dI/dV) maps; isolated molecules, hydrogen bonded dimers and supramolecular polymers of EHUT were distinguishable through their electronic properties.

Structural and optical properties of Ag-doped copper oxide thin films on polyethylene napthalate substrate prepared by low temperature microwave annealing

NASA Astrophysics Data System (ADS)

Das, Sayantan; Alford, T. L.

2013-06-01

Silver doped cupric oxide thin films are prepared on polyethylene naphthalate (flexible polymer) substrates. Thin films Ag-doped CuO are deposited on the substrate by co-sputtering followed by microwave assisted oxidation of the metal films. The low temperature tolerance of the polymer substrates led to the search for innovative low temperature processing techniques. Cupric oxide is a p-type semiconductor with an indirect band gap and is used as selective absorption layer solar cells. X-ray diffraction identifies the CuO phases. Rutherford backscattering spectrometry measurements confirm the stoichiometry of each copper oxide formed. The surface morphology is determined by atomic force microscopy. The microstructural properties such as crystallite size and the microstrain for (-111) and (111) planes are calculated and discussed. Incorporation of Ag led to the lowering of band gap in CuO. Consequently, it is determined that Ag addition has a strong effect on the structural, morphological, surface, and optical properties of CuO grown on flexible substrates by microwave annealing. Tauc's plot is used to determine the optical band gap of CuO and Ag doped CuO films. The values of the indirect and direct band gap for CuO are found to be 2.02 eV and 3.19 eV, respectively.

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

Emelianov, A. V., E-mail: emmsowton@gmail.com; Romashkin, A. V.; Tsarik, K. A.

This study is devoted to the fabrication of molecular semiconductor channels based on polymer molecules with nanoscale electrodes made of single-walled carbon nanotubes. A reproducible technology for forming nanoscale gaps in carbon nanotubes using a focused Ga{sup +} ion beam is proposed. Polyaniline molecules are deposited into nanogaps up to 30 nm wide between nanotubes by electrophoresis from N-methyl-2-pyrrolidone solution. As a result, molecular organic transistors are fabricated, in which the field effect is studied and the molecular-channel mobility is determined as 0.1 cm{sup 2}/(V s) at an on/off current ratio of 5 × 10{sup 2}.

Synthesis of Conjugated Small Molecules and Polymers by a Palladium Catalyzed Cyclopentannulation Strategy: Towards New Organic Semiconductors

NASA Astrophysics Data System (ADS)

Bheemireddy, Sambasiva Reddy

The utility of conjugated small molecules and polymers as organic semiconductors have seen a tremendous growth in research and development in academia as well as industry because of their processability and flexibility advantages in comparison to inorganic semiconductors. The extensive research over the years has produced a large number of p-type (hole conducting) and n-type (electron conducting) semiconductors that can be used to construct organic electronic devices. Of these materials, p-type semiconductors are more established and extensively studied because of the ease of preparation as well as their better general stability in comparison to n-type materials. Despite recent research into the development of n-type materials, fullerene (C60 and C 70) and its derivatives are still the predominant materials used as electron acceptors for OPV applications. By taking advantage of the electron accepting behavior of cyclopenta[hi]aceanthrylene fragment of C70, we have designed and synthesized new materials based on cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs). By using a newly developed palladium catalyzed cyclopentannulation methodology, 1,2,6,7- tetraarylcyclopenta[hi]aceanthrylenes were prepared by treating diarylethynylenes with 9,10-dibromoanthracene. Scholl cyclodehydrogenation was used to close the externally fused aryl groups to provide access to contorted 2,7,13,18- tetraalkoxytetrabenzo[f,h,r,t]rubicenes. The contortion provides access to more soluble materials than their planar counterparts but still ii allows significant pi-pi stacking between molecules. Using a modified palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction, a nonconventional synthesis of CP-PAH embedded ladder polymers was also achieved. These ladder polymers possess broad UV-Vis absorptions and narrow optical gaps of 1.17-1.29 eV. The synthesis of new donor-acceptor copolymers incorporating electron accepting 1,2,6,7- tetra(4-dodecylphenyl)dicyclopenta[cd,jk]pyrene was also achieved. The donor unit was varied between thiophene, bithiophene, and 1,4-diethynyl-2,5-bis((2-octyldodecyl)oxy)-benzene producing polymers with high molecular weights and considerably low band gaps. This newly developed cyclopentannulation method was also used to synthesize a new class of stabilized pentacene derivatives with externally fused five-membered rings. The target compounds were synthesized via chemical manipulation of a partially saturated 6,13-dibromopentacene precursor that can be fully aromatized in a final step via a DDQ mediated dehydrogenation reaction. Photodegradation studies reveal the new 1,2,8,9-tetraphenyldicyclopenta[fg,qr]pentacene derivatives are more photostable than TIPS-pentacene, and possess narrow optical gaps of 1.2 eV. Because anthradithophene (ADT) is more stable than pentacene while maintaining good electronic properties, the synthesis of cyclopentannulated anthradithiophenes (CP-ADTs) was also explored. Synthesis of a highly contorted ADT analogue was achieved by treating 5,11-dibromo-anthradithiophene with 3,3'-dimethoxy,1,1'-diphenyl acetylene under palladium catalyzed cyclopentannulation conditions followed by Scholl cyclodehydrogenation.

Effect of hole injection layer/hole transport layer polymer and device structure on the properties of white OLED.

PubMed

Cho, Ho Young; Park, Eun Jung; Kim, Jin-Hoo; Park, Lee Soon

2008-10-01

Copolymers containing carbazole and aromatic amine unit were synthesized by using Pd-catalyzed polycondensation reaction. The polymers were characterized in terms of their molecular weight and thermal stability and their UV and PL properties in solution and film state. The band gap energy of the polymers was also determined by the UV absorption and HOMO energy level data. The polymers had high HOMO energy level of 5.19-5.25 eV and work function close to that of ITO. The polymers were thus tested as hole injection/transport layer in the white organic light emitting diodes (OLED) by using 4,4'-bis(2,2-diphenyl-ethen-1-yl)diphenyl (DPVBi) as blue emitting material and 5,6,11,12-tetraphenylnaphthacene (Rubrene) as orange emitting dopant. The synthesized polymer, poly bis[6-bromo-N-(2-ethylhexyl)-carbazole-3-yl] was found to be useful as hole injection layer/hole transport layer (HIL/HTL) multifunctional material with high luminance efficiency and stable white color coordinate in the wide range of applied voltage.

Stepwise assembly of a semiconducting coordination polymer [Cd8S(SPh)14(DMF)(bpy)]n and its photodegradation of organic dyes.

PubMed

Xu, Chao; Hedin, Niklas; Shi, Hua-Tian; Xin, ZhiFeng; Zhang, Qian-Feng

2015-04-14

Chalcogenolate clusters can be interlinked with organic linkers into semiconducting coordination polymers with photocatalytic properties. Here, discrete clusters of Cd8S(SPh)14(DMF)3 were interlinked with 4,4'-bipyridine into a one dimensional coordination polymer of [Cd8S(SPh)14(DMF)(bpy)]n with helical chains. A stepwise mechanism for the assembly of the coordination polymer in DMF was revealed by an ex situ dynamic light scattering study. The cluster was electrostatically neutral and showed a penta-supertetrahedral structure. During the assembly each cluster was interlinked with two 4,4'-bipyridine molecules, which replaced the two terminal DMF molecules of the clusters. In their solid-state forms, the cluster and the coordination polymer were semiconductors with wide band gaps of 3.08 and 2.80 ev. They photocatalytically degraded rhodamine B and methylene blue in aqueous solutions. The moderate conditions used for the synthesis could allow for further in situ studies of the reaction-assembly of related clusters and coordination polymers.

Modification of Optical, Structural and Dielectric Properties of MeV Ions Irradiated PS/Cu Nanocomposites.

PubMed

Gavade, Chaitali; Singh, N L; Khanna, P K; Shah, Sunil

2015-12-01

In order to study structural, thermal, optical and dielectric behaviors of composites, the films of Cu/polystyrene nanocomposites were synthesized at different concentrations of Cu-nanoparticles. These polymer nanocomposites were irradiated with carbon (85 MeV) and silicon (120 MeV) ions at different fluences. The samples were characterized using different techniques viz: X-ray diffraction, UV-visible spectroscopy, differential scanning calorimetry, and impedance gain phase analyzer. A noticeable increase in the intensity of X-ray diffraction peaks was observed after irradiation with 120 MeV Si-ions, which may be attributed to radiation-induced cross-linking in polymer. Optical properties like band gap was estimated for pure polymer and nanocomposite films from their optical absorption spectra in the wavelength region 200-800 nm. It was found that the band gap value shifted to lower energy (from 4.38 eV to 3.40 eV) on doping with silver nanoparticles and also upon irradiation. Differential scanning calorimetry analysis revealed an increase in the glass transition temperature upon irradiation, which may be attributed to cross linking of polymer chain due to ion beam irradiation which is also corroborated with XRD analysis. Dependence of dielectric properties on frequency, ions and filler concentration was studied. The results revealed the enhancement in dielectric properties after doping nanoparticles and also upon irradiation. It was observed that the effect of Si-beam is more effectual than the C-beam because of large electronic energy loss of heavy ion.

Controlled conjugated backbone twisting for an increased open-circuit voltage while having a high short-circuit current in poly(hexylthiophene) derivatives.

PubMed

Ko, Sangwon; Hoke, Eric T; Pandey, Laxman; Hong, Sanghyun; Mondal, Rajib; Risko, Chad; Yi, Yuanping; Noriega, Rodrigo; McGehee, Michael D; Brédas, Jean-Luc; Salleo, Alberto; Bao, Zhenan

2012-03-21

Conjugated polymers with nearly planar backbones have been the most commonly investigated materials for organic-based electronic devices. More twisted polymer backbones have been shown to achieve larger open-circuit voltages in solar cells, though with decreased short-circuit current densities. We systematically impose twists within a family of poly(hexylthiophene)s and examine their influence on the performance of polymer:fullerene bulk heterojunction (BHJ) solar cells. A simple chemical modification concerning the number and placement of alkyl side chains along the conjugated backbone is used to control the degree of backbone twisting. Density functional theory calculations were carried out on a series of oligothiophene structures to provide insights on how the sterically induced twisting influences the geometric, electronic, and optical properties. Grazing incidence X-ray scattering measurements were performed to investigate how the thin-film packing structure was affected. The open-circuit voltage and charge-transfer state energy of the polymer:fullerene BHJ solar cells increased substantially with the degree of twist induced within the conjugated backbone--due to an increase in the polymer ionization potential--while the short-circuit current decreased as a result of a larger optical gap and lower hole mobility. A controlled, moderate degree of twist along the poly(3,4-dihexyl-2,2':5',2''-terthiophene) (PDHTT) conjugated backbone led to a 19% enhancement in the open-circuit voltage (0.735 V) vs poly(3-hexylthiophene)-based devices, while similar short-circuit current densities, fill factors, and hole-carrier mobilities were maintained. These factors resulted in a power conversion efficiency of 4.2% for a PDHTT:[6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM) blend solar cell without thermal annealing. This simple approach reveals a molecular design avenue to increase open-circuit voltage while retaining the short-circuit current.

Antimicrobial Synthetic Polymers: An Update on Structure-Activity Relationships.

PubMed

Ergene, Cansu; Palermo, Edmund F

2018-01-01

The rising incidence of antibiotic-resistant infections, combined with a declining number of new antibiotic drug approvals, has generated an alarming therapeutic gap that critically undermines public health. Host Defense Peptides (HDPs), sometimes referred to as "Nature's Antibiotics", are short chain, amphiphilic and cationic peptide sequences found in all multicellular organisms as part of their innate immunity. While there is a vast diversity in terms of HDP sequence and secondary structure, they all seem to share physiochemical characteristics that can be appropriated for macromolecular design by the synthetic polymer chemist. Over the past decade, remarkable progress has been made in the design and synthesis of polymer-based materials that effectively mimic HDP action - broad-spectrum antibacterial potency, rapid bactericidal kinetics, and minimal toxicity to human cells - while offering the additional benefits of low cost, high scalability, and lower propensity to induce resistance, relative to their peptide-based counterparts. A broad range of different macromolecular structures and architectures have been explored in this design space, including polynorbornenes, poly(meth)acrylates, poly(meth)acrylamides, nylon-2 polymers, and polycarbonates, to name a just few. Across all of these diverse chemical categories, the key determinants of antibacterial and hemolytic activity are the same as in HDPs: net cationic charge at neutral pH, well-balanced facial amphiphilicity, and the molecular weight of the compounds. In this review, we focus in particular on recent progress in the polymethacrylate category first pioneered by Kuroda and DeGrado and later modified, expanded upon and rigorously optimized by Kuroda's and many other groups. Key findings and future challenges will be highlighted. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Chlorination of Side Chains: A Strategy for Achieving a High Open Circuit Voltage Over 1.0 V in Benzo[1,2-b:4,5-b']dithiophene-Based Non-Fullerene Solar Cells

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

Chao, Pengjie; Mu, Zhao; Wang, Huan

Here, a benzo[1,2-b:4,5-b']dithiophene-based donor material with chlorine atoms substituted on its side chains, named PBClT, was designed and developed for application in non-fullerene solar cells to enhance the open-circuit voltage ( V oc) without decreasing charge carrier transfer in the corresponding blend films. The results demonstrated that the chlorinated PBClT polymer was an efficient donor in non-fullerene polymer solar cells (PSCs) and exhibited a blue-shifted absorbance, resulting in more complementary light absorption with non-fullerene acceptors, such as ITIC. In addition, the chlorine substitution decreased the HOMO level of PBClT, and as a result, the V oc of the corresponding solarmore » cell increased dramatically to 1.01 V, which is much higher than that of the non-chlorine analog, PTB7-Th, with a V oc of approximately 0.82 V. The 2D-GIWAX results illustrated that the PBClT/ITIC blend film exhibited a “face-on” orientation, which suggested that the chlorine substituents on the side chains favored π-π stacking in the direction perpendicular to the electron flow in photovoltaic devices. Furthermore, the PBClT/ITIC blend film showed a π-π stacking distance of 3.85 Å, which was very close to that of its non-chlorine analog blend film with a distance of approximately 3.74 Å. Based on this result, the introduction of multiple chlorine atoms on the conjugated side chains not only adjusted the energy level of the low-band-gap polymer through the electron withdrawing ability of the chlorine atoms but also subtly avoided obvious morphological changes that could result from strong steric hindrance in the main chain of the polymers. The PBClT/ITIC-based PSCs exhibited a maximum PCE of 8.46% with a V oc of 1.01 V, which is an increase in the PCE of approximately 22% compared to the PTB7-Th-based device based on our parallel experiments.« less

Chlorination of Side Chains: A Strategy for Achieving a High Open Circuit Voltage Over 1.0 V in Benzo[1,2-b:4,5-b']dithiophene-Based Non-Fullerene Solar Cells

DOE PAGES

Chao, Pengjie; Mu, Zhao; Wang, Huan; ...

2018-04-23

Here, a benzo[1,2-b:4,5-b']dithiophene-based donor material with chlorine atoms substituted on its side chains, named PBClT, was designed and developed for application in non-fullerene solar cells to enhance the open-circuit voltage ( V oc) without decreasing charge carrier transfer in the corresponding blend films. The results demonstrated that the chlorinated PBClT polymer was an efficient donor in non-fullerene polymer solar cells (PSCs) and exhibited a blue-shifted absorbance, resulting in more complementary light absorption with non-fullerene acceptors, such as ITIC. In addition, the chlorine substitution decreased the HOMO level of PBClT, and as a result, the V oc of the corresponding solarmore » cell increased dramatically to 1.01 V, which is much higher than that of the non-chlorine analog, PTB7-Th, with a V oc of approximately 0.82 V. The 2D-GIWAX results illustrated that the PBClT/ITIC blend film exhibited a “face-on” orientation, which suggested that the chlorine substituents on the side chains favored π-π stacking in the direction perpendicular to the electron flow in photovoltaic devices. Furthermore, the PBClT/ITIC blend film showed a π-π stacking distance of 3.85 Å, which was very close to that of its non-chlorine analog blend film with a distance of approximately 3.74 Å. Based on this result, the introduction of multiple chlorine atoms on the conjugated side chains not only adjusted the energy level of the low-band-gap polymer through the electron withdrawing ability of the chlorine atoms but also subtly avoided obvious morphological changes that could result from strong steric hindrance in the main chain of the polymers. The PBClT/ITIC-based PSCs exhibited a maximum PCE of 8.46% with a V oc of 1.01 V, which is an increase in the PCE of approximately 22% compared to the PTB7-Th-based device based on our parallel experiments.« less

NovaChip pilot project : Route 5, Waterboro, Brownfield, & Fryeburg.

DOT National Transportation Integrated Search

2011-02-01

In July & August, 2010, MaineDOT conducted experimental applications of NovaChip on 16 miles : of highway in western Maine. Novachip is a proprietary pavement process that applies an ultrathin, : gap-graded, hot mix wearing course over a polymer rich...

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

Yin, Wen-Yu; Zhuang, Guo-Yong; Huang, Zuo-Long

Three cadmium coordination polymers, [Cd(bismip)]{sub n} (1), {[Cd(bismip)(phen)]·H_2O}{sub n} (2) and {[Cd_2(bismip)_2(4,4′-bipy)]·2H_2O}{sub n} (3) (H{sub 2}bismip=5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid, phen=1,10-phenanthroline, 4,4′-bipy=4,4′-bipyridine) have been prepared under solvothermal conditions. In 1, the [Cd{sub 4}(bismip){sub 3}] units are jointed by bismip ligands to afford a three-dimensional (3D) architecture. Complex 2 exhibits a 3D supramolecular framework based on the interconnection of 1D chains through hydrogen bonding interactions and π-π packing interactions. 3 is a two-fold interpenetrating 3D architecture with a (4·8{sup 2})(4{sup 2}·8{sup 4}) Schläfli symbol in which 2D layers are interlinked by 4,4′-bipy ligands. The diverse structures of compounds 1–3 indicate that the auxiliary ligandsmore » have significant effects on the final structures. The photoluminescent properties and photocatalytic properties of these coordination polymers in the solid state were also investigated. Remarkably, 3 shows the wide gap semiconductor nature and exhibit excellent photocatalytic performance. - Graphical abstract: Three cadmium coordination polymers with different architectures based on 5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid have been prepared. Their photoluminescent properties were also investigated. - Highlights: • Three new Cd(II) Cps were synthesized based on H{sub 2}bismip. • Compounds 1 and 3 show 3D networks and 2 exhibits a 1D chain. • Compoud 3 exhibits good catalytic activity of methylene blue photodegradation.« less

Three coordination polymers based on a star-like geometry 4, 4', 4'' -nitrilotribenzoic acid ligand and their framework dependent luminescent properties

NASA Astrophysics Data System (ADS)

Hu, Zhiyong; Zhao, Meng; Su, Jian; Xu, Shasha; Hu, Lei; Liu, Hui; Zhang, Qiong; Zhang, Jun; Wu, Jieying; Tian, Yupeng

2018-02-01

Three novel coordination polymers, [Zn(μ2-HTCA)(Phen)]n (1), {[Cd(μ3-HTCA)(Phen)]·2H2O}n (2), [Mn(μ2-HTCA)(Phen)(H2O)]n (3) were prepared by hydrothermal synthesis from the 4, 4', 4''-nitrilotribenzoicacid (H3TCA) and 1, 10-phenanthroline monohydrate (Phen) with different transition metal salts, which were characterized by elemental analysis, IR spectra, powder and single-crystal X-ray diffraction and thermogravimetric analysis. The photophysical properties of the complexes were investigated by solid-state diffuse reflectance spectra, photoluminescent properties, lifetime and quantum yield. For these complexes, it was found that the band gaps follow the order: 3 ＜ 2 ＜ 1 ＜ 2.80 eV, fluorescence intensity order: 1 ＞ H3TCA ＞ 2 ＞ 3; quantum yield order: H3TCA ＞ 1 ＞ 2 ＞ 3; while the lifetime order: 1 ＞ 2 ＞ H3TCA ＞ 3.

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

NASA Astrophysics Data System (ADS)

Gao, Bowen; Meng, Jing

2018-07-01

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

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

NASA Astrophysics Data System (ADS)

Gao, Bowen; Meng, Jing

2018-04-01

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

Superconducting Vacuum-Gap Crossovers for High Performance Microwave Applications

NASA Technical Reports Server (NTRS)

Denis, Kevin L.; Brown, Ari D.; Chang, Meng-Ping; Hu, Ron; U-Yen, Kongpop; Wollack, Edward J.

2016-01-01

The design and fabrication of low-loss wide-bandwidth superconducting vacuum-gap crossovers for high performance millimeter wave applications are described. In order to reduce ohmic and parasitic losses at millimeter wavelengths a vacuum gap is preferred relative to dielectric spacer. Here, vacuum-gap crossovers were realized by using a sacrificial polymer layer followed by niobium sputter deposition optimized for coating coverage over an underlying niobium signal layer. Both coplanar waveguide and microstrip crossover topologies have been explored in detail. The resulting fabrication process is compatible with a bulk micro-machining process for realizing waveguide coupled detectors, which includes sacrificial wax bonding, and wafer backside deep reactive ion etching for creation of leg isolated silicon membrane structures. Release of the vacuum gap structures along with the wax bonded wafer after DRIE is implemented in the same process step used to complete the detector fabrication. ?

Incorporation of fused tetrathiafulvalenes (TTFs) into polythiophene architectures: varying the electroactive dominance of the TTF species in hybrid systems.

PubMed

Berridge, Rory; Skabara, Peter J; Pozo-Gonzalo, Cristina; Kanibolotsky, Alexander; Lohr, Jan; McDouall, Joseph J W; McInnes, Eric J L; Wolowska, Joanna; Winder, Christoph; Sariciftci, N Serdar; Harrington, Ross W; Clegg, William

2006-02-23

A novel polythienylenevinylene (PTV) and two new polythiophenes (PTs), featuring fused tetrathiafulvalene (TTF) units, have been prepared and characterized by ultraviolet-visible (UV-vis) and electron paramagnetic resonance (EPR) spectroelectrochemistry. All polymers undergo two sequential, reversible oxidation processes in solution. Structures in which the TTF species is directly linked to the polymer backbone (2 and 4) display redox behavior which is dictated by the fulvalene system. Once the TTF is spatially removed from the polymer chain by a nonconjugated link (polymer 3), the electroactivity of both TTF and polythiophene moieties can be detected. Computational studies confirm the delocalization of charge over both electroactive centers (TTF and PT) and the existence of a triplet dication intermediate. PTV 4 has a low band gap (1.44 eV), is soluble in common organic solvents, and is stable under ambient conditions. Organic solar cells of polymer 4:[6,6]-phenyl-C(61) butyric acid methyl ester (PCBM) have been fabricated. Under illumination, a photovoltaic effect is observed with a power conversion efficiency of 0.13% under AM1.5 solar simulated light. The onset of photocurrent at 850 nm is consistent with the onset of the pi-pi absorption band of the polymer. Remarkably, UV-vis spectroelectrochemistry of polymer 4 reveals that the conjugated polymer chain remains unchanged during the oxidation of the polymer.

Crowding-facilitated macromolecular transport in attractive micropost arrays.

PubMed

Chien, Fan-Tso; Lin, Po-Keng; Chien, Wei; Hung, Cheng-Hsiang; Yu, Ming-Hung; Chou, Chia-Fu; Chen, Yeng-Long

2017-05-02

Our study of DNA dynamics in weakly attractive nanofabricated post arrays revealed crowding enhances polymer transport, contrary to hindered transport in repulsive medium. The coupling of DNA diffusion and adsorption to the microposts results in more frequent cross-post hopping and increased long-term diffusivity with increased crowding density. We performed Langevin dynamics simulations and found maximum long-term diffusivity in post arrays with gap sizes comparable to the polymer radius of gyration. We found that macromolecular transport in weakly attractive post arrays is faster than in non-attractive dense medium. Furthermore, we employed hidden Markov analysis to determine the transition of macromolecular adsorption-desorption on posts and hopping between posts. The apparent free energy barriers are comparable to theoretical estimates determined from polymer conformational fluctuations.

Density functional theory investigation of opto-electronic properties of thieno[3,4-b]thiophene and benzodithiophene polymer and derivatives and their applications in solar cell

NASA Astrophysics Data System (ADS)

Khoshkholgh, Mehri Javan; Marsusi, Farah; Abolhassani, Mohammad Reza

2015-02-01

PTBs polymers with thieno[3,4-b]thiophene [TT] and benzodithiophene [BDT] units have particular properties, which demonstrate it as one of the best group of donor materials in organic solar cells. In the present work, density functional theory (DFT) is applied to investigate the optimized structure, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), band gap and dihedral angle of PTB7 at B3LYP/6-31G(d). Two different approaches are applied to carry out these investigations: Oligomer extrapolation technique and periodic boundary condition (PBC) method. The results obtained from PBC-DFT method are in fair agreement with experiments. Based on these reliable outcomes; the investigations continued to perform some derivatives of PTB7. In this study, sulfur is substituted by nitrogen, oxygen, silicon, phosphor or selenium atoms in pristine PTB7. Due to the shift of HOMO and LUMO levels, smaller band gaps are predicted to appear in some derivatives in comparison with PTB7. Maximum theoretical efficiencies, η, of the mentioned derivatives as well as local difference of dipole moments between the ground and excited states (Δμge) are computed. The results indicate that substitution of sulfur by nitrogen or oxygen in BDT unit, and silicon or phosphor in TT unit of pristine PTB7 leads to a higher η as well as Δμge.

Density functional theory investigation of opto-electronic properties of thieno[3,4-b]thiophene and benzodithiophene polymer and derivatives and their applications in solar cell.

PubMed

Khoshkholgh, Mehri Javan; Marsusi, Farah; Abolhassani, Mohammad Reza

2015-02-05

PTBs polymers with thieno[3,4-b]thiophene [TT] and benzodithiophene [BDT] units have particular properties, which demonstrate it as one of the best group of donor materials in organic solar cells. In the present work, density functional theory (DFT) is applied to investigate the optimized structure, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), band gap and dihedral angle of PTB7 at B3LYP/6-31G(d). Two different approaches are applied to carry out these investigations: Oligomer extrapolation technique and periodic boundary condition (PBC) method. The results obtained from PBC-DFT method are in fair agreement with experiments. Based on these reliable outcomes; the investigations continued to perform some derivatives of PTB7. In this study, sulfur is substituted by nitrogen, oxygen, silicon, phosphor or selenium atoms in pristine PTB7. Due to the shift of HOMO and LUMO levels, smaller band gaps are predicted to appear in some derivatives in comparison with PTB7. Maximum theoretical efficiencies, η, of the mentioned derivatives as well as local difference of dipole moments between the ground and excited states (Δμge) are computed. The results indicate that substitution of sulfur by nitrogen or oxygen in BDT unit, and silicon or phosphor in TT unit of pristine PTB7 leads to a higher η as well as Δμge. Copyright © 2014 Elsevier B.V. All rights reserved.

Technical advisory guide (TAG) for bonded wearing course pilot projects.

DOT National Transportation Integrated Search

2003-10-01

A bonded wearing course (BWC) is a gap graded, ultra thin hot-mix asphalt (HMA) mixture applied : over a thick polymer modified asphalt emulsion membrane. The emulsion membrane seals the : existing surface and produces high binder content at the inte...

Construction and performance of ultra thin asphalt friction course

DOT National Transportation Integrated Search

1997-09-01

The Novachip process, also known as ultrathin friction course, was developed in France in 1986. The process utilizes a single piece of equipment to place a thin, gap-graded hot mix asphalt (HMA) onto a relatively thick layer of polymer modified aspha...

Effect of Branched Gap Synthesis Parameters on Mechanical Properties of Rocket Propellants

DTIC Science & Technology

1995-12-01

modulus hydroxyl functionality glycidyl azide polymer hexanetriol hydroxy-terminated polybutadiene isophorone diisocyanate hydroxyl equivalent... hexanetriol (HT), glycerol and polyethylene glycol (PEG) with MW 600. The reaction was carried out with one polyol or a blend of two polyols and

Chlorination of low-band-gap polymers: Toward high-performance polymer solar cells

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

Mo, Daize; Wang, Huan; Chen, Hui

Here, halogenation is an effective way to tune the energy levels of organic semiconducting materials. To date, fluorination of organic semiconducting materials to fabricate polymer solar cells (PSCs) has been used far more than chlorination; however, fluorine exchange reactions suffer from low yields and the resulting fluorinated polymer always comes with higher price, which will greatly hinder their commercial applications. Herein, we designed and synthesized a series of chlorinated donor-acceptor (D-A) type polymers, in which benzo[1,2-b:4,5- b]dithiophene and chlorinated benzothiadiazole units are connected by thiophene π-bridges with an asymmetric alkyl chain. These chlorinated polymers showed deep highest occupied molecular orbitalmore » energy levels, which promoted the efficiency of their corresponding PSCs by increasing the device open circuit voltage. The asymmetric alkyl chain on the thiophene moieties gave the final polymer sufficient solubility for solution processing and strong π-π stacking in films allowed for high mobility. Although the introduction of a large chlorine atom increased the torsion angle of the polymer backbone, the chlorinated polymers maintained high crystallinity and a favorable backbone orientation in the blended films. These factors contributed to respectable device performances from thick-film devices, which showed PCEs as high as 9.11% for a 250 nm-thick active layer. These results demonstrate that chlorination is a promising method to fine tune the energy levels of conjugated polymers, and chlorinated benzothiadiazole may be a versatile building block in materials for efficient solar energy conversion.« less

Chlorination of low-band-gap polymers: Toward high-performance polymer solar cells

DOE PAGES

Mo, Daize; Wang, Huan; Chen, Hui; ...

2017-03-08

Here, halogenation is an effective way to tune the energy levels of organic semiconducting materials. To date, fluorination of organic semiconducting materials to fabricate polymer solar cells (PSCs) has been used far more than chlorination; however, fluorine exchange reactions suffer from low yields and the resulting fluorinated polymer always comes with higher price, which will greatly hinder their commercial applications. Herein, we designed and synthesized a series of chlorinated donor-acceptor (D-A) type polymers, in which benzo[1,2-b:4,5- b]dithiophene and chlorinated benzothiadiazole units are connected by thiophene π-bridges with an asymmetric alkyl chain. These chlorinated polymers showed deep highest occupied molecular orbitalmore » energy levels, which promoted the efficiency of their corresponding PSCs by increasing the device open circuit voltage. The asymmetric alkyl chain on the thiophene moieties gave the final polymer sufficient solubility for solution processing and strong π-π stacking in films allowed for high mobility. Although the introduction of a large chlorine atom increased the torsion angle of the polymer backbone, the chlorinated polymers maintained high crystallinity and a favorable backbone orientation in the blended films. These factors contributed to respectable device performances from thick-film devices, which showed PCEs as high as 9.11% for a 250 nm-thick active layer. These results demonstrate that chlorination is a promising method to fine tune the energy levels of conjugated polymers, and chlorinated benzothiadiazole may be a versatile building block in materials for efficient solar energy conversion.« less

Developing Customized Dental Miniscrew Surgical Template from Thermoplastic Polymer Material Using Image Superimposition, CAD System, and 3D Printing

PubMed Central

Yu, Jian-Hong; Lo, Lun-Jou; Hsu, Pin-Hsin

2017-01-01

This study integrates cone-beam computed tomography (CBCT)/laser scan image superposition, computer-aided design (CAD), and 3D printing (3DP) to develop a technology for producing customized dental (orthodontic) miniscrew surgical templates using polymer material. Maxillary bone solid models with the bone and teeth reconstructed using CBCT images and teeth and mucosa outer profile acquired using laser scanning were superimposed to allow miniscrew visual insertion planning and permit surgical template fabrication. The customized surgical template CAD model was fabricated offset based on the teeth/mucosa/bracket contour profiles in the superimposition model and exported to duplicate the plastic template using the 3DP technique and polymer material. An anterior retraction and intrusion clinical test for the maxillary canines/incisors showed that two miniscrews were placed safely and did not produce inflammation or other discomfort symptoms one week after surgery. The fitness between the mucosa and template indicated that the average gap sizes were found smaller than 0.5 mm and confirmed that the surgical template presented good holding power and well-fitting adaption. This study addressed integrating CBCT and laser scan image superposition; CAD and 3DP techniques can be applied to fabricate an accurate customized surgical template for dental orthodontic miniscrews. PMID:28280726

Morphological and physicochemical properties of dip-coated poly {(2,5-diyl pyrrole) [4-nitrobenzylidène]} (PPNB) thin films: towards photovoltaic applications

NASA Astrophysics Data System (ADS)

Mouchaal, Younes; Gherrass, Hamou; Bendoukha Reguig, Abdelkarim; Hachemaoui, Aïcha; Yahiaoui, Ahmed; Makha, Mohamed; Khelil, Abdelbacet; Bernede, Jean-Christian

2015-02-01

A new material: conjugated poly {(2,5-diyl pyrrole) [4-nitrobenzylidène]}, that we called (PPNB), has been synthesized and characterized. The cyclic voltammetry has been used in order to estimate first oxidation (Ep) and reduction (En) potentials of our polymer. These values have been assigned, respectively, to the position of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) and determination of the energy band gap which have been estimated to be 6.16, 3.89 and 2.27 eV respectively. Energy levels values of the HOMO and LUMO of the PPNB polymeric donor material were evaluated and the results are compatible with an electron transfer to C60 within an eventual junction, such values show that PPNB could be probed for applications in organic solar cells as donor material. PPNB Thin films have been deposited by dip-coating technique from Dichloromethane solvent with different polymer concentrations, and a dipping speed of 3.0 cm/min. For morphological characterization of the films scanning electron microscopy (SEM) was carried out. The samples, when observed by SEM, reveals that the films deposited are less dense, uniform. Cross-sectional SEM micrographs PPNB films show that thickness of the layers is homogeneous and has value of 35-40 nm. Optical characteristics of the polymer thin films were studied using UV-vis spectroscopy; absorption of wide range of wavelengths from 350 to 700 nm was observed. The optical band gap energy ranges between 1.9 eV and 1.94 eV. Based on these analyzes we realized heterojunction organic solar cells with the structure: ITO/Au/PPNB/C60/BCP/Al, the cells had a photovoltaique effect after J-V measuring, however the efficiency of photo generation under AM1.5 illumination was weak (about 0.02%) and needs to be improved.

Transient response of nonlinear polymer networks: A kinetic theory

NASA Astrophysics Data System (ADS)

Vernerey, Franck J.

2018-06-01

Dynamic networks are found in a majority of natural materials, but also in engineering materials, such as entangled polymers and physically cross-linked gels. Owing to their transient bond dynamics, these networks display a rich class of behaviors, from elasticity, rheology, self-healing, or growth. Although classical theories in rheology and mechanics have enabled us to characterize these materials, there is still a gap in our understanding on how individuals (i.e., the mechanics of each building blocks and its connection with others) affect the emerging response of the network. In this work, we introduce an alternative way to think about these networks from a statistical point of view. More specifically, a network is seen as a collection of individual polymer chains connected by weak bonds that can associate and dissociate over time. From the knowledge of these individual chains (elasticity, transient attachment, and detachment events), we construct a statistical description of the population and derive an evolution equation of their distribution based on applied deformation and their local interactions. We specifically concentrate on nonlinear elastic response that follows from the strain stiffening response of individual chains of finite size. Upon appropriate averaging operations and using a mean field approximation, we show that the distribution can be replaced by a so-called chain distribution tensor that is used to determine important macroscopic measures such as stress, energy storage and dissipation in the network. Prediction of the kinetic theory are then explored against known experimental measurement of polymer responses under uniaxial loading. It is found that even under the simplest assumptions of force-independent chain kinetics, the model is able to reproduce complex time-dependent behaviors of rubber and self-healing supramolecular polymers.

Calculation of longitudinal polarizability and second hyperpolarizability of polyacetylene with the coupled perturbed Hartree-Fock/Kohn-Sham scheme: where it is shown how finite oligomer chains tend to the infinite periodic polymer.

PubMed

Lacivita, Valentina; Rèrat, Michel; Orlando, Roberto; Ferrero, Mauro; Dovesi, Roberto

2012-03-21

The longitudinal polarizability, α(xx), and second hyperpolarizability, γ(xxxx), of polyacetylene are evaluated by using the coupled perturbed Hartree-Fock/Kohn-Sham (HF/KS) scheme as implemented in the periodic CRYSTAL code and a split valence type basis set. Four different density functionals, namely local density approximation (LDA) (pure local), Perdew-Becke-Ernzerhof (PBE) (gradient corrected), PBE0, and B3LYP (hybrid), and the Hartree-Fock Hamiltonian are compared. It is shown that very tight computational conditions must be used to obtain well converged results, especially for γ(xxxx), that is, very sensitive to the number of k(->) points in reciprocal space when the band gap is small (as for LDA and PBE), and to the extension of summations of the exact exchange series (HF and hybrids). The band gap in LDA is only 0.01 eV: at least 300 k(->) points are required to obtain well converged total energy and equilibrium geometry, and 1200 for well converged optical properties. Also, the exchange series convergence is related to the band gap. The PBE0 band gap is as small as 1.4 eV and the exchange summation must extend to about 130 Å from the origin cell. Total energy, band gap, equilibrium geometry, polarizability, and second hyperpolarizability of oligomers -(C(2)H(2))(m)-, with m up to 50 (202 atoms), and of the polymer have been compared. It turns out that oligomers of that length provide an extremely poor representation of the infinite chain polarizability and hyperpolarizability when the gap is smaller than 0.2 eV (that is, for LDA and PBE). Huge differences are observed on α(xx) and γ(xxxx) of the polymer when different functionals are used, that is in connection to the well-known density functional theory (DFT) overshoot, reported in the literature about short oligomers: for the infinite model the ratio between LDA (or PBE) and HF becomes even more dramatic (about 500 for α(xx) and 10(10) for γ(xxxx)). On the basis of previous systematic comparisons of results obtained with various approaches including DFT, HF, Moller-Plesset (MP2) and coupled cluster for finite chains, we can argue that, for the infinite chain, the present HF results are the most reliable. © 2012 American Institute of Physics

Giant Stark effect in double-stranded porphyrin ladder polymers

NASA Astrophysics Data System (ADS)

Pramanik, Anup; Kang, Hong Seok

2011-03-01

Using the first-principles calculations, we have investigated the stability and the electronic structure of two types of recently synthesized one-dimensional nanoribbons, i.e., double-stranded zinc(II) porphyrin ladder polymer (LADDER) arrays. First, electronic structure calculations were used to show that the LADDER is a semiconductor. Most importantly, the application of a transverse electric field significantly reduces the band gap of the LADDER, ultimately converting the LADDER to a metal at a field strength of 0.1 V/Å. The giant Stark effect in this case is almost as strong as that in boron nitride nanotubes and nanoribbons. In the presence of an electric field, hole conduction and electronic conduction will occur entirely through spatially separated strands, rendering these materials useful for nanoelectronic devices. Second, the substitution of hydrogen atoms in the porphyrin units or that of zinc ions with other kinds of chemical species is found to increase the binding strength of the LADDER and reduce the band gap.

Modification of polymer velvet cathode via metallic Mo coating for enhancement of high-current electron emission performances

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

Xiong, Ying; Wang, Bing; Yi, Yong

2013-09-15

The effect of surface Mo coating on the high-current electron emission performances for polymer velvet cathode has been investigated in a diode with A-K gap of 11.5 cm by the combination of time-resolved electrical diagnostic and temporal pressure variation. Compared with uncoated polymer velvet cathode under the single-pulsed emission mode, the Mo-coated one shows lower outgassing levels (∼0.40 Pa L), slower cathode plasma expansion velocity (∼2.30 cm/μs), and higher emission stability as evidences by the change in cathode current, temporal pressure variation, and diode perveance. Moreover, after Mo coating, the emission consistency of the polymer velvet cathode between two adjacentmore » pulses is significantly improved in double-pulsed emission mode with ∼500 ns interval between two pulses, which further confirms the effectiveness of Mo coating for enhancement of electron emission performance of polymer velvet cathodes. These results should be of interest to the high-repetitive high-power microwave systems with cold cathodes.« less

On compression and damage evolution in two thermoplastics

PubMed Central

Garcea, S. C.; Eastwood, D. S.; Parry, S.; Rau, C.; Withers, P. J.; McDonald, S. A.; Brown, E. N.

2017-01-01

The well-known Taylor cylinder impact test, which follows the impact of a flat-ended cylindrical rod onto a rigid stationary anvil, is conducted over a range of impact speeds for two polymers, polytetrafluoroethylene (PTFE) and polyetheretherketone (PEEK). In previous work, experiments and a model were developed to capture the deformation behaviour of the cylinder after impact. These works showed a region in which spatial and temporal variation of both longitudinal and radial deformation provided evidence of changes in phase within the material. In this further series of experiments, this region is imaged in a range of impacted targets at the Diamond synchrotron. Further techniques were fielded to resolve compressed regions within the recovered polymer cylinders that showed a fracture zone in the impact region. The combination of macroscopic high-speed photography and three-dimensional X-ray imaging has identified the development of failure with these polymers and shown that there is no abrupt transition in behaviours but rather a continuous range of responses to competing operating mechanisms. The behaviours noted in PEEK in these polymers show critical gaps in understanding of polymer high strain-rate response. PMID:28265185

Luminol modified polycarbazole and poly(o-anisidine): Theoretical insights compared with experimental data.

PubMed

Jadoun, Sapana; Verma, Anurakshee; Riaz, Ufana

2018-06-07

With the aim to explore the effect of luminol as a multifunctional dopant for conjugated polymers, the present study reports the ultrasound-assisted doping of polycarbazole (PCz) and poly(o-anisidine) (PAnis) with luminol in basic, acidic and neutral media. The synthesized homopolymers and luminol doped polymers were characterized using FT-IR, UV-visible and XRD studies while the photo-physical properties were investigated via fluorescence spectroscopy. Density functional theory (DFT) calculations were performed to get insights into the structural, optical, and electronic properties of homopolymers of polycarbazole (PCz) and poly(o-anisidine) (PAnis). Vibrational bands B3LYP/6-311G (d,p) level, UV-vis spectral bands and electronic properties such as ionization potentials (IP), electron affinities (EA) and HOMO-LUMO band gap energies of the homopolymers and doped polymers were calculated and compared. Results revealed that luminol doped polymers showed different photo-physical characteristics in acidic, basic and neutral media which could be tuned to obtain near infrared (NIR) emitting polymers. Copyright © 2018 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

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

Electrically induced formation of uncapped, hollow polymeric microstructures

NASA Astrophysics Data System (ADS)

Lee, Sung Hun; Kim, Pilnam; Jeong, Hoon Eui; Suh, Kahp Y.

2006-11-01

Uncapped, hollow polymeric microstructures were fabricated on a silicon substrate using electric field induced stretching and detachment. Initially, square or cylinder microposts were generated using a solvent-assisted capillary molding technique, and a featureless electrode mask was positioned on the top of the microstructure with spacers maintaining an air gap (~20 µm). Upon exposure to an external electric field (1.0-3.0 V µm-1), the hollow microstructures were destabilized and stretched by the well-known electrohydrodynamic instability, resulting in contact of the top polymer surface with the mask. Subsequently, detachment of the capping layer occurred upon removal of the mask due to larger adhesion forces at the polymer/mask interface than cohesion forces of the polymer. These hollow microstructures were tested to capture the budding yeast, Saccharomyces cerevisiae, for shear protection.

Empirically based device modeling of bulk heterojunction organic photovoltaics

NASA Astrophysics Data System (ADS)

Pierre, Adrien; Lu, Shaofeng; Howard, Ian A.; Facchetti, Antonio; Arias, Ana Claudia

2013-10-01

An empirically based, open source, optoelectronic model is constructed to accurately simulate organic photovoltaic (OPV) devices. Bulk heterojunction OPV devices based on a new low band gap dithienothiophene- diketopyrrolopyrrole donor polymer (P(TBT-DPP)) are blended with PC70BM and processed under various conditions, with efficiencies up to 4.7%. The mobilities of electrons and holes, bimolecular recombination coefficients, exciton quenching efficiencies in donor and acceptor domains and optical constants of these devices are measured and input into the simulator to yield photocurrent with less than 7% error. The results from this model not only show carrier activity in the active layer but also elucidate new routes of device optimization by varying donor-acceptor composition as a function of position. Sets of high and low performance devices are investigated and compared side-by-side.

ReaDDy - A Software for Particle-Based Reaction-Diffusion Dynamics in Crowded Cellular Environments

PubMed Central

Schöneberg, Johannes; Noé, Frank

2013-01-01

We introduce the software package ReaDDy for simulation of detailed spatiotemporal mechanisms of dynamical processes in the cell, based on reaction-diffusion dynamics with particle resolution. In contrast to other particle-based reaction kinetics programs, ReaDDy supports particle interaction potentials. This permits effects such as space exclusion, molecular crowding and aggregation to be modeled. The biomolecules simulated can be represented as a sphere, or as a more complex geometry such as a domain structure or polymer chain. ReaDDy bridges the gap between small-scale but highly detailed molecular dynamics or Brownian dynamics simulations and large-scale but little-detailed reaction kinetics simulations. ReaDDy has a modular design that enables the exchange of the computing core by efficient platform-specific implementations or dynamical models that are different from Brownian dynamics. PMID:24040218

Study of flowability effect on self-planarization performance at SOC materials

NASA Astrophysics Data System (ADS)

Yun, Huichan; Kim, Jinhyung; Park, Youjung; Kim, Yoona; Jeong, Seulgi; Baek, Jaeyeol; Yoon, Byeri; Lim, Sanghak

2017-03-01

For multilayer process, importance of carbon-based spin-on hardmask material that replaces amorphous carbon layer (ACL) is ever increasing. Carbon-based spin-on hardmask is an organic polymer with high carbon content formulated in organic solvents for spin-coating application that is cured through baking. In comparison to CVD process for ACL, carbon-based spin-on hardmask material can offer several benefits: lower cost of ownership (CoO) and improved process time, as well as better gap-fill and planarization performances. Thus carbon-based spin-on hardmask material of high etch resistance, good gap-fill properties and global planarization performances over various pattern topographies are desired to achieve the fine patterning and high aspect ratio (A/R). In particular, good level of global planarization of spin coated layer over the underlying pattern topographies is important for self-aligned double patterning (SADP) process as it dictates the photolithographic margin. Herein, we report a copolymer carbon-based spin-on hardmask resin formulation that exhibits favorable film shrinkage profile and good etch resistance properties. By combining the favorable characteristics of each resin - one resin with good shrinkage property and the other with excellent etch resistance into the copolymer, it was possible to achieve a carbonbased spin-on hardmask formulation with desirable level of etch resistance and the planarization performances across various underlying substrate pattern topographies.

Molecular Approach to Conjugated Polymers with Biomimetic Properties.

PubMed

Baek, Paul; Voorhaar, Lenny; Barker, David; Travas-Sejdic, Jadranka

2018-06-13

The field of bioelectronics involves the fascinating interplay between biology and human-made electronics. Applications such as tissue engineering, biosensing, drug delivery, and wearable electronics require biomimetic materials that can translate the physiological and chemical processes of biological systems, such as organs, tissues. and cells, into electrical signals and vice versa. However, the difference in the physical nature of soft biological elements and rigid electronic materials calls for new conductive or electroactive materials with added biomimetic properties that can bridge the gap. Soft electronics that utilize organic materials, such as conjugated polymers, can bring many important features to bioelectronics. Among the many advantages of conjugated polymers, the ability to modulate the biocompatibility, solubility, functionality, and mechanical properties through side chain engineering can alleviate the issues of mechanical mismatch and provide better interface between the electronics and biological elements. Additionally, conjugated polymers, being both ionically and electrically conductive through reversible doping processes provide means for direct sensing and stimulation of biological processes in cells, tissues, and organs. In this Account, we focus on our recent progress in molecular engineering of conjugated polymers with tunable biomimetic properties, such as biocompatibility, responsiveness, stretchability, self-healing, and adhesion. Our approach is general and versatile, which is based on functionalization of conjugated polymers with long side chains, commonly polymeric or biomolecules. Applications for such materials are wide-ranging, where we have demonstrated conductive, stimuli-responsive antifouling, and cell adhesive biointerfaces that can respond to external stimuli such as temperature, salt concentration, and redox reactions, the processes that in turn modify and reversibly switch the surface properties. Furthermore, utilizing the advantageous chemical, physical, mechanical and functional properties of the grafts, we progressed into grafting of the long side chains onto conjugated polymers in solution, with the vision of synthesizing solution-processable conjugated graft copolymers with biomimetic functionalities. Examples of the developed materials to date include rubbery and adhesive photoluminescent plastics, biomolecule-functionalized electrospun biosensors, thermally and dually responsive photoluminescent conjugated polymers, and tunable self-healing, adhesive, and stretchable strain sensors, advanced functional biocidal polymers, and filtration membranes. As outlined in these examples, the applications of these biomimetic, conjugated polymers are still in the development stage toward truly printable, organic bioelectronic devices. However, in this Account, we advocate that molecular engineering of conjugated polymers is an attractive approach to a versatile class of organic electronics with both ionic and electrical conductivity as well as mechanical properties required for next-generation bioelectronics.

Bimolecular crystals with an intercalated structure improve poly(p-phenylenevinylene)-based organic photovoltaic cells.

PubMed

Lim, Kyung-Geun; Park, Jun-Mo; Mangold, Hannah; Laquai, Frédéric; Choi, Tae-Lim; Lee, Tae-Woo

2015-01-01

The exciton dissociation, recombination, and charge transport of bulk heterojunction organic photovoltaic cells (OPVs) is influenced strongly by the nanomorphology of the blend, such as the grain size and the molecular packing. Although it is well known that polymers based on amorphous poly(p-phenylenevinylene) (PPV) have a fundamental limit to their efficiency because of low carrier mobility, which leads to increased recombination and unbalanced charge extraction, herein, we demonstrate that the issue can be overcome by forming bimolecular crystals of an amorphous PPV-based polymer:phenyl-C61 -butyric acid methyl ester (PCBM) intercalated structure. We used amorphous poly(2,5-dioctyloxy-p-phenylene vinylene-alt-2',5'-thienylene vinylene) (PPVTV), which has a simple chemical structure. A reasonably high power conversion efficiency (∼3.5 %) was obtained, although the material has an intrinsically amorphous structure and a relatively large band gap (2.0 eV). We demonstrate a correlation between a well-ordered bimolecular crystal of PPVTV:PCBM and an improved hole mobility of a PPVTV:PCBM film compared to a pristine PPVTV film by using 2 D grazing incidence XRD and space-charge-limited current measurements. Furthermore, we show that the bimolecular crystal structure in high-performance OPVs is related to an optimum molecular packing, which is influenced by the PPVTV:PCBM blending ratio, side-chain length, and molecular weight of the PPVTV polymer. Improved charge transport in PPVTV:PCBM bimolecular crystals leads to a fast sweep out of charges and thus suppression of nongeminate recombination under the operating conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal tuning the reversible optical band gap of self-assembled polystyrene photonic crystals

NASA Astrophysics Data System (ADS)

Vakili Tahami, S. H.; Pourmahdian, S.; Shirkavand Hadavand, B.; Azizi, Z. S.; Tehranchi, M. M.

2016-11-01

Nano-sized polymeric colloidal particles could undergo self-organization into three-dimensional structures to produce desired optical properties. In this research, a facile emulsifier-free emulsion polymerization method was employed to synthesize highly mono-disperse sub-micron polystyrene colloids. A high quality photonic crystal (PhC) structure was prepared by colloidal polystyrene. The reversible thermal tuning effect on photonic band gap position as well as the attenuation of the band gap was investigated in detail. The position of PBG can be tuned from 420 nm to 400 nm by varying the temperature of the PhC structure, reversibly. This reversible effect provides a reconfigurable PhC structure which could be used as thermo-responsive shape memory polymers.

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

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

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

2014-05-07

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

Textural analyses of carbon fiber materials by 2D-FFT of complex images obtained by high frequency eddy current imaging (HF-ECI)

NASA Astrophysics Data System (ADS)

Schulze, Martin H.; Heuer, Henning

2012-04-01

Carbon fiber based materials are used in many lightweight applications in aeronautical, automotive, machine and civil engineering application. By the increasing automation in the production process of CFRP laminates a manual optical inspection of each resin transfer molding (RTM) layer is not practicable. Due to the limitation to surface inspection, the quality parameters of multilayer 3 dimensional materials cannot be observed by optical systems. The Imaging Eddy- Current (EC) NDT is the only suitable inspection method for non-resin materials in the textile state that allows an inspection of surface and hidden layers in parallel. The HF-ECI method has the capability to measure layer displacements (misaligned angle orientations) and gap sizes in a multilayer carbon fiber structure. EC technique uses the variation of the electrical conductivity of carbon based materials to obtain material properties. Beside the determination of textural parameters like layer orientation and gap sizes between rovings, the detection of foreign polymer particles, fuzzy balls or visualization of undulations can be done by the method. For all of these typical parameters an imaging classification process chain based on a high resolving directional ECimaging device named EddyCus® MPECS and a 2D-FFT with adapted preprocessing algorithms are developed.

Synthesis, characterization and optical studies of conjugated Schiff base polymer containing thieno[3,2-b]thiophene and 1,2,4-triazole groups

NASA Astrophysics Data System (ADS)

Cetin, Adnan; Korkmaz, Adem; Kaya, Esin

2018-02-01

A conjugated polyschiff base (poly(N-thieno[3,2-b]thiophen-2-yl)methylene)-1H-1,2,4-triazol-5-amine) poly(TTMA)) was synthesized by condensation polymerization between thieno[3,2-b]thiophene-2,5-dicarboxaldehyde and 3,5-diamino-1,2,4-triazole. The poly(TTMA) was characterized by FT-IR, 1H NMR, 13C NMR spectra and thermal analysis. The number average molecular weight (Mn) and polydispersity index of the poly(TTMA) were determined by gel permeation chromatography (GPC). In addition, the optical properties of the poly(TTMA) solutions were investigated at different molarities. The band gap Eg value of the poly(TTMA) decreased with the increasing molarity. The absorption band edge values of the poly(TTMA) decreased as the molarity increased. The average transmittance values of the poly(TTMA) increased with the increasing molarity and the highest values of molar extinction coefficient also were found in the near ultraviolet region. Its values decreased with the increasing molarity. These results showed that the poly(TTMA) can be used for the fabrication of many optoelectronic devices due to its suitable optical properties and low optical band gap.

Nano-Gap Embedded Plasmonic Gratings for Surface Plasmon Enhanced Fluorescence

NASA Astrophysics Data System (ADS)

Bhatnagar, Kunal; Bok, Sangho; Korampally, Venumadhav; Gangopadhyay, Shubhra

2012-02-01

Plasmonic nanostructures have been extensively used in the past few decades for applications in sub-wavelength optics, data storage, optoelectronic circuits, microscopy and bio-photonics. The enhanced electromagnetic field produced at the metal/dielectric interface by the excitation of surface plasmons via incident radiation can be used for signal enhancement in fluorescence and surface enhanced Raman scattering studies. Novel plasmonic structures on the sub wavelength scale have been shown to provide very efficient and extreme light concentration at the nano-scale. The enhanced electric field produced within a few hundred nanometers of these structures can be used to excite fluorophores in the surrounding environment. Fluorescence based bio-detection and bio-imaging are two of the most important tools in the life sciences. Improving the qualities and capabilities of fluorescence based detectors and imaging equipment has been a big challenge to the industry manufacturers. We report the novel fabrication of nano-gap embedded periodic grating substrates on the nanoscale using micro-contact printing and polymethylsilsesquioxane (PMSSQ) polymer. Fluorescence enhancement of up to 118 times was observed with these silver nanostructures in conjugation with Rhodamine-590 fluorescent dye. These substrates are ideal candidates for low-level fluorescence detection and single molecule imaging.

Organic Solar Cells: Degradation Processes and Approaches to Enhance Performance

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

Fungura, Fadzai

2016-12-17

Intrinsic photodegradation of organic solar cells, theoretically attributed to C-H bond rearrangement/breaking, remains a key commercialization barrier. This work presents, via dark electron paramagnetic resonance (EPR), the first experimental evidence for metastable C dangling bonds (DBs) (g=2.0029±0.0004) formed by blue/UV irradiation of polymer:fullerene blend films in nitrogen. The DB density increased with irradiation and decreased ~4 fold after 2 weeks in the dark. The dark EPR also showed increased densities of other spin-active sites in photodegraded polymer, fullerene, and polymer:fullerene blend films, consistent with broad electronic measurements of fundamental properties, including defect/gap state densities. The EPR enabled identification of defectmore » states, whether in the polymer, fullerene, or at the donor/acceptor (D/A) interface. Importantly, the EPR results indicate that the DBs are at the D/A interface, as they were present only in the blend films. The role of polarons in interface DB formation is also discussed.« less

Characterization, liquid crystalline behavior, electrochemical and optoelectrical properties of new poly(azomethine)s and a poly(imide) with siloxane linkages

NASA Astrophysics Data System (ADS)

Iwan, Agnieszka; Schab-Balcerzak, Ewa; Pociecha, Damian; Krompiec, Michal; Grucela, Marzena; Bilski, Pawel; Kłosowski, Mariusz; Janeczek, Henryk

2011-11-01

New siloxane-containing poly(azomethine)s and a six-membered poly(imide) have been developed from siloxane-containing diamine with four different dialdehydes and 3,4,9,10-perylenetetracarboxylic dianhydride, and their thermotropic behavior, optoelectrical and electrochemical properties were examined. Mesomorphic behavior of the polymers was investigated via differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (WAXRD, SAXRD) studies. The electrochemical behavior of poly(azomethine)s and poly(imide) was studied by differential pulse voltammetry (DPV). The HOMO levels of these polymers were in the range of -5.13 to -5.90 eV. UV-vis properties of the polymers were investigated in solid state as thin films and in chloroform solution. Optical energy band gap ( Egopt.) was calculated from absorption spectra and absorption coefficients α. The photoluminescence properties (PL) of obtained polymers were studied in chloroform solution. The investigated poly(azomethine)s emitted blue light, while the poly(imide) emitted green light. The polymers were irradiated with a test dose of 1 Gy Co-60 gamma-rays to detect their thermoluminescence properties in the temperature range of 50-200 °C. Polymer monolayer (ITO/polymer/Al) and bulk heterojunction (BHJ) (ITO/polymer:PCBM/Al and ITO/PEDOT:PSS/polymer:PCBM/Al) devices were prepared with PAZ and PI used as active layers and I- U curves were measured in the dark and during irradiation with light (under illumination of 1000 W/m 2). Poly(azomethine)s were blended with [6,6]-phenyl C 61 butyric acid methyl ester (PCBM). Selected properties of the investigated polymers with siloxane linkages were compared with the polymers ( PAZ1a- PAZ3a, PIa) prepared from the same dialdehydes or dianhydride and poly(1,4-butanediol)bis(4-aminobenzoate).

A study of optical, mechanical and electrical properties of poly(methacrylic acid)/TiO2 nanocomposite

NASA Astrophysics Data System (ADS)

AL-Baradi, Ateyyah M.; Al-Shehri, Samar F.; Badawi, Ali; Merazga, Amar; Atta, A. A.

2018-06-01

This work is concerned with the study of the effect of titanium dioxide (TiO2) nanofillers on the optical, mechanical and electrical properties of poly(methacrylic acid) (PMAA) networks as a function of TiO2 concentration and crosslink density. The structure of the prepared samples was investigated by X-ray diffractometry (XRD) and Transmittance Electron Microscope (TEM). XRD results showed a single phase for the nanocomposites indicating that no large TiO2 aggregates in the polymer matrix. The optical properties of the prepared samples including the absorption, transmittance, energy band gap and refractive index were explored using Spectrophotometer. These measurements showed that there is a red-shift in the absorption caused by the increase of TiO2 concentration. However, the crosslink density in the polymer plays no role in changing the absorption. The energy band gap (Eg) decreases with increasing the concentration of TiO2 in the polymer matrix; whereas Eg increases with increasing the crosslink density. Moreover, the mechanical properties of PMAA/TiO2 nanocomposites by Dynamic Mechanical Analysis (DMA) showed that the viscoelasticity of PMAA decreases with adding TiO2 nanoparticles and the glass transition temperature (Tg) was also found to drop from 130 °C to 114 °C. Finally, the DC conductivity of the obtained systems was found to increase with increasing TiO2 nanoparticles in the matrix.

Manufacturing of polymer optical waveguides using self-assembly effect on pre-conditioned 3D-thermoformed flexible substrates

NASA Astrophysics Data System (ADS)

Hoffmann, Gerd-Albert; Wolfer, Tim; Zeitler, Jochen; Franke, Jörg; Suttmann, Oliver; Overmeyer, Ludger

2017-02-01

Optical data communication is increasingly interesting for many applications in industrial processes. Therefore mass production is required to meet the requested price and lot sizes. Polymer optical waveguides show great promises to comply with price requirements while providing sufficient optical quality for short range data transmission. A high efficient fabrication technology using polymer materials could be able to create the essential backbone for 3D-optical data transmission in the future. The approach for high efficient fabrication technology of micro optics described in this paper is based on a self-assembly effect of fluids on preconditioned 3D-thermoformed polymer foils. Adjusting the surface energy on certain areas on the flexible substrate by flexographic printing mechanism is presented in this paper. With this technique conditioning lines made of silicone containing UV-varnish are printed on top of the foils and create gaps with the exposed substrate material in between. Subsequent fabrication processes are selected whether the preconditioned foil is coated with acrylate containing waveguide material prior or after the thermoforming process. Due to the different surface energy this material tends to dewet from the conditioning lines. It acts like regional barriers and sets the width of the arising waveguides. With this fabrication technology it is possible to produce multiple waveguides with a single coating process. The relevant printing process parameters that affect the quality of the generated waveguides are discussed and results of the produced waveguides with width ranging from 10 to 300 μm are shown.

Polymorphism and electronic structure of polyimine and its potential significance for prebiotic chemistry on Titan.

PubMed

Rahm, Martin; Lunine, Jonathan I; Usher, David A; Shalloway, David

2016-07-19

The chemistry of hydrogen cyanide (HCN) is believed to be central to the origin of life question. Contradictions between Cassini-Huygens mission measurements of the atmosphere and the surface of Saturn's moon Titan suggest that HCN-based polymers may have formed on the surface from products of atmospheric chemistry. This makes Titan a valuable "natural laboratory" for exploring potential nonterrestrial forms of prebiotic chemistry. We have used theoretical calculations to investigate the chain conformations of polyimine (pI), a polymer identified as one major component of polymerized HCN in laboratory experiments. Thanks to its flexible backbone, the polymer can exist in several different polymorphs, which are relatively close in energy. The electronic and structural variability among them is extraordinary. The band gap changes over a 3-eV range when moving from a planar sheet-like structure to increasingly coiled conformations. The primary photon absorption is predicted to occur in a window of relative transparency in Titan's atmosphere, indicating that pI could be photochemically active and drive chemistry on the surface. The thermodynamics for adding and removing HCN from pI under Titan conditions suggests that such dynamics is plausible, provided that catalysis or photochemistry is available to sufficiently lower reaction barriers. We speculate that the directionality of pI's intermolecular and intramolecular =N-H(…)N hydrogen bonds may drive the formation of partially ordered structures, some of which may synergize with photon absorption and act catalytically. Future detailed studies on proposed mechanisms and the solubility and density of the polymers will aid in the design of future missions to Titan.

Ab-initio and DFT methodologies for computing hyperpolarizabilities and susceptibilities of highly conjugated organic compounds for nonlinear optical applications

NASA Astrophysics Data System (ADS)

Karakas, A.; Karakaya, M.; Ceylan, Y.; El Kouari, Y.; Taboukhat, S.; Boughaleb, Y.; Sofiani, Z.

2016-06-01

In this talk, after a short introduction on the methodologies used for computing dipole polarizability (α), second and third-order hyperpolarizability and susceptibility; the results of theoretical studies performed on density functional theory (DFT) and ab-initio quantum mechanical calculations of nonlinear optical (NLO) properties for a few selected organic compounds and polymers will be explained. The electric dipole moments (μ) and dispersion-free first hyperpolarizabilities (β) for a family of azo-azulenes and a styrylquinolinium dye have been determined by DFT at B3LYP level. To reveal the frequency-dependent NLO behavior, the dynamic α, second hyperpolarizabilities (γ), second (χ(2)) and third-order (χ(3)) susceptibilites have been evaluated using time-dependent HartreeFock (TDHF) procedure. To provide an insight into the third-order NLO phenomena of a series of pyrrolo-tetrathiafulvalene-based molecules and pushpull azobenzene polymers, two-photon absorption (TPA) characterizations have been also investigated by means of TDHF. All computed results of the examined compounds are compared with their previous experimental findings and the measured data for similar structures in the literature. The one-photon absorption (OPA) characterizations of the title molecules have been theoretically obtained by configuration interaction (CI) method. The highest occupied molecular orbitals (HOMO), the lowest unoccupied molecular orbitals (LUMO) and the HOMO-LUMO band gaps have been revealed by DFT at B3LYP level for azo-azulenes, styrylquinolinium dye, push-pull azobenzene polymers and by parametrization method 6 (PM6) for pyrrolo-tetrathiafulvalene-based molecules.

Electronic structure changes during the on-surface synthesis of nitrogen-doped chevron-shaped graphene nanoribbons

NASA Astrophysics Data System (ADS)

Maaß, Friedrich; Utecht, Manuel; Stremlau, Stephan; Gille, Marie; Schwarz, Jutta; Hecht, Stefan; Klamroth, Tillmann; Tegeder, Petra

2017-07-01

Utilizing suitable precursor molecules, a thermally activated and surface-assisted synthesis results in the formation of defect-free graphene nanoribbons (GNRs), which exhibit electronic properties that are not present in extended graphene. Most importantly, they have a band gap in the order of a few electron volts, depending on the nanoribbon width. In this study, we investigate the electronic structure changes during the formation of GNRs, nitrogen-doped (singly and doubly N-doped) as well as non-N-doped chevron-shaped CGNRs on Au(111). Thus we determine the optical gaps of the precursor molecules, the intermediate nonaromatic polymers, and finally the aromatic GNRs, using high-resolution electron energy loss spectroscopy and density functional theory calculations. As expected, we find no influence of N-doping on the size of the optical gaps. The gap of the precursor molecules is around 4.5 eV. Polymerization leads to a reduction of the gap to a value of 3.2 eV due to elongation and thus enhanced delocalization. The CGNRs exhibit a band gap of 2.8 eV, thus the gap is further reduced in the nanoribbons, since they exhibit an extended delocalized π -electron system.

Rational design for enhancing inflammation-responsive in vivo chemiluminescence via nanophotonic energy relay to near-infrared AIE-active conjugated polymer.

PubMed

Seo, Young Hun; Singh, Ajay; Cho, Hong-Jun; Kim, Youngsun; Heo, Jeongyun; Lim, Chang-Keun; Park, Soo Young; Jang, Woo-Dong; Kim, Sehoon

2016-04-01

H2O2-specific peroxalate chemiluminescence is recognized as a potential signal for sensitive in vivo imaging of inflammation but the effect of underlying peroxalate-emitter energetics on its efficiency has rarely been understood. Here we report a simple nanophotonic way of boosting near-infrared chemiluminescence with no need of complicated structural design and synthesis of an energetically favored emitter. The signal enhancement was attained from the construction of a nanoparticle imaging probe (∼26 nm in size) by dense nanointegration of multiple molecules possessing unique photonic features, i.e., i) a peroxalate as a chemical fuel generating electronic excitation energy in response to inflammatory H2O2, ii) a low-bandgap conjugated polymer as a bright near-infrared emitter showing aggregation-induced emission (AIE), and iii) an energy gap-bridging photonic molecule that relays the chemically generated excitation energy to the emitter for its efficient excitation. From static and kinetic spectroscopic studies, a green-emissive BODIPY dye has proven to be an efficient relay molecule to bridge the energy gap between the AIE polymer and the chemically generated excited intermediate of H2O2-reacted peroxalates. The energy-relayed nanointegration of AIE polymer and peroxalate in water showed a 50-times boosted sensing signal compared to their dissolved mixture in THF. Besides the high H2O2 detectability down to 10(-9) M, the boosted chemiluminescence presented a fairly high tissue penetration depth (>12 mm) in an ex vivo condition, which enabled deep imaging of inflammatory H2O2 in a hair-covered mouse model of peritonitis. Copyright © 2016 Elsevier Ltd. All rights reserved.

From macro- to microplastics - Analysis of EU regulation along the life cycle of plastic bags.

PubMed

Steensgaard, Ida M; Syberg, Kristian; Rist, Sinja; Hartmann, Nanna B; Boldrin, Alessio; Hansen, Steffen Foss

2017-05-01

Plastic pollution and its environmental effects has received global attention the recent years. However, limited attention has so far been directed towards how plastics are regulated in a life cycle perspective and how regulatory gaps can be addressed in order to limit and prevent environmental exposure and hazards of macro- and microplastics. In this paper, we map European regulation taking outset in the life cycle perspective of plastic carrier bags: from plastic bag production to when it enters the environment. Relevant regulatory frameworks, directives and authorities along the life cycle are identified and their role in regulation of plastics is discussed. Most important regulations were identified as: the EU chemical Regulation, the Packaging and Packaging Waste Directive including the amending Directive regarding regulation of the consumption of lightweight plastic carrier bags, the Waste Framework Directive and the Directive on the Landfill of Waste. The main gaps identified relate to lack of clear definitions of categories of polymers, unambitious recycling rates and lack of consideration of macro- and microplastics in key pieces of legislation. We recommend that polymers are categorized according to whether they are polymers with the same monomer constituents (homopolymers) or with different monomer constituents (copolymers) and that polymers are no longer exempt from registration and evaluation under REACH. Plastics should furthermore have the same high level of monitoring and reporting requirements as hazardous waste involving stricter requirements to labelling, recordkeeping, monitoring and control over the whole lifecycle. Finally, we recommend that more ambitious recycle and recovery targets are set across the EU. Regulation of the consumption of lightweight plastic carrier bags should also apply to heavyweight plastic carrier bags. Last, the Marine and Water Framework Directives should specifically address plastic waste affecting water quality. Copyright © 2017 Elsevier Ltd. All rights reserved.

Charge-flow structures as polymeric early-warning fire alarm devices. M.S. Thesis; [metal oxide semiconductors

NASA Technical Reports Server (NTRS)

Sechen, C. M.; Senturia, S. D.

1977-01-01

The charge-flow transistor (CFT) and its applications for fire detection and gas sensing were investigated. The utility of various thin film polymers as possible sensing materials was determined. One polymer, PAPA, showed promise as a relative humidity sensor; two others, PFI and PSB, were found to be particularly suitable for fire detection. The behavior of the charge-flow capacitor, which is basically a parallel-plate capacitor with a polymer-filled gap in the metallic tip electrode, was successfully modeled as an RC transmission line. Prototype charge-flow transistors were fabricated and tested. The effective threshold voltage of this metal oxide semiconductor was found to be dependent on whether surface or bulk conduction in the thin film was dominant. Fire tests with a PFI-coated CFT indicate good sensitivity to smouldering fires.

A Combined Molecular Dynamics and Experimental Study of Doped Polypyrrole.

PubMed

Fonner, John M; Schmidt, Christine E; Ren, Pengyu

2010-10-01

Polypyrrole (PPy) is a biocompatible, electrically conductive polymer that has great potential for battery, sensor, and neural implant applications. Its amorphous structure and insolubility, however, limit the experimental techniques available to study its structure and properties at the atomic level. Previous theoretical studies of PPy in bulk are also scarce. Using ab initio calculations, we have constructed a molecular mechanics force field of chloride-doped PPy (PPyCl) and undoped PPy. This model has been designed to integrate into the OPLS force field, and parameters are available for the Gromacs and TINKER software packages. Molecular dynamics (MD) simulations of bulk PPy and PPyCl have been performed using this force field, and the effects of chain packing and electrostatic scaling on the bulk polymer density have been investigated. The density of flotation of PPyCl films has been measured experimentally. Amorphous X-ray diffraction of PPyCl was obtained and correlated with atomic structures sampled from MD simulations. The force field reported here is foundational for bridging the gap between experimental measurements and theoretical calculations for PPy based materials.

Mechanistic modeling of modular co-rotating twin-screw extruders.

PubMed

Eitzlmayr, Andreas; Koscher, Gerold; Reynolds, Gavin; Huang, Zhenyu; Booth, Jonathan; Shering, Philip; Khinast, Johannes

2014-10-20

In this study, we present a one-dimensional (1D) model of the metering zone of a modular, co-rotating twin-screw extruder for pharmaceutical hot melt extrusion (HME). The model accounts for filling ratio, pressure, melt temperature in screw channels and gaps, driving power, torque and the residence time distribution (RTD). It requires two empirical parameters for each screw element to be determined experimentally or numerically using computational fluid dynamics (CFD). The required Nusselt correlation for the heat transfer to the barrel was determined from experimental data. We present results for a fluid with a constant viscosity in comparison to literature data obtained from CFD simulations. Moreover, we show how to incorporate the rheology of a typical, non-Newtonian polymer melt, and present results in comparison to measurements. For both cases, we achieved excellent agreement. Furthermore, we present results for the RTD, based on experimental data from the literature, and found good agreement with simulations, in which the entire HME process was approximated with the metering model, assuming a constant viscosity for the polymer melt. Copyright © 2014. Published by Elsevier B.V.

Bi-diketopyrrolopyrrole (Bi-DPP) as a novel electron accepting compound in low band gap π-conjugated donor–acceptor copolymers/oligomers

PubMed Central

Ahner, Johannes; Nowotny, Jürgen; Schubert, Ulrich S.; Hager, Martin D.

2017-01-01

Abstract The synthesis and characterization of a novel 2,5-diketopyrrolo[3,4-c]pyrrole(DPP)-based accepting building block with the scheme DPP-neutral small linker-DPP (Bi-DPP) is presented, which was utilized as electron accepting moiety for low band gap π-conjugated donor–acceptor copolymers as well as for a donor–acceptor small molecule. The electron accepting moiety Bi-DPP was prepared via a novel synthetic pathway by building up two DPP moieties step by step simultaneously starting from a neutral phenyl core unit. Characterization of the synthesized oligomeric and polymeric materials via cyclic voltammetry afford LUMO energy levels from −3.49 to −3.59 eV as well as HOMO energy levels from −5.07 to −5.34 eV resulting in low energy band gaps from 1.52 to 1.81 eV. Spin coating of the prepared donor–acceptor oligomers/polymers resulted in well-defined films. Moreover, UV–vis measurements of the investigated donor–acceptor systems showed a broad absorption over the whole visible region. It is demonstrated that Bi-DPP as an electron accepting moiety in donor–acceptor systems offer potential properties for organic solar cell devices. PMID:29491794

Drug Release Kinetics and Transport Mechanisms of Non-degradable and Degradable Polymeric Delivery Systems

PubMed Central

Fu, Yao; Kao, Weiyuan John

2010-01-01

Importance of the field The advancement in material design and engineering has led to the rapid development of novel materials with increasing complexity and functions. Both non-degradable and degradable polymers have found wide applications in the controlled delivery field. Studies on drug release kinetics provide important information into the function of material systems. To elucidate the detailed transport mechanism and the structure-function relationship of a material system, it is critical to bridge the gap between the macroscopic data and the transport behavior at the molecular level. Areas covered in this review The structure and function information of selected non-degradable and degradable polymers have been collected and summarized from literatures published after 1990s. The release kinetics of selected drug compounds from various material systems will be discussed in case studies. Recent progresses in the mathematical models based on different transport mechanisms will be highlighted. What the reader will gain This article aims to provide an overview of structure-function relationships of selected non-degradable and degradable polymers as drug delivery matrices. Take home message Understanding the structure-function relationship of the material system is key to the successful design of a delivery system for a particular application. Moreover, developing complex polymeric matrices requires more robust mathematical models to elucidate the solute transport mechanisms. PMID:20331353

Preparation of flexible organic solar cells with highly conductive and transparent metal-oxide multilayer electrodes based on silver oxide.

PubMed

Yun, Jungheum; Wang, Wei; Bae, Tae Sung; Park, Yeon Hyun; Kang, Yong-Cheol; Kim, Dong-Ho; Lee, Sunghun; Lee, Gun-Hwan; Song, Myungkwan; Kang, Jae-Wook

2013-10-23

We report that significantly more transparent yet comparably conductive AgOx films, when compared to Ag films, are synthesized by the inclusion of a remarkably small amount of oxygen (i.e., 2 or 3 atom %) in thin Ag films. An 8 nm thick AgOx (O/Ag=2.4 atom %) film embedded between 30 nm thick ITO films (ITO/AgOx/ITO) achieves a transmittance improvement of 30% when compared to a conventional ITO/Ag/ITO electrode with the same configuration by retaining the sheet resistance in the range of 10-20 Ω sq(-1). The high transmittance provides an excellent opportunity to improve the power-conversion efficiency of organic solar cells (OSCs) by successfully matching the transmittance spectral range of the electrode to the optimal absorption region of low band gap photoactive polymers, which is highly limited in OSCs utilizing conventional ITO/Ag/ITO electrodes. An improvement of the power-conversion efficiency from 4.72 to 5.88% is achieved from highly flexible organic solar cells (OSCs) fabricated on poly(ethylene terephthalate) polymer substrates by replacing the conventional ITO/Ag/ITO electrode with the ITO/AgOx/ITO electrode. This novel transparent electrode can facilitate a cost-effective, high-throughput, room-temperature fabrication solution for producing large-area flexible OSCs on heat-sensitive polymer substrates with excellent power-conversion efficiencies.

The photocurrent response in the perovskite device based on coordination polymers: structure, topology, band gap and matched energy levels.

PubMed

Luo, Hai-Qiang; Xing, Xiao-Han; Zhang, Pan; Yan, Zhi-Shuo; Zhou, Qing-Feng; Gong, Yun; Lin, Jian-Hua

2017-06-28

Using a rigid ditopic ligand, 4,5-di(4'-carboxylphenyl)benzene (H 2 L), three coordination polymers (CPs) formulated as MnL(H 2 O) 2 (1), CdL(H 2 O) (2) and Mn 2 L 2 (DMF) 3 (3) have been synthesized and structurally characterized by single-crystal X-ray diffraction. These three CPs display 2D architectures but with different topologies. The experimental data and DFT calculation indicate that CP 2 is a semiconductor, and its CB/VB energy levels match with those of the perovskite CH 3 NH 3 PbI 3 . A FTO/TiO 2 /CH 3 NH 3 PbI 3 /CP 2 device is fabricated and the CP-based device shows much larger photoresponse under visible light illumination (650 nm > λ > 350 nm, 100 mW cm -2 ) than the individual CP 2. At 0 V vs. AgCl/Ag, the largest photocurrent density yielded by the CP-based perovskite device is ca. 200 times that of CP 2, which is due to the matched energy levels of all the materials in the device, leading the photogenerated electron-hole pairs to be separated effectively. Meanwhile, the coverage of the insoluble CP on the surface of the perovskite CH 3 NH 3 PbI 3 can improve the stability of the perovskite against water.

Polymer-Based Black Phosphorus (bP) Hybrid Materials by in Situ Radical Polymerization: An Effective Tool To Exfoliate bP and Stabilize bP Nanoflakes

PubMed Central

2018-01-01

Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) toward both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes (bPn) exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: (i) the mixing of conventionally liquid-phase exfoliated bP (in dimethyl sulfoxide, DMSO) with poly(methyl methacrylate) (PMMA) solution; (ii) the direct exfoliation of bP in a polymeric solution; (iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn–MMA by sonication-assisted liquid-phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of the bPn is particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-solid state NMR studies) and are particularly stable to air and UV light exposure. The feasibility of this approach, capable of efficiently exfoliating bP while protecting the bPn, has been then verified by using different vinyl monomers (styrene and N-vinylpyrrolidone), thus obtaining hybrids where the nanoflakes are embedded in polymer matrices with a variety of intriguing thermal, mechanical, and solubility characteristics.

Future of photorefractive based holographic 3D display

NASA Astrophysics Data System (ADS)

Blanche, P.-A.; Bablumian, A.; Voorakaranam, R.; Christenson, C.; Lemieux, D.; Thomas, J.; Norwood, R. A.; Yamamoto, M.; Peyghambarian, N.

2010-02-01

The very first demonstration of our refreshable holographic display based on photorefractive polymer was published in Nature early 20081. Based on the unique properties of a new organic photorefractive material and the holographic stereography technique, this display addressed a gap between large static holograms printed in permanent media (photopolymers) and small real time holographic systems like the MIT holovideo. Applications range from medical imaging to refreshable maps and advertisement. Here we are presenting several technical solutions for improving the performance parameters of the initial display from an optical point of view. Full color holograms can be generated thanks to angular multiplexing, the recording time can be reduced from minutes to seconds with a pulsed laser, and full parallax hologram can be recorded in a reasonable time thanks to parallel writing. We also discuss the future of such a display and the possibility of video rate.

Benzothiadiazole Versus Thiophene: Influence of the Auxiliary Acceptor on the Photovoltaic Properties of Donor-Acceptor-Based Copolymers.

PubMed

Li, Zongbo; Weng, Kangkang; Chen, Aihua; Sun, Xiaobo; Wei, Donghui; Yu, Mingming; Huo, Lijun; Sun, Yanming

2018-01-01

Two donor-acceptor (D-A) type conjugated copolymers, P1 and P2, are designed and synthesized. A classical benzothiadiazole acceptor is used to replace a thiophene unit in the polymer chain of P1 to obtain P2 terpolymer. Compared with P1, P2 exhibits broader absorption spectra, higher absorption coefficient, deeper lowest unoccupied molecular orbital level, and a relatively lower band gap. As a result, the P2-based solar cell exhibits a high power conversion efficiency (PCE) of 6.60%, with a short-circuit current (J sc ) of 12.43 mA cm -2 , and a fill factor (FF) of 73.1%, which are higher than those of the P1-based device with a PCE of 4.70%, a J sc of 9.43 mA cm -2 , and an FF of 61.6%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On compression and damage evolution in two thermoplastics

DOE PAGES

Bourne, N. K.; Garcea, S. C.; Eastwood, D. S.; ...

2017-01-18

The well-known Taylor cylinder impact test, which follows the impact of a flat-ended cylindrical rod onto a rigid stationary anvil, is conducted over a range of impact speeds for two polymers, polytetrafluoroethylene (PTFE) and polyetheretherketone (PEEK). In previous work, experiments and a model were developed to capture the deformation behaviour of the cylinder after impact. These works showed a region in which spatial and temporal variation of both longitudinal and radial deformation provided evidence of changes in phase within the material. In this further series of experiments, this region is imaged in a range of impacted targets at the Diamondmore » synchrotron. Further techniques were fielded to resolve compressed regions within the recovered polymer cylinders that showed a fracture zone in the impact region. The combination of macroscopic high-speed photography and three-dimensional X-ray imaging has identified the development of failure with these polymers and shown that there is no abrupt transition in behaviours but rather a continuous range of responses to competing operating mechanisms. The behaviours noted in PEEK in these polymers show critical gaps in understanding of polymer high strain-rate response.« less

Hole transfer from CdSe nanoparticles to TQ1 polymer in hybrid solar cell device

NASA Astrophysics Data System (ADS)

Sohail, Muhammad; Shah, Zawar Hussain; Saeed, Shomaila; Bibi, Nasreen; Shahbaz, Sadia; Ahmed, Safeer; Shabbir, Saima; Siddiq, Muhammad; Iqbal, Azhar

2018-05-01

In view of realizing the economic viability, we fabricate a solar cell device containing low band gap and easily processable polymer 5-yl-8-(thiophene-2,5-diyl)-2,3-bis(3-(octyloxy)phenyl) quinoxaline (TQ1) and CdSe nanoparticles (NPs) and investigate its charge transport properties. When the TQ1 is combined with the CdSe NPs a strong photoluminescence quenching and shortening of photoluminescence lifetime of the TQ1 is observed indicating exciton transfer from TQ1 to the CdSe NPs. The time-resolved photoluminescence further reveals that the exciton transfer from the polymer to CdSe NPs is very efficient (68%) and it occurs in <1 ns. The exciton transfer from TQ1 to the NPs and electron-hole pair separation followed by hole transfer from the NPs to the TQ1 at the interface indeed increases the lifetime of the charge carriers. This in turn increases the efficiency of the solar cell as compared to polymer only device. These observations suggest the importance of other II-VI semiconductor NPs to achieve higher efficiency for photovoltaic devices containing TQ1 polymer.

A versatile approach to organic photovoltaics evaluation using white light pulse and microwave conductivity.

PubMed

Saeki, Akinori; Yoshikawa, Saya; Tsuji, Masashi; Koizumi, Yoshiko; Ide, Marina; Vijayakumar, Chakkooth; Seki, Shu

2012-11-21

State-of-the-art low band gap conjugated polymers have been investigated for application in organic photovoltaic cells (OPVs) to achieve efficient conversion of the wide spectrum of sunlight into electricity. A remarkable improvement in power conversion efficiency (PCE) has been achieved through the use of innovative materials and device structures. However, a reliable technique for the rapid screening of the materials and processes is a prerequisite toward faster development in this area. Here we report the realization of such a versatile evaluation technique for bulk heterojunction OPVs by the combination of time-resolved microwave conductivity (TRMC) and submicrosecond white light pulse from a Xe-flash lamp. Xe-flash TRMC allows examination of the OPV active layer without requiring fabrication of the actual device. The transient photoconductivity maxima, involving information on generation efficiency, mobility, and lifetime of charge carriers in four well-known low band gap polymers blended with phenyl-C(61)-butyric acid methyl ester (PCBM), were confirmed to universally correlate with the PCE divided by the open circuit voltage (PCE/V(oc)), offering a facile way to predict photovoltaic performance without device fabrication.

Luminescence study of ZnSe/PVA (polyvinyl alcohol) composite film

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

Lahariya, Vikas

The ZnSe nanocrystals have been prepared into poly vinyl alcohol(PVA) polymer matrix on glass using ZnCl2 and Na2SeSO3 as zinc and selenium source respectively. Poly vinyl Alcohol (PVA) used as polymer matrix cum capping agent due to their high viscosity and water solubility. It is transparent for visible region and prevents Se- ions to photo oxidation. The ZnSe/PVA composite film was deposited on glass substrate. The film was characterized by X Ray Diffraction (XRD) and UV-Visible absorption Spectroscopy and Photoluminescence. The X Ray Diffraction (XRD) study confirms the nanometer size (10 nm) particle formation within PVA matrix with cubic zinc blendmore » crystal structure. The UV-Visible Absorption spectrum of ZnSe/PVA composite film shown blue shift in absorption edge indicating increased band gap due to quantum confinement. The calculated energy band gap from the absorption edge using Tauc relation is 3.4 eV. From the Photoluminescence study a broad peak at 435 nm has been observed in violet blue region due to recombination of surface states.« less

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

NASA Astrophysics Data System (ADS)

Steiner, Christian; Gebhardt, Julian; Ammon, Maximilian; Yang, Zechao; Heidenreich, Alexander; Hammer, Natalie; Görling, Andreas; Kivala, Milan; Maier, Sabine

2017-03-01

The fabrication of nanostructures in a bottom-up approach from specific molecular precursors offers the opportunity to create tailored materials for applications in nanoelectronics. However, the formation of defect-free two-dimensional (2D) covalent networks remains a challenge, which makes it difficult to unveil their electronic structure. Here we report on the hierarchical on-surface synthesis of nearly defect-free 2D covalent architectures with carbonyl-functionalized pores on Au(111), which is investigated by low-temperature scanning tunnelling microscopy in combination with density functional theory calculations. The carbonyl-bridged triphenylamine precursors form six-membered macrocycles and one-dimensional (1D) chains as intermediates in an Ullmann-type coupling reaction that are subsequently interlinked to 2D networks. The electronic band gap is narrowed when going from the monomer to 1D and 2D surface-confined π-conjugated organic polymers comprising the same building block. The significant drop of the electronic gap from the monomer to the polymer confirms an efficient conjugation along the triphenylamine units within the nanostructures.

Cholesteric liquid crystal gels with a graded mechanical stress

NASA Astrophysics Data System (ADS)

Agez, Gonzague; Relaix, Sabrina; Mitov, Michel

2014-02-01

In cholesteric liquid-crystalline gels, the mechanical role of the polymer network over the structure of the whole gel has been ignored. We show that it is the stress gradient exerted by the network over the helical structure that drives the broadening of the optical band gap, as evidenced by the absence of a gradient in chiral species. Model calculations and finite-difference time-domain simulations show that the network acts as a spring with a stiffness gradient. The present results indicate a revision to the common understanding of the physical properties of liquid-crystalline gels is necessary when a concentration gradient in a polymer network is present.

Cholesteric liquid crystal gels with a graded mechanical stress.

PubMed

Agez, Gonzague; Relaix, Sabrina; Mitov, Michel

2014-02-01

In cholesteric liquid-crystalline gels, the mechanical role of the polymer network over the structure of the whole gel has been ignored. We show that it is the stress gradient exerted by the network over the helical structure that drives the broadening of the optical band gap, as evidenced by the absence of a gradient in chiral species. Model calculations and finite-difference time-domain simulations show that the network acts as a spring with a stiffness gradient. The present results indicate a revision to the common understanding of the physical properties of liquid-crystalline gels is necessary when a concentration gradient in a polymer network is present.

Theoretical study on naphthobischalcogenadiazole conjugated polymer systems and C61 derivative as organic photovoltaic semiconductors

NASA Astrophysics Data System (ADS)

Fujita, Takehiro; Matsui, Toru; Sumita, Masato; Imamura, Yutaka; Morihashi, Kenji

2018-02-01

We investigated the charge-transfer reactions of solar cells including a quaterthiophene copolymer with naphtho-bis-thiadiazole (PNTz4T) and naphtho-bis-oxadiazole (PNOz4T) using constrained density functional theory (CDFT). According to our calculations, the high electron-transfer rate results in a highly efficient solar cell, and the stable charge-transfer state results in low energy loss. Our computations imply that the following three factors are crucial to improve the performance of semiconducting polymers: (i) large structural changes following charge-transfer, (ii) narrow band gap, and (iii) spatially delocalized lowest unoccupied molecular orbital (LUMO) of the ground state.

Structural parameter study on polymer-based ultrasonic motor

NASA Astrophysics Data System (ADS)

Wu, Jiang; Mizuno, Yosuke; Nakamura, Kentaro

2017-11-01

Our previous study has shown that traveling-wave rotary ultrasonic motors using polymer-based vibrators can work in the same way as conventional motors with metal-based vibrators. It is feasible to enhance the performance, particularly output torques, of polymer-based motors by adjusting several key dimensions of their vibrators. In this study, poly phenylene sulfide, a functional polymer exhibiting low attenuation at ultrasonic frequency, is selected as the vibrating body, which is activated with a piezoelectric ceramic element bonded on its back surface. The optimal thicknesses of the polymer-based motors are higher than those of metal-based motors. When the same voltages were applied, the maximum torques and output powers available with the polymer-based motors were lower than the values of the metal-based motors with the same structures. The reasons for the lower torque were explained on the basis of vibration modes. First, the force factors of the polymer-based vibrators are lower than those of metal-based vibrators owing to the great difference in the mechanical constants between polymers and piezoelectric ceramics. Subsequently, though the force factors of polymer-based vibrators can be slightly enhanced by increasing their thicknesses, the unavoidable radial vibrations become higher and cause undesirable friction loss, which reduces the output torques. Though the polymer-based motors have rotation speeds comparable to those of metal-based motors, their output power are lower due to the low electromechanical coupling factors of the polymer-based vibrators.

First principles based multiparadigm modeling of electronic structures and dynamics

NASA Astrophysics Data System (ADS)

Xiao, Hai

Electronic structures and dynamics are the key to linking the material composition and structure to functionality and performance. An essential issue in developing semiconductor devices for photovoltaics is to design materials with optimal band gaps and relative positioning of band levels. Approximate DFT methods have been justified to predict band gaps from KS/GKS eigenvalues, but the accuracy is decisively dependent on the choice of XC functionals. We show here for CuInSe2 and CuGaSe2, the parent compounds of the promising CIGS solar cells, conventional LDA and GGA obtain gaps of 0.0-0.01 and 0.02-0.24 eV (versus experimental values of 1.04 and 1.67 eV), while the historically first global hybrid functional, B3PW91, is surprisingly the best, with band gaps of 1.07 and 1.58 eV. Furthermore, we show that for 27 related binary and ternary semiconductors, B3PW91 predicts gaps with a MAD of only 0.09 eV, which is substantially better than all modern hybrid functionals, including B3LYP (MAD of 0.19 eV) and screened hybrid functional HSE06 (MAD of 0.18 eV). The laboratory performance of CIGS solar cells (> 20% efficiency) makes them promising candidate photovoltaic devices. However, there remains little understanding of how defects at the CIGS/CdS interface affect the band offsets and interfacial energies, and hence the performance of manufactured devices. To determine these relationships, we use the B3PW91 hybrid functional of DFT with the AEP method that we validate to provide very accurate descriptions of both band gaps and band offsets. This confirms the weak dependence of band offsets on surface orientation observed experimentally. We predict that the CBO of perfect CuInSe2/CdS interface is large, 0.79 eV, which would dramatically degrade performance. Moreover we show that band gap widening induced by Ga adjusts only the VBO, and we find that Cd impurities do not significantly affect the CBO. Thus we show that Cu vacancies at the interface play the key role in enabling the tunability of CBO. We predict that Na further improves the CBO through electrostatically elevating the valence levels to decrease the CBO, explaining the observed essential role of Na for high performance. Moreover we find that K leads to a dramatic decrease in the CBO to 0.05 eV, much better than Na. We suggest that the efficiency of CIGS devices might be improved substantially by tuning the ratio of Na to K, with the improved phase stability of Na balancing phase instability from K. All these defects reduce interfacial stability slightly, but not significantly. A number of exotic structures have been formed through high pressure chemistry, but applications have been hindered by difficulties in recovering the high pressure phase to ambient conditions (i.e., one atmosphere and room temperature). Here we use dispersion-corrected DFT (PBE-ulg flavor) to predict that above 60 GPa the most stable form of N2O (the laughing gas in its molecular form) is a 1D polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03-0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions both polymers relax below 14 GPa to the same stable non-planar trans-polymer, accompanied by possible electronic structure transitions. The predicted phonon spectrum and dissociation kinetics validate the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a new type of conducting polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions. Modeling non-adiabatic electron dynamics has been a long-standing challenge for computational chemistry and materials science, and the eFF method presents a cost-efficient alternative. However, due to the deficiency of FSG representation, eFF is limited to low-Z elements with electrons of predominant s-character. To overcome this, we introduce a formal set of ECP extensions that enable accurate description of p-block elements. The extensions consist of a model representing the core electrons with the nucleus as a single pseudo particle represented by FSG, interacting with valence electrons through ECPs. We demonstrate and validate the ECP extensions for complex bonding structures, geometries, and energetics of systems with p-block character (C, O, Al, Si) and apply them to study materials under extreme mechanical loading conditions. Despite its success, the eFF framework has some limitations, originated from both the design of Pauli potentials and the FSG representation. To overcome these, we develop a new framework of two-level hierarchy that is a more rigorous and accurate successor to the eFF method. (Abstract shortened by UMI.).

Quantized conductance operation near a single-atom point contact in a polymer-based atomic switch

NASA Astrophysics Data System (ADS)

Krishnan, Karthik; Muruganathan, Manoharan; Tsuruoka, Tohru; Mizuta, Hiroshi; Aono, Masakazu

2017-06-01

Highly-controlled conductance quantization is achieved near a single-atom point contact in a redox-based atomic switch device, in which a poly(ethylene oxide) (PEO) film is sandwiched between Ag and Pt electrodes. Current-voltage measurements revealed reproducible quantized conductance of ˜1G 0 for more than 102 continuous voltage sweep cycles under a specific condition, indicating the formation of a well-defined single-atom point contact of Ag in the PEO matrix. The device exhibited a conductance state distribution centered at 1G 0, with distinct half-integer multiples of G 0 and small fractional variations. First-principles density functional theory simulations showed that the experimental observations could be explained by the existence of a tunneling gap and the structural rearrangement of an atomic point contact.

A polymer dataset for accelerated property prediction and design.

PubMed

Huan, Tran Doan; Mannodi-Kanakkithodi, Arun; Kim, Chiho; Sharma, Vinit; Pilania, Ghanshyam; Ramprasad, Rampi

2016-03-01

Emerging computation- and data-driven approaches are particularly useful for rationally designing materials with targeted properties. Generally, these approaches rely on identifying structure-property relationships by learning from a dataset of sufficiently large number of relevant materials. The learned information can then be used to predict the properties of materials not already in the dataset, thus accelerating the materials design. Herein, we develop a dataset of 1,073 polymers and related materials and make it available at http://khazana.uconn.edu/. This dataset is uniformly prepared using first-principles calculations with structures obtained either from other sources or by using structure search methods. Because the immediate target of this work is to assist the design of high dielectric constant polymers, it is initially designed to include the optimized structures, atomization energies, band gaps, and dielectric constants. It will be progressively expanded by accumulating new materials and including additional properties calculated for the optimized structures provided.

Thermodynamic analysis of solid-fuel mixtures glycidyl azide polymer (GAP)/RDX for miniengines of microelectromechanical systems

NASA Astrophysics Data System (ADS)

Fut'ko, S. I.; Ermolaeva, E. M.; Dobrego, K. V.; Bondarenko, V. P.; Dolgii, L. N.

2011-09-01

On the basis of thermodynamic calculations we show that solid-fuel mixtures glycidyl azide polymer/RDX are promising for use in miniengines made on the basis of technologies of microelectromechanical systems of semiconductor microelectronics. It has been shown that small (up to 20 mass percent) additives of RDX to the glycidyl azide polymer markedly increase the values of the theoretical specific impulse and the thermal efficiency of the engine and decrease the quantity of undesirable solid carbon formed in combustion products of the mixed fuel. In so doing, these mixtures provide fairly low combustion temperatures not exceeding the thermostability limit of crystal silicon from which the miniengine case is made. The physicochemical factors influencing the value of the theoretical specific impulse of the mixed solid-fuel charge have been elucidated, and methods for its maximization have been proposed.

Preparation of Highly Conductive Yarns by an Optimized Impregnation Process

NASA Astrophysics Data System (ADS)

Amba Sankar, K. N.; Mohanta, Kallol

2017-12-01

We report the development of the electrical conductivity in textile yarns through impregnation and post-treatment of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). The conductive polymer is deposited on fibers, which fills the gap space within the hierarchical structure of the yarns. Organic nonpolar solvents act as reducing agent to increase the density of PEDOT moieties on the yarns, galvanizing increment in conductivity values. Post-treatment by ethylene glycol transforms the resonance configuration of the conductive moieties of conjugated polymer, which helps in further enhancement of electrical conductivity of the yarns. We have optimized the method in terms of loading and conformal change of the polymer to have a lesser resistance of the coated conductive yarns. The minimum resistance achieved has a value of 77 Ωcm-1. This technique of developing conductivity in conventional yarns enables retaining the flexibility of yarns and feeling of softness which would find suitable applications for wearable electronics.

A polarization-independent liquid crystal phase modulation using polymer-network liquid crystal with orthogonal alignment layers

NASA Astrophysics Data System (ADS)

Chen, Ming-Syuan; Lin, Wei-Chih; Tsou, Yu-Shih; Lin, Yi-Hsin

2012-10-01

A polarization-independent liquid crystal (LC) phase modulation using polymer-network liquid crystals with orthogonal alignments layers (T-PNLC) is demonstrated. T-PNLC consists of three layers. LC directors in the two layers near glass substrates are orthogonal to each other. In the middle layer, LC directors are perpendicular to the glass substrate. The advantages of such T-PNLC include polarizer-free, larger phase shift (~0.4π rad) than the residual phase type (<0.05π rad), and low operating voltage (< 30Vrms). It does not require bias voltage for avoiding scattering because the refractive index of liquid crystals matches that of polymers. The phase shift of T-PNLC is affected by the cell gap and the curing voltages. The potential applications are laser beam steering, spatial light modulators and electrically tunable micro-lens arrays.

Preparation of Highly Conductive Yarns by an Optimized Impregnation Process

NASA Astrophysics Data System (ADS)

Amba Sankar, K. N.; Mohanta, Kallol

2018-03-01

We report the development of the electrical conductivity in textile yarns through impregnation and post-treatment of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). The conductive polymer is deposited on fibers, which fills the gap space within the hierarchical structure of the yarns. Organic nonpolar solvents act as reducing agent to increase the density of PEDOT moieties on the yarns, galvanizing increment in conductivity values. Post-treatment by ethylene glycol transforms the resonance configuration of the conductive moieties of conjugated polymer, which helps in further enhancement of electrical conductivity of the yarns. We have optimized the method in terms of loading and conformal change of the polymer to have a lesser resistance of the coated conductive yarns. The minimum resistance achieved has a value of 77 Ωcm-1. This technique of developing conductivity in conventional yarns enables retaining the flexibility of yarns and feeling of softness which would find suitable␣applications for wearable electronics.

Nanocomposites for enhancing current collection in organic solar cells

NASA Astrophysics Data System (ADS)

Peterson, Eric David

The enhancement of charge collection in organic photovoltaics by using nanocomposite materials is investigated. Two such approaches are detailed in this thesis. Chapter 1 addresses the addition of metal nanorods to the PEDOT layer of an organic solar cell in an attempt to focus incident light for better absorption by the polymer layer. Composites designed to facilitate charge transfer from nanoparticles to the polymer/fullerene system are the focus of the second chapter. Chapter 3 details a refinement to the research presented in chapter 2, adding fullerenes to the mix and creating ternary systems and providing an analytical framework for evaluating these systems. The material choices are expanded in chapter 4; we investigate a new, lower band gap conjugated polymer (PCPDTBT) as well as core-shell nanoparticles and how they interact in the system. Results are reported and further avenues of research are suggested.

Polymer coating embolism from intravascular medical devices - a clinical literature review.

PubMed

Chopra, Amitabh M; Mehta, Monik; Bismuth, Jean; Shapiro, Maksim; Fishbein, Michael C; Bridges, Alina G; Vinters, Harry V

Over the past three decades, lubricious (hydrophobic and/or hydrophilic) polymer-coated devices have been increasingly adopted by interventional physicians and vascular surgeons to access and treat a wider range of clinical presentations. Recent clinical literature highlights the presence of polymer coating emboli within the anatomy - a result of coating separation from an intravascular device - and associates it with a range of adverse clinical sequelae. The 2015 U.S. Food and Drug Administration safety communication titled "Lubricious Coating Separation from Intravascular Medical Devices" acknowledges these concerns and concludes that it will work with stakeholders to develop nonclinical test methodologies, establish performance criteria, and identify gaps in current national and international device standards for coating integrity performance. Despite this communication and multiple case reports from interventional physicians, pathologists, dermatologists and other involved physician specialties, polymer coating embolism remains clinically underrecognized. This article consolidates the available literature on polymer coating embolism (1986-2016) and highlights the following relevant information for the physician: (a) the history and elusive nature of polymer coating embolism; (b) potential incidence rates of this phenomenon; (c) reported histologic findings and clinical effects of polymer emboli in the anatomy; (d) the importance of the collaborative clinician-pathologist partnership to report polymer embolism findings; and (e) the importance to study particulate release from intravascular devices so as to further understand and potentially evolve coated interventional technologies. Preliminary research on coatings highlights the potential of using iterations of coatings on medical devices that attain the desired therapeutic result and mitigate or eliminate particulates altogether. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Cloning strategy for producing brush-forming protein-based polymers.

PubMed

Henderson, Douglas B; Davis, Richey M; Ducker, William A; Van Cott, Kevin E

2005-01-01

Brush-forming polymers are being used in a variety of applications, and by using recombinant DNA technology, there exists the potential to produce protein-based polymers that incorporate unique structures and functions in these brush layers. Despite this potential, production of protein-based brush-forming polymers is not routinely performed. For the design and production of new protein-based polymers with optimal brush-forming properties, it would be desirable to have a cloning strategy that allows an iterative approach wherein the protein based-polymer product can be produced and evaluated, and then if necessary, it can be sequentially modified in a controlled manner to obtain optimal surface density and brush extension. In this work, we report on the development of a cloning strategy intended for the production of protein-based brush-forming polymers. This strategy is based on the assembly of modules of DNA that encode for blocks of protein-based polymers into a commercially available expression vector; there is no need for custom-modified vectors and no need for intermediate cloning vectors. Additionally, because the design of new protein-based biopolymers can be an iterative process, our method enables sequential modification of a protein-based polymer product. With at least 21 bacterial expression vectors and 11 yeast expression vectors compatible with this strategy, there are a number of options available for production of protein-based polymers. It is our intent that this strategy will aid in advancing the production of protein-based brush-forming polymers.

A primer on polymer nomenclature: Structure-based, sourced-based and trade names

USDA-ARS?s Scientific Manuscript database

Polymer nomenclature is important because it is part of the language of polymer science and is needed for polymer identification, reference, and documentation. A primer on polymer nomenclature is provided herein for people new to the field or for instructional use. Both structure-based and source-...

Fabrication of solution processed 3D nanostructured CuInGaS₂ thin film solar cells.

PubMed

Chu, Van Ben; Cho, Jin Woo; Park, Se Jin; Hwang, Yun Jeong; Park, Hoo Keun; Do, Young Rag; Min, Byoung Koun

2014-03-28

In this study we demonstrate the fabrication of CuInGaS₂ (CIGS) thin film solar cells with a three-dimensional (3D) nanostructure based on indium tin oxide (ITO) nanorod films and precursor solutions (Cu, In and Ga nitrates in alcohol). To obtain solution processed 3D nanostructured CIGS thin film solar cells, two different precursor solutions were applied to complete gap filling in ITO nanorods and achieve the desirable absorber film thickness. Specifically, a coating of precursor solution without polymer binder material was first applied to fill the gap between ITO nanorods followed by deposition of the second precursor solution in the presence of a binder to generate an absorber film thickness of ∼1.3 μm. A solar cell device with a (Al, Ni)/AZO/i-ZnO/CdS/CIGS/ITO nanorod/glass structure was constructed using the CIGS film, and the highest power conversion efficiency was measured to be ∼6.3% at standard irradiation conditions, which was 22.5% higher than the planar type of CIGS solar cell on ITO substrate fabricated using the same precursor solutions.

Surface Lewis acid-base properties of polymers measured by inverse gas chromatography.

PubMed

Shi, Baoli; Zhang, Qianru; Jia, Lina; Liu, Yang; Li, Bin

2007-05-18

Surface Lewis acid-base properties are significant for polymers materials. The acid constant, K(a) and base constant, K(b) of many polymers were characterized by some researchers with inverse gas chromatography (IGC) in recent years. In this paper, the surface acid-base constants, K(a) and K(b) of 20 kinds of polymers measured by IGC in recent years are summarized and discussed, including seven polymers characterized in this work. After plotting K(b) versus K(a), it is found that the polymers can be encircled by a triangle. They scatter in two regions of the triangle. Four polymers exist in region I. K(b)/K(a) of the polymers in region I are 1.4-2.1. The other polymers exist in region II. Most of the polymers are relative basic materials.

Functionalization of polymer surfaces by medium frequency non-thermal plasma

NASA Astrophysics Data System (ADS)

Felix, T.; Trigueiro, J. S.; Bundaleski, N.; Teodoro, O. M. N. D.; Sério, S.; Debacher, N. A.

2018-01-01

This work addresses the surface modification of different polymers by argon dielectric barrier discharge, using bromoform vapours. Atomic Force Microscopy and Scanning Electron Microscopy showed that plasma etching occurs in stages and may be related to the reach of the species generated and obviously the gap between the electrodes. In addition, the stages of flatten surface or homogeneity may be the result of the transient crosslinking promoted by the intense UV radiation generated by the non- thermal plasma. X-ray Photoelectron Spectroscopy analysis showed that bromine was inserted on the polymer surface as Csbnd Br bonds and as adsorbed HBr. The obtained results demonstrate that the highest degree of bromofunctionalization was achieved on polypropylene surface, which contains about 8,5% of Br. After its derivatization in ammonia, Br disappeared and about 6% of nitrogen in the form of amine group was incorporated at the surface. This result can be considered as a clear fingerprint of the Br substitution by the amine group, thus illustrating the efficiency of the proposed method for functionalization of polymer surfaces.

Measurements of Photo-induced Changes in Conjugated Polymers

DOE R&D Accomplishments Database

Seager, C. H.; Sinclair, M. B.; Mc Branch, D.; Heeger, A. J.; Baker, G. L.

1991-01-01

We have used the highly sensitive technique of Photothermal Deflection Spectroscopy (PDS) to measure changes in the infrared absorption spectra of MEHPPV, P3HT and Polydiacetylene-4BCMU induced by pumping these polymers with light above the {pi} - {pi}* transition energy. In contrast to previous chopped light transmission measurements of these effects, the PDS technique can directly measure the buildup or decay of the absorption coefficient, {alpha}, on the time scale of second to days. In the case of MEHPPV we observe that the time scale of seconds to days. In the case of MEHPPV we observe that above-gap light causes the appearance of a broad infrared peak in {alpha}, which continues to grow-in hours after the pump light is first applied. For this polymer the general shape of the absorption spectra in the unpumped state mimics the photo-induced changes, suggesting that remnant photo-induced states determine the maximum transparency observed under normal experimental conditions. For P3HT and to a lesser extent, MEHPPV, we also observe irreversible photo-induced absorption components which we tentatively identify with photo-induced oxidation of the polymer matrix.

Polymorphism and electronic structure of polyimine and its potential significance for prebiotic chemistry on Titan

NASA Astrophysics Data System (ADS)

Rahm, Martin; Lunine, Jonathan I.; Usher, David A.; Shalloway, David

2016-07-01

The chemistry of hydrogen cyanide (HCN) is believed to be central to the origin of life question. Contradictions between Cassini-Huygens mission measurements of the atmosphere and the surface of Saturn’s moon Titan suggest that HCN-based polymers may have formed on the surface from products of atmospheric chemistry. This makes Titan a valuable “natural laboratory” for exploring potential nonterrestrial forms of prebiotic chemistry. We have used theoretical calculations to investigate the chain conformations of polyimine (pI), a polymer identified as one major component of polymerized HCN in laboratory experiments. Thanks to its flexible backbone, the polymer can exist in several different polymorphs, which are relatively close in energy. The electronic and structural variability among them is extraordinary. The band gap changes over a 3-eV range when moving from a planar sheet-like structure to increasingly coiled conformations. The primary photon absorption is predicted to occur in a window of relative transparency in Titan’s atmosphere, indicating that pI could be photochemically active and drive chemistry on the surface. The thermodynamics for adding and removing HCN from pI under Titan conditions suggests that such dynamics is plausible, provided that catalysis or photochemistry is available to sufficiently lower reaction barriers. We speculate that the directionality of pI’s intermolecular and intramolecular =N-H…N hydrogen bonds may drive the formation of partially ordered structures, some of which may synergize with photon absorption and act catalytically. Future detailed studies on proposed mechanisms and the solubility and density of the polymers will aid in the design of future missions to Titan.

Effects of humidity and solution viscosity on electrospun fiber morphology.

PubMed

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

2013-10-01

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

Effects of Humidity and Solution Viscosity on Electrospun Fiber Morphology

PubMed Central

Nezarati, Roya M.; Eifert, Michelle B.

2013-01-01

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

Polymorphism and electronic structure of polyimine and its potential significance for prebiotic chemistry on Titan

PubMed Central

Rahm, Martin; Lunine, Jonathan I.; Usher, David A.; Shalloway, David

2016-01-01

The chemistry of hydrogen cyanide (HCN) is believed to be central to the origin of life question. Contradictions between Cassini–Huygens mission measurements of the atmosphere and the surface of Saturn’s moon Titan suggest that HCN-based polymers may have formed on the surface from products of atmospheric chemistry. This makes Titan a valuable “natural laboratory” for exploring potential nonterrestrial forms of prebiotic chemistry. We have used theoretical calculations to investigate the chain conformations of polyimine (pI), a polymer identified as one major component of polymerized HCN in laboratory experiments. Thanks to its flexible backbone, the polymer can exist in several different polymorphs, which are relatively close in energy. The electronic and structural variability among them is extraordinary. The band gap changes over a 3-eV range when moving from a planar sheet-like structure to increasingly coiled conformations. The primary photon absorption is predicted to occur in a window of relative transparency in Titan’s atmosphere, indicating that pI could be photochemically active and drive chemistry on the surface. The thermodynamics for adding and removing HCN from pI under Titan conditions suggests that such dynamics is plausible, provided that catalysis or photochemistry is available to sufficiently lower reaction barriers. We speculate that the directionality of pI’s intermolecular and intramolecular =N–H…N hydrogen bonds may drive the formation of partially ordered structures, some of which may synergize with photon absorption and act catalytically. Future detailed studies on proposed mechanisms and the solubility and density of the polymers will aid in the design of future missions to Titan. PMID:27382167

The effect of cycling deflection on the injection-molded thermoplastic denture base resins.

PubMed

Hamanaka, Ippei; Iwamoto, Misa; Lassila, Lippo Vj; Vallittu, Pekka K; Shimizu, Hiroshi; Takahashi, Yutaka

2016-01-01

The aim of this study was to evaluate the effect of cycling deflection on the flexural behavior of injection-molded thermoplastic resins. Six injection-molded thermoplastic resins (two polyamides, two polyesters, one polycarbonate, one polymethyl methacrylate) and, as a control, a conventional heat-polymerized denture based polymer of polymethyl methacrylate (PMMA) were used in this study. The cyclic constant magnitude (1.0 mm) of 5000 cycles was applied using a universal testing machine to demonstrate plasticization of the polymer. Loading was carried out in water at 23ºC with eight specimens per group (n = 8). Cycling load (N) and deformation (mm) were measured. Force required to deflect the specimens during the first loading cycle and final loading cycle was statistically significantly different (p < 0.05) with one polyamide based polymer (Valplast) and PMMA based polymers (Acrytone and Acron). The other polyamide based polymer (LucitoneFRS), polyester based polymers (EstheShot and EstheShotBright) and polycarbonate based polymer (ReigningN) did not show significant differences (p > 0.05). None of the materials fractured during the loading test. One polyamide based polymer (Valplast) displayed the highest deformation and PMMA based polymers (Acrytone and Acron) exhibited the second highest deformation among the denture base materials. It can be concluded that there were considerable differences in the flexural behavior of denture base polymers. This may contribute to the fatigue resistance of the materials.

Blue Shifting Tuning of the Selective Reflection of Polymer Stabilized Cholesteric Liquid Crystals (Postprint)

DTIC Science & Technology

2017-08-08

deformation then affects the anchoring of the low-molar mass CLC mixture resulting in broadening of the reflection band due to nonuniformity in the pitch...confirmed that the tuning is a result of nonuniform pitch displacement across the cell gap.17 In this contribution, we report on the realization of yet

Collaborative Center in Polymer Photonics

DTIC Science & Technology

2009-02-28

the inorganic residue in the thermogravimetric analysis TGA of the samples, Figure 6. It can be noticed that only approximately 1/3 of the...photonics, nanoparticles , structure, organic-inorganic hybrids, nanocomposites, photonic band gap, plasma-enhanced chemical vapor deposition, discotic liquid...the surface structure of nanoparticles made us focus our study on the morphological and thermodynamic properties of metallic nanoparticles . We cannot

Adhesion properties in systems of laminated pigmented polymers, carbon-graphite fiber composite framework and titanium surfaces in implant suprastructures.

PubMed

Segerström, Susanna; Ruyter, I Eystein

2009-09-01

For long-term stability the adhering interfaces of an implant-retained supraconstruction of titanium/carbon-graphite fiber-reinforced (CGFR) polymer/opaquer layer/denture base polymer/denture teeth must function as a unity. The aim was to evaluate adhesion of CGFR polymer to a titanium surface or CGFR polymer to two different opaquer layers/with two denture base polymers. Titanium plates were surface-treated and silanized and combined with a bolt of CGFR polymer or denture base polymer (Probase Hot). Heat-polymerized plates of CGFR polymer (47 wt% fiber) based on poly(methyl methacrylate) and a copolymer matrix were treated with an opaquer (Sinfony or Ropak) before a denture base polymer bolt was attached (Probase Hot or Lucitone 199). All specimens were heat-polymerized, water saturated (200 days) and thermally cycled (5000 cycles, 5/55 degrees C) before shear bond testing. Silicatized titanium surfaces gave higher bond strength to CGFR polymer (16.2+/-2.34 and 18.6+/-1.32) MPa and cohesive fracture than a sandblasted surface (5.9+/-2.11) MPa where the fracture was adhesive. The opaquer Sinfony gave higher adhesion values and mainly cohesive fractures than the opaquer Ropak. Different surface treatments (roughened or polished) of the CGFR polymer had no effect on bond strength. The fracture surfaces of silicatized titanium/CGFR polymer/opaquer layer (Sinfony)/denture base polymers were mainly cohesive. A combination of these materials in an implant-retained supraconstruction is promising for in vivo evaluation.

Influence of gap states on the nonresonant second hyperpolarizabilities of conjugated organic polymers

NASA Technical Reports Server (NTRS)

Beratan, David N.

1989-01-01

The presence of conjugation and substitution defects introduces gap states in finite polyenes that are shown to influence the size and sign of the second molecular hyperpolarizability (SMH). Using a one-electron tight-binding model, the dependence of SMH on the defect-state occupancy and energy in finite polyenes is calculated. Defects can cause a significant decrease or enhancement of SMH by impeding charge delocalization or by creating partly filled bands (mimicking the one-band limit), respectively. Concomitant sign changes in SMH are predicted. Calculation results suggest strategies for designing molecules that can be either photochemically or electrochemically switched between states with considerably different SMHs.

Mapping the electromagnetic field confinement in the gap of germanium nanoantennas with plasma wavelength of 4.5 micrometers

NASA Astrophysics Data System (ADS)

Calandrini, Eugenio; Venanzi, Tommaso; Appugliese, Felice; Badioli, Michela; Giliberti, Valeria; Baldassarre, Leonetta; Biagioni, Paolo; De Angelis, Francesco; Klesse, Wolfgang M.; Scappucci, Giordano; Ortolani, Michele

2016-09-01

We study plasmonic nanoantennas for molecular sensing in the mid-infrared made of heavily doped germanium, epitaxially grown with a bottom-up doping process and featuring free carrier density in excess of 1020 cm-3. The dielectric function of the 250 nm thick germanium film is determined, and bow-tie antennas are designed, fabricated, and embedded in a polymer. By using a near-field photoexpansion mapping technique at λ = 5.8 μm, we demonstrate the existence in the antenna gap of an electromagnetic energy density hotspot of diameter below 100 nm and confinement volume 105 times smaller than λ3.

A Primer on Polymer Nomenclature: Structure-Based, Sourced- Based, and Trade Names

ERIC Educational Resources Information Center

Cheng, H. N.; Howell, Bob A.

2017-01-01

Polymer nomenclature is important because it is part of the language of polymer science and is needed for polymer identification, reference, and documentation. A primer on polymer nomenclature is provided herein for people new to the field or for instructional use. Both structurebased and source-based nomenclatures, together with trivial and trade…

40 CFR 721.10036 - Acetaldehyde based polymer (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acetaldehyde based polymer (generic... Specific Chemical Substances § 721.10036 Acetaldehyde based polymer (generic). (a) Chemical substance and... based polymer (PMN P-02-406) is subject to reporting under this section for the significant new uses...

40 CFR 721.10036 - Acetaldehyde based polymer (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Acetaldehyde based polymer (generic... Specific Chemical Substances § 721.10036 Acetaldehyde based polymer (generic). (a) Chemical substance and... based polymer (PMN P-02-406) is subject to reporting under this section for the significant new uses...

40 CFR 721.10036 - Acetaldehyde based polymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Acetaldehyde based polymer (generic... Specific Chemical Substances § 721.10036 Acetaldehyde based polymer (generic). (a) Chemical substance and... based polymer (PMN P-02-406) is subject to reporting under this section for the significant new uses...

40 CFR 721.10036 - Acetaldehyde based polymer (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Acetaldehyde based polymer (generic... Specific Chemical Substances § 721.10036 Acetaldehyde based polymer (generic). (a) Chemical substance and... based polymer (PMN P-02-406) is subject to reporting under this section for the significant new uses...

40 CFR 721.10036 - Acetaldehyde based polymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Acetaldehyde based polymer (generic... Specific Chemical Substances § 721.10036 Acetaldehyde based polymer (generic). (a) Chemical substance and... based polymer (PMN P-02-406) is subject to reporting under this section for the significant new uses...

A molecular heterojunction of zinc phthalocyanine and peanut-shaped fullerene polymer: A density functional study

NASA Astrophysics Data System (ADS)

Tanikawa, Kousei; Ohno, Kaoru; Noda, Yusuke; Ono, Shota; Kuwahara, Riichi; Takashima, Akito; Nakaya, Masato; Onoe, Jun

2017-10-01

We have performed first-principles density functional calculations of a molecular heterojunction of a zinc phthalocyanine (ZnPc) molecule and a peanut-shaped fullerene polymer (PSFP) made from several coalesced cross-linked C60 molecules. The PSFP has many isomers and all have both spatially localized (near ZnPc) and metallic conducting levels. Here we consider four typical isomers. From the resulting electronic structure, we discuss the applicability of these isomers to organic photovoltaics (OPV), electrodes, and light harvesting materials. If one of the isomers called T3, which has the largest energy gap, is used together with ZnPc for OPV, this system shows more than 20% energy conversion efficiency.

Production of atmospheric pressure microwave plasma with dielectric half-mirror resonator and its application to polymer surface treatment

NASA Astrophysics Data System (ADS)

Sasai, Kensuke; Keyamura, Kazuki; Suzuki, Haruka; Toyoda, Hirotaka

2018-06-01

For the surface treatment of a polymer tube, a ring-shaped atmospheric pressure microwave plasma (APMP) using a coaxial waveguide is studied. In this APMP, a dielectric plate is used not only as a partial mirror for cavity resonation but also for the precise alignment of the discharge gap for ring-shaped plasma production. The optimum position of the dielectric plate is investigated by electromagnetic wave simulation. On the basis of simulation results, a ring-shaped plasma with good uniformity along the ring is produced. The coaxial APMP is applied to the surface treatment of ethylene tetrafluoroethylene. A very fast surface modification within 3 s is observed.

Quantitative property-structural relation modeling on polymeric dielectric materials

NASA Astrophysics Data System (ADS)

Wu, Ke

Nowadays, polymeric materials have attracted more and more attention in dielectric applications. But searching for a material with desired properties is still largely based on trial and error. To facilitate the development of new polymeric materials, heuristic models built using the Quantitative Structure Property Relationships (QSPR) techniques can provide reliable "working solutions". In this thesis, the application of QSPR on polymeric materials is studied from two angles: descriptors and algorithms. A novel set of descriptors, called infinite chain descriptors (ICD), are developed to encode the chemical features of pure polymers. ICD is designed to eliminate the uncertainty of polymer conformations and inconsistency of molecular representation of polymers. Models for the dielectric constant, band gap, dielectric loss tangent and glass transition temperatures of organic polymers are built with high prediction accuracy. Two new algorithms, the physics-enlightened learning method (PELM) and multi-mechanism detection, are designed to deal with two typical challenges in material QSPR. PELM is a meta-algorithm that utilizes the classic physical theory as guidance to construct the candidate learning function. It shows better out-of-domain prediction accuracy compared to the classic machine learning algorithm (support vector machine). Multi-mechanism detection is built based on a cluster-weighted mixing model similar to a Gaussian mixture model. The idea is to separate the data into subsets where each subset can be modeled by a much simpler model. The case study on glass transition temperature shows that this method can provide better overall prediction accuracy even though less data is available for each subset model. In addition, the techniques developed in this work are also applied to polymer nanocomposites (PNC). PNC are new materials with outstanding dielectric properties. As a key factor in determining the dispersion state of nanoparticles in the polymer matrix, the surface tension components of polymers are modeled using ICD. Compared to the 3D surface descriptors used in a previous study, the model with ICD has a much improved prediction accuracy and stability particularly for the polar component. In predicting the enhancement effect of grafting functional groups on the breakdown strength of PNC, a simple local charge transfer model is proposed where the electron affinity (EA) and ionization energy (IE) determines the main charge trap depth in the system. This physical model is supported by first principle computation. QSPR models for EA and IE are also built, decreasing the computation time of EA and IE for a single molecule from several hours to less than one second. Furthermore, the designs of two web-based tools are introduced. The tools represent two commonly used applications for QSPR studies: data inquiry and prediction. Making models and data public available and easy to use is particularly crucial for QSPR research. The web tools described in this work should provide a good guidance and starting point for the further development of information tools enabling more efficient cooperation between computational and experimental communities.

Skin-Inspired Hierarchical Polymer Architectures with Gradient Stiffness for Spacer-Free, Ultrathin, and Highly Sensitive Triboelectric Sensors.

PubMed

Ha, Minjeong; Lim, Seongdong; Cho, Soowon; Lee, Youngoh; Na, Sangyun; Baig, Chunggi; Ko, Hyunhyub

2018-04-24

The gradient stiffness between stiff epidermis and soft dermis with interlocked microridge structures in human skin induces effective stress transmission to underlying mechanoreceptors for enhanced tactile sensing. Inspired by skin structure and function, we fabricate hierarchical nanoporous and interlocked microridge structured polymers with gradient stiffness for spacer-free, ultrathin, and highly sensitive triboelectric sensors (TESs). The skin-inspired hierarchical polymers with gradient elastic modulus enhance the compressibility and contact areal differences due to effective transmission of the external stress from stiff to soft layers, resulting in highly sensitive TESs capable of detecting human vital signs and voice. In addition, the microridges in the interlocked polymers provide an effective variation of gap distance between interlocked layers without using the bulk spacer and thus facilitate the ultrathin and flexible design of TESs that could be worn on the body and detect a variety of pressing, bending, and twisting motions even in humid and underwater environments. Our TESs exhibit the highest power density (46.7 μW/cm 2 ), pressure (0.55 V/kPa), and bending (∼0.1 V/°) sensitivities ever reported on flexible TESs. The proposed design of hierarchical polymer architectures for the flexible and wearable TESs can find numerous applications in next-generation wearable electronics.

A magnetic resonance (MR) microscopy system using a microfluidically cryo-cooled planar coil.

PubMed

Koo, Chiwan; Godley, Richard F; Park, Jaewon; McDougall, Mary P; Wright, Steven M; Han, Arum

2011-07-07

We present the development of a microfluidically cryo-cooled planar coil for magnetic resonance (MR) microscopy. Cryogenically cooling radiofrequency (RF) coils for magnetic resonance imaging (MRI) can improve the signal to noise ratio (SNR) of the experiment. Conventional cryostats typically use a vacuum gap to keep samples to be imaged, especially biological samples, at or near room temperature during cryo-cooling. This limits how close a cryo-cooled coil can be placed to the sample. At the same time, a small coil-to-sample distance significantly improves the MR imaging capability due to the limited imaging depth of planar MR microcoils. These two conflicting requirements pose challenges to the use of cryo-cooling in MR microcoils. The use of a microfluidic based cryostat for localized cryo-cooling of MR microcoils is a step towards eliminating these constraints. The system presented here consists of planar receive-only coils with integrated cryo-cooling microfluidic channels underneath, and an imaging surface on top of the planar coils separated by a thin nitrogen gas gap. Polymer microfluidic channel structures fabricated through soft lithography processes were used to flow liquid nitrogen under the coils in order to cryo-cool the planar coils to liquid nitrogen temperature (-196 °C). Two unique features of the cryo-cooling system minimize the distance between the coil and the sample: (1) the small dimension of the polymer microfluidic channel enables localized cooling of the planar coils, while minimizing thermal effects on the nearby imaging surface. (2) The imaging surface is separated from the cryo-cooled planar coil by a thin gap through which nitrogen gas flows to thermally insulate the imaging surface, keeping it above 0 °C and preventing potential damage to biological samples. The localized cooling effect was validated by simulations, bench testing, and MR imaging experiments. Using this cryo-cooled planar coil system inside a 4.7 Tesla MR system resulted in an average image SNR enhancement of 1.47 ± 0.11 times relative to similar room-temperature coils. This journal is © The Royal Society of Chemistry 2011

A Magnetic Resonance (MR) Microscopy System using a Microfluidically Cryo-Cooled Planar Coil

PubMed Central

Koo, Chiwan; Godley, Richard F.; Park, Jaewon; McDougall, Mary P.; Wright, Steven M.; Han, Arum

2011-01-01

We present the development of a microfluidically cryo-cooled planar coil for magnetic resonance (MR) microscopy. Cryogenically cooling radiofrequency (RF) coils for magnetic resonance imaging (MRI) can improve the signal to noise ratio (SNR) of the experiment. Conventional cryostats typically use a vacuum gap to keep samples to be imaged, especially biological samples, at or near room temperature during cryo-cooling. This limits how close a cryo-cooled coil can be placed to the sample. At the same time, a small coil-to-sample distance significantly improves the MR imaging capability due to the limited imaging depth of planar MR microcoils. These two conflicting requirements pose challenges to the use of cryo-cooling in MR microcoils. The use of a microfluidic based cryostat for localized cryo-cooling of MR microcoils is a step towards eliminating these constraints. The system presented here consists of planar receive-only coils with integrated cryo-cooling microfluidic channels underneath, and an imaging surface on top of the planar coils separated by a thin nitrogen gas gap. Polymer microfluidic channel structures fabricated through soft lithography processes were used to flow liquid nitrogen under the coils in order to cryo-cool the planar coils to liquid nitrogen temperature (−196°C). Two unique features of the cryo-cooling system minimize the distance between the coil and the sample: 1) The small dimension of the polymer microfluidic channel enables localized cooling of the planar coils, while minimizing thermal effects on the nearby imaging surface. 2) The imaging surface is separated from the cryo-cooled planar coil by a thin gap through which nitrogen gas flows to thermally insulate the imaging surface, keeping it above 0°C and preventing potential damage to biological samples. The localized cooling effect was validated by simulations, bench testing, and MR imaging experiments. Using this cryo-cooled planar coil system inside a 4.7 Tesla MR system resulted in an average image SNR enhancement of 1.47 ± 0.11 times relative to similar room-temperature coils. PMID:21603723

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

Influence of charge carrier mobility and morphology on solar cell parameters in devices of mono- and bis-fullerene adducts.

PubMed

Muth, Mathis-Andreas; Mitchell, William; Tierney, Steven; Lada, Thomas A; Xue, Xiang; Richter, Henning; Carrasco-Orozco, Miguel; Thelakkat, Mukundan

2013-12-06

Herein, we analyze charge carrier mobility and morphology of the active blend layer in thin film organic solar cells and correlate them with device parameters. A low band gap donor-acceptor copolymer in combination with phenyl-C61-butyric acid methyl ester (PCBM) or two bis-adduct fullerenes, bis-PCBM and bis-o-quino-dimethane C60 (bis-oQDMC), is investigated. We study the charge transport of polymer:fullerene blends in hole- and electron-only devices using the space-charge limited current method. Lower electron mobilities are observed in both bis-adduct fullerene blends. Hole mobility, however, is decreased only in the blend containing bis-oQDMC. Both bis-adduct fullerene blends show very high open circuit voltage in solar cell devices, but poor photocurrent compared to the standard PCBM blend for an active layer thickness of 200 nm. Therefore, a higher short circuit current is feasible for the polymer:bis-PCBM blend by reducing the active layer thickness in order to compensate for the low electron mobility, which results in a PCE of 4.3%. For the polymer:bis-oQDMC blend, no such improvement is achieved due to an unfavorable morphology in this particular blend system. The results are supported by external quantum efficiency measurements, atomic force microscopy, transmission electron microscopy and UV/vis spectroscopy. Based on these results, the investigations presented herein give a more scientific basis for the optimization of solar cells.

Escalation of polymerization in a thermal gradient

PubMed Central

Mast, Christof B.; Schink, Severin; Gerland, Ulrich; Braun, Dieter

2013-01-01

For the emergence of early life, the formation of biopolymers such as RNA is essential. However, the addition of nucleotide monomers to existing oligonucleotides requires millimolar concentrations. Even in such optimistic settings, no polymerization of RNA longer than about 20 bases could be demonstrated. How then could self-replicating ribozymes appear, for which recent experiments suggest a minimal length of 200 nt? Here, we demonstrate a mechanism to bridge this gap: the escalated polymerization of nucleotides by a spatially confined thermal gradient. The gradient accumulates monomers by thermophoresis and convection while retaining longer polymers exponentially better. Polymerization and accumulation become mutually self-enhancing and result in a hyperexponential escalation of polymer length. We describe this escalation theoretically under the conservative assumption of reversible polymerization. Taking into account the separately measured thermophoretic properties of RNA, we extrapolate the results for primordial RNA polymerization inside a temperature gradient in pores or fissures of rocks. With a dilute, nanomolar concentration of monomers the model predicts that a pore length of 5 cm and a temperature difference of 10 K suffice to polymerize 200-mers of RNA in micromolar concentrations. The probability to generate these long RNAs is raised by a factor of >10600 compared with polymerization in a physical equilibrium. We experimentally validate the theory with the reversible polymerization of DNA blocks in a laser-driven thermal trap. The results confirm that a thermal gradient can significantly enlarge the available sequence space for the emergence of catalytically active polymers. PMID:23630280

Optical properties of thin fibrous PVP/SiO2 composite mats prepared via the sol-gel and electrospinning methods

NASA Astrophysics Data System (ADS)

Tański, Tomasz; Matysiak, Wiktor; Krzemiński, Łukasz; Jarka, Paweł; Gołombek, Klaudiusz

2017-12-01

The aim of the research was to create thin, nanofibrous composite mats with a polyvinylpyrrolidone (PVP) matrix, with the reinforcing phase in the form of silicon oxide (SiO2) nanoparticles. SiO2 nanopowder was obtained using the zol-gel method with a mixture of tetraethyl orthosilicate (TEOS, Si (OC2H5)), hydrochloric acid (HCl), ethanol (C3H5OH) and distilled water. The produced colloidal suspension was subjected to a drying process and a calcination process at 550 °C, resulting in an amorphous silica nanopowder with an average particle diameter of 20 nm. The morphology and structure of the manufactured SiO2 nanoparticles was tested using transmission electron microscopy (TEM) and X-ray diffraction analysis (XRD). Then, using the electrospinning method with a 15% (weight) solution of PVP in ethanol and a 15% solution of PVP/EtOH containing the produced nanoparticles equivalent to 5% of the mass concentration relative to the polymer matrix, polymer PVP nanofibres and PVP/SiO2 composite nanofibres/SiO2 nanoparticles were produced. The morphology and chemical composition of the produced polymer and composite nanofibres were tested using a scanning electron microscope (SEM) with an energy dispersive spectrometer (EDS). The analysis of the impact of the reinforcing phase on the absorption of electromagnetic radiation was conducted on the basis of UV-vis spectra, based on which the rated values of band gaps of the produced thin fibrous mats were assessed.

40 CFR 721.463 - Acrylate of polymer based on isophorone diisocyanate (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acrylate of polymer based on... New Uses for Specific Chemical Substances § 721.463 Acrylate of polymer based on isophorone... substance identified generically as acrylate of polymer based on isophorone diisocyanate (PMN P-00-0626) is...

40 CFR 721.463 - Acrylate of polymer based on isophorone diisocyanate (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Acrylate of polymer based on... New Uses for Specific Chemical Substances § 721.463 Acrylate of polymer based on isophorone... substance identified generically as acrylate of polymer based on isophorone diisocyanate (PMN P-00-0626) is...

40 CFR 721.463 - Acrylate of polymer based on isophorone diisocyanate (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Acrylate of polymer based on... New Uses for Specific Chemical Substances § 721.463 Acrylate of polymer based on isophorone... substance identified generically as acrylate of polymer based on isophorone diisocyanate (PMN P-00-0626) is...

40 CFR 721.463 - Acrylate of polymer based on isophorone diisocyanate (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Acrylate of polymer based on... New Uses for Specific Chemical Substances § 721.463 Acrylate of polymer based on isophorone... substance identified generically as acrylate of polymer based on isophorone diisocyanate (PMN P-00-0626) is...

40 CFR 721.463 - Acrylate of polymer based on isophorone diisocyanate (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Acrylate of polymer based on... New Uses for Specific Chemical Substances § 721.463 Acrylate of polymer based on isophorone... substance identified generically as acrylate of polymer based on isophorone diisocyanate (PMN P-00-0626) is...

Charge transfer complex in diketopyrrolopyrrole polymers and fullerene blends: Implication for organic solar cell efficiency

NASA Astrophysics Data System (ADS)

Moghe, D.; Yu, P.; Kanimozhi, C.; Patil, S.; Guha, S.

2012-02-01

Copolymers based on diketopyrrolopyrrole (DPP) have recently gained potential in organic photovoltaics. When blended with another acceptor such as PCBM, intermolecular charge transfer occurs which may result in the formation of charge transfer (CT) states. We present here the spectral photocurrent characteristics of two donor-acceptor DPP based copolymers, PDPP-BBT and TDPP-BBT, blended with PCBM to identify the CT states. The spectral photocurrent measured using Fourier-transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) methods are compared with P3HT:PCBM, where the CT state is well known. PDPP-BBT:PCBM shows a stable CT state while TDPP-BBT does not. Our analysis shows that the larger singlet state energy difference between TDPP-BBT and PCBM along with the lower optical gap of TDPP-BBT obliterates the formation of a midgap CT state resulting in an enhanced photovoltaic efficiency over PDPP-BBT:PCBM.

Selection of optimal sensors for predicting performance of polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Mao, Lei; Jackson, Lisa

2016-10-01

In this paper, sensor selection algorithms are investigated based on a sensitivity analysis, and the capability of optimal sensors in predicting PEM fuel cell performance is also studied using test data. The fuel cell model is developed for generating the sensitivity matrix relating sensor measurements and fuel cell health parameters. From the sensitivity matrix, two sensor selection approaches, including the largest gap method, and exhaustive brute force searching technique, are applied to find the optimal sensors providing reliable predictions. Based on the results, a sensor selection approach considering both sensor sensitivity and noise resistance is proposed to find the optimal sensor set with minimum size. Furthermore, the performance of the optimal sensor set is studied to predict fuel cell performance using test data from a PEM fuel cell system. Results demonstrate that with optimal sensors, the performance of PEM fuel cell can be predicted with good quality.

Molecular design toward highly efficient photovoltaic polymers based on two-dimensional conjugated benzodithiophene.

PubMed

Ye, Long; Zhang, Shaoqing; Huo, Lijun; Zhang, Maojie; Hou, Jianhui

2014-05-20

As researchers continue to develop new organic materials for solar cells, benzo[1,2-b:4,5-b']dithiophene (BDT)-based polymers have come to the fore. To improve the photovoltaic properties of BDT-based polymers, researchers have developed and applied various strategies leading to the successful molecular design of highly efficient photovoltaic polymers. Novel polymer materials composed of two-dimensional conjugated BDT (2D-conjugated BDT) have boosted the power conversion efficiency of polymer solar cells (PSCs) to levels that exceed 9%. In this Account, we summarize recent progress related to the design and synthesis of 2D-conjugated BDT-based polymers and discuss their applications in highly efficient photovoltaic devices. We introduce the basic considerations for the construction of 2D-conjugated BDT-based polymers and systematic molecular design guidelines. For example, simply modifying an alkoxyl-substituted BDT to form an alkylthienyl-substituted BDT can improve the polymer hole mobilities substantially with little effect on their molecular energy level. Secondly, the addition of a variety of chemical moieties to the polymer can produce a 2D-conjugated BDT unit with more functions. For example, the introduction of a conjugated side chain with electron deficient groups (such as para-alkyl-phenyl, meta-alkoxyl-phenyl, and 2-alkyl-3-fluoro-thienyl) allowed us to modulate the molecular energy levels of 2D-conjugated BDT-based polymers. Through the rational design of BDT analogues such as dithienobenzodithiophene (DTBDT) or the insertion of larger π bridges, we can tune the backbone conformations of these polymers and modulate their photovoltaic properties. We also discuss the influence of 2D-conjugated BDT on polymer morphology and the blends of these polymers with phenyl-C61 (or C71)-butyric acid methyl ester (PCBM). Finally, we summarize the various applications of the 2D-conjugated BDT-based polymers in highly efficient PSC devices. Overall, this Account correlates the molecular structures of the 2D-conjugated BDT-based polymers with their photovoltaic properties. As a result, this Account can guide the molecular design of organic photovoltaic materials and the development of organic materials for other types of optoelectronic devices.

Tunable Optical Polymer Systems (TOPS)

DTIC Science & Technology

2001-05-01

pixelation o1 displays is done. One team member has combined this work with self-assembling layers so that it is possible to make three-dimensional...I THERMOCHROMISM I ELECTROCHEMILUMINESCENCE (ECL) I MAGNETOCHROMISM I TUNABLE ELECTROLUMINESCENCE (EL) PROTONIC BAND GAP (PBG) SELECTIVE...via Selective Reflection • Chiral-nematic liquid crystalline film as a helical stack of quasinematic layers , illustrated below with a LH structure

Polymer Electrolyte Membranes for Water Photo-Electrolysis

PubMed Central

Aricò, Antonino S.; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-01-01

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion® 115) and quaternary ammonium-based (Fumatech® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion®-based cell when just TiO2 anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion. PMID:28468242

Polymer Electrolyte Membranes for Water Photo-Electrolysis.

PubMed

Aricò, Antonino S; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-04-29

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion ® 115) and quaternary ammonium-based (Fumatech ® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion ® -based cell when just TiO₂ anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion.

Exploring the role of peptides in polymer-based gene delivery.

PubMed

Sun, Yanping; Yang, Zhen; Wang, Chunxi; Yang, Tianzhi; Cai, Cuifang; Zhao, Xiaoyun; Yang, Li; Ding, Pingtian

2017-09-15

Polymers are widely studied as non-viral gene vectors because of their strong DNA binding ability, capacity to carry large payload, flexibility of chemical modifications, low immunogenicity, and facile processes for manufacturing. However, high cytotoxicity and low transfection efficiency substantially restrict their application in clinical trials. Incorporating functional peptides is a promising approach to address these issues. Peptides demonstrate various functions in polymer-based gene delivery systems, such as targeting to specific cells, breaching membrane barriers, facilitating DNA condensation and release, and lowering cytotoxicity. In this review, we systematically summarize the role of peptides in polymer-based gene delivery, and elaborate how to rationally design polymer-peptide based gene delivery vectors. Polymers are widely studied as non-viral gene vectors, but suffer from high cytotoxicity and low transfection efficiency. Incorporating short, bioactive peptides into polymer-based gene delivery systems can address this issue. Peptides demonstrate various functions in polymer-based gene delivery systems, such as targeting to specific cells, breaching membrane barriers, facilitating DNA condensation and release, and lowering cytotoxicity. In this review, we highlight the peptides' roles in polymer-based gene delivery, and elaborate how to utilize various functional peptides to enhance the transfection efficiency of polymers. The optimized peptide-polymer vectors should be able to alter their structures and functions according to biological microenvironments and utilize inherent intracellular pathways of cells, and consequently overcome the barriers during gene delivery to enhance transfection efficiency. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Integrated polymer micro-ring resonators for optical sensing applications

NASA Astrophysics Data System (ADS)

Girault, Pauline; Lorrain, Nathalie; Poffo, Luiz; Guendouz, Mohammed; Lemaitre, Jonathan; Carré, Christiane; Gadonna, Michel; Bosc, Dominique; Vignaud, Guillaume

2015-03-01

Micro-resonators (MR) have become a key element for integrated optical sensors due to their integration capability and their easy fabrication with low cost polymer materials. Nowadays, there is a growing need on MRs as highly sensitive and selective functions especially in the areas of food and health. The context of this work is to implement and study integrated micro-ring resonators devoted to sensing applications. They are fabricated by processing SU8 polymer as core layer and PMATRIFE polymer as lower cladding layer. The refractive index of the polymers and of the waveguide structure as a function of the wavelength is presented. Using these results, a theoretical study of the coupling between ring and straight waveguides has been undertaken in order to define the MR design. Sub-micronic gaps of 0.5 μm to 1 μm between the ring and the straight waveguides have been successfully achieved with UV (i-lines) photolithography. Different superstrates such as air, water, and aqueous solutions with glucose at different concentrations have been studied. First results show a good normalized transmission contrast of 0.98, a resonator quality factor around 1.5 × 104 corresponding to a coupling ratio of 14.7%, and ring propagation losses around 5 dB/cm. Preliminary sensing experiments have been performed for different concentrations of glucose; a sensitivity of 115 ± 8 nm/RIU at 1550 nm has been obtained with this couple of polymers.

Development of controlled drug release systems based on thiolated polymers.

PubMed

Bernkop-Schnürch, A; Scholler, S; Biebel, R G

2000-05-03

The purpose of the present study was to generate mucoadhesive matrix-tablets based on thiolated polymers. Mediated by a carbodiimide, L-cysteine was thereby covalently linked to polycarbophil (PCP) and sodium carboxymethylcellulose (CMC). The resulting thiolated polymers displayed 100+/-8 and 1280+/-84 micromol thiol groups per gram, respectively (means+/-S.D.; n=6-8). In aqueous solutions these modified polymers were capable of forming inter- and/or intramolecular disulfide bonds. The velocity of this process augmented with increase of the polymer- and decrease of the proton-concentration. The oxidation proceeded more rapidly within thiolated PCP than within thiolated CMC. Due to the formation of disulfide bonds within thiol-containing polymers, the stability of matrix-tablets based on such polymers could be strongly improved. Whereas tablets based on the corresponding unmodified polymer disintegrated within 2 h, the swollen carrier matrix of thiolated CMC and PCP remained stable for 6.2 h (mean, n=4) and more than 48 h, respectively. Release studies of the model drug rifampicin demonstrated that a controlled release can be provided by thiolated polymer tablets. The combination of high stability, controlled drug release and mucoadhesive properties renders matrix-tablets based on thiolated polymers useful as novel drug delivery systems.

Dye-Incorporated Polynaphthalenediimide Acceptor for Additive-Free High-Performance All-Polymer Solar Cells.

PubMed

Chen, Dong; Yao, Jia; Chen, Lie; Yin, Jingping; Lv, Ruizhi; Huang, Bin; Liu, Siqi; Zhang, Zhi-Guo; Yang, Chunhe; Chen, Yiwang; Li, Yongfang

2018-04-16

All-polymer solar cells (all-PSCs) can offer unique advantages for applications in flexible devices, and naphthalene diimide (NDI)-based polymer acceptors are the widely used polymer acceptors. However, their power conversion efficiency (PCE) still lags behind that of state-of-the-art polymer solar cells, due to low light absorption, suboptimal energy levels and the strong aggregation of the NDI-based polymer acceptor. Herein, a rhodanine-based dye molecule was introduced into the NDI-based polymer acceptor by simple random copolymerization and showed an improved light absorption coefficient, an up-shifted lowest unoccupied molecular orbital level and reduced crystallization. Consequently, additive-free all-PSCs demonstrated a high PCE of 8.13 %, which is one of the highest performance characteristics reported for all-PSCs to date. These results indicate that incorporating a dye into the n-type polymer gives insight into the precise design of high-performance polymer acceptors for all-PSCs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and photovoltaic properties of 2,6-bis(2-thienyl) benzobisazole and 4,8-bis(thienyl)-benzo[1,2- B :4,5- B' ]dithiophene copolymers

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

Bhuwalka, Achala; Ewan, Monique D.; Elshobaki, Moneim

2015-08-22

In an effort to design efficient low-cost polymers for use in organic photovoltaic cells the easily prepared donor–acceptor–donor triad of a either cis-benzobisoxazole, trans-benzobisoxazole or trans-benzobisthiazole flanked by two thiophene rings was combined with the electron-rich 4,8-bis(5-(2-ethylhexyl)-thien-2-yl)-benzo[1,2-b:4,5-b']dithiophene. The electrochemical, optical, morphological, charge transport, and photovoltaic properties of the resulting terpolymers were investigated. Although the polymers differed in the arrangement and/or nature of the chalcogens, they all had similar highest occupied molecular orbital energy levels (-5.2 to -5.3 eV) and optical band gaps (2.1–2.2 eV). However, the lowest unoccupied molecular orbital energy levels ranged from -3.1 to -3.5 eV. When themore » polymers were used as electron donors in bulk heterojunction photovoltaic devices with PC71BM ([6,6]-phenyl C71-butyric acid methyl ester) as the acceptor, the trans-benzobisoxazole polymer had the best performance with a power conversion efficiency of 2.8%.« less

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

Qu, Shiwei; Wang, Huan; Mo, Daize

A new family of thieno[3,4-b]thiophene benzodithiophene terpolymers (PBTClx) have been designed and synthesized, in which the chlorine/fluorine content has been adjusted and optimized. As the content of chlorine is increased in polymers, the twist angle between the donor and acceptor is increased, which leads to a diminishment in the planarity and conjugation. As a result, the UV vis absorption is continuous blue-shifted, and the band gap increases from 1.57 to 2.04 eV when the chlorinated moieties increased from 0 to 100%. The highest occupied molecular orbital (HOMO) levels of those polymers are decreased by increasing the content of chlorinated moiety,more » which opens a window to constantly modify the V-oc values and eventually meets a balance point for optimized solar energy conversion. The highest power conversion efficiency of 8.31% is obtained by using PBTCl25 as the donor and PC71BM as the acceptor in polymer solar cells (PSCs), in which the Voc increased from 0.79 to 0.82 V after 25% chlorinated monomer involved in copolymerization. Herein, the chlorine replacement could be a good method to further pump the solar conversion by increasing the open circuit voltage without reducing other factors of the polymer solar cells.« less

Polymers for electronics and spintronics.

PubMed

Bujak, Piotr; Kulszewicz-Bajer, Irena; Zagorska, Malgorzata; Maurel, Vincent; Wielgus, Ireneusz; Pron, Adam

2013-12-07

This critical review is devoted to semiconducting and high spin polymers which are of great scientific interest in view of further development of the organic electronics and the emerging organic spintronic fields. Diversified synthetic strategies are discussed in detail leading to high molecular mass compounds showing appropriate redox (ionization potential (IP), electron affinity (EA)), electronic (charge carrier mobility, conductivity), optoelectronic (electroluminescence, photoconductivity) and magnetic (magnetization, ferromagnetic spin interactions) properties and used as active components of devices such as n- and p-channel field effect transistors, ambipolar light emitting transistors, light emitting diodes, photovoltaic cells, photodiodes, magnetic photoswitches, etc. Solution processing procedures developed with the goal of depositing highly ordered and oriented films of these polymers are also described. This is completed by the description of principal methods that are used for characterizing these macromolecular compounds both in solution and in the solid state. These involve various spectroscopic methods (UV-vis-NIR, UPS, pulse EPR), electrochemistry and spectroelectrochemistry, magnetic measurements (SQUID), and structural and morphological investigations (X-ray diffraction, STM, AFM). Finally, four classes of polymers are discussed in detail with special emphasis on the results obtained in the past three years: (i) high IP, (ii) high |EA|, (iii) low band gap and (iv) high spin ones.

Thermoplastic Ribbon-Ply Bonding Model

NASA Technical Reports Server (NTRS)

Hinkley, Jeffrey A.; Marchello, Joseph M.; Messier, Bernadette C.

1996-01-01

The aim of the present work was to identify key variables in rapid weldbonding of thermoplastic tow (ribbon) and their relationship to matrix polymer properties and to ribbon microstructure. Theoretical models for viscosity, establishment of ply-ply contact, instantaneous (Velcro) bonding, molecular interdiffusion (healing), void growth suppression, and gap filling were reviewed and synthesized. Consideration of the theoretical bonding mechanisms and length scales and of the experimental weld/peel data allow the prediction of such quantities as the time and pressure required to achieve good contact between a ribbon and a flat substrate, the time dependence of bond strength, pressures needed to prevent void growth from dissolved moisture and conditions for filling gaps and smoothing overlaps.

Design of Functional Materials based on Liquid Crystalline Droplets.

PubMed

Miller, Daniel S; Wang, Xiaoguang; Abbott, Nicholas L

2014-01-14

This brief perspective focuses on recent advances in the design of functional soft materials that are based on confinement of low molecular weight liquid crystals (LCs) within micrometer-sized droplets. While the ordering of LCs within micrometer-sized domains has been explored extensively in polymer-dispersed LC materials, recent studies performed with LC domains with precisely defined size and interfacial chemistry have unmasked observations of confinement-induced ordering of LCs that do not follow previously reported theoretical predictions. These new findings, which are enabled in part by advances in the preparation of LCs encapsulated in polymeric shells, are opening up new opportunities for the design of soft responsive materials based on surface-induced ordering transitions. These materials are also providing new insights into the self-assembly of biomolecular and colloidal species at defects formed by LCs confined to micrometer-sized domains. The studies presented in this perspective serve additionally to highlight gaps in knowledge regarding the ordering of LCs in confined systems.

Spectroscopic investigations upon 100MeV oxygen ions irradiation on polyaniline and poly-o-toluidine

NASA Astrophysics Data System (ADS)

Patil, Harshada K.; Deshmukh, Megha A.; Bodkhe, Gajanan A.; Asokan, K.; Shirsat, Mahendra D.

2018-05-01

Conducting polymers are the materials been extensively studied in the field of organic devise applications. The extended π-orbital which enables electron to move from one to another end of polymer made it flexible in tailoring different properties and therefore are known to be the considerably attractive materials. Here in this report Polyaniline (PANI) and Poly-o-toluidine (PoT) the derivative of PANI where one hydrogen atom of main polymer chain is substituted with the methyl group are studied upon irradiation with 100MeV oxygen ions irradiation at different fluences. PANI and PoT consist of interesting properties viz. electrochemical and optical properties, moderate conductivity, as well as environmental stability, may be applicable to the chemical sensing applications. Swift Heavy Ions (SHI) irradiation is the exclusively applied tool in detrimental modifications of solid materials. The effects of SHI irradiation on PANI and PoT were studied using UV - Vis spectroscopy and Raman spectroscopy. The band gap studies were done with Tauc plot calculations.

Sequence Effects in Conjugated Donor-Acceptor Trimers and Polymers.

PubMed

Zhang, Shaopeng; Hutchison, Geoffrey R; Meyer, Tara Y

2016-06-01

To investigate the sequence effect on donor-acceptor conjugated oligomers and polymers, the trimeric isomers PBP and BPP, comprising dialkoxy phenylene vinylene (P), benzothiadiazole vinylene (B), and alkyl endgroups with terminal olefins, are synthesized. Sequence effects are evident in the optical/electrochemical properties and thermal properties. Absorption maxima for PBP and BPP differ by 41 nm and the electrochemical band gaps by 0.1 V. The molar emission intensity is five times greater in PBP than BPP. Both trimers are crystalline and the melting points differ by 17 °C. The PBP and BPP trimers are used as macromonomers in an acyclic diene metathesis polymerization to give PolyPBP and PolyBPP. The optical and electrochemical properties are similar to those of their trimer precursors-sequence effects are still evident. These results suggest that sequence is a tunable variable for electronic materials and that the polymerization of oligomeric sequences is a useful approach to introducing sequence into polymers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonvolatile Solid-State Charged-Polymer Gating of Topological Insulators into the Topological Insulating Regime

NASA Astrophysics Data System (ADS)

Ireland, R. M.; Wu, Liang; Salehi, M.; Oh, S.; Armitage, N. P.; Katz, H. E.

2018-04-01

We demonstrate the ability to reduce the carrier concentration of thin films of the topological insulator (TI) Bi2 Se3 by utilizing a nonvolatile electrostatic gating via corona charging of electret polymers. Sufficient electric field can be imparted to a polymer-TI bilayer to result in significant electron density depletion, even without the continuous connection of a gate electrode or the chemical modification of the TI. We show that the Fermi level of Bi2 Se3 is shifted toward the Dirac point with this method. Using terahertz spectroscopy, we find that the surface chemical potential is lowered into the bulk band gap (approximately 50 meV above the Dirac point and 170 meV below the conduction-band minimum), and it is stabilized in the intrinsic regime while enhancing electron mobility. The mobility of surface state electrons is enhanced to a value as high as approximately 1600 cm2/V s at 5 K.

Probing nanoscale ion dynamics in ultrathin films of polymerized ionic liquids by broadband dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Sangoro, Joshua; Heres, Maximilian; Cosby, Tyler

Continuous progress in energy storage and conversion technologies necessitates novel experimental approaches that can provide fundamental insights regarding the impact of reduced dimensions on the functional properties of materials. In this talk, a nondestructive experimental approach to probe nanoscale ion dynamics in ultrathin films of polymerized ionic liquids over a broad frequency range spanning over six orders of magnitude by broadband dielectric spectroscopy will be presented. The approach involves using an electrode configuration with lithographically patterned silica nanostructures, which allow for an air gap between the confined ion conductor and one of the electrodes. It is observed that the characteristic ion dynamics rates significantly slow down with decreasing film thicknesses above the calorimetric glass transition of the bulk polymer. However, the mean rates remain bulk-like at lower temperatures. These results highlight the increasing influence of the polymer/substrate interactions with decreasing film thickness on ion dynamics. The authors gratefully acknowledge the National Science Foundation for financial support through the Polymers Program award DMR-1508394.

A polymer dataset for accelerated property prediction and design

DOE PAGES

Huan, Tran Doan; Mannodi-Kanakkithodi, Arun; Kim, Chiho; ...

2016-03-01

Emerging computation- and data-driven approaches are particularly useful for rationally designing materials with targeted properties. Generally, these approaches rely on identifying structure-property relationships by learning from a dataset of sufficiently large number of relevant materials. The learned information can then be used to predict the properties of materials not already in the dataset, thus accelerating the materials design. Herein, we develop a dataset of 1,073 polymers and related materials and make it available at http://khazana.uconn.edu/. This dataset is uniformly prepared using first-principles calculations with structures obtained either from other sources or by using structure search methods. Because the immediate targetmore » of this work is to assist the design of high dielectric constant polymers, it is initially designed to include the optimized structures, atomization energies, band gaps, and dielectric constants. As a result, it will be progressively expanded by accumulating new materials and including additional properties calculated for the optimized structures provided.« less

Electrical and optical properties of nitrile rubber modified by ion implantation

NASA Astrophysics Data System (ADS)

S, Najidha; Predeep, P.

2014-10-01

Implantation of N+ ion beams are performed on to a non-conjugated elastomer, acrylonirtle butadiene rubber (NBR) with energy 60 keV in the fluence range of 1014 to 1016 ions/cm2. A decrease in the resistivity of the sample by about eight orders of magnitude is observed in the implanted samples along with color changes. The ion exposed specimens were characterized by means of UV/Vis spectroscopy which shows a shift in the absorption edge value for the as deposited polymer towards higher wavelengths. The band gap is evaluated from the absorption spectra and is found to decrease with increasing fluence. This study can possibly throw light on ion induced changes in the polymer surface.

Selective CO2 conversion to formate in water using a CZTS photocathode modified with a ruthenium complex polymer.

PubMed

Arai, Takeo; Tajima, Shin; Sato, Shunsuke; Uemura, Keiko; Morikawa, Takeshi; Kajino, Tsutomu

2011-12-21

Highly selective photoelectrochemical CO(2) reduction (>80% selectivity) in water was successfully achieved by combining Cu(2)ZnSnS(4) (CZTS) with a metal-complex electrocatalyst. CZTS, a sulfide semiconductor that possesses a narrow band gap and consists of earth-abundant elements, is demonstrated to be a candidate photoabsorber for a CO(2) reduction hybrid photocatalyst.

Elimination of Perchlorate Oxidizers from Pyrotechnic Flare Compositions

DTIC Science & Technology

2007-03-09

in candelas ( cd ), where the candela is defined as, 1 cd = 1 lumen /steradian-1. DSC A thermal analysis technique known as Differential...Shorter Wavelength Infrared band routinely monitored in decoy flare performance tests. TGA A thermal analysis technique known as Thermogravimetric ...Scanning Calorimetry DTA A thermal analysis technique known as Differential Thermal Analysis GAP Glycidyl Azide Polymer used as a curable binder in some

Tunable photonic crystals with partial bandgaps from blue phase colloidal crystals and dielectric-doped blue phases.

PubMed

Stimulak, Mitja; Ravnik, Miha

2014-09-07

Blue phase colloidal crystals and dielectric nanoparticle/polymer doped blue phases are demonstrated to combine multiple components with different symmetries in one photonic material, creating a photonic crystal with variable and micro-controllable photonic band structure. In this composite photonic material, one contribution to the band structure is determined by the 3D periodic birefringent orientational profile of the blue phases, whereas the second contribution emerges from the regular array of the colloidal particles or from the dielectric/nanoparticle-doped defect network. Using the planewave expansion method, optical photonic bands of the blue phase I and II colloidal crystals and related nanoparticle/polymer doped blue phases are calculated, and then compared to blue phases with no particles and to face-centred-cubic and body-centred-cubic colloidal crystals in isotropic background. We find opening of local band gaps at particular points of Brillouin zone for blue phase colloidal crystals, where there were none in blue phases without particles or dopants. Particle size and filling fraction of the blue phase defect network are demonstrated as parameters that can directly tune the optical bands and local band gaps. In the blue phase I colloidal crystal with an additionally doped defect network, interestingly, we find an indirect total band gap (with the exception of one point) at the entire edge of SC irreducible zone. Finally, this work demonstrates the role of combining multiple - by symmetry - differently organised components in one photonic crystal material, which offers a novel approach towards tunable soft matter photonic materials.

One-dimensional mercury(II) halide coordination polymers of 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine ligand: Synthesis, crystal structure, spectroscopic and DFT studies

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

Saghatforoush, Lotfali, E-mail: saghatforoush@gmail.com; Khoshtarkib, Zeinab; Amani, Vahid

2016-01-15

Three new coordination polymers, [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl (1), Br (2)) and [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} (3) (bptz=3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) were synthesized. X-ray structural analysis indicated that compounds 1 and 2 are composed of one-dimensional (1D) linear chains while the compound 3 has 1D stair-stepped structure. The electronic band structure along with density of states (DOS) calculated by the DFT method indicates that compound 1 and 2 are direct band gap semiconductors; however, compound 3 is an indirect semiconductor. The linear optical properties of the compounds are also calculated by DFT method. According to the DFT calculations, the observed emission bandmore » of the compounds in solid state is due to electron transfer from an excited bptz-π* state (CBs) to the top of VBs. {sup 1}H NMR spectra of the compounds indicate that, in solution phase, the compounds don’t decompose completely. Thermal stability of the compounds is studied using TG, DTA methods. - Graphical abstract: Synthesis, crystal structure and emission spectra of [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl and Br) and [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} are presented. The electronic band structure and linear optical properties of the compounds are calculated by the DFT method. - Highlights: • Three 1D Hg(II) halide coordination polymers with bptz ligand have been prepared. • The structures of the compounds are determined by single crystal XRD. • DFT calculations show that [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl and Br) have a direct band gap. • DFT calculations show that [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} has an indirect band gap. • The compounds show an intraligand electron transfer emission band in solid state.« less

Zero point motion effect on the electronic properties of diamond, trans-polyacetylene and polyethylene

NASA Astrophysics Data System (ADS)

Cannuccia, E.; Marini, A.

2012-09-01

It has been recently shown, using ab-initio methods, that bulk diamond is characterized by a large band-gap renormalization (˜0.6 eV) induced by the electron-phonon interaction. In this work we show that in polymers, compared to bulk materials, the larger amplitude of the atomic vibrations makes the real excitations of the system be composed by entangled electron-phonon states. We prove that these states carry only a fraction of the electronic charge, thus leading, inevitably, to the failure of the electronic picture. The present results cast doubts on the accuracy of purely electronic calculations. They also lead to a critical revision of the state-of-the-art description of carbon-based nanostructures, opening a wealth of potential implications.

Distribution of dopant ions around poly(3,4-ethylenedioxythiophene) chains: a theoretical study.

PubMed

Casanovas, Jordi; Zanuy, David; Alemán, Carlos

2017-04-12

The effect of counterions and multiple polymer chains on the properties and structure of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with ClO 4 - has been examined using density functional theory (DFT) calculations with periodic boundary conditions (PBCs). Calculations on a one-dimensional periodic model with four explicit polymer repeat units and two ClO 4 - molecules indicate that the latter are separated as much as possible, with the salt structure and band gap obtained from such ClO 4 - distribution being in excellent agreement with those determined experimentally. On the other hand, DFT calculations on periodic models that include two chains indicate that neighboring PEDOT chains are shifted along the molecular axis by a half of the repeat unit length, with dopant ions intercalated between the polymer molecules acting as cement. In order to support these structural features, classical molecular dynamics (MD) simulations have been performed on a multiphasic system consisting of 69 explicit PEDOT chains anchored onto a steel surface, explicit ClO 4 - anions embedded in the polymer matrix, and an acetonitrile phase layer onto the polymer matrix. Analyses of the radial distribution functions indicate that the all-anti conformation, the relative disposition of adjacent PEDOT chains and the distribution of ClO 4 - dopant ions are fully consistent with periodic DFT predictions. The agreement between two such different methodologies allows reinforcing the microscopic understanding of the PEDOT film structure.

High-Performance All-Polymer Solar Cells Achieved by Fused Perylenediimide-Based Conjugated Polymer Acceptors.

PubMed

Yin, Yuli; Yang, Jing; Guo, Fengyun; Zhou, Erjun; Zhao, Liancheng; Zhang, Yong

2018-05-09

We report three n-type polymeric electron acceptors (PFPDI-TT, PFPDI-T, and PFPDI-Se) based on the fused perylene diimide (FPDI) and thieno[3,2- b]thiophene, thiophene, or selenophene units for all-polymer solar cells (all-PSCs). These FPDI-based polymer acceptors exhibit strong absorption between 350 and 650 nm with wide optical bandgap of 1.86-1.91 eV, showing good absorption compensation with the narrow bandgap polymer donor. The lowest unoccupied molecular orbital (LUMO) energy levels were located at around -4.11 eV, which are comparable with those of the fullerene derivatives and other small molecular electron acceptors. The conventional all-PSCs based on the three polymer acceptors and PTB7-Th as polymer donor gave remarkable power conversion efficiencies (PCEs) of >6%, and the PFPDI-Se-based all-PSC achieved the highest PCE of 6.58% with a short-circuit current density ( J sc ) of 13.96 mA/cm 2 , an open-circuit voltage ( V oc ) of 0.76 V, and a fill factor (FF) of 62.0%. More interestingly, our results indicate that the photovoltaic performances of the FPDI-based polymer acceptors are mainly determined by the FPDI unit with a small effect from the comonomers, which is quite different from the others reported rylenediimide-based polymer acceptors. This intriguing phenomenon is speculated as the huge geometry configuration of the FPDI unit, which minimizes the effect of the comonomer. These results highlight a promising future for the application of the FPDI-based polymer acceptors in the highly efficient all-PSCs.

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.

Amylose-Based Cationic Star Polymers for siRNA Delivery.

PubMed

Nishimura, Tomoki; Umezaki, Kaori; Mukai, Sada-atsu; Sawada, Shin-ichi; Akiyoshi, Kazunari

2015-01-01

A new siRNA delivery system using a cationic glyco-star polymer is described. Spermine-modified 8-arm amylose star polymer (with a degree of polymerization of approximately 60 per arm) was synthesized by chemoenzymatic methods. The cationic star polymer effectively bound to siRNA and formed spherical complexes with an average hydrodynamic diameter of 230 nm. The cationic 8-arm star polymer complexes showed superior cellular uptake characteristics and higher gene silencing effects than a cationic 1-arm polymer. These results suggest that amylose-based star polymers are a promising nanoplatform for glycobiomaterials.

Recent Progress in the Development of Conducting Polymer-Based Nanocomposites for Electrochemical Biosensors Applications: A Mini-Review.

PubMed

Naseri, Maryam; Fotouhi, Lida; Ehsani, Ali

2018-06-01

Among various immobilizing materials, conductive polymer-based nanocomposites have been widely applied to fabricate the biosensors, because of their outstanding properties such as excellent electrocatalytic activity, high conductivity, and strong adsorptive ability compared to conventional conductive polymers. Electrochemical biosensors have played a significant role in delivering the diagnostic information and therapy monitoring in a rapid, simple, and low cost portable device. This paper reviews the recent developments in conductive polymer-based nanocomposites and their applications in electrochemical biosensors. The article starts with a general and concise comparison between the properties of conducting polymers and conducting polymer nanocomposites. Next, the current applications of conductive polymer-based nanocomposites of some important conducting polymers such as PANI, PPy, and PEDOT in enzymatic and nonenzymatic electrochemical biosensors are overviewed. This review article covers an 8-year period beginning in 2010. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer and small molecule based hybrid light source

DOEpatents

Choong, Vi-En; Choulis, Stelios; Krummacher, Benjamin Claus; Mathai, Mathew; So, Franky

2010-03-16

An organic electroluminescent device, includes: a substrate; a hole-injecting electrode (anode) coated over the substrate; a hole injection layer coated over the anode; a hole transporting layer coated over the hole injection layer; a polymer based light emitting layer, coated over the hole transporting layer; a small molecule based light emitting layer, thermally evaporated over the polymer based light emitting layer; and an electron-injecting electrode (cathode) deposited over the electroluminescent polymer layer.

Polyethylenimine Interfacial Layers in Inverted Organic Photovoltaic Devices: Effects of Ethoxylation and Molecular Weight on Efficiency and Temporal Stability.

PubMed

Courtright, Brett A E; Jenekhe, Samson A

2015-12-02

We report a comparative study of polyethylenimine (PEI) and ethoxylated-polyethylenimine (PEIE) cathode buffer layers in high performance inverted organic photovoltaic devices. The work function of the indium-tin oxide (ITO)/zinc oxide (ZnO) cathode was reduced substantially (Δφ = 0.73-1.09 eV) as the molecular weight of PEI was varied from 800 g mol(-1) to 750 000 g mol(-1) compared with the observed much smaller reduction when using a PEIE thin film (Δφ = 0.56 eV). The reference inverted polymer solar cells based on the small band gap polymer PBDTT-FTTE (ITO/ZnO/PBDTT-FTTE:PC70BM/MoO3/Ag), without a cathode buffer layer, had an average power conversion efficiency (PCE) of 6.06 ± 0.22%. Incorporation of a PEIE cathode buffer layer in the same PBDTT-FTTE:PC70BM blend devices gave an enhanced performance with a PCE of 7.37 ± 0.53%. In contrast, an even greater photovoltaic efficiency with a PCE of 8.22 ± 0.10% was obtained in similar PBDTT-FTTE:PC70BM blend solar cells containing a PEI cathode buffer layer. The temporal stability of the inverted polymer solar cells was found to increase with increasing molecular weight of the cathode buffer layer. The results show that PEI is superior to PEIE as a cathode buffer layer in high performance organic photovoltaic devices and that the highest molecular weight PEI interlayer provides the highest temporal stability.

Characterization of novel soybean-oil-based thermosensitive amphiphilic polymers for drug delivery applications

USDA-ARS?s Scientific Manuscript database

Characterization, aggregation behavior, physical properties and drug-polymer interaction of novel soybean oil-based polymers i.e., hydrolyzed polymers of (epoxidized) soybean oil (HPESO), were studied. The surface tension method was used to determine the critical micelle concentration (CMC). CMC w...

Exploitation of molecular mobilities for advanced organic optoelectronic and photonic nano-materials

NASA Astrophysics Data System (ADS)

Gray, Tomoko O.

Electro-optically active organic materials have shown great potential in advanced technologies such as ultrafast electro-optical switches for broadband communication, light-emitting diodes, and photovoltaic cells. Currently, the maturity of chemical synthesis enables a sophisticated integration of the active elements into complex macromolecules. Also, the structure-property relationships of the isolated single electrically/optically active elements are well established. Unfortunately, such correlations involving single molecule are not applicable to complex unstructured condensed systems, in which unique mesoscale properties and complex dynamics of super-/supra-molecular structures are present. Our current challenge arises, in particular, from a deficiency of appropriate characterization tools that close the gap between phenomenological measurements and theoretical models. This work addresses submolecular mobilities relevant for opto-electronic functionalities of photoluminescent polymers and non-linear optical (NLO) materials. Thereby, I will introduce novel nanoscale thermomechanical characterization tools that are based on scanning force microscopy. From nanoscale thermomechanical measurements sub-/super-molecular mobilities of novel optoelectronic materials can be inferred and to some degree controlled. For instance, we have explored interfacial constraints as a engineering tool to control molecular mobility. This will be illustrated with electroluminescent polymers, which are prone to undesired pi-pi aggregation due to the rod-like structure---intrinsic to all conjugated polymers. The nanoscale confinement is used to reduced chain mobility, and thus, hinders undesired aggregation, and consequently, yields superior spectral stability. From the nanomaterial design perspective, I will also address mobility control with targeted molecular designs. This involves two classes of novel NLO materials, side-chain dendronized polymers and self-assembling molecular glasses. The side-chain dendronized polymers are, due to the structural complexity, self-constrained systems. Our thermomechanical investigations identified that a local relaxation mode associated to the NLO side-chain is the critical design parameter in yielding high mobility to the active element. Relaxation processes of the self-assembling molecular glasses are discussed from a thermodynamic perspective involving both enthalpic and entropic contributions, considering the very special nature of interactions for the NLO molecular glasses, i.e., the formation and dissociation of phenyl/perfluorophenyl quadrupol pairs.

Development of PVA based micro-porous polymer electrolyte by a novel preferential polymer dissolution process

NASA Astrophysics Data System (ADS)

Subramania, A.; Kalyana Sundaram, N. T.; Sukumar, N.

A micro-porous polymer electrolyte based on PVA was obtained from PVA-PVC based polymer blend film by a novel preferential polymer dissolution technique. The ionic conductivity of micro-porous polymer electrolyte increases with increase in the removal of PVC content. Finally, the effect of variation of lithium salt concentration is studied for micro-porous polymer electrolyte of high ionic conductivity composition. The ionic conductivity of the micro-porous polymer electrolyte is measured in the temperature range of 301-351 K. It is observed that a 2 M LiClO 4 solution of micro-porous polymer electrolyte has high ionic conductivity of 1.5055 × 10 -3 S cm -1 at ambient temperature. Complexation and surface morphology of the micro-porous polymer electrolytes are studied by X-ray diffraction and SEM analysis. TG/DTA analysis informs that the micro-porous polymer electrolyte is thermally stable upto 277.9 °C. Chronoamperommetry and linear sweep voltammetry studies were made to find out lithium transference number and stability of micro-porous polymer electrolyte membrane, respectively. Cyclic voltammetry study was performed for carbon/micro-porous polymer electrolyte/LiMn 2O 4 cell to reveal the compatibility and electrochemical stability between electrode materials.

Influence of additives on thermoresponsive polymers in aqueous media: a case study of poly(N-isopropylacrylamide).

PubMed

Umapathi, Reddicherla; Reddy, P Madhusudhana; Rani, Anjeeta; Venkatesu, Pannuru

2018-04-18

Thermoresponsive polymers (TRPs) in different solvent media have been studied over a long period and are important from both scientific and technical points of view. Despite numerous studies on the behavior of TRPs with various additives, the interactions of additives with TRPs are still poorly understood. Moreover, despite the vast available literature regarding the biomolecular interactions between various TRPs and naturally occurring additives, it is not possible to provide a unifying declaration about the behavior of different additives, in particular at the phase transition temperature of the polymer. However, potential reviews that describe the behavior of additives as stimuli upon the phase transition of TRPs are also absent. A lack of sufficient knowledge regarding the responses of TRPs to additives as stimuli has hindered the expansion of the wide spectrum of applications of these polymers. Therefore, it was proposed to review the responses of TRPs in the presence of various additives in aqueous media. In-depth knowledge acquired via a literature survey has drawn our attention towards filling this gap by analyzing the interactions of TRPs with different additives. In this perspective, we have systematically examined the stability, aggregation, and phase transition behaviours of various polymers in the presence of different additives. The perspective on the influence of additives as stimuli on the behavior of TRPs in an aqueous medium will provide new reliable information about intramolecular interactions between interior polymer segments as well as intermolecular interactions between TRPs and additive molecules, which will be helpful for industrialists in the preparation of new polymeric materials for drug-delivery systems.

Performance evaluation of cross-flow single-phase liquid-to-gas polymer tube heat exchanger

NASA Astrophysics Data System (ADS)

Dewanjee, Sujan; Hossain, Md. Rakibul; Rahman, Md. Ashiqur

2017-06-01

Reduced core weight and material cost, higher corrosion resistance are some of the major eye catching properties to study polymers over metal in heat exchanger applications in spite of the former's relatively low thermal conductivity and low strength. In the present study, performance of polymer parallel thin tube heat exchanger is numerically evaluated for cross flow liquid to air applications for a wide range of design and operating parameters such as tube diameter, thickness, fluid velocity and temperature, etc. using Computational Fluid Dynamics (CFD). Among a range of available polymeric materials, those with a moderate to high thermal conductivity and strength are selected for this study. A 90 cm × 1 cm single unit of polymer tubes, with appropriate number of tubes such that at least a gap of 5 mm is maintained in between the tubes, is used as a basic unit and multiple combination in the transverse direction of this single unit is simulated to measure the effect. The tube inner diameter is varied from 2 mm to 4 mm and the pressure drop is measured to have a relative idea of pumping cost. For each inner diameter the thickness is varied from .5 mm to 2.5 mm. The water velocity and the air velocity are varied from 0.4 m/s to 2 m/s and 1 m/s to 5 m/s, respectively. The performance of the polymer heat exchanger is compared with that of metal heat exchanger through and an optimum design for polymer heat exchanger is sought out.

Evaluation of flexural strength and surface properties of prepolymerized CAD/CAM PMMA-based polymers used for digital 3D complete dentures.

PubMed

Arslan, Mustafa; Murat, Sema; Alp, Gulce; Zaimoglu, Ali

2018-01-01

The objectives of this in vitro study were to evaluate the flexural strength (FS), surface roughness (Ra), and hydrophobicity of polymethylmethacrylate (PMMA)-based computer-aided design/computer-aided manufacturing (CAD/CAM) polymers and to compare the properties of different CAD/CAM PMMA-based polymers with conventional heat-polymerized PMMA following thermal cycling. Twenty rectangular-shaped specimens (64 × 10 × 3.3 mm) were fabricated from three CAD/CAM PMMA-based polymers (M-PM Disc [M], AvaDent Puck Disc [A], and Pink CAD/CAM Disc Polident [P], and one conventional heat-polymerized PMMA (Promolux [C]), according to ISO 20795-1:2013 standards. The specimens were divided into two subgroups (n = 10), a control and a thermocycled group. The specimens in the thermocycled group were subjected to 5000 thermal cycling procedures (5 to 55°C; 30 s dwell times). The Ra value was measured using a profilometer. Contact angle (CA) was assessed using the sessile drop method to evaluate surface hydrophobicity. In addition, the FS of the specimens was tested in a universal testing machine at a crosshead speed of 1.0 mm/min. Surface texture of the materials was assessed using scanning electron microscope (SEM). The data were analyzed using two-way analysis of variance (ANOVA), followed by Tukey's HSD post-hoc test (α < 0.05). CAD/CAM PMMA-based polymers showed significantly higher FS than conventional heat-polymerized PMMA for each group (P < 0.001). CAD/CAM PMMA-based polymer [P] showed the highest FS, whereas conventional PMMA [C] showed the lowest FS before and after thermal cycling (P < 0.001). There were no significant differences among the Ra values of the tested denture base polymers in the control group (P > 0.05). In the thermocycled group, the lowest Ra value was observed for CAD/CAM PMMA-based polymer [M] (P < 0.001), whereas CAD/CAM PMMA-based polymers [A] and [P], and conventional PMMA [C] had similar Ra values (P > 0.05). Conventional PMMA [C] had a significantly lower CA and consequently lower hydrophobicity compared to the CAD/CAM polymers in the control group (P < 0.001). In the thermocycled group, CAD/CAM PMMA-based polymer [A] and conventional PMMA [C] had significantly higher CA, and consequently higher hydrophobicity when compared to CAD/CAM polymers [M] and [P] (P < 0.001). However, no significant differences were found among the other materials (P > 0.05). The FS and hydrophobicity of the CAD/CAM PMMA-based polymers were higher than the conventional heat-polymerized PMMA, whereas the CAD/CAM PMMA-based polymers had similar Ra values to the conventional PMMA. Thermocycling had a significant effect on FS and hydrophobicity except for the Ra of denture base materials.

Design, synthesis, and structure-property relationships of isoindigo-based conjugated polymers.

PubMed

Lei, Ting; Wang, Jie-Yu; Pei, Jian

2014-04-15

Conjugated polymers have developed rapidly due to their promising applications in low-cost, lightweight, and flexible electronics. The development of the third-generation donor-acceptor (D-A) polymers greatly improved the device performance in organic solar cells (OSCs) and field-effect transistors (FETs). However, for further improvement of device performance, scientists need to develop new building blocks, in particular electron-deficient aromatics, and gain an in-depth understanding of the structure-property relationships. Recently, isoindigo has been used as a new acceptor of D-A conjugated polymers. An isomer of indigo, isoindigo is a less well-known dye and can be isolated as a by-product from certain biological processes. It has two lactam rings and exhibits strong electron-withdrawing character. This electron deficiency gives isoindigo-based polymers intriguing properties, such as broad absorption and high open circuit voltage in OSCs, as well as high mobility and good ambient stability in FETs. In this Account, we review our recent progress on the design, synthesis, and structure-property relationship study of isoindigo-based polymers for FETs. Starting with some discussion on carrier transport in polymer films, we provide some basic strategies towards high-performance polymer FETs. We discuss the stability issue of devices, the impediment of the alkyl side chains, and the choice of the donor part of conjugated polymers. We demonstrate that introducing the isoindigo core effectively lowers the HOMO levels of polymers and provides FETs with long-time stability. In addition, we have found that when we use inappropriate alkyl side chains or non-centrosymmetric donors, the device performance of isoindigo polymers suffers. To further improve device performance and ambient stability, we propose several design strategies, such as using farther branched alkyl chains, modulating polymer energy levels, and extending π-conjugated backbones. We have found that using farther branched alkyl chains can effectively decrease interchain π-π stacking distance and improve carrier mobility. When we introduce electron-deficient functional groups on the isoindigo core, the LUMO levels of the polymers markedly decrease, which significantly improves the electron mobility and device stability. In addition, we present a new polymer system called BDOPV, which is based on the concept of π-extended isoindigo. By application of some strategies successfully used in isoindigo-based polymers, BDOPV-based polymers exhibit high mobility and good stability both in n-type and in ambipolar FETs. We believe that a synergy of molecular engineering strategies towards the isoindigo core, donor units, and side chains may further improve the performance and broaden the application of isoindigo-based polymers.

Amylose-Based Cationic Star Polymers for siRNA Delivery

PubMed Central

Nishimura, Tomoki; Umezaki, Kaori; Mukai, Sada-atsu; Sawada, Shin-ichi; Akiyoshi, Kazunari

2015-01-01

A new siRNA delivery system using a cationic glyco-star polymer is described. Spermine-modified 8-arm amylose star polymer (with a degree of polymerization of approximately 60 per arm) was synthesized by chemoenzymatic methods. The cationic star polymer effectively bound to siRNA and formed spherical complexes with an average hydrodynamic diameter of 230 nm. The cationic 8-arm star polymer complexes showed superior cellular uptake characteristics and higher gene silencing effects than a cationic 1-arm polymer. These results suggest that amylose-based star polymers are a promising nanoplatform for glycobiomaterials. PMID:26539548

Designing polymers with sugar-based advantages for bioactive delivery applications.

PubMed

Zhang, Yingyue; Chan, Jennifer W; Moretti, Alysha; Uhrich, Kathryn E

2015-12-10

Sugar-based polymers have been extensively explored as a means to increase drug delivery systems' biocompatibility and biodegradation. Here,we review he use of sugar-based polymers for drug delivery applications, with a particular focus on the utility of the sugar component(s) to provide benefits for drug targeting and stimuli responsive systems. Specifically, numerous synthetic methods have been developed to reliably modify naturally-occurring polysaccharides, conjugate sugar moieties to synthetic polymer scaffolds to generate glycopolymers, and utilize sugars as a multifunctional building block to develop sugar-linked polymers. The design of sugar-based polymer systems has tremendous implications on both the physiological and biological properties imparted by the saccharide units and are unique from synthetic polymers. These features include the ability of glycopolymers to preferentially target various cell types and tissues through receptor interactions, exhibit bioadhesion for prolonged residence time, and be rapidly recognized and internalized by cancer cells. Also discussed are the distinct stimuli-sensitive properties of saccharide-modified polymers to mediate drug release under desired conditions. Saccharide-based systems with inherent pH- and temperature-sensitive properties, as well as enzyme-cleavable polysaccharides for targeted bioactive delivery, are covered. Overall, this work emphasizes inherent benefits of sugar-containing polymer systems for bioactive delivery.

Effects of the Substituents of Boron Atoms on Conjugated Polymers Containing B←N Units.

PubMed

Liu, Jun; Wang, Tao; Dou, Chuandong; Wang, Lixiang

2018-06-15

Organoboron chemistry is a new tool to tune the electronic structures and properties of conjugated polymers, which are important for applications in organic opto-electronic devices. To investigate the effects of substituents of boron atoms on conjugated polymers, we synthesized three conjugated polymers based on double B←N bridged bipyridine (BNBP) with various substituents on the boron atoms. By changing the substituents from four phenyl groups and two phenyl groups/two fluorine atoms to four fluorine atoms, the BNBP-based polymers show the blue-shifted absorption spectra, decreased LUMO/HOMO energy levels and enhanced electron affinities, as well as the increased electron mobilities. Moreover, these BNBP-based polymers can be used as electron acceptors for all-polymer solar cells. These results demonstrate that the substituents of boron atoms can effectively modulate the electronic properties and applications of conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microbial conversion of biomass into bio-based polymers.

PubMed

Kawaguchi, Hideo; Ogino, Chiaki; Kondo, Akihiko

2017-12-01

The worldwide market for plastics is rapidly growing, and plastics polymers are typically produced from petroleum-based chemicals. The overdependence on petroleum-based chemicals for polymer production raises economic and environmental sustainability concerns. Recent progress in metabolic engineering has expanded fermentation products from existing aliphatic acids or alcohols to include aromatic compounds. This diversity provides an opportunity to expand the development and industrial uses of high-performance bio-based polymers. However, most of the biomonomers are produced from edible sugars or starches that compete directly with food and feed uses. The present review focuses on recent progress in the microbial conversion of biomass into bio-based polymers, in which fermentative products from renewable feedstocks serve as biomonomers for the synthesis of bio-based polymers. In particular, the production of biomonomers from inedible lignocellulosic feedstocks by metabolically engineered microorganisms and the synthesis of bio-based engineered plastics from the biological resources are discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthetic Polymers from Readily Available Monosaccharides

NASA Astrophysics Data System (ADS)

Galbis, J. A.; García-Martín, M. G.

The low degradability of petroleum-based polymers and the massive use of these materials constitute a serious problem because of the environmental pollution that they can cause. Thus, sustained efforts have been extensively devoted to produce new polymers based on natural renewing resources and with higher degradability. Of the different natural sources, carbohydrates stand out as highly convenient raw materials because they are inexpensive, readily available, and provide great stereochemical diversity. New polymers, analogous to the more accredited technical polymers, but based on chiral monomers, have been synthesized from natural and available sugars. This chapter describes the potential of sugar-based monomers as precursors to a wide variety of macromolecular materials.

Ferulic Acid-Based Polymers with Glycol Functionality as a Versatile Platform for Topical Applications.

PubMed

Ouimet, Michelle A; Faig, Jonathan J; Yu, Weiling; Uhrich, Kathryn E

2015-09-14

Ferulic acid-based polymers with aliphatic linkages have been previously synthesized via solution polymerization methods, yet they feature relatively slow ferulic acid release rates (∼11 months to 100% completion). To achieve a more rapid release rate as required in skin care formulations, ferulic acid-based polymers with ethylene glycol linkers were prepared to increase hydrophilicity and, in turn, increase ferulic acid release rates. The polymers were characterized using nuclear magnetic resonance and Fourier transform infrared spectroscopies to confirm chemical composition. The molecular weights, thermal properties (e.g., glass transition temperature), and contact angles were also obtained and the polymers compared. Polymer glass transition temperature was observed to decrease with increasing linker molecule length, whereas increasing oxygen content decreased polymer contact angle. The polymers' chemical structures and physical properties were shown to influence ferulic acid release rates and antioxidant activity. In all polymers, ferulic acid release was achieved with no bioactive decomposition. These polymers demonstrate the ability to strategically release ferulic acid at rates and concentrations relevant for topical applications such as skin care products.

Electroactive Reactive Oligomers and Polymers as Device Components

DTIC Science & Technology

2009-02-03

promise to impact the development of reflective and transmissive color-changing systems spanning ’smart’ polyclu’omic glassing technologies and e-papers...mediated cross-coupling reactions. While the first substitution is expected to have the largest impact on the energy gap of the donor-acceptor system, a...transmissive device applications, it is expected that processable black to transmissive analogues will impact the development of EC windows, e- papers and

Preparation of TiO2/(TiO2-V2O5)/polypyrrole nanocomposites and a study on catalytic activities of the hybrid materials under UV/Visible light and in the dark

NASA Astrophysics Data System (ADS)

Piewnuan, C.; Wootthikanokkhan, J.; Ngaotrakanwiwat, P.; Meeyoo, V.; Chiarakorn, S.

2014-11-01

Hybrid metal oxides/polymer nanocomposites, namely TiO2/(TiO2-V2O5)/polypyrrole (PPy), were synthesized via in situ polymerization. Structures of the products were characterized by SEM-EDX, XRD, and FTIR techniques. The light absorbance and band gap energy values of the materials were evaluated by UV/Visible spectroscopy. The catalytic activity of the materials was determined from a degradation of methylene blue. It was found that, regardless of the polymerization time, the absorbance of TiO2/(TiO2-V2O5)/PPy was greater than those of TiO2/PPy and the neat TiO2, respectively. This was in accordance with the decrease in the band gap energy of the materials. The catalytic activity of TiO2/(TiO2-V2O5) was also observed in the dark. After polymerization, the catalytic activity of nanocomposite under UV/Visible light and in the dark was compromised. The above effects are discussed in the light of the energy storage ability of V2O5 and capability of the polymer in acting as a binder for the system.

Modifications of the optical properties for DAM-ADC nuclear track detector exposed to alpha particles

NASA Astrophysics Data System (ADS)

Rammah, Y. S.; Awad, E. M.

2018-05-01

Modifications of the optical properties of diallyl maleate-allyl diglycol carbonate (DAM-ADC) nuclear detector induced by alpha particles are described. DAM-ADC samples were irradiated perpendicularly by thin 241Am disk source that emits alpha particles with 5.48 MeV. The optical absorption has been measured using the ultraviolet-visible (UV-1100) spectroscopy. It was found that DAM-ADC polymer shows substantial modifications in its optical characteristics upon irradiated with alpha particles with different energies. The optical energy band gap (Egap) for the detector was calculated for the direct and the indirect allowed transitions in K-space using two approaches (Tauc's model and absorption spectrum fitting (ASF) method). Urbach's energy (Ea), number of carbon atoms per conjugated length (N), number of carbon atoms per cluster (M), and refractive index (n) for the present samples were determined. Results reveal that the values of energy gap in direct transition are greater than those of indirect, before and after irradiation. (Egap), (Ea), (N), (M), and (n) of the present samples are changed significantly with irradiation time and value of alpha energy. Results reflect the possibility of using DAM-ADC polymer track detectors to estimate alpha particle energies using the variation of the absorbance.

Electro–optical properties of poly(vinyl acetate)/polyindole composite film

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

Bhagat, D. J., E-mail: bhagatd@rediffmail.com; Dhokane, G. R.; Bajaj, N. S.

2016-05-06

In present work, electrical and optical properties of poly(vinyl acetate)/polyindole (PVAc/PIN) composite film are reported. The prepared composite was characterized via X–ray diffraction (XRD), UV–Vis spectroscopy and DC conductivity measurements. The polymer chain separation was determined using XRD analysis. An attempt has been made to study the temperature dependence of DC conductivity of PVAc/PIN composite in temperature range 308–373 K. The DC conductivity initially increases and reaches to 2.45×10–7 S/cm. The optical band gap value of composite is determined as 4.77 eV. The semiconducting nature of composite observed from electronic as well as optical band gap and Arrhenius behavior of DCmore » plot.« less

Cascade use indicators for selected biopolymers: Are we aiming for the right solutions in the design for recycling of bio-based polymers?

PubMed

Hildebrandt, Jakob; Bezama, Alberto; Thrän, Daniela

2017-04-01

When surveying the trends and criteria for the design for recycling (DfR) of bio-based polymers, priorities appear to lie in energy recovery at the end of the product life of durable products, such as bio-based thermosets. Non-durable products made of thermoplastic polymers exhibit good properties for material recycling. The latter commonly enjoy growing material recycling quotas in countries that enforce a landfill ban. Quantitative and qualitative indicators are needed for characterizing progress in the development towards more recycling friendly bio-based polymers. This would enable the deficits in recycling bio-based plastics to be tracked and improved. The aim of this paper is to analyse the trends in the DfR of bio-based polymers and the constraints posed by the recycling infrastructure on plastic polymers from a systems perspective. This analysis produces recommendations on how life cycle assessment indicators can be introduced into the dialogue between designers and recyclers in order to promote DfR principles to enhance the cascading use of bio-based polymers within the bioeconomy, and to meet circular economy goals.

Cascade use indicators for selected biopolymers: Are we aiming for the right solutions in the design for recycling of bio-based polymers?

PubMed Central

Hildebrandt, Jakob; Bezama, Alberto; Thrän, Daniela

2017-01-01

When surveying the trends and criteria for the design for recycling (DfR) of bio-based polymers, priorities appear to lie in energy recovery at the end of the product life of durable products, such as bio-based thermosets. Non-durable products made of thermoplastic polymers exhibit good properties for material recycling. The latter commonly enjoy growing material recycling quotas in countries that enforce a landfill ban. Quantitative and qualitative indicators are needed for characterizing progress in the development towards more recycling friendly bio-based polymers. This would enable the deficits in recycling bio-based plastics to be tracked and improved. The aim of this paper is to analyse the trends in the DfR of bio-based polymers and the constraints posed by the recycling infrastructure on plastic polymers from a systems perspective. This analysis produces recommendations on how life cycle assessment indicators can be introduced into the dialogue between designers and recyclers in order to promote DfR principles to enhance the cascading use of bio-based polymers within the bioeconomy, and to meet circular economy goals. PMID:28097922

Direct observation of single flexible polymers using single stranded DNA†

PubMed Central

Brockman, Christopher; Kim, Sun Ju

2012-01-01

Over the last 15 years, double stranded DNA (dsDNA) has been used as a model polymeric system for nearly all single polymer dynamics studies. However, dsDNA is a semiflexible polymer with markedly different molecular properties compared to flexible chains, including synthetic organic polymers. In this work, we report a new system for single polymer studies of flexible chains based on single stranded DNA (ssDNA). We developed a method to synthesize ssDNA for fluorescence microscopy based on rolling circle replication, which generates long strands (>65 kb) of ssDNA containing “designer” sequences, thereby preventing intramolecular base pair interactions. Polymers are synthesized to contain amine-modified bases randomly distributed along the backbone, which enables uniform labelling of polymer chains with a fluorescent dye to facilitate fluorescence microscopy and imaging. Using this approach, we synthesized ssDNA chains with long contour lengths (>30 μm) and relatively low dye loading ratios (~1 dye per 100 bases). In addition, we used epifluorescence microscopy to image single ssDNA polymer molecules stretching in flow in a microfluidic device. Overall, we anticipate that ssDNA will serve as a useful model system to probe the dynamics of polymeric materials at the molecular level. PMID:22956981

A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal-Organic Framework Materials.

PubMed

Einkauf, Jeffrey D; Clark, Jessica M; Paulive, Alec; Tanner, Garrett P; de Lill, Daniel T

2017-05-15

Luminescent lanthanides containing coordination polymers and metal-organic frameworks hold great potential in many applications due to their distinctive spectroscopic properties. While the ability to design coordination polymers for specific functions is often mentioned as a major benefit bestowed on these compounds, the lack of a meaningful understanding of the luminescence in lanthanide coordination polymers remains a significant challenge toward functional design. Currently, the study of these compounds is based on the antenna effect as derived from molecular systems, where organic antennae are used to facilitate lanthanide-centered luminescence. This molecular-based approach does not take into account the unique features of extended network solids, particularly the formation of band structure. While guidelines for the antenna effect are well established, they require modification before being applied to coordination polymers. A series of nine coordination polymers with varying topologies and organic linkers were studied to investigate the accuracy of the antenna effect in coordination polymer systems. By comparing a molecular-based approach to a band-based one, it was determined that the band structure that occurs in aggregated organic solids needs to be considered when evaluating the luminescence of lanthanide coordination polymers.

Jeffamine® based polymers as highly conductive polymer electrolytes and cathode binder materials for battery application

NASA Astrophysics Data System (ADS)

Aldalur, Itziar; Zhang, Heng; Piszcz, Michał; Oteo, Uxue; Rodriguez-Martinez, Lide M.; Shanmukaraj, Devaraj; Rojo, Teofilo; Armand, Michel

2017-04-01

We report a simple synthesis route towards a new type of comb polymer material based on polyether amines oligomer side chains (i.e., Jeffamine® compounds) and a poly(ethylene-alt-maleic anhydride) backbone. Reaction proceeds by imide ring formation through the NH2 group allowing for attachment of side chains. By taking advantage of the high configurational freedoms and flexibility of propylene oxide/ethylene oxide units (PO/EO) in Jeffamine® compounds, novel polymer matrices were obtained with good elastomeric properties. Fully amorphous solid polymer electrolytes (SPEs) based on lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and Jeffamine®-based polymer matrices show low glass transition temperatures around -40 °C, high ionic conductivities and good electrochemical stabilities. The ionic conductivities of Jeffamine-based SPEs (5.3 × 10-4 S cm-1 at 70 °C and 4.5 × 10-5 S cm-1 at room temperature) are higher than those of the conventional SPEs comprising of LiTFSI and linear poly(ethylene oxide) (PEO), due to the amorphous nature and the high concentration of mobile end-groups of the Jeffamine-based polymer matrices rather than the semi-crystalline PEO The feasibility of Jeffamine-based compounds in lithium metal batteries is further demonstrated by the implementation of Jeffamine®-based polymer as a binder for cathode materials, and the stable cycling of Li|SPE|LiFePO4 and Li|SPE|S cells using Jeffamine-based SPEs.

Developments in the Field of Conducting and Non-conducting Polymer Based Potentiometric Membrane Sensors for Ions Over the Past Decade

PubMed Central

Faridbod, Farnoush; Ganjali, Mohammad Reza; Dinarvand, Rassoul; Norouzi, Parviz

2008-01-01

Many research studies have been conducted on the use of conjugated polymers in the construction of chemical sensors including potentiometric, conductometric and amperometric sensors or biosensors over the last decade. The induction of conductivity on conjugated polymers by treating them with suitable oxidizing agents won Heeger, MacDiarmid and Shirakawa the 2000 Nobel Prize in Chemistry. Common conjugated polymers are poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, poly(terthiophene)s, poly(aniline)s, poly(fluorine)s, poly(3-alkylthiophene)s, polytetrathiafulvalenes, poly-napthalenes, poly(p-phenylene sulfide), poly(p-phenylenevinylene)s, poly(3,4-ethylene-dioxythiophene), polyparaphenylene, polyazulene, polyparaphenylene sulfide, poly-carbazole and polydiaminonaphthalene. More than 60 sensors for inorganic cations and anions with different characteristics based on conducting polymers have been reported. There have also been reports on the application of non-conducting polymers (nCPs), i.e. PVC, in the construction of potentiometric membrane sensors for determination of more than 60 inorganic cations and anions. However, the leakage of ionophores from the membranes based on these polymers leads to relatively lower life times. In this article, we try to give an overview of Solid-Contact ISE (SCISE), Single-Piece ISE (SPISE), Conducting Polymer (CP)-Based, and also non-conducting polymer PVC-based ISEs for various ions which their difference is in the way of the polymer used with selective\\ membrane. In SCISEs and SPISEs, the plasticized PVC containing the ionophore and ionic additives govern the selectivity behavior of the electrode and the conducting polymer is responsible of ion-to-electron transducer. However, in CPISEs, the conducting polymer layer is doped with a suitable ionophore which enhances the ion selectivity of the CP while its redox response has to be suppressed. PMID:27879825

Multifunctional Diketopyrrolopyrrole-Based Conjugated Polymers with Perylene Bisimide Side Chains.

PubMed

Li, Cheng; Yu, Changshi; Lai, Wenbin; Liang, Shijie; Jiang, Xudong; Feng, Guitao; Zhang, Jianqi; Xu, Yunhua; Li, Weiwei

2017-11-24

Two conjugated polymers based on diketopyrrolopyrrole (DPP) in the main chain with different content of perylene bisimide (PBI) side chains are developed. The influence of PBI side chain on the photovoltaic performance of these DPP-based conjugated polymers is systematically investigated. This study suggests that the PBI side chains can not only alter the absorption spectrum and energy level but also enhance the crystallinity of conjugated polymers. As a result, such polymers can act as electron donor, electron acceptor, and single-component active layer in organic solar cells. These findings provide a new guideline for the future molecular design of multifunctional conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-dimensional electron beam charging model for polymer films

NASA Technical Reports Server (NTRS)

Reeves, R. D.; Balmain, K. G.

1981-01-01

A two-dimensional model is developed to describe the charging of strips of thin polymer films above a grounded substrate exposed to a uniform mono-energetic electron beam. The study is motivated by the observed anomalous behavior of geosynchronous satellites, which has been attributed to differential charging of the satellite surfaces exposed to magnetospheric electrons. Surface and bulk electric fields are calcuated at steady state in order to identify regions of high electrical stress, with emphasis on behavior near the material's edge. The model is used to study the effects of some of the experimental parameters, notably beam energy, beam angle of incidence, beam current density, material thickness and material width. Also examined are the consequences of a central gap in the material and a discontinuity in the material thickness.

Electrical and optical properties of nitrile rubber modified by ion implantation

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

S, Najidha; Predeep, P.

2014-10-15

Implantation of N{sup +} ion beams are performed on to a non-conjugated elastomer, acrylonirtle butadiene rubber (NBR) with energy 60 keV in the fluence range of 10{sup 14} to 10{sup 16} ions/cm{sup 2}. A decrease in the resistivity of the sample by about eight orders of magnitude is observed in the implanted samples along with color changes. The ion exposed specimens were characterized by means of UV/Vis spectroscopy which shows a shift in the absorption edge value for the as deposited polymer towards higher wavelengths. The band gap is evaluated from the absorption spectra and is found to decrease withmore » increasing fluence. This study can possibly throw light on ion induced changes in the polymer surface.« less

Dynamic covalent polymers

PubMed Central

García, Fátima

2016-01-01

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

Statistical and Detailed Analysis on Fiber Reinforced Self-Compacting Concrete Containing Admixtures- A State of Art of Review

NASA Astrophysics Data System (ADS)

Athiyamaan, V.; Mohan Ganesh, G.

2017-11-01

Self-Compacting Concrete is one of the special concretes that have ability to flow and consolidate on its own weight, completely fill the formwork even in the presence of dense reinforcement; whilst maintaining its homogeneity throughout the formwork without any requirement for vibration. Researchers all over the world are developing high performance concrete by adding various Fibers, admixtures in different proportions. Various different kinds Fibers like glass, steel, carbon, Poly propylene and aramid Fibers provide improvement in concrete properties like tensile strength, fatigue characteristic, durability, shrinkage, impact, erosion resistance and serviceability of concrete[6]. It includes fundamental study on fiber reinforced self-compacting concrete with admixtures; its rheological properties, mechanical properties and overview study on design methodology statistical approaches regarding optimizing the concrete performances. The study has been classified into seven basic chapters: introduction, phenomenal study on material properties review on self-compacting concrete, overview on fiber reinforced self-compacting concrete containing admixtures, review on design and analysis of experiment; a statistical approach, summary of existing works on FRSCC and statistical modeling, literature review and, conclusion. It is so eminent to know the resent studies that had been done on polymer based binder materials (fly ash, metakaolin, GGBS, etc.), fiber reinforced concrete and SCC; to do an effective research on fiber reinforced self-compacting concrete containing admixtures. The key aim of the study is to sort-out the research gap and to gain a complete knowledge on polymer based Self compacting fiber reinforced concrete.

Differences in time-dependent mechanical properties between extruded and molded hydrogels

PubMed Central

Ersumo, N; Witherel, CE; Spiller, KL

2016-01-01

The mechanical properties of hydrogels used in biomaterials and tissue engineering applications are critical determinants of their functionality. Despite the recent rise of additive manufacturing, and specifically extrusion-based bioprinting, as a prominent biofabrication method, comprehensive studies investigating the mechanical behavior of extruded constructs remain lacking. To address this gap in knowledge, we compared the mechanical properties and swelling properties of crosslinked gelatin-based hydrogels prepared by conventional molding techniques or by 3D bioprinting using a BioBots Beta pneumatic extruder. A preliminary characterization of the impact of bioprinting parameters on construct properties revealed that both Young's modulus and optimal extruding pressure increased with polymer content, and that printing resolution increased with both printing speed and nozzle gauge. High viability (>95%) of encapsulated NIH 3T3 fibroblasts confirmed the cytocompatibility of the construct preparation process. Interestingly, the Young's moduli of extruded and molded constructs were not different, but extruded constructs did show increases in both the rate and extent of time-dependent mechanical behavior observed in creep. Despite similar polymer densities, extruded hydrogels showed greater swelling over time compared to molded hydrogels, suggesting that differences in creep behavior derived from differences in microstructure and fluid flow. Because of the crucial roles of time-dependent mechanical properties, fluid flow, and swelling properties on tissue and cell behavior, these findings highlight the need for greater consideration of the effects of the extrusion process on hydrogel properties. PMID:27550945

Electrochemical determination of the glass transition temperature of thin polyelectrolyte brushes at solid-liquid interfaces by impedance spectroscopy.

PubMed

Alonso-García, Teodoro; Rodríguez-Presa, María José; Gervasi, Claudio; Moya, Sergio; Azzaroni, Omar

2013-07-16

Devising strategies to assess the glass transition temperature (Tg) of polyelectrolyte assemblies at solid-electrolyte interfaces is very important to understand and rationalize the temperature-dependent behavior of polyelectrolyte films in a wide range of settings. Despite the evolving perception of the importance of measuring Tg under aqueous conditions in thin film configurations, its straightforward measurement poses a challenging situation that still remains elusive in polymer and materials science. Here, we describe a new method based on electrochemical impedance spectroscopy (EIS) to estimate the glass transition temperature of planar polyelectrolyte brushes at solid-liquid interfaces. To measure Tg, the charge transfer resistance (Rct) of a redox probe diffusing through the polyelectrolyte brush was measured, and the temperature corresponding to the discontinuous change in Rct was identified as Tg. Furthermore, we demonstrate that impedance measurements not only facilitate the estimation of Tg but also enable a reliable evaluation of the transport properties of the polymeric interface, i.e., determination of diffusion coefficients, close to the thermal transition. We consider that this approach bridges the gap between electrochemistry and the traditional tools used in polymer science and offers new opportunities to characterize the thermal behavior of complex polymeric interfaces and macromolecular assemblies.

Computational screening of organic polymer dielectrics for novel accelerator technologies

DOE PAGES

Pilania, Ghanshyam; Weis, Eric; Walker, Ethan M.; ...

2018-06-18

The use of infrared lasers to power accelerating dielectric structures is a developing area of research. Within this technology, the choice of the dielectric material forming the accelerating structures, such as the photonic band gap (PBG) structures, is dictated by a range of interrelated factors including their dielectric and optical properties, amenability to photo-polymerization, thermochemical stability and other target performance metrics of the particle accelerator. In this direction, electronic structure theory aided computational screening and design of dielectric materials can play a key role in identifying potential candidate materials with the targeted functionalities to guide experimental synthetic efforts. In anmore » attempt to systematically understand the role of chemistry in controlling the electronic structure and dielectric properties of organic polymeric materials, here we employ empirical screening and density functional theory (DFT) computations, as a part of our multi-step hierarchal screening strategy. Our DFT based analysis focused on the bandgap, dielectric permittivity, and frequency-dependent dielectric losses due to lattice absorption as key properties to down-select promising polymer motifs. In addition to the specific application of dielectric laser acceleration, the general methodology presented here is deemed to be valuable in the design of new insulators with an attractive combination of dielectric properties.« less

Phase-breaking effect on polaron transport in organic conjugated polymers

DOE PAGES

Meng, Ruixuan; Yin, Sun; Zheng, Yujun; ...

2017-06-15

Despite intense investigations and many accepted viewpoints on theory and experiment, the coherent and incoherent carrier transport in organic semiconductors remains an unsettled topic due to the strong electron-phonon coupling. Based on the tight-binding Su-Schrieffer-Heeger (SSH) model combined with a non-adiabatic dynamics method, we study the effect of phase-breaking on polaron transport by introducing a group of phase-breaking factors into π-electron wave-functions in organic conjugated polymers. Two approaches are applied: the modification of the transfer integral and the phase-breaking addition to the wave-function. Within the former, it is found that a single site phase-breaking can trap a polaron. However, withmore » a larger regular phase-breaking a polaron becomes more delocalized and lighter. Additionally, a group of disordered phase-breaking factors can make the polaron disperse in transport process. Within the latter approach, we show that the phase-breaking can render the delocalized state in valence band discrete and the state in the gap more localized. Consequently, the phase-breaking frequency and intensity can reduce the stability of a polaron. Furthermore, the phase-breaking in organic systems is the main factor that degrades the coherent transport and destroys the carrier stability.« less

Phase-breaking effect on polaron transport in organic conjugated polymers

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

Meng, Ruixuan; Yin, Sun; Zheng, Yujun

Despite intense investigations and many accepted viewpoints on theory and experiment, the coherent and incoherent carrier transport in organic semiconductors remains an unsettled topic due to the strong electron-phonon coupling. Based on the tight-binding Su-Schrieffer-Heeger (SSH) model combined with a non-adiabatic dynamics method, we study the effect of phase-breaking on polaron transport by introducing a group of phase-breaking factors into π-electron wave-functions in organic conjugated polymers. Two approaches are applied: the modification of the transfer integral and the phase-breaking addition to the wave-function. Within the former, it is found that a single site phase-breaking can trap a polaron. However, withmore » a larger regular phase-breaking a polaron becomes more delocalized and lighter. Additionally, a group of disordered phase-breaking factors can make the polaron disperse in transport process. Within the latter approach, we show that the phase-breaking can render the delocalized state in valence band discrete and the state in the gap more localized. Consequently, the phase-breaking frequency and intensity can reduce the stability of a polaron. Furthermore, the phase-breaking in organic systems is the main factor that degrades the coherent transport and destroys the carrier stability.« less

Channeling Polyolefin Molecular Structure - Bulk Property Correlation Strategies for Industrial Applicability

NASA Astrophysics Data System (ADS)

Hule, Rohan; Thurman, Derek; Doufas, Antonios

Polyolefins occupy a significant volume of the polymer products portfolio in commodity and high value applications. Quantifying and optimizing structure-property relationships enables growth in new markets. It is well recognized that coupling lab-based, comprehensive methodologies with bulk properties of interest to industrial environments offer the greatest potential of technology advancement, ultimately leading to commercial success. It is imperative to recognize the existing gap of knowledge translation between lab measurements and industrial-scale operability. This study highlights experimental HDPEs synthesized from dual, single-site, co-supported catalysts that exhibit enhanced solid-state properties such as stiffness, impact and ESCR surpassing conventional trends. Commercial resins across distinct sub-families were included as well. Commonality amongst these resins is bimodality and broad MW distribution with well-defined splits and spreads. Investigations on commercially relevant parameters such as melt strength, melt elasticity and shear thinning established excellent performance for experimental bimodals, corroborating potential benefits compared to commercial HDPEs. To summarize, the effort highlights well-recognized pathways such as improvements in mechanical and melt properties that can be attributed to apposite tuning of polymer chain architecture and MW distribution with implications across myriad markets. Ultimately, this may serve as a pathway for producing innovative products that deliver business success and growth.

The origin of high PCE in PTB7 based photovoltaics: proper charge neutrality level and free energy of charge separation at PTB7/PC71BM interface

PubMed Central

Park, Soohyung; Jeong, Junkyeong; Hyun, Gyeongho; Kim, Minju; Lee, Hyunbok; Yi, Yeonjin

2016-01-01

The energy level alignments at donor/acceptor interfaces in organic photovoltaics (OPVs) play a decisive role in device performance. However, little is known about the interfacial energetics in polymer OPVs due to technical issues of the solution process. Here, the frontier ortbial line-ups at the donor/acceptor interface in high performance polymer OPVs, PTB7/PC71BM, were investigated using in situ UPS, XPS and IPES. The evolution of energy levels during PTB7/PC71BM interface formation was investigated using vacuum electrospray deposition, and was compared with that of P3HT/PC61BM. At the PTB7/PC71BM interface, the interface dipole and the band bending were absent due to their identical charge neutrality levels. In contrast, a large interfacial dipole was observed at the P3HT/PC61BM interface. The measured photovoltaic energy gap (EPVG) was 1.10 eV for PTB7/PC71BM and 0.90 eV for P3HT/PC61BM. This difference in the EPVG leads to a larger open-circuit voltage of PTB7/PC71BM than that of P3HT/PC61BM. PMID:27734957

The origin of high PCE in PTB7 based photovoltaics: proper charge neutrality level and free energy of charge separation at PTB7/PC71BM interface.

PubMed

Park, Soohyung; Jeong, Junkyeong; Hyun, Gyeongho; Kim, Minju; Lee, Hyunbok; Yi, Yeonjin

2016-10-13

The energy level alignments at donor/acceptor interfaces in organic photovoltaics (OPVs) play a decisive role in device performance. However, little is known about the interfacial energetics in polymer OPVs due to technical issues of the solution process. Here, the frontier ortbial line-ups at the donor/acceptor interface in high performance polymer OPVs, PTB7/PC 71 BM, were investigated using in situ UPS, XPS and IPES. The evolution of energy levels during PTB7/PC 71 BM interface formation was investigated using vacuum electrospray deposition, and was compared with that of P3HT/PC 61 BM. At the PTB7/PC 71 BM interface, the interface dipole and the band bending were absent due to their identical charge neutrality levels. In contrast, a large interfacial dipole was observed at the P3HT/PC 61 BM interface. The measured photovoltaic energy gap (E PVG ) was 1.10 eV for PTB7/PC 71 BM and 0.90 eV for P3HT/PC 61 BM. This difference in the E PVG leads to a larger open-circuit voltage of PTB7/PC 71 BM than that of P3HT/PC 61 BM.

Hydrophilic Polymer Embolism: Implications for Manufacturing, Regulation, and Postmarket Surveillance of Coated Intravascular Medical Devices.

PubMed

Mehta, Rashi I; Mehta, Rupal I

2018-03-19

Hydrophilic polymers are ubiquitously applied as surface coatings on catheters and intravascular medical technologies. Recent clinical literature has heightened awareness on the complication of hydrophilic polymer embolism, the phenomenon wherein polymer coating layers separate from catheter and device surfaces, and may be affiliated with a range of unanticipated adverse reactions. Significant system barriers have limited and delayed reporting on this iatrogenic complication, the full effects of which remain underrecognized by healthcare providers and manufacturers of various branded devices. In 2015, the United States Food and Drug Administration acknowledged rising clinical concerns and stated that the agency would work with stakeholders to further evaluate gaps that exist in current national and international device standards for coated intravascular medical technologies. The present article reviews current knowledge on this complication as well as factors that played a role in delaying detection and dissemination of information and new knowledge once hazards and clinical risks were identified. Furthermore, organ-specific effects and adverse reaction patterns are summarized, along with implications for device manufacturing, safety assurance, and regulation. Qualitative and quantitative particulate testing are needed to optimize coated intravascular device technologies. Moreover, general enhanced processes for medical device surveillance are required for timely adverse event management and to ensure patient safety.

Enhancement of the optical, thermal and electrical properties of PEO/PAM:Li polymer electrolyte films doped with Ag nanoparticles

NASA Astrophysics Data System (ADS)

Morsi, M. A.; El-Khodary, Sherif A.; Rajeh, A.

2018-06-01

Both lithium bromide (LiBr) and biosynthesized silver nanoparticles (Ag NPs) with average size 2-30 nm have been incorporated into the polymeric matrix of polyethylene oxide and polyacrylamide (PEO/PAM) blend by the casting method. FT-IR analysis indicates the formation of hydrogen bond between the blend components. Also, LiBr and Ag NPs interact with the functional groups of PEO/PAM matrix. The results of XRD analysis depict the semi-crystalline nature of these polymer samples and the degree of crystallinity is decreased due to the addition process. The values of optical energy gap from UV-Vis. data are decreased from 3.55 eV for blend to 3.26 for the nanocomposite sample in the indirect transition. LiBr/Ag NPs assist the improvement of the thermal stability of the PEO/PAM blend, as evidenced by TGA and DTA techniques. Upon the addition of LiBr and Ag NPs, an improvement for the conductivity, dielectric permittivity (έ) and dielectric loss (ἕ) of PEO/PAM solid polymer electrolytes are observed. It's clear that the improvement of the electrical conductivity and dielectric parameters for PEO/PAM: Li+/Ag NPs polymer electrolyte system makes it as a promising candidate for solid-state Li battery applications.

Dihedral angle control to improve the charge transport properties of conjugated polymers in organic field effect transistors

NASA Astrophysics Data System (ADS)

Dharmapurikar, Satej S.; Chithiravel, Sundaresan; Mane, Manoj V.; Deshmukh, Gunvant; Krishnamoorthy, Kothandam

2018-03-01

Diketopyrrolopyrrole (DPP) and i-Indigo (i-Ind) are two monomers that are widely explored as active materials in organic field effect transistor and solar cells. These two molecules showed impressive charge carrier mobility due to better packing that are facilitated by quadrupoles. We hypothesized that the copolymers of these monomers would also exhibit high charge carrier mobility. However, we envisioned that the dihedral angle at the connecting point between the monomers will play a crucial role in packing as well as charge transport. To understand the impact of dihedral angle on charge transport, we synthesized three copolymers, wherein the DPP was sandwiched between benzenes, thiophenes and furans. The copolymer of i-Indigo and furan comprising DPP showed a band gap of 1.4 eV with a very high dihedral angle of 179°. The polymer was found to pack better and the coherence length was found to be 112 Å. The hole carrier mobility of these polymer was found to be highest among the synthesized polymer i.e. 0.01 cm2/vs. The copolymer comprising benzene did not transport hole and electrons. The dihedral angle at the connecting point between i and Indigo and benzene DPP was 143 Å, which the packing and consequently charge transport properties.

Advanced membrane electrode assemblies for fuel cells

DOEpatents

Kim, Yu Seung; Pivovar, Bryan S.

2012-07-24

A method of preparing advanced membrane electrode assemblies (MEA) for use in fuel cells. A base polymer is selected for a base membrane. An electrode composition is selected to optimize properties exhibited by the membrane electrode assembly based on the selection of the base polymer. A property-tuning coating layer composition is selected based on compatibility with the base polymer and the electrode composition. A solvent is selected based on the interaction of the solvent with the base polymer and the property-tuning coating layer composition. The MEA is assembled by preparing the base membrane and then applying the property-tuning coating layer to form a composite membrane. Finally, a catalyst is applied to the composite membrane.

Advanced membrane electrode assemblies for fuel cells

DOEpatents

Kim, Yu Seung; Pivovar, Bryan S

2014-02-25

A method of preparing advanced membrane electrode assemblies (MEA) for use in fuel cells. A base polymer is selected for a base membrane. An electrode composition is selected to optimize properties exhibited by the membrane electrode assembly based on the selection of the base polymer. A property-tuning coating layer composition is selected based on compatibility with the base polymer and the electrode composition. A solvent is selected based on the interaction of the solvent with the base polymer and the property-tuning coating layer composition. The MEA is assembled by preparing the base membrane and then applying the property-tuning coating layer to form a composite membrane. Finally, a catalyst is applied to the composite membrane.

Concurrent release of admixed antimicrobials and salicylic acid from salicylate-based poly(anhydride-esters)

PubMed Central

Johnson, Michelle L.; Uhrich, Kathryn E.

2008-01-01

A polymer blend consisting of antimicrobials (chlorhexidine, clindamycin, and minocycline) physically admixed at 10% by weight into a salicylic acid-based poly (anhydride-ester) (SA-based PAE) was developed as an adjunct treatment for periodontal disease. The SA-based PAE/antimicrobial blends were characterized by multiple methods, including contact angle measurements and differential scanning calorimetry. Static contact angle measurements showed no significant differences in hydrophobicity between the polymer and antimicrobial matrix surfaces. Notable decreases in the polymer glass transition temperature (Tg) and the antimicrobials' melting points (Tm) were observed indicating that the antimicrobials act as plasticizers within the polymer matrix. In vitro drug release of salicylic acid from the polymer matrix and for each physically admixed antimicrobial was concurrently monitored by high pressure liquid chromatography during the course of polymer degradation and erosion. Although the polymer/antimicrobial blends were immiscible, the initial 24 h of drug release correlated to the erosion profiles. The SA-based PAE/antimicrobial blends are being investigated as an improvement on current localized drug therapies used to treat periodontal disease. PMID:19180627

Directed assembly of nanomaterials for miniaturized sensors by dip-pen nanolithography using precursor inks

NASA Astrophysics Data System (ADS)

Su, Ming

The advent of nanomaterials with enhanced properties and the means to pattern them in a controlled fashion have paved the way to construct miniaturized sensors for improved detection. However it remains a challenge for the traditional methods to create such sensors and sensor arrays. Dip pen nanolithography (DPN) can form nanostructures on a substrate by controlling the transfer of molecule inks. However, previous DPN can not pattern solid materials on insulating surfaces, which are necessary to form functional electronic devices. In the dissertation, the concept of reactive precursor inks for DPN is developed for the generation of solid functional nanostructures of the following materials: organic molecule, sol-gel material, and conducting polymer. First, the covalent bonding is unnecessary for DPN as shown in the colored ink DPN; therefore the numbers of molecules that can be patterned is extended beyond thiol or thiolated molecules. Subsequently, a reactive precursor strategy (sol) is developed to pattern inorganic or organic/inorganic composite nanostructures on silicon based substrates. The method works by hydrolysis of metal precursors in the water meniscus and allows the preparation of solid structures with controlled geometry beyond the individual molecule level. Then the SnO 2 nanostructures patterned between the gaps of electrodes are tested as gas sensors. Proof-of-concept experiments are demonstrated on miniaturized sensors that show fast response and recovery to certain gases. Furthermore, an eight-unit sensor array is fabricated on a chip using SnO2 sols that are doped with different metals. The multiplexed device can recognize different gases by comparing the response patterns with the reference patterns of known gases generated on the same array. At last, the idea of precursor ink for DPN is extended to construct conducting polymer based devices. By using an acid promoted polymerization approach, conducting polymers are patterned on silicon dioxide substrates. The patterned organic solids response to light and behave as miniaturized photo-detectors. The microstructures are studied using microscopic and spectroscopic techniques.

Recent Advances in Edible Polymer Based Hydrogels as a Sustainable Alternative to Conventional Polymers.

PubMed

Ali, Akbar; Ahmed, Shakeel

2018-06-26

The over increasing demand of eco-friendly materials to counter various problems, such as environmental issues, economics, sustainability, biodegradability, and biocompatibility, open up new fields of research highly focusing on nature-based products. Edible polymer based materials mainly consisting of polysaccharides, proteins, and lipids could be a prospective contender to handle such problems. Hydrogels based on edible polymer offer many valuable properties compared to their synthetic counterparts. Edible polymers can contribute to the reduction of environmental contamination, advance recyclability, provide sustainability, and thereby increase its applicability along with providing environmentally benign products. This review is highly emphasizing on toward the development of hydrogels from edible polymer, their classification, properties, chemical modification, and their potential applications. The application of edible polymer hydrogels covers many areas including the food industry, agricultural applications, drug delivery to tissue engineering in the biomedical field and provide more safe and attractive products in the pharmaceutical, agricultural, and environmental fields, etc.

Synthesis and characterization of hybrid nanocomposites as highly-efficient conducting CH4 gas sensor.

PubMed

Aldalbahi, Ali; Feng, Peter; Alhokbany, Norah; Al-Farraj, Eida; Alshehri, Saad M; Ahamad, Tansir

2017-02-15

Functionalized (MWCNTs-COOH), non-functionalized multiwalled carbon nanotubes (MWCNTs) and polyaniline (PANI) based conducting nanocomposites (PANI/polymer/MWCNTs and PANI/polymer/MWCNTs-COOH) have been prepared in polymer matrix. The prepared nanocomposites were characterized via FTIR, TGA, Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). It was observed that the prepared conducting nanocomposites show excellent sensing performances toward CH 4 at room temperature and both the response and recovery time were recorded at around 5s, respectively, at the room. The PANI/polymer/MWCNTs based detector had quicker/shorter response time (<1s), as well as higher sensitivity (3.1%) than that of the PANI/polymer/MWCNTs-COOH based detector. This was attributed to nonconductive -COOH that results in a poor sensitivity of PANI/polymer/MWCNTs-COOH-based prototype. The PANI/polymer/MWCNTs-COOH nanocomposites show almost 10 time higher sensitivity at higher temperature (60°C) than that at room temperature. Copyright © 2016. Published by Elsevier B.V.

Photonic band gap templating using optical interference lithography

NASA Astrophysics Data System (ADS)

Chan, Timothy Y. M.; Toader, Ovidiu; John, Sajeev

2005-04-01

We describe the properties of three families of inversion-symmetric, large photonic band-gap (PBG) template architectures defined by iso-intensity surfaces in four beam laser interference patterns. These templates can be fabricated by optical interference (holographic) lithography in a suitable polymer photo-resist. PBG materials can be synthesized from these templates using two stages of infiltration and inversion, first with silica and second with silicon. By considering point and space group symmetries to produce laser interference patterns with the smallest possible irreducible Brillouin zones, we obtain laser beam intensities, directions, and polarizations which generate a diamond-like (fcc) crystal, a novel body-centered cubic (bcc) architecture, and a simple-cubic (sc) structure. We obtain laser beam parameters that maximize the intensity contrasts of the interference patterns. This optimizes the robustness of the holographic lithography to inhomogeneity in the polymer photo-resist. When the optimized iso-intensity surface defines a silicon to air boundary (dielectric contrast of 11.9 to 1), the fcc, bcc, and sc crystals have PBG to center frequency ratios of 25%, 21%, and 11%, respectively. A full PBG forms for the diamond-like crystal when the refractive index contrast exceeds 1.97 to 1. We illustrate a noninversion symmetric PBG architecture that interpolates between a simple fcc structure and a diamond network structure. This crystal exhibits two distinct and complete photonic band gaps. We also describe a generalized class of tetragonal photonic crystals that interpolate between and extrapolate beyond the diamond-like crystal and the optimized bcc crystal. We demonstrate the extent to which the resulting PBG materials are robust against perturbations to the laser beam amplitudes and polarizations, and template inhomogeneity. The body centered cubic structure exhibits the maximum robustness overall.

Polymer Scaffolds with Preferential Parallel Grooves Enhance Nerve Regeneration

PubMed Central

Mobasseri, Atefeh; Faroni, Alessandro; Minogue, Ben M.; Downes, Sandra; Reid, Adam J.

2015-01-01

We have modified the surface topography of poly ɛ-caprolactone (PCL) and polylactic acid (PLA) blended films to improve cell proliferation and to guide the regeneration of peripheral nerves. Films with differing shaped grooves were made using patterned silicon templates, sloped walls (SL), V-shaped (V), and square-shaped (SQ), and compared with nongrooved surfaces with micropits. The solvent cast films were tested in vitro using adult adipose-derived stem cells differentiated to Schwann cell-like cells. Cell attachment, proliferation, and cell orientation were all improved on the grooved surfaces, with SL grooves giving the best results. We present in vivo data on Sprague-Dawley rat sciatic nerve injury with a 10-mm gap, evaluating nerve regeneration at 3 weeks across a polymer nerve conduit modified with intraluminal grooves (SL, V, and SQ) and differing wall thicknesses (70, 100, 120, and 210 μm). The SL-grooved nerve conduit showed a significant improvement over the other topographical-shaped grooves, while increasing the conduit wall thickness saw no positive effect on the biological response of the regenerating nerve. Furthermore, the preferred SL-grooved conduit (C) with 70 μm wall thickness was compared with the current clinical gold standard of autologous nerve graft (Ag) in the rat 10-mm sciatic nerve gap model. At 3 weeks postsurgery, all nerve gaps across both groups were bridged with regenerated nerve fibers. At 16 weeks, features of regenerated axons were comparable between the autograft (Ag) and conduit (C) groups. End organ assessments of muscle weight, electromyography, and skin reinnervation were also similar between the groups. The comparable experimental outcome between conduit and autograft, suggests that the PCL/PLA conduit with inner lumen microstructured grooves could be used as a potential alternative treatment for peripheral nerve repair. PMID:25435096

Polymer-based materials to be used as the active element in microsensors: a scanning force microscopy study

PubMed

Porter; Eastman; Pace; Bradley

2000-09-01

Polymer-based materials can be incorporated as the active sensing elements in chemiresistor devices. Most of these devices take advantage of the fact that certain polymers will swell when exposed to gaseous analytes. To measure this response, a conducting material such as carbon black is incorporated within the nonconducting polymer matrix. In response to analytes, polymer swelling results in a measurable change in the conductivity of the polymer/carbon composite material. Arrays of these sensors may be used in conjunction with pattern recognition techniques for purposes of analyte recognition and quantification. We have used the technique of scanning force microscopy (SFM) to investigate microstructural changes in carbon-polymer composites formed from the polymers poly (isobutylene) (PIB), poly (vinyl alcohol) (PVA), and poly (ethylene-vinyl acetate) (PEVA) when exposed to the analytes hexane, toluene, water, ethanol, and acetone. Using phase-contrast imaging (PI), changes in the carbon nanoparticle distribution on the surface of the polymer matrix are measured as the polymers are exposed to the analytes in vapor phase. In some but not all cases, the changes were reversible (at the scale of the SFM measurements) upon removal of the analyte vapor. In this paper, we also describe a new type of microsensor based on piezoresistive microcantilever technology. With these new devices, polymeric volume changes accompanying exposure to analyte vapor are measured directly by a piezoresistive microcantilever in direct contact with the polymer. These devices may offer a number of advantages over standard chemiresistor-based sensors.

Process to prepare stable trifluorostyrene containing compounds grafted to base polymers using a solvent/water mixture

DOEpatents

Roelofs, Mark Gerrit; Yang, Zhen-Yu; Han, Amy Qi

2010-06-15

A fluorinated ion exchange polymer is prepared by grafting at least one grafting monomer derived from trifluorostyrene on to at least one base polymer in a organic solvent/water mixture. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.

Development of buccal drug delivery systems based on a thiolated polymer.

PubMed

Langoth, Nina; Kalbe, Jochen; Bernkop-Schnürch, Andreas

2003-02-18

The purpose of the present study was to investigate the benefit of thiolated polymers (thiomers) for the development of buccal drug delivery systems. L-Cysteine was thereby covalently attached to polycarbophil (PCP) mediated by a carbodiimide. The resulting conjugate displayed 140.5+/-8.4 microM thiol groups per gram polymer. Disintegration studies were carried out with tablets based on unmodified polymer and conjugated polymer, respectively. Due to the formation of disulfide bonds within the thiolated polymer, the stability of matrix-tablets based on this polymer was strongly improved. Additionally tensile studies were carried out, which were in good correlation with further results obtained by mucoadhesion studies, using the rotating cylinder method. These results showed that tablets based on thiolated PCP remained attached on freshly excised porcine mucosa 1.8 times longer than the corresponding control. Moreover, the enzyme inhibitory properties of polymers were evaluated as well. Thiolated PCP increased the stability of the synthetic substrate for aminopeptidase N-leu-p-nitroanilide (N-leu-pNA) and the model drug leucin-enkephalin (leu-enkephalin) against enzymatic degradation on buccal mucosa. Due to the use of thiolated polymers also a controlled drug release for leu-enkephalin was guaranteed over a time period for more than 24 h. Results of the present studies suggest that thiolated polymers represent a very useful tool for buccal delivery of peptide drugs.

To study the linear and nonlinear optical properties of Se-Te-Bi-Sn/PVP (polyvinylpyrrolidone) nanocomposites

NASA Astrophysics Data System (ADS)

Tyagi, Chetna; Yadav, Preeti; Sharma, Ambika

2018-05-01

The present work reveals the optical study of Se82Te15Bi1.0Sn2.0/polyvinylpyrrolidone (PVP) nanocomposites. Bulk glasses of chalcogenide was prepared by well-known melt quenching technique. Wet chemical technique is proposed for making the composite of Se82Te15Bi1.0Sn2.0 and PVP polymer as it is easy to handle and cost effective. The composites films were made on glass slide from the solution of Se-Te-Bi-Sn and PVP polymer using spin coating technique. The transmission as well as absorbance is recorded by using UV-Vis-NIR spectrophotometer in the spectral range 350-700 nm. The linear refractive index (n) of polymer nanocomposites are calculated by Swanepoel approach. The linear refractive index (n) PVP doped Se82Te15Bi1.0Sn2.0 chalcogenide is found to be 1.7. The optical band gap has been evaluated by means of Tauc extrapolation method. Tichy and Ticha model was utilized for the characterization of nonlinear refractive index (n2).

Multi-scale modeling of diffusion-controlled reactions in polymers: renormalisation of reactivity parameters.

PubMed

Everaers, Ralf; Rosa, Angelo

2012-01-07

The quantitative description of polymeric systems requires hierarchical modeling schemes, which bridge the gap between the atomic scale, relevant to chemical or biomolecular reactions, and the macromolecular scale, where the longest relaxation modes occur. Here, we use the formalism for diffusion-controlled reactions in polymers developed by Wilemski, Fixman, and Doi to discuss the renormalisation of the reactivity parameters in polymer models with varying spatial resolution. In particular, we show that the adjustments are independent of chain length. As a consequence, it is possible to match reactions times between descriptions with different resolution for relatively short reference chains and to use the coarse-grained model to make quantitative predictions for longer chains. We illustrate our results by a detailed discussion of the classical problem of chain cyclization in the Rouse model, which offers the simplest example of a multi-scale descriptions, if we consider differently discretized Rouse models for the same physical system. Moreover, we are able to explore different combinations of compact and non-compact diffusion in the local and large-scale dynamics by varying the embedding dimension.

First-principles study of the effect of functional groups on polyaniline backbone

PubMed Central

Chen, X. P.; Jiang, J. K.; Liang, Q. H.; Yang, N.; Ye, H. Y.; Cai, M.; Shen, L.; Yang, D. G.; Ren, T. L.

2015-01-01

We present a first-principles density functional theory study focused on how the chemical and electronic properties of polyaniline are adjusted by introducing suitable substituents on a polymer backbone. Analyses of the obtained energy barriers, reaction energies and minimum energy paths indicate that the chemical reactivity of the polyaniline derivatives is significantly enhanced by protonic acid doping of the substituted materials. Further study of the density of states at the Fermi level, band gap, HOMO and LUMO shows that both the unprotonated and protonated states of these polyanilines are altered to different degrees depending on the functional group. We also note that changes in both the chemical and electronic properties are very sensitive to the polarity and size of the functional group. It is worth noting that these changes do not substantially alter the inherent chemical and electronic properties of polyaniline. Our results demonstrate that introducing different functional groups on a polymer backbone is an effective approach to obtain tailored conductive polymers with desirable properties while retaining their intrinsic properties, such as conductivity. PMID:26584671

Polymer gel dosimeter with AQUAJOINT® as hydrogel matrix

NASA Astrophysics Data System (ADS)

Maeyama, Takuya; Ishida, Yasuhiro; Kudo, Yoshihiro; Fukasaku, Kazuaki; Ishikawa, Kenichi L.; Fukunishi, Nobuhisa

2018-05-01

We report a polymer gel dosimeter based on a new gel matrix (AQUAJOINT®) that is a thermo-irreversible hydrogel formed by mixing two types of water-based liquids at room temperature. Normoxic N-vinylpyrrolidone-based polymer gels were prepared with AQUAJOINT® instead of gelatin. This AQUAJOINT®-based gel dosimeter exhibits a 2.5-fold increase in sensitivity over a gelatin-based gel dosimeter and a linear dose-response in the dose range of 0-8 Gy. This gel has heat resistance in a jar and controlled gel properties such as viscoelastic and mechanical characters, which may be useful for deformable polymer gel dosimetry.

Water-soluble polymers bearing phosphorylcholine group and other zwitterionic groups for carrying DNA derivatives.

PubMed

Lin, Xiaojie; Ishihara, Kazuhiko

2014-01-01

Water-soluble polymers with equal positive and negative charges in the same monomer unit, such as the phosphorylcholine group and other zwitterionic groups, exhibit promising potential in gene delivery with appreciable transfection efficiency, compared with the traditional poly(ethylene glycol)-based polycation-gene complexes. These zwitterionic polymers with various architectural structures and properties have been synthesized by various polymerization methods, such as conventional radical polymerization, atom-transfer radical-polymerization, reversible addition-fragmentation chain-transfer polymerization, and nitroxide-mediated radical polymerization. These techniques have been used to efficiently facilitate gene therapy by fabrication of non-viral vectors with high cytocompatibility, large gene-carrying capacity, effective cell-membrane permeability, and in vivo gene-loading/releasing functionality. Zwitterionic polymer-based gene delivery vectors systems can be categorized into soluble-polymer/gene mixing, molecular self-assembly, and polymer-gene conjugation systems. This review describes the preparation and characterization of various zwitterionic polymer-based gene delivery vectors, specifically water-soluble phospholipid polymers for carrying gene derivatives.

Polymer-Based Nanocomposites: An Internship Program for Deaf and Hard of Hearing Students

NASA Astrophysics Data System (ADS)

Cebe, Peggy; Cherdack, Daniel; Seyhan Ince-Gunduz, B.; Guertin, Robert; Haas, Terry; Valluzzi, Regina

2007-03-01

We report on our summer internship program in Polymer-Based Nanocomposites, for deaf and hard of hearing undergraduates who engage in classroom and laboratory research work in polymer physics. The unique attributes of this program are its emphasis on: 1. Teamwork; 2. Performance of a start-to-finish research project; 3. Physics of materials approach; and 4. Diversity. Students of all disability levels have participated in this program, including students who neither hear nor voice. The classroom and laboratory components address the materials chemistry and physics of polymer-based nanocomposites, crystallization and melting of polymers, the interaction of X-rays and light with polymers, mechanical properties of polymers, and the connection between thermal processing, structure, and ultimate properties of polymers. A set of Best Practices is developed for accommodating deaf and hard of hearing students into the laboratory setting. The goal is to bring deaf and hard of hearing students into the larger scientific community as professionals, by providing positive scientific experiences at a formative time in their educational lives.

High-speed, Low Voltage, Miniature Electro-optic Modulators Based on Hybrid Photonic-Crystal/Polymer/Sol-Gel Technology

DTIC Science & Technology

2012-02-01

code) 01/02/2012 FINAL 15/11/2008 - 15/11/2011 High-speed, Low Voltage, Miniature Electro - optic Modulators Based on Hybrid Photonic-Crystal/Polymer... optic modulator, silicon photonics, integrated optics, electro - optic polymer, avionics, optical communications, sol-gel, nanotechnology U U U UU 25...2011 Program Manager: Dr. Charles Y-C Lee High-speed, Low Voltage, Miniature Electro - optic Modulators Based on Hybrid Photonic-Crystal/Polymer/Sol

Polymer-lipid hybrid systems: merging the benefits of polymeric and lipid-based nanocarriers to improve oral drug delivery.

PubMed

Rao, Shasha; Prestidge, Clive A

2016-01-01

A number of biobarriers limit efficient oral drug absorption; both polymer-based and lipid-based nanocarriers have demonstrated properties and delivery mechanisms to overcome these biobarriers in preclinical settings. Moreover, in order to address the multifaceted oral drug delivery challenges, polymer-lipid hybrid systems are now being designed to merge the beneficial features of both polymeric and lipid-based nanocarriers. Recent advances in the development of polymer-lipid hybrids with a specific focus on their viability in oral delivery are reviewed. Three classes of polymer-lipid hybrids have been identified, i.e. lipid-core polymer-shell systems, polymer-core lipid-shell systems, and matrix-type polymer-lipid hybrids. We focus on their application to overcome the various biological barriers to oral drug absorption, as exemplified by selected preclinical studies. Numerous studies have demonstrated the superiority of polymer-lipid hybrid systems to their non-hybrid counterparts in providing improved drug encapsulation, modulated drug release, and improved cellular uptake. These features have encouraged their applications in the delivery of chemotherapeutics, proteins, peptides, and vaccines. With further research expected to optimize the manufacturing and scaling up processes and in-depth pre-clinical pharmacological and toxicological assessments, these multifaceted drug delivery systems will have significant clinical impact on the oral delivery of pharmaceuticals and biopharmaceuticals.

Characterization of argon dielectric barrier discharges applied to ethyl lactate plasma polymerization

NASA Astrophysics Data System (ADS)

Laurent, Morgane; Desjardins, Edouard; Meichelboeck, Maximilian; Naudé, Nicolas; Stafford, Luc; Gherardi, Nicolas; Laroche, Gaétan

2017-11-01

The influence of the input voltage frequency (35 and 150 kHz), interelectrode gap (1 and 2 mm) and precursor concentration (250, 350, and 450 ppm) on the electron temperature (T e), number density of metastable Ar atoms (n(Ar m )), and discharge current density (proportional to the electron density ne) is studied in an argon-ethyl lactate dielectric barrier discharge (DBD). An argon-ammonia Penning mixture is also considered as reference. These results are correlated to the chemistry (XPS, IR) and topography (AFM) of the ethyl-lactate-based plasma polymer coatings. Low T e values from 0.3 to 0.5 eV were obtained for all discharges. This observation, in addition to resemblances with the Ar-NH3 mixture, suggested that the ionization kinetics of ethyl lactate-based discharges is driven by Penning reactions. Among the investigated parameters, the dissipated power obtained through changes of the excitation frequency had the largest impact on both the coatings properties and the discharge behavior.

Electrochemical testing of industrially produced PEO-based polymer electrolytes

NASA Astrophysics Data System (ADS)

Appetecchi, G. B.; Alessandrini, F.; Duan, R. G.; Arzu, A.; Passerini, S.

The present report describes the results of the electrochemical tests performed on polyethyleneoxide-based polymer electrolyte thin films industrially manufactured by blown-extrusion. The polymer electrolyte composition was PEO 20 LiCF 3SO 3: 16.7% γLiAlO 2. The polymer electrolyte film was tested to evaluate the ionic conductivity as well as the interfacial properties with lithium metal anodes. The work was developed within the advanced lithium polymer electrolyte (ALPE) project, an Italian project devoted to the realization of lithium polymer batteries for electric vehicle applications, in collaboration with Union Carbide.

Optical characterization of polymer liquid crystal cell exhibiting polymer blue phases.

PubMed

Zhang, Bao-Yan; Meng, Fan-Bao; Cong, Yue-Hua

2007-08-06

The optical properties of polymer liquid crystal cell exhibiting polymer blue phases (PBPs) have been determined using ultraviolet-visible spectrophotometry, polarizing optical microscopy (POM), differential scanning calorimetry (DSC), X-ray measurements, FTIR imaging and optical rotation technique. PBPs are thermodynamically stabile mesophases, which appear in chiral systems between isotropic and liquid crystal phases. A series of cyclosiloxane-based blue phase polymers were synthesized using a cholesteric LC monomer and a nematic LC monomer, and some of the polymers exhibit PBPs in temperature range over 300 degrees in cooling cycles. The unique property based on their structure and different twists formed and expect to open up new photonic application and enrich polymer blue phase contents and theory.

Investigation of a single barrier discharge in submillimeter air gaps. Nonuniform field

NASA Astrophysics Data System (ADS)

Bondarenko, P. N.; Emel'yanov, O. A.; Shemet, M. V.

2014-08-01

Pulse characteristics of single barrier discharges as well as parameters of charges accumulated on the surface of a dielectric under the atmospheric pressure in the "needle-(0.1-2.0)-mm air gap-polymer barrier-plane" system are investigated. It is found experimentally that for the positive polarity of the needle, the voltage for the discharge initiation is higher than in the case of the negative polarity by ˜25-35%. The reversal of the needle polarity from negative to positive increases the amplitude of the discharge current and the accumulated surface charge by ˜1.5-3 times. For the positive polarity of the needle, the discharge is governed by a streamer mechanism, while for the negative polarity, the discharge is initiated by the formation of a single Trichel pulse. The single pulse regime is observed for the discharge current up to a certain electrode gap d CR. For the positive needle and for air gap width d air > d CR ≈ 1.5 mm, a multipulse burst corona is formed, while for the negative needle and d air > d CR ≈ 0.9 mm, a damped sequence of Trichel pulses evolves in the system.

High Photon-to-Current Conversion in Solar Cells Based on Light-Absorbing Silver Bismuth Iodide.

PubMed

Zhu, Huimin; Pan, Mingao; Johansson, Malin B; Johansson, Erik M J

2017-06-22

Here, a lead-free silver bismuth iodide (AgI/BiI 3 ) with a crystal structure with space group R3‾ m is investigated for use in solar cells. Devices based on the silver bismuth iodide deposited from solution on top of TiO 2 and the conducting polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) as a hole-transport layer are prepared and the photovoltaic performance is very promising with a power conversion efficiency over 2 %, which is higher than the performance of previously reported bismuth-halide materials for solar cells. Photocurrent generation is observed between 350 and 700 nm, and the maximum external quantum efficiency is around 45 %. The results are compared to solar cells based on the previously reported material AgBi 2 I 7 , and we observe a clearly higher performance for the devices with the new silver and bismuth iodides composition and different crystal structure. The X-ray diffraction spectrum of the most efficient silver bismuth iodide material shows a hexagonal crystal structure with space group R3‾ m, and from the light absorption spectrum we obtain an indirect band gap energy of 1.62 eV and a direct band gap energy of 1.85 eV. This report shows the possibility for finding new structures of metal-halides efficient in solar cells and points out new directions for further exploration of lead-free metal-halide solar cells. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Review on State-of-the-art in Polymer Based pH Sensors

PubMed Central

Korostynska, Olga; Arshak, Khalil; Gill, Edric; Arshak, Arousian

2007-01-01

This paper reviews current state-of-the-art methods of measuring pH levels that are based on polymer materials. These include polymer-coated fibre optic sensors, devices with electrodes modified with pH-sensitive polymers, fluorescent pH indicators, potentiometric pH sensors as well as sensors that use combinatory approach for ion concentration monitoring. PMID:28903277

Comparison of two DSC-based methods to predict drug-polymer solubility.

PubMed

Rask, Malte Bille; Knopp, Matthias Manne; Olesen, Niels Erik; Holm, René; Rades, Thomas

2018-04-05

The aim of the present study was to compare two DSC-based methods to predict drug-polymer solubility (melting point depression method and recrystallization method) and propose a guideline for selecting the most suitable method based on physicochemical properties of both the drug and the polymer. Using the two methods, the solubilities of celecoxib, indomethacin, carbamazepine, and ritonavir in polyvinylpyrrolidone, hydroxypropyl methylcellulose, and Soluplus® were determined at elevated temperatures and extrapolated to room temperature using the Flory-Huggins model. For the melting point depression method, it was observed that a well-defined drug melting point was required in order to predict drug-polymer solubility, since the method is based on the depression of the melting point as a function of polymer content. In contrast to previous findings, it was possible to measure melting point depression up to 20 °C below the glass transition temperature (T g ) of the polymer for some systems. Nevertheless, in general it was possible to obtain solubility measurements at lower temperatures using polymers with a low T g . Finally, for the recrystallization method it was found that the experimental composition dependence of the T g must be differentiable for compositions ranging from 50 to 90% drug (w/w) so that one T g corresponds to only one composition. Based on these findings, a guideline for selecting the most suitable thermal method to predict drug-polymer solubility based on the physicochemical properties of the drug and polymer is suggested in the form of a decision tree. Copyright © 2018 Elsevier B.V. All rights reserved.

Silicone Polymer Composites for Thermal Protection System: Fiber Reinforcements and Microstructures

DTIC Science & Technology

2010-01-01

angles were tested. Detailed microstructural, mass loss, and peak erosion analyses were conducted on the phenolic -based matrix composite (control) and...silicone-based matrix composites to understand their protective mechanisms. Keywords silicone polymer matrix composites, phenolic polymer matrix...erosion analyses were conducted on the phenolic -based matrix composite (control) and silicone-based matrix composites to understand their protective

Preliminary Evaluations of Polymer-based Lithium Battery Electrolytes Under Development for the Polymer Electrolyte Rechargeable Systems Program

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Bennett, William R.

2003-01-01

A component screening facility has been established at The NASA Glenn Research Center (GRC) to evaluate candidate materials for next generation, lithium-based, polymer electrolyte batteries for aerospace applications. Procedures have been implemented to provide standardized measurements of critical electrolyte properties. These include ionic conductivity, electronic resistivity, electrochemical stability window, cation transference number, salt diffusion coefficient and lithium plating efficiency. Preliminary results for poly(ethy1ene oxide)-based polymer electrolyte and commercial liquid electrolyte are presented.

Clinically advancing and promising polymer-based therapeutics.

PubMed

Souery, Whitney N; Bishop, Corey J

2018-02-01

In this review article, we will examine the history of polymers and their evolution from provisional World War II materials to medical therapeutics. To provide a comprehensive look at the current state of polymer-based therapeutics, we will classify technologies according to targeted areas of interest, including central nervous system-based and intraocular-, gastrointestinal-, cardiovascular-, dermal-, reproductive-, skeletal-, and neoplastic-based systems. Within each of these areas, we will consider several examples of novel, clinically available polymer-based therapeutics; in addition, this review will also include a discussion of developing therapies, ranging from the in vivo to clinical trial stage, for each targeted area of treatment. Finally, we will emphasize areas of patient care in need of more effective, accessible, and targeted treatment approaches where polymer-based therapeutics may offer potential solutions. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Giant nonlinear response at a plasmonic nanofocus drives efficient four-wave mixing

NASA Astrophysics Data System (ADS)

Nielsen, Michael P.; Shi, Xingyuan; Dichtl, Paul; Maier, Stefan A.; Oulton, Rupert F.

2017-12-01

Efficient optical frequency mixing typically must accumulate over large interaction lengths because nonlinear responses in natural materials are inherently weak. This limits the efficiency of mixing processes owing to the requirement of phase matching. Here, we report efficient four-wave mixing (FWM) over micrometer-scale interaction lengths at telecommunications wavelengths on silicon. We used an integrated plasmonic gap waveguide that strongly confines light within a nonlinear organic polymer. The gap waveguide intensifies light by nanofocusing it to a mode cross-section of a few tens of nanometers, thus generating a nonlinear response so strong that efficient FWM accumulates over wavelength-scale distances. This technique opens up nonlinear optics to a regime of relaxed phase matching, with the possibility of compact, broadband, and efficient frequency mixing integrated with silicon photonics.

Experimental Investigation and Thermodynamic Assessment of Phase Equilibria in the PLLA/Dioxane/Water Ternary System for Applications in the Biomedical Field.

PubMed

Ruggiero, Flavia; Netti, Paolo Antonio; Torino, Enza

2015-12-01

Fundamental understanding of thermodynamic of phase separation plays a key role in tuning the desired features of biomedical devices. In particular, phase separation of ternary solution is of remarkable interest in processes to obtain biodegradable and biocompatible architectures applied as artificial devices to repair, replace, or support damaged tissues or organs. In these perspectives, thermally induced phase separation (TIPS) is the most widely used technique to obtained porous morphologies and, in addition, among different ternary systems, polylactic acid (PLLA)/dioxane/water has given promising results and has been largely studied. However, to increase the control of TIPS-based processes and architectures, an investigation of the basic energetic phenomena occurring during phase separation is still required. Here we propose an experimental investigation of the selected ternary system by using isothermal titration calorimetric approach at different solvent/antisolvent ratio and a thermodynamic explanation related to the polymer-solvents interactions in terms of energetic contribution to the phase separation process. Furthermore, relevant information about the phase diagrams and interaction parameters of the studied systems are furnished in terms of liquid-liquid miscibility gap. Indeed, polymer-solvents interactions are responsible for the mechanism of the phase separation process and, therefore, of the final features of the morphologies; the knowledge of such data is fundamental to control processes for the production of membranes, scaffolds and several nanostructures. The behavior of the polymer at different solvent/nonsolvent ratios is discussed in terms of solvation mechanism and a preliminary contribution to the understanding of the role of the hydrogen bonding in the interface phenomena is also reported. It is the first time that thermodynamic data of a ternary system are collected by mean of nano-isothermal titration calorimetry (nano-ITC). Supporting Information is available.

Surface-induced effects in fluctuation-based measurements of single-polymer elasticity: A direct probe of the radius of gyration

NASA Astrophysics Data System (ADS)

Innes-Gold, Sarah N.; Morgan, Ian L.; Saleh, Omar A.

2018-03-01

Single-molecule measurements of polymer elasticity are powerful, direct probes of both biomolecular structure and principles of polymer physics. Recent work has revealed low-force regimes in which biopolymer elasticity is understood through blob-based scaling models. However, the small tensions required to observe these regimes have the potential to create measurement biases, particularly due to the increased interactions of the polymer chain with tethering surfaces. Here, we examine one experimentally observed bias, in which fluctuation-based estimates of elasticity report an unexpectedly low chain compliance. We show that the effect is in good agreement with predictions based on quantifying the exclusion effect of the surface through an image-method calculation of available polymer configurations. The analysis indicates that the effect occurs at an external tension inversely proportional to the polymer's zero-tension radius of gyration. We exploit this to demonstrate a self-consistent scheme for estimating the radius of gyration of the tethered polymer. This is shown in measurements of both hyaluronic acid and poly(ethylene glycol) chains.

Polymers as Reference Partitioning Phase: Polymer Calibration for an Analytically Operational Approach To Quantify Multimedia Phase Partitioning.

PubMed

Gilbert, Dorothea; Witt, Gesine; Smedes, Foppe; Mayer, Philipp

2016-06-07

Polymers are increasingly applied for the enrichment of hydrophobic organic chemicals (HOCs) from various types of samples and media in many analytical partitioning-based measuring techniques. We propose using polymers as a reference partitioning phase and introduce polymer-polymer partitioning as the basis for a deeper insight into partitioning differences of HOCs between polymers, calibrating analytical methods, and consistency checking of existing and calculation of new partition coefficients. Polymer-polymer partition coefficients were determined for polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and organochlorine pesticides (OCPs) by equilibrating 13 silicones, including polydimethylsiloxane (PDMS) and low-density polyethylene (LDPE) in methanol-water solutions. Methanol as cosolvent ensured that all polymers reached equilibrium while its effect on the polymers' properties did not significantly affect silicone-silicone partition coefficients. However, we noticed minor cosolvent effects on determined polymer-polymer partition coefficients. Polymer-polymer partition coefficients near unity confirmed identical absorption capacities of several PDMS materials, whereas larger deviations from unity were indicated within the group of silicones and between silicones and LDPE. Uncertainty in polymer volume due to imprecise coating thickness or the presence of fillers was identified as the source of error for partition coefficients. New polymer-based (LDPE-lipid, PDMS-air) and multimedia partition coefficients (lipid-water, air-water) were calculated by applying the new concept of a polymer as reference partitioning phase and by using polymer-polymer partition coefficients as conversion factors. The present study encourages the use of polymer-polymer partition coefficients, recognizing that polymers can serve as a linking third phase for a quantitative understanding of equilibrium partitioning of HOCs between any two phases.

Achieving high performance polymer tandem solar cells via novel materials design

NASA Astrophysics Data System (ADS)

Dou, Letian

Organic photovoltaic (OPV) devices show great promise in low-cost, flexible, lightweight, and large-area energy-generation applications. Nonetheless, most of the materials designed today always suffer from the inherent disadvantage of not having a broad absorption range, and relatively low mobility, which limit the utilization of the full solar spectrum. Tandem solar cells provide an effective way to harvest a broader spectrum of solar radiation by combining two or more solar cells with different absorption bands. However, for polymer solar cells, the performance of tandem devices lags behind single-layer solar cells mainly due to the lack of suitable low-bandgap polymers (near-IR absorbing polymers). In this dissertation, in order to achieve high performance, we focus on design and synthesis of novel low bandgap polymers specifically for tandem solar cells. In Chapter 3, I demonstrate highly efficient single junction and tandem polymer solar cells featuring a spectrally matched low-bandgap conjugated polymer (PBDTT-DPP: bandgap, ˜1.44 eV). The polymer has a backbone based on alternating benzodithiophene and diketopyrrolopyrrole units. A single-layer device based on the polymer provides a power conversion efficiency of ˜6%. When the polymer is applied to tandem solar cells, a power conversion efficiency of 8.62% is achieved, which was the highest certified efficiency for a polymer solar cell. To further improve this material system, in Chapter 4, I show that the reduction of the bandgap and the enhancement of the charge transport properties of the low bandgap polymer PBDTT-DPP can be accomplished simultaneously by substituting the sulfur atoms on the DPP unit with selenium atoms. The newly designed polymer PBDTT-SeDPP (Eg = 1.38 eV) shows excellent photovoltaic performance in single junction devices with PCEs over 7% and photo-response up to 900 nm. Tandem polymer solar cells based on PBDTT-SeDPP are also demonstrated with a 9.5% PCE, which are more than 10% enhancement over those based on PBDTT-DPP. Finally, in Chapter 5, I demonstrate a new polymer system based on alternating dithienopyran and benzothiadiazole units with a bandgap of 1.38 eV, high mobility, deep highest occupied molecular orbital. As a result, a single-junction device shows high external quantum efficiency of >60% and spectral response that extends to 900 nm, with a power conversion efficiency of 7.9%. The polymer enables a solution processed tandem solar cell with certified 10.6% power conversion efficiency under standard reporting conditions, which is the first certified polymer solar cell efficiency over 10%.

Structure-Property Relationships of Semiconducting Polymers for Flexible and Durable Polymer Field-Effect Transistors.

PubMed

Kim, Min Je; Jung, A-Ra; Lee, Myeongjae; Kim, Dongjin; Ro, Suhee; Jin, Seon-Mi; Nguyen, Hieu Dinh; Yang, Jeehye; Lee, Kyung-Koo; Lee, Eunji; Kang, Moon Sung; Kim, Hyunjung; Choi, Jong-Ho; Kim, BongSoo; Cho, Jeong Ho

2017-11-22

We report high-performance top-gate bottom-contact flexible polymer field-effect transistors (FETs) fabricated by flow-coating diketopyrrolopyrrole (DPP)-based and naphthalene diimide (NDI)-based polymers (P(DPP2DT-T2), P(DPP2DT-TT), P(DPP2DT-DTT), P(NDI2OD-T2), P(NDI2OD-F2T2), and P(NDI2OD-Se2)) as semiconducting channel materials. All of the polymers displayed good FET characteristics with on/off current ratios exceeding 10 7 . The highest hole mobility of 1.51 cm 2 V -1 s -1 and the highest electron mobility of 0.85 cm 2 V -1 s -1 were obtained from the P(DPP2DT-T2) and P(NDI2OD-Se2) polymer FETs, respectively. The impacts of the polymer structures on the FET performance are well-explained by the interplay between the crystallinity, the tendency of the polymer backbone to adopt an edge-on orientation, and the interconnectivity of polymer fibrils in the film state. Additionally, we demonstrated that all of the flexible polymer-based FETs were highly resistant to tensile stress, with negligible changes in their carrier mobilities and on/off ratios after a bending test. Conclusively, these high-performance, flexible, and durable FETs demonstrate the potential of semiconducting conjugated polymers for use in flexible electronic applications.

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.

Liquid scintillators with near infrared emission based on organoboron conjugated polymers.

PubMed

Tanaka, Kazuo; Yanagida, Takayuki; Yamane, Honami; Hirose, Amane; Yoshii, Ryousuke; Chujo, Yoshiki

2015-11-15

The organic liquid scintillators based on the emissive polymers are reported. A series of conjugated polymers containing organoboron complexes which show the luminescence in the near infrared (NIR) region were synthesized. The polymers showed good solubility in common organic solvents. From the comparison of the luminescent properties of the synthesized polymers between optical and radiation excitation, similar emission bands were detected. In addition, less significant degradation was observed. These data propose that the organoboron conjugated polymers are attractive platforms to work as an organic liquid scintillator with the emission in the NIR region. Copyright © 2015 Elsevier Ltd. All rights reserved.

Atomistic simulation of graphene-based polymer nanocomposites

NASA Astrophysics Data System (ADS)

Rissanou, Anastassia N.; Bačová, Petra; Harmandaris, Vagelis

2016-05-01

Polymer/graphene nanostructured systems are hybrid materials which have attracted great attention the last years both for scientific and technological reasons. In the present work atomistic Molecular Dynamics simulations are performed for the study of graphene-based polymer nanocomposites composed of pristine, hydrogenated and carboxylated graphene sheets dispersed in polar (PEO) and nonpolar (PE) short polymer matrices (i.e., matrices containing chains of low molecular weight). Our focus is twofold; the one is the study of the structural and dynamical properties of short polymer chains and the way that they are affected by functionalized graphene sheets while the other is the effect of the polymer matrices on the behavior of graphene sheets.

Highly efficient flexible piezoelectric nanogenerator and femtosecond two-photon absorption properties of nonlinear lithium niobate nanowires

NASA Astrophysics Data System (ADS)

Gupta, Manoj Kumar; Aneesh, Janardhanakurup; Yadav, Rajesh; Adarsh, K. V.; Kim, Sang-Woo

2017-05-01

We present a high performance flexible piezoelectric nanogenerator (NG) device based on the hydrothermally grown lead-free piezoelectric lithium niobate (LiNbO3) nanowires (NWs) for scavenging mechanical energies. The non-linear optical coefficient and optical limiting properties of LiNbO3 were analyzed using femtosecond laser pulse assisted two photon absorption techniques for the first time. Further, a flexible hybrid type NG using a composite structure of the polydimethylsiloxane polymer and LiNbO3 NWs was fabricated, and their piezoelectric output signals were measured. A large output voltage of ˜4.0 V and a recordable large current density of about 1.5 μA cm-2 were obtained under the cyclic compressive force of 1 kgf. A subsequent UV-Vis analysis of the as-prepared sample provides a remarkable increase in the optical band gap (UV absorption cut-off, ˜251 nm) due to the nanoscale size effect. The high piezoelectric output voltage and current are discussed in terms of large band gap, significant nonlinear optical response, and electric dipole alignments under poling effects. Such high performance and unique optical properties of LiNbO3 show its great potential towards various next generation smart electronic applications and self-powered optoelectronic devices.

Star-Shaped Conjugated Molecules with Oxa- or Thiadiazole Bithiophene Side Arms.

PubMed

Kotwica, Kamil; Kostyuchenko, Anastasia S; Data, Przemyslaw; Marszalek, Tomasz; Skorka, Lukasz; Jaroch, Tomasz; Kacka, Sylwia; Zagorska, Malgorzata; Nowakowski, Robert; Monkman, Andrew P; Fisyuk, Alexander S; Pisula, Wojciech; Pron, Adam

2016-08-08

Star-shaped conjugated molecules, consisting of a benzene central unit symmetrically trisubstituted with either oxa- or thiadiazole bithiophene groups, were synthesized as promising molecules and building blocks for application in (opto)electronics and electrochromic devices. Their optical (Eg (opt)) as well as electrochemical (Eg (electro)) band gaps depended on the type of the side arm and the number of solubilizing alkyl substituents. Oxadiazole derivatives showed Eg (opt) slightly below 3 eV and by 0.2 eV larger than those determined for thiadiazole-based compounds. The presence of alkyl substituents in the arms additionally lowered the band gap. The obtained compounds were efficient electroluminophores in guest/host-type light-emitting diodes. They also showed a strong tendency to self-organize in monolayers deposited on graphite, as evidenced by scanning tunneling microscopy. The structural studies by X-ray scattering revealed the formation of supramolecular columnar stacks in which the molecules were organized. Differences in macroscopic alignment in the specimen indicated variations in the self-assembly mechanism between the molecules. The compounds as trifunctional monomers were electrochemically polymerized to yield the corresponding polymer network. As shown by UV/Vis-NIR spectroelectrochemical studies, these networks exhibited reversible electrochromic behavior both in the oxidation and in the reduction modes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The second green revolution? Production of plant-based biodegradable plastics.

PubMed

Mooney, Brian P

2009-03-01

Biodegradable plastics are those that can be completely degraded in landfills, composters or sewage treatment plants by the action of naturally occurring micro-organisms. Truly biodegradable plastics leave no toxic, visible or distinguishable residues following degradation. Their biodegradability contrasts sharply with most petroleum-based plastics, which are essentially indestructible in a biological context. Because of the ubiquitous use of petroleum-based plastics, their persistence in the environment and their fossil-fuel derivation, alternatives to these traditional plastics are being explored. Issues surrounding waste management of traditional and biodegradable polymers are discussed in the context of reducing environmental pressures and carbon footprints. The main thrust of the present review addresses the development of plant-based biodegradable polymers. Plants naturally produce numerous polymers, including rubber, starch, cellulose and storage proteins, all of which have been exploited for biodegradable plastic production. Bacterial bioreactors fed with renewable resources from plants--so-called 'white biotechnology'--have also been successful in producing biodegradable polymers. In addition to these methods of exploiting plant materials for biodegradable polymer production, the present review also addresses the advances in synthesizing novel polymers within transgenic plants, especially those in the polyhydroxyalkanoate class. Although there is a stigma associated with transgenic plants, especially food crops, plant-based biodegradable polymers, produced as value-added co-products, or, from marginal land (non-food), crops such as switchgrass (Panicum virgatum L.), have the potential to become viable alternatives to petroleum-based plastics and an environmentally benign and carbon-neutral source of polymers.

Molecularly Engineered Polymer-Based Systems in Drug Delivery and Regenerative Medicine.

PubMed

Piluso, Susanna; Soultan, Al Halifa; Patterson, Jennifer

2017-01-01

Polymer-based systems are attractive in drug delivery and regenerative medicine due to the possibility of tailoring their properties and functions to a specific application. The present review provides several examples of molecularly engineered polymer systems, including stimuli responsive polymers and supramolecular polymers. The advent of controlled polymerization techniques has enabled the preparation of polymers with controlled molecular weight and well-defined architecture. By using these techniques coupled to orthogonal chemical modification reactions, polymers can be molecularly engineered to incorporate functional groups able to respond to small changes in the local environment or to a specific biological signal. This review highlights the properties and applications of stimuli-responsive systems and polymer therapeutics, such as polymer-drug conjugates, polymer-protein conjugates, polymersomes, and hyperbranched systems. The applications of polymeric membranes in regenerative medicine are also discussed. The examples presented in this review suggest that the combination of membranes with polymers that are molecularly engineered to respond to specific biological functions could be relevant in the field of regenerative medicine. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Modifying Silicates for Better Dispersion in Nanocomposites

NASA Technical Reports Server (NTRS)

Campbell, Sandi

2005-01-01

An improved chemical modification has been developed to enhance the dispersion of layered silicate particles in the formulation of a polymer/silicate nanocomposite material. The modification involves, among other things, the co-exchange of an alkyl ammonium ion and a monoprotonated diamine with interlayer cations of the silicate. The net overall effects of the improved chemical modification are to improve processability of the nanocomposite and maximize the benefits of dispersing the silicate particles into the polymer. Some background discussion is necessary to give meaning to a description of this development. Polymer/silicate nanocomposites are also denoted polymer/clay composites because the silicate particles in them are typically derived from clay particles. Particles of clay comprise layers of silicate platelets separated by gaps called "galleries." The platelet thickness is 1 nm. The length varies from 30 nm to 1 m, depending on the silicate. In order to fully realize the benefits of polymer/silicate nanocomposites, it is necessary to ensure that the platelets become dispersed in the polymer matrices. Proper dispersion can impart physical and chemical properties that make nanocomposites attractive for a variety of applications. In order to achieve nanometer-level dispersion of a layered silicate into a polymer matrix, it is typically necessary to modify the interlayer silicate surfaces by attaching organic functional groups. This modification can be achieved easily by ion exchange between the interlayer metal cations found naturally in the silicate and protonated organic cations - typically protonated amines. Long-chain alkyl ammonium ions are commonly chosen as the ion-exchange materials because they effectively lower the surface energies of the silicates and ease the incorporation of organic monomers or polymers into the silicate galleries. This completes the background discussion. In the present improved modification of the interlayer silicate surfaces, the co-ion exchange strengthens the polymer/silicate interface and ensures irreversible separation of the silicate layers. One way in which it does this is to essentially tether one amine of each diamine molecule to a silicate surface, leaving the second amine free for reaction with monomers during the synthesis of a polymer. In addition, the incorporation of alkyl ammonium ions into the galleries at low concentration helps to keep low the melt viscosity of the oligomer formed during synthesis of the polymer and associated processing - a consideration that is particularly important in the case of a highly cross-linked, thermosetting polymer. Because of the chemical bonding between the surface-modifying amines and the monomers, even when the alkyl ammonium ions become degraded at high processing temperature, the silicate layers do not aggregate and, hence, nanometer-level dispersion is maintained.

Analytical theory of polymer-network-mediated interaction between colloidal particles

PubMed Central

Di Michele, Lorenzo; Zaccone, Alessio; Eiser, Erika

2012-01-01

Nanostructured materials based on colloidal particles embedded in a polymer network are used in a variety of applications ranging from nanocomposite rubbers to organic-inorganic hybrid solar cells. Further, polymer-network-mediated colloidal interactions are highly relevant to biological studies whereby polymer hydrogels are commonly employed to probe the mechanical response of living cells, which can determine their biological function in physiological environments. The performance of nanomaterials crucially relies upon the spatial organization of the colloidal particles within the polymer network that depends, in turn, on the effective interactions between the particles in the medium. Existing models based on nonlocal equilibrium thermodynamics fail to clarify the nature of these interactions, precluding the way toward the rational design of polymer-composite materials. In this article, we present a predictive analytical theory of these interactions based on a coarse-grained model for polymer networks. We apply the theory to the case of colloids partially embedded in cross-linked polymer substrates and clarify the origin of attractive interactions recently observed experimentally. Monte Carlo simulation results that quantitatively confirm the theoretical predictions are also presented. PMID:22679289

Characterization of the gas sensors based on polymer-coated resonant microcantilevers for the detection of volatile organic compounds.

PubMed

Dong, Ying; Gao, Wei; Zhou, Qin; Zheng, Yi; You, Zheng

2010-06-25

The gas sensors based on polymer-coated resonant microcantilevers for volatile organic compounds (VOCs) detection are investigated. A method to characterize the gas sensors through sensor calibration is proposed. The expressions for the estimation of the characteristic parameters are derived. The effect of the polymer coating location on the sensor's sensitivity is investigated and the formula to calculate the polymer-analyte partition coefficient without knowing the polymer coating features is presented for the first time. Three polymers: polyethyleneoxide (PEO), polyethylenevinylacetate (PEVA) and polyvinylalcohol (PVA) are used to perform the experiments. Six organic solvents: toluene, benzene, ethanol, acetone, hexane and octane are used as analytes. The response time, reversibility, hydrophilicity, sensitivity and selectivity of the polymer layers are discussed. According to the results, highly sensitive sensors for each of the analytes are proposed. Based on the characterization method, a convenient and flexible way to the construction of electric nose system by the polymer-coated resonant microcantilevers can be achieved. Copyright 2010 Elsevier B.V. All rights reserved.

An Internship Program for Deaf and Hard of Hearing Students in Polymer-Based Nanocomposites

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

Cebe,P.; Cherdack, D.; Guertin, R.

2006-01-01

We report on our summer internship program in Polymer-Based Nanocomposites, for deaf and hard of hearing undergraduates who engage in classroom and laboratory research work in polymer physics. The unique attributes of this program are its emphasis on: 1. Teamwork; 2. Performance of a start-to-finish research project; 3. Physics of materials approach; and 4. Diversity. Students of all disability levels have participated in this program, including students who neither hear nor voice. The classroom and laboratory components address the materials chemistry and physics of polymer-based nanocomposites, crystallization and melting of polymers, the interaction of X-rays and light with polymers, mechanicalmore » properties of polymers, and the connection between thermal processing, structure, and ultimate properties of polymers. A set of Best Practices is developed for accommodating deaf and hard of hearing students into the laboratory setting. The goal is to bring deaf and hard of hearing students into the larger scientific community as professionals, by providing positive scientific experiences at a formative time in their educational lives.« less

Selenium-substituted polymers for improved photovoltaic performance.

PubMed

Yu, Jiangsheng; Ding, Guanqun; Hai, Jiefeng; Zhu, Enwei; Yin, Xinxing; Xu, Zhongsheng; Zhou, Baojing; Zhang, Fujun; Ma, Wanli; Tang, Weihua

2016-03-21

Four isostructural donor-acceptor alternating polymers of benzodithiophene (BDT)/naphthodifuran (NDF) and benzoselenadiazole (BSe)/benzothiadiazole (BT) have been developed and evaluated for organic photovoltaics. The substitution of one-atom (Se for S) in the accepting units exerts remarkable impact on the optoelectronic properties of polymers. Extended absorption, narrowed bandgap and higher HOMO energy levels were observed for Se-containing polymers in comparison to their S-containing counterparts. Theoretical calculations confirmed the measurable effect on energy levels as found in experimental studies. Bulk-heterojuction solar cells based on the BDT-BSe copolymer and [6,6]-phenyl-C71-butyric acid methyl ester (1 : 2, w/w) blend films deliver the best PCE of 5.40%. BSe-based polymers showed enhanced photovoltaic performances than BT-based polymers. The device performance is found to be strongly dependent on the processing conditions and morphology of the active layers.

Radiation-resistant composite for biological shield of personnel

NASA Astrophysics Data System (ADS)

Barabash, D. E.; Barabash, A. D.; Potapov, Yu B.; Panfilov, D. V.; Perekalskiy, O. E.

2017-10-01

This article presents the results of theoretical and practical justification for the use of polymer concrete based on nonisocyanate polyurethanes in biological shield structures. We have identified the impact of ratio: polymer - radiation-resistant filling compound on the durability and protection properties of polymer concrete. The article expounds regression dependence of the change of basic properties of the aforementioned polymer concrete on the absorbed radiation dose rate. Synergy effect in attenuation of radioactivity release in case of conjoint use of hydrogenous polymer base and radiation-resistant powder is also addressed herein.

Supramolecular structure of polymer binders and composites: targeted control based on the hierarchy

NASA Astrophysics Data System (ADS)

Matveeva, Larisa; Belentsov, Yuri

2017-10-01

The article discusses the problem of targeted control over properties by modifying the supramolecular structure of polymer binders and composites based on their hierarchy. Control over the structure formation of polymers and introduction of modifying additives should be tailored to the specific hierarchical structural levels. Characteristics of polymer materials are associated with structural defects, which also display a hierarchical pattern. Classification of structural defects in polymers is presented. The primary structural level (nano level) of supramolecular formations is of great importance to the reinforcement and regulation of strength characteristics.

Methods for Introducing Inorganic Polymer Concepts throughout the Undergraduate Curriculum

ERIC Educational Resources Information Center

de Lill, Daniel T.; Carraher, Charles E., Jr.

2017-01-01

Inorganic polymers can be introduced in a variety of undergraduate courses to discuss concepts related to polymer chemistry. Inorganic polymers such as silicates and polysiloxanes are simple materials that can be incorporated into an introductory or descriptive inorganic course. Polymers based on inorganic carbon, including diamond and graphite,…

Synthesis of a Self-Healing Polymer Based on Reversible Diels-Alder Reaction: An Advanced Undergraduate Laboratory at the Interface of Organic Chemistry and Materials Science

ERIC Educational Resources Information Center

Weizman, Haim; Nielsen, Christian; Weizman, Or S.; Nemat-Nasser, Sia

2011-01-01

This laboratory experiment exposes students to the chemistry of self-healing polymers based on a Diels-Alder reaction. Students accomplish a multistep synthesis of a monomer building block and then polymerize it to form a cross-linked polymer. The healing capability of the polymer is verified by differential scanning calorimetry (DSC) experiments.…

Molecular Design and Device Application of Radical Polymers for Improved Charge Extraction in Organic Photovoltaic Cells

DTIC Science & Technology

2015-07-29

a. “Engineering Optoelectronically-active Macromolecules for Polymer-based Photovoltaic and Thermoelectric Devices,” Boudouris, B. W. Current...Presentation. Oral Presentation. “Non-conjugated Radical Polymers as an Emerging Class of Transparent Conductors in Organic Photovoltaic and Thermoelectric ...for Polymer-based Photovoltaic and Thermoelectric Devices,” Boudouris, B. W. Current Opinion in Chemical Engineering 2013, 2, 294-301. 2. “Controlled

Narrow Gap, High Mobility, and Stable Pi Conjugated Polymers

DTIC Science & Technology

2012-09-20

wide-angle X-ray scattering (2D-WAXS) of P5.1 (extruded at 210oC). This trend is reflected in conventional bulk- heterojunction OPV devices as shown...Additives in Molecular Bulk Heterojunction Solar Cells Using a bithiophene capped, isoindigo core, DAD molecule as the donor phase, and PCBM as the...PCE values of 3.7% as illustrated in Figure 11. Figure 11. Combining interface control using MoOx as an electron transport material and PDMS

Preparation and electrochemical characterization of polymer electrolytes based on electrospun poly(vinylidene fluoride- co-hexafluoropropylene)/polyacrylonitrile blend/composite membranes for lithium batteries

NASA Astrophysics Data System (ADS)

Raghavan, Prasanth; Zhao, Xiaohui; Shin, Chorong; Baek, Dong-Ho; Choi, Jae-Won; Manuel, James; Heo, Min-Yeong; Ahn, Jou-Hyeon; Nah, Changwoon

Apart from PEO based solid polymer electrolytes, tailor-made gel polymer electrolytes based on blend/composite membranes of poly(vinylidene fluoride- co-hexafluoropropylene) and polyacrylonitrile are prepared by electrospinning using 14 wt% polymer solution in dimethylformamide. The membranes show uniform morphology with an average fiber diameter of 320-490 nm, high porosity and electrolyte uptake. Polymer electrolytes are prepared by soaking the electrospun membranes in 1 M lithium hexafluorophosphate in ethylene carbonate/dimethyl carbonate. Temperature dependent ionic conductivity and their electrochemical performance are studied. The blend/composite polymer electrolytes show good ionic conductivity in the range of 10 -3 S cm -1 at ambient temperature and good electrochemical performance. All the Polymer electrolytes show an anodic stability >4.6 V with stable interfacial resistance with storage time. The prototype cell shows good charge-discharge properties and stable cycle performance with comparable capacity fade compared to liquid electrolyte under the test conditions.

Stepwise heating in Stille polycondensation toward no batch-to-batch variations in polymer solar cell performance.

PubMed

Lee, Sang Myeon; Park, Kwang Hyun; Jung, Seungon; Park, Hyesung; Yang, Changduk

2018-05-14

For a given π-conjugated polymer, the batch-to-batch variations in molecular weight (M w ) and polydispersity index (Ð) can lead to inconsistent process-dependent material properties and consequent performance variations in the device application. Using a stepwise-heating protocol in the Stille polycondensation in conjunction with optimized processing, we obtained an ultrahigh-quality PTB7 polymer having high M w and very narrow Ð. The resulting ultrahigh-quality polymer-based solar cells demonstrate up to 9.97% power conversion efficiencies (PCEs), which is over 24% enhancement from the control devices fabricated with commercially available PTB7. Moreover, we observe almost negligible batch-to-batch variations in the overall PCE values from ultrahigh-quality polymer-based devices. The proposed stepwise polymerization demonstrates a facile and effective strategy for synthesizing high-quality semiconducting polymers that can significantly improve device yield in polymer-based solar cells, an important factor for the commercialization of organic solar cells, by mitigating device-to-device variations.

Reduced voltage losses yield 10% efficient fullerene free organic solar cells with >1 V open circuit voltages.

PubMed

Baran, D; Kirchartz, T; Wheeler, S; Dimitrov, S; Abdelsamie, M; Gorman, J; Ashraf, R S; Holliday, S; Wadsworth, A; Gasparini, N; Kaienburg, P; Yan, H; Amassian, A; Brabec, C J; Durrant, J R; McCulloch, I

2016-12-01

Optimization of the energy levels at the donor-acceptor interface of organic solar cells has driven their efficiencies to above 10%. However, further improvements towards efficiencies comparable with inorganic solar cells remain challenging because of high recombination losses, which empirically limit the open-circuit voltage ( V oc ) to typically less than 1 V. Here we show that this empirical limit can be overcome using non-fullerene acceptors blended with the low band gap polymer PffBT4T-2DT leading to efficiencies approaching 10% (9.95%). We achieve V oc up to 1.12 V, which corresponds to a loss of only E g / q - V oc = 0.5 ± 0.01 V between the optical bandgap E g of the polymer and V oc . This high V oc is shown to be associated with the achievement of remarkably low non-geminate and non-radiative recombination losses in these devices. Suppression of non-radiative recombination implies high external electroluminescence quantum efficiencies which are orders of magnitude higher than those of equivalent devices employing fullerene acceptors. Using the balance between reduced recombination losses and good photocurrent generation efficiencies achieved experimentally as a baseline for simulations of the efficiency potential of organic solar cells, we estimate that efficiencies of up to 20% are achievable if band gaps and fill factors are further optimized.

Polymer Nomenclature--or What's in a Name?

ERIC Educational Resources Information Center

Carraher, Charles, E., Jr.; And Others

1987-01-01

Discusses the diversity of names used for various types of polymeric materials. Concentrates on the naming of linear organic polymers. Delineates these polymers by discussing common names, source-based names, characteristic group names, and structure-based names. Introduces the specifications of tacticity and geometric isomerism. (TW)

Study of soybean oil-based polymers for controlled release anticancer drugs

USDA-ARS?s Scientific Manuscript database

Soybean oil-based polymers were prepared by the ring-opening polymerization of epoxidized soybean oil with Lewis acid catalyst. The formed polymers (HPESO) could be converted into hydrogels through hydrolysis. Characterization and viscoelastic properties of this soy hydrogel and application in contr...

Toward a versatile toolbox for cucurbit[n]uril-based supramolecular hydrogel networks through in situ polymerization.

PubMed

Liu, Ji; Soo Yun Tan, Cindy; Lan, Yang; Scherman, Oren A

2017-09-15

The success of exploiting cucurbit[ n ]uril (CB[ n ])-based molecular recognition in self-assembled systems has sparked a tremendous interest in polymer and materials chemistry. In this study, polymerization in the presence of host-guest complexes is applied as a modular synthetic approach toward a diverse set of CB[8]-based supramolecular hydrogels with desirable properties, such as mechanical strength, toughness, energy dissipation, self-healing, and shear-thinning. A range of vinyl monomers, including acrylamide-, acrylate-, and imidazolium-based hydrophilic monomers, could be easily incorporated as the polymer backbones, leading to a library of CB[8] hydrogel networks. This versatile strategy explores new horizons for the construction of supramolecular hydrogel networks and materials with emergent properties in wearable and self-healable electronic devices, sensors, and structural biomaterials. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3105-3109.

Thermally responsive polymer systems for self-healing, reversible adhesion and shape memory applications

NASA Astrophysics Data System (ADS)

Luo, Xiaofan

Responsive polymers are "smart" materials that are capable of performing prescribed, dynamic functions under an applied stimulus. In this dissertation, we explore several novel design strategies to develop thermally responsive polymers and polymer composites for self-healing, reversible adhesion and shape memory applications. In the first case described in Chapters 2 and 3, a thermally triggered self-healing material was prepared by blending a high-temperature epoxy resin with a thermoplastic polymer, poly(epsilon-caprolactone) (PCL). The initially miscible system undergoes polymerization induced phase separation (PIPS) during the curing of epoxy and yields a variety of compositionally dependent morphologies. At a particular PCL loading, the cured blend displays a "bricks-and-mortar" morphology in which epoxy exists as interconnected spheres ("bricks") within a continuous PCL matrix ("mortar"). A heat induced "bleeding" phenomenon was observed in the form of spontaneous wetting of all free surfaces by the molten PCL, and is attributed to the volumetric thermal expansion of PCL above its melting point in excess of epoxy brick expansion, which we term differential expansive bleeding (DEB). This DEB is capable of healing damage such as cracks. In controlled self-healing experiments, heating of a cracked specimen led to PCL bleeding from the bulk that yields a liquid layer bridging the crack gap. Upon cooling, a "scar" composed of PCL crystals was formed at the site of the crack, restoring a significant portion of mechanical strength. We further utilized DEB to enable strong and thermally-reversible adhesion of the material to itself and to metallic substrates, without any requirement for macroscopic softening or flow. After that, Chapters 4--6 present a novel composite strategy for the design and fabrication of shape memory polymer composites. The basic approach involves physically combining two or more functional components into an interpenetrating fiber/matrix structure, allowing them to function in a synergistic fashion yet remain physically separated. This latter aspect is critical since it enables the control of overall composite properties and functions by separately tuning each component. Utilizing the intrinsic versatility of this approach, composites with novel properties and functions (in addition to "regular" shape memory) have been developed, including (1) shape memory elastomeric composites (SMECs; Chapter 4), (2) triple-shape polymeric composites (TSPCs; Chapter 5), and (3) electrically conductive nanocomposites (Chapter 6). Then in Chapter 7, by combining the success in both thermoplastic based self-healing and shape memory polymer composites, we demonstrate a thermally triggered self-healing coating. This coating features a unique "shape memory assisted self-healing" mechanism in which crack closure (via shape memory) and crack re-bonding (via melting and diffusion of the thermoplastic healing agent) are achieved simultaneously upon a single heating step, leading to both structural and functional (corrosion resistance) recovery. Finally, Chapter 8 presents for the first time the preparation of functionally graded shape memory polymers (SMPs) that, unlike conventional SMPs, have a range of glass transition temperatures that are spatially graded. This was achieved using a temperature gradient curing method that imposes different vitrification limits at different positions along the gradient. The resulting material is capable of responding to a wide range of thermal triggers and a good candidate for low-cost, material based temperature sensors. All the aforementioned materials and methods show great potential for practical applications due to their high performance, low cost and broad applicability. Some recommendations for future research and development are given in Chapter 9.

Layer-by-layer assembled composite films of side-functionalized poly(3-hexylthiophene) and CdSe nanocrystals: electrochemical, spectroelectrochemical and photovoltaic properties.

PubMed

De Girolamo, Julia; Reiss, Peter; Zagorska, Malgorzata; De Bettignies, Remi; Bailly, Severine; Mevellec, Jean-Yves; Lefrant, Serge; Travers, Jean-Pierre; Pron, Adam

2008-07-21

Regioregular poly(3-hexylthiophene) containing one diaminopyrimidine side group per ten repeat units (P3HT-co-P3(ODAP)HT) can form molecular composites with 1-(6-mercaptohexyl)thymine capped CdSe nanocrystals (CdSe(MHT)) via hydrogen bonds directed molecular recognition. Here we report complementary spectroscopic, electrochemical and spectroelectrochemical investigations of both the functionalized poly(thiophene) and its composite with the nanocrystals, the latter being fabricated using the layer-by-layer (LbL) deposition technique. UV-Vis-NIR and Raman spectroelectrochemical investigations unequivocally show that the onset of the first anodic peak in the cyclic voltammogram of the copolymer can be attributed to the oxidation of the pi-conjugated backbone in the polymer chains. For this reason, it is possible to determine the width and the position of its band gap (corresponding to the pi-pi* transition) by UV-Vis spectroscopy combined with cyclic voltammetry. These studies show that the polymer exhibits a slightly larger band gap with the HOMO level insignificantly lower in energy (by 0.03 eV) as compared to the case of regioregular poly(3-hexylthiophene) of comparable degree of polymerization. Hydrogen bond interactions of the polymer with CdSe(MHT) in the molecular composite result in a hypsochromic shift of the band corresponding to the pi-pi* transition from 504 nm to 488 nm. This can be taken as a spectroscopic manifestation of the conformational changes induced by shortening of the conjugation length. The observed spectral modifications are consistent with electrochemically determined lowering of the polymer HOMO level (from -4.91 eV in the pure polymer to -4.99 eV in the composite). Cyclic voltammetry studies supported by spectroelectrochemistry also show that the redox stability of CdSe(MHT) in the molecular composite with P3HT-co-P3(ODAP)HT is lower than that determined for stearate-capped nanocrystals. Their irreversible oxidation starts at E = +0.7 V vs. Ag/0.1 M Ag(+)i.e. at potentials by ca. 0.3 V lower than the oxidation of stearate stabilized CdSe nanocrystals of the same size. We show that-despite these modifications-the alignment of the HOMO and LUMO levels of the composite components remains appropriate for its use in hybrid solar cells, which is demonstrated by the photovoltaic effect observed for the LbL-processed composite sandwiched between two electrodes.

Probing the Energy Level Alignment and the Correlation with Open-Circuit Voltage in Solution-Processed Polymeric Bulk Heterojunction Photovoltaic Devices.

PubMed

Yang, Qing-Dan; Li, Ho-Wa; Cheng, Yuanhang; Guan, Zhiqiang; Liu, Taili; Ng, Tsz-Wai; Lee, Chun-Sing; Tsang, Sai-Wing

2016-03-23

Energy level alignment at the organic donor and acceptor interface is a key to determine the photovoltaic performance in organic solar cells, but direct probing of such energy alignment is still challenging especially for solution-processed bulk heterojunction (BHJ) thin films. Here we report a systematic investigation on probing the energy level alignment with different approaches in five commonly used polymer:[6,6]-phenyl-C71-butyric acid methyl ester (PCBM) BHJ systems. We find that by tuning the weight ratio of polymer to PCBM the electronic features from both polymer and PCBM can be obtained by photoemission spectroscopy. Using this approach, we find that some of the BHJ blends simply follow vacuum level alignment, but others show strong energy level shifting as a result of Fermi level pinning. Independently, by measuring the temperature-dependent open-circuit voltage (VOC), we find that the effective energy gap (Eeff), the energy difference between the highest occupied molecular orbital of the polymer donor (EHOMO-D) and lowest unoccupied molecular orbital of the PCBM acceptor (ELUMO-A), obtained by photoemission spectroscopy in all polymer:PCBM blends has an excellent agreement with the extrapolated VOC at 0 K. Consequently, the photovoltage loss of various organic BHJ photovoltaic devices at room temperature is in a range of 0.3-0.6 V. It is believed that the demonstrated direct measurement approach of the energy level alignment in solution-processed organic BHJ will bring deeper insight into the origin of the VOC and the corresponding photovoltage loss mechanism in organic photovoltaic cells.

Biodegradation of plastics: current scenario and future prospects for environmental safety.

PubMed

Ahmed, Temoor; Shahid, Muhammad; Azeem, Farrukh; Rasul, Ijaz; Shah, Asad Ali; Noman, Muhammad; Hameed, Amir; Manzoor, Natasha; Manzoor, Irfan; Muhammad, Sher

2018-03-01

Plastic is a general term used for a wide range of high molecular weight organic polymers obtained mostly from the various hydrocarbon and petroleum derivatives. There is an ever-increasing trend towards the production and consumption of plastics due to their extensive industrial and domestic applications. However, a wide spectrum of these polymers is non-biodegradable with few exceptions. The extensive use of plastics, lack of waste management, and casual community behavior towards their proper disposal pose a significant threat to the environment. This has raised growing concerns among various stakeholders to devise policies and innovative strategies for plastic waste management, use of biodegradable polymers especially in packaging, and educating people for their proper disposal. Current polymer degradation strategies rely on chemical, thermal, photo, and biological procedures. In the presence of proper waste management strategies coupled with industrially controlled biodegradation facilities, the use of biodegradable plastics for some applications such as packaging or health industry is a promising and attractive option for economic, environmental, and health benefits. This review highlights the classification of plastics with special emphasis on biodegradable plastics and their rational use, the identified mechanisms of plastic biodegradation, the microorganisms involved in biodegradation, and the current insights into the research on biodegradable plastics. The review has also identified the research gaps in plastic biodegradation followed by future research directions.

Elaboration, structural and optical investigations of ZnO/epoxy nanocomposites

NASA Astrophysics Data System (ADS)

Moussa, S.; Namouchi, F.; Guermazi, H.

2015-07-01

Hybrid nanocomposites were elaborated by incorporating ZnO nanoparticles into a transparent epoxy polymer matrix, using the direct dispersion method. The effect of the nanoparticles on the structural and optical properties of the polymer matrix was investigated using Fourier transform infrared (FTIR), Raman and UV-Visible spectroscopies. Nanocomposites FTIR spectra showed a variation of band intensities attributed to nanoparticles agglomeration within the polymer. The UV-Visible measurements showed a redshift on the band gap energy of the nanocomposites differently from neat epoxy resin, caused by interactions between ZnO NPs and polymer chains. Raman spectra confirm these interactions and the formation of hydrogen bonds in the nanocomposites. The UV-Visible transmittance spectra revealed that addition of a very low concentration (0.2wt%) of ZnO nanoparticles to a transparent epoxy matrix would maintain high visible-light transparency. The decrease of transmittance with increasing ZnO percentage is due to light scattering which originates from the agglomeration of nanoparticles in the matrix, the mismatch between the refractive index of ZnO and that of the epoxy matrix, and the increase of the surface roughness of the nanocomposite with increasing ZnO addition. Moreover, the UV-vis absorption spectra revealed that adding more than 1wt% ZnO leads to the improvement of the UV shielding properties of the nanocomposites. These results prove that the elaborated ZnO/epoxy nanocomposites can be used as UV shielding materials.

Molecular weight dependent charge carrier mobility in poly(3,3' '-dioctyl-2,2':5',2' '-terthiophene).

PubMed

Verilhac, Jean-Marie; Pokrop, Rafal; LeBlevennec, Gilles; Kulszewicz-Bajer, Irena; Buga, Katarzyna; Zagorska, Malgorzata; Sadki, Said; Pron, Adam

2006-07-13

Poly(3,3' '-dioctyl-2,2':5',2' '-terthiophene), a polymer recently used for the fabrication of organic field effect transistors, has been fractionated into five fractions distinctly differing in their molecular weights (Mn), with the goal of determining the influence of the degree of polymerization (DPn) on its principal physicochemical parameters. It has been demonstrated that within the Mn range studied (from 1.5 kDa to 10.5 kDa by SEC), corresponding to DPn from 10 to 38, the polymer band gap steadily decreases with growing molecular weight, which is clearly manifested by an increasing bathochromic shift of the band originating from the pi-pi* transition. The same trend is observed for the HOMO level, determined from the onset of the p-doping in cyclic voltammetry, which shifts from -5.10 eV to -4.90 eV for the lowest and the highest molecular weight fractions, respectively. The most pronounced influence of DPn has been found for the charge carriers' mobility-one of the most important parameters of field effect transistors (FETs) fabricated from this polymer. A fourfold increase in DPn results in an increase of the carriers' mobility by more than 3 orders of magnitude. Comparison of these results with those obtained for fractionated regioregular poly(3-hexylthiophene) shows a strikingly similar behavior of both polymers with respect to the molecular weight.

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.

Research Trends of Soft Actuators based on Electroactive Polymers and Conducting Polymers

NASA Astrophysics Data System (ADS)

Kaneto, K.

2016-04-01

Artificial muscles (or soft actuators) based on electroactive polymers (EAPs) are attractive power sources to drive human-like robots in place of electrical motor, because they are quiet, powerful, light weight and compact. Among EAPs for soft actuators, conducting polymers are superior in strain, stress, deformation form and driving voltage compared with the other EAPs. In this paper, the research trends of EAPs and conducting polymers are reviewed by retrieval of the papers and patents. The research activity of EAP actuators showed the maximum around 2010 and somehow declining now days. The reasons for the reducing activity are found to be partly due to problems of conducting polymer actuators for the practical application. The unique characteristics of conducting polymer actuators are mentioned in terms of the basic mechanisms of actuation, creeping, training effect and shape retention under high tensile loads. The issues and limitation of conducting polymer soft actuators are discussed.

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

EFRC: Polymer-Based Materials for Harvesting Solar Energy (stimulus)"

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

Russell, Thomas P.

The University of Massachusetts Amherst is proposing an Energy Frontier Research Center (EFRC) on Polymer-Based Materials for Harvesting Solar Energy that will integrate the widely complementary experimental and theoretical expertise of 23 faculty at UMass-Amherst Departments with researchers from the University of Massachusetts Lowell, University of Pittsburgh, the Pennsylvania State University and Konarka Technologies, Inc. Collaborative efforts with researchers at the Oak Ridge National Laboratory, the University of Bayreuth, Seoul National University and Tohoku University will complement and expand the experimental efforts in the EFRC. Our primary research aim of this EFRC is the development of hybrid polymer-based devices withmore » efficiencies more than twice the current organic-based devices, by combining expertise in the design and synthesis of photoactive polymers, the control and guidance of polymer-based assemblies, leadership in nanostructured polymeric materials, and the theory and modeling of non-equilibrium structures. A primary goal of this EFRC is to improve the collection and conversion efficiency of a broader spectral range of solar energy using the directed self-assembly of polymer-based materials so as to optimize the design and fabrication of inexpensive devices.« less

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

Aromatic carboxylate effect on dimensionality of three bis(benzimidazole)-based cobalt(II) coordination polymers: Syntheses, structures and properties

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

Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li

2013-09-15

Three new metal-organic coordination polymers [Co(4-bbc){sub 2}(bbbm)] (1), [Co(3,5-pdc)(bbbm)]·2H{sub 2}O (2) and [Co(1,4-ndc)(bbbm)] (3) (4-Hbbc=4-bromobenzoic acid, 3,5-H{sub 2}pdc=3,5-pyridinedicarboxylic acid, 1,4-H{sub 2}ndc=1,4-naphthalenedicarboxylic acid and bbbm=1,1-(1,4-butanediyl)bis-1H-benzimidazole) were hydrothermally synthesized and structurally characterized. Polymer 1 is a 1D chain formed by the bbbm ligands and Co{sup II} ions. Polymer 2 exhibits a 2D network with a (3·4·5)(3{sup 2}·4·5·6{sup 2}·7{sup 4}) topology. Polymer 3 possesses a 3D three-fold interpenetrating framework. The versatile structures of title polymers indicate that the aromatic carboxylates have an important influence on the dimensionality of 1–3. Moreover, the thermal stability, electrochemical and luminescent properties of 1–3 were investigated. - graphicalmore » abstract: Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were hydrothermally synthesized and structurally characterized. The aromatic carboxylates play a key role in the dimensionality of three polymers. The electrochemical and luminescent properties of three polymers were investigated. Display Omitted - Highlights: • Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were obtained. • The aromatic carboxylates have an important influence on the dimensionality of three polymers. • The electrochemical and luminescent properties of three polymers were investigated.« less

Design principles for shift current photovoltaics

DOE PAGES

Cook, Ashley M.; M. Fregoso, Benjamin; de Juan, Fernando; ...

2017-01-25

While the basic principles of conventional solar cells are well understood, little attention has gone towards maximizing the efficiency of photovoltaic devices based on shift currents. Furthermore, by analysing effective models, here we outline simple design principles for the optimization of shift currents for frequencies near the band gap. This method allows us to express the band edge shift current in terms of a few model parameters and to show it depends explicitly on wavefunctions in addition to standard band structure. We use our approach to identify two classes of shift current photovoltaics, ferroelectric polymer films and single-layer orthorhombic monochalcogenidesmore » such as GeS, which display the largest band edge responsivities reported so far. Moreover, exploring the parameter space of the tight-binding models that describe them we find photoresponsivities that can exceed 100 mA W -1 . Our results illustrate the great potential of shift current photovoltaics to compete with conventional solar cells.« less

Design principles for shift current photovoltaics

PubMed Central

Cook, Ashley M.; M. Fregoso, Benjamin; de Juan, Fernando; Coh, Sinisa; Moore, Joel E.

2017-01-01

While the basic principles of conventional solar cells are well understood, little attention has gone towards maximizing the efficiency of photovoltaic devices based on shift currents. By analysing effective models, here we outline simple design principles for the optimization of shift currents for frequencies near the band gap. Our method allows us to express the band edge shift current in terms of a few model parameters and to show it depends explicitly on wavefunctions in addition to standard band structure. We use our approach to identify two classes of shift current photovoltaics, ferroelectric polymer films and single-layer orthorhombic monochalcogenides such as GeS, which display the largest band edge responsivities reported so far. Moreover, exploring the parameter space of the tight-binding models that describe them we find photoresponsivities that can exceed 100 mA W−1. Our results illustrate the great potential of shift current photovoltaics to compete with conventional solar cells. PMID:28120823

Application of laser driven fast high density plasma blocks for ion implantation

NASA Astrophysics Data System (ADS)

Sari, Amir H.; Osman, F.; Doolan, K. R.; Ghoranneviss, M.; Hora, H.; Höpfl, R.; Benstetter, G.; Hantehzadeh, M. H.

2005-10-01

The measurement of very narrow high density plasma blocks of high ion energy from targets irradiated with ps-TW laser pulses based on a new skin depth interaction process is an ideal tool for application of ion implantation in materials, especially of silicon, GaAs, or conducting polymers, for micro-electronics as well as for low cost solar cells. A further application is for ion sources in accelerators with most specifications of many orders of magnitudes advances against classical ion sources. We report on near band gap generation of defects by implantation of ions as measured by optical absorption spectra. A further connection is given for studying the particle beam transforming of n-type semiconductors into p-type and vice versa as known from sub-threshold particle beams. The advantage consists in the use of avoiding aggressive or rare chemical materials when using the beam techniques for industrial applications.

Solar-Driven Hydrogen Peroxide Production Using Polymer-Supported Carbon Dots as Heterogeneous Catalyst

NASA Astrophysics Data System (ADS)

Gogoi, Satyabrat; Karak, Niranjan

2017-10-01

Safe, sustainable, and green production of hydrogen peroxide is an exciting proposition due to the role of hydrogen peroxide as a green oxidant and energy carrier for fuel cells. The current work reports the development of carbon dot-impregnated waterborne hyperbranched polyurethane as a heterogeneous photo-catalyst for solar-driven production of hydrogen peroxide. The results reveal that the carbon dots possess a suitable band-gap of 2.98 eV, which facilitates effective splitting of both water and ethanol under solar irradiation. Inclusion of the carbon dots within the eco-friendly polymeric material ensures their catalytic activity and also provides a facile route for easy catalyst separation, especially from a solubilizing medium. The overall process was performed in accordance with the principles of green chemistry using bio-based precursors and aqueous medium. This work highlights the potential of carbon dots as an effective photo-catalyst.

Design principles for shift current photovoltaics

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

Cook, Ashley M.; M. Fregoso, Benjamin; de Juan, Fernando

While the basic principles of conventional solar cells are well understood, little attention has gone towards maximizing the efficiency of photovoltaic devices based on shift currents. Furthermore, by analysing effective models, here we outline simple design principles for the optimization of shift currents for frequencies near the band gap. This method allows us to express the band edge shift current in terms of a few model parameters and to show it depends explicitly on wavefunctions in addition to standard band structure. We use our approach to identify two classes of shift current photovoltaics, ferroelectric polymer films and single-layer orthorhombic monochalcogenidesmore » such as GeS, which display the largest band edge responsivities reported so far. Moreover, exploring the parameter space of the tight-binding models that describe them we find photoresponsivities that can exceed 100 mA W -1 . Our results illustrate the great potential of shift current photovoltaics to compete with conventional solar cells.« less

Polymer containing functional end groups is base for new polymers

NASA Technical Reports Server (NTRS)

Hirshfield, S. M.

1971-01-01

Butadiene is polymerized with lithium-p-lithiophenoxide to produce linear polymer containing oxy-lithium group at one end and active carbon-lithium group at other end. Living polymers represent new approach to preparation of difunctional polymers in which structural features, molecular weight, type and number of end groups are controlled.

Injection Molding and Mechanical Properties of Bio-Based Polymer Nanocomposites.

PubMed

Mistretta, Maria Chiara; Botta, Luigi; Morreale, Marco; Rifici, Sebastiano; Ceraulo, Manuela; La Mantia, Francesco Paolo

2018-04-17

The use of biodegradable/bio-based polymers is of great importance in addressing several issues related to environmental protection, public health, and new, stricter legislation. Yet some applications require improved properties (such as barrier or mechanical properties), suggesting the use of nanosized fillers in order to obtain bio-based polymer nanocomposites. In this work, bionanocomposites based on two different biodegradable polymers (coming from the Bioflex and MaterBi families) and two different nanosized fillers (organo-modified clay and hydrophobic-coated precipitated calcium carbonate) were prepared and compared with traditional nanocomposites with high-density polyethylene (HDPE) as matrix. In particular, the injection molding processability, as well as the mechanical and rheological properties of the so-obtained bionanocomposites were investigated. It was found that the processability of the two biodegradable polymers and the related nanocomposites can be compared to that of the HDPE-based systems and that, in general, the bio-based systems can be taken into account as suitable alternatives.

Injection Molding and Mechanical Properties of Bio-Based Polymer Nanocomposites

PubMed Central

Mistretta, Maria Chiara; Rifici, Sebastiano; Ceraulo, Manuela

2018-01-01

The use of biodegradable/bio-based polymers is of great importance in addressing several issues related to environmental protection, public health, and new, stricter legislation. Yet some applications require improved properties (such as barrier or mechanical properties), suggesting the use of nanosized fillers in order to obtain bio-based polymer nanocomposites. In this work, bionanocomposites based on two different biodegradable polymers (coming from the Bioflex and MaterBi families) and two different nanosized fillers (organo-modified clay and hydrophobic-coated precipitated calcium carbonate) were prepared and compared with traditional nanocomposites with high-density polyethylene (HDPE) as matrix. In particular, the injection molding processability, as well as the mechanical and rheological properties of the so-obtained bionanocomposites were investigated. It was found that the processability of the two biodegradable polymers and the related nanocomposites can be compared to that of the HDPE-based systems and that, in general, the bio-based systems can be taken into account as suitable alternatives. PMID:29673143

Engineering thermoplastics for additive manufacturing: a critical perspective with experimental evidence to support functional applications.

PubMed

Cicala, Gianluca; Latteri, Alberta; Del Curto, Barbara; Lo Russo, Alessio; Recca, Giuseppe; Farè, Silvia

2017-01-28

Among additive manufacturing techniques, the filament-based technique involves what is referred to as fused deposition modeling (FDM). FDM materials are currently limited to a selected number of polymers. The present study focused on investigating the potential of using high-end engineering polymers in FDM. In addition, a critical review of the materials available on the market compared with those studied here was completed. Different engineering thermoplastics, ranging from industrial grade polycarbonates to novel polyetheretherketones (PEEKs), were processed by FDM. Prior to this, for innovative filaments based on PEEK, extrusion processing was carried out. Mechanical properties (i.e., tensile and flexural) were investigated for each extruded material. An industrial-type FDM machine (Stratasys Fortus® 400 mc) was used to fully characterize the effect of printing parameters on the mechanical properties of polycarbonate. The obtained properties were compared with samples obtained by injection molding. Finally, FDM samples made of PEEK were also characterized and compared with those obtained by injection molding. The effect of raster to raster air gap and raster angle on tensile and flexural properties of printed PC was evidenced; the potential of PEEK filaments, as novel FDM material, was highlighted in comparison to state of the art materials. Comparison with injection molded parts allowed to better understand FDM potential for functional applications. The study discussed pros and cons of the different materials. Finally, the development of novel PEEK filaments achieved important results offering a novel solution to the market when high mechanical and thermal properties are required.

Synthetic (polymer) biology (membrane): functionalization of polymer scaffolds for membrane proteins.

PubMed

Hu, Zhaolong; Ho, James C S; Nallani, Madhavan

2017-08-01

A plethora of polymer-based scaffolds have been designed to facilitate biochemical and biophysical investigation of membrane proteins, with a common goal to stabilize and present them in a functional format. In this review, an up-to-date account of such polymer-based supports and incorporation methodologies are presented. Furthermore, conceptual and imminent technological advances, with associated technical challenges are proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

An electroactive conducting polymer actuator based on NBR/RTIL solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

2007-04-01

This paper reports the fabrication of a dry-type conducting polymer actuator using nitrile rubber (NBR) as the base material in a solid polymer electrolyte. The conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique. Room-temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X (where X = BF4-, PF6-, (CF3SO2)2N-), were absorbed into the composite film. The compatibility between the ionic liquids and the NBR polymer was confirmed by DMA. The effect of the anion size of the ionic liquids on the displacement of the actuator was examined. The displacement increased with increasing anion size of the ionic liquids. The cyclic voltammetry responses and the redox switching dynamics of the actuators were examined in different ionic liquids.

p-π Conjugated Polymers Based on Stable Triarylborane with n-Type Behavior in Optoelectronic Devices.

PubMed

Meng, Bin; Ren, Yi; Liu, Jun; Jäkle, Frieder; Wang, Lixiang

2018-02-19

p-π conjugation with embedded heteroatoms offers unique opportunities to tune the electronic structure of conjugated polymers. An approach is presented to form highly electron-deficient p-π conjugated polymers based on triarylboranes, demonstrate their n-type behavior, and explore device applications. By combining alternating [2,4,6-tris(trifluoromethyl)phenyl]di(thien-2-yl)borane (FBDT) and electron-deficient isoindigo (IID)/pyridine-flanked diketopyrrolopyrrole (DPPPy) units, we achieve low-lying lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels, high electron mobilities, and broad absorptions in the visible region. All-polymer solar cells with these polymers as electron acceptors exhibit encouraging photovoltaic performance with power conversion efficiencies of up to 2.83 %. These results unambiguously prove the n-type behavior and demonstrate the photovoltaic applications of p-π conjugated polymers based on triarylborane. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of a Polymer Coating and the Compacting Pressure on the Magnetic Properties of Cobalt-Based Amorphous Alloys

NASA Astrophysics Data System (ADS)

Skulkina, N. A.; Ivanov, O. A.; Mazeeva, A. K.; Kuznetsov, P. A.; Stepanova, E. A.; Blinova, O. V.; Mikhalitsyna, E. A.; Denisov, N. D.; Chekis, V. I.

2017-12-01

The influence of a polymer coating applied in the manufacture of magnetic shields on magnetic properties has been studied based on the example of ribbons of a cobalt-based soft magnetic alloy (Co-Fe-Ni-Cr-Mn-Si-B) with the saturation magnetostriction close to zero. The influence of polymer coating has been separated from the effect of the compacting pressure applied upon its formation. The polymer coating was formed on the ribbon in the states with different signs of the saturation magnetostriction. It has been shown that the compacting pressure and the polymer coating have opposite effects on the properties of the ribbon and that these impacts partly level off upon the formation of the coating. The degree of the influence of the polymer coating on the magnetic properties depends on the state of the ribbon and on the sign of the saturation magnetostriction in this state.

White Polymer Light-Emitting Diodes Based on Exciplex Electroluminescence from Polymer Blends and a Single Polymer.

PubMed

Liang, Junfei; Zhao, Sen; Jiang, Xiao-Fang; Guo, Ting; Yip, Hin-Lap; Ying, Lei; Huang, Fei; Yang, Wei; Cao, Yong

2016-03-09

In this Article, we designed and synthesized a series of polyfluorene derivatives, which consist of the electron-rich 4,4'-(9-alkyl-carbazole-3,6-diyl)bis(N,N-diphenylaniline) (TPA-Cz) in the side chain and the electron-deficient dibenzothiophene-5,5-dioxide (SO) unit in the main chain. The resulting copolymer PF-T25 that did not comprise the SO unit exhibited blue light-emission with the Commission Internationale de L'Eclairage coordinates of (0.16, 0.10). However, by physically blending PF-T25 with a blue light-emitting SO-based oligomer, a novel low-energy emission correlated to exciplex emerged due to the appropriate energy level alignment of TPA-Cz and the SO-based oligomers, which showed extended exciton lifetime as confirmed by time-resolved photoluminescent spectroscopy. The low-energy emission was also identified in copolymers consisting of SO unit in the main chain, which can effectively compensate for the high-energy emission to produce binary white light-emission. Polymer light-emitting diodes based on the exciplex-type single greenish-white polymer exhibit the peak luminous efficiency of 2.34 cd A(-1) and the maximum brightness of 12 410 cd m(-2), with Commission Internationale de L'Eclairage color coordinates (0.27, 0.39). The device based on such polymer showed much better electroluminescent stability than those based on blending films. These observations indicated that developing a single polymer with the generated exciplex emission can be a novel and effective molecular design strategy toward highly stable and efficient white polymer light-emitting diodes.

Characterization of PEEK, PET and PI implanted with Mn ions and sub-sequently annealed

NASA Astrophysics Data System (ADS)

Mackova, A.; Malinsky, P.; Miksova, R.; Pupikova, H.; Khaibullin, R. I.; Slepicka, P.; Gombitová, A.; Kovacik, L.; Svorcik, V.; Matousek, J.

2014-04-01

Polyimide (PI), polyetheretherketone (PEEK) and polyethylene terephthalate (PET) foils were implanted with 80 keV Mn+ ions at room temperature at fluencies of 1.0 × 1015-1.0 × 1016 cm-2. Mn depth profiles determined by RBS were compared to SRIM 2012 and TRIDYN simulations. The processes taking place in implanted polymers under the annealing procedure were followed. The measured projected ranges RP differ slightly from the SRIM and TRIDYN simulation and the depth profiles are significantly broader (up to 2.4 times) than those simulated by SRIM, while TRIDYN simulations were in a reasonable agreement up to the fluence 0.5 × 1016 in PEEK. Oxygen and hydrogen escape from the implanted layer was examined using RBS and ERDA techniques. PET, PEEK and PI polymers exhibit oxygen depletion up to about 40% of its content in virgin polymers. The compositional changes induced by implantation to particular ion fluence are similar for all polymers examined. After annealing no significant changes of Mn depth distribution was observed even the further oxygen and hydrogen desorption from modified layers appeared. The surface morphology of implanted polymers was characterized using AFM. The most significant change in the surface roughness was observed on PEEK. Implanted Mn atoms tend to dissipate in the polymer matrix, but the Mn nanoparticles are too small to be observed on TEM micrographs. The electrical, optical and structural properties of the implanted and sub-sequently annealed polymers were investigated by sheet resistance measurement and UV-Vis spectroscopy. With increasing ion fluence, the sheet resistance decreases and UV-Vis absorbance increases simultaneously with the decline of optical band gap Eg. The most pronounced change in the resistance was found on PEEK. XPS spectroscopy shows that Mn appears as a mixture of Mn oxides. Mn metal component is not present. All results were discussed in comparison with implantation experiment using the various ion species (Ni, Co) and energies used in our former experiments. Interesting differences were found in Mn concentration distribution, Mn nano-particle creation and structural changes comparing to Ni, Co ions implantation into the same polymers.

Investigation of Fluorination on Donor Moiety of Donor-Acceptor 4,7-Dithienylbenzothiadiazole-Based Conjugated Polymers toward Enhanced Photovoltaic Efficiency.

PubMed

Li, Yonghai; Wang, Junyi; Liu, Yan; Qiu, Meng; Wen, Shuguang; Bao, Xichang; Wang, Ning; Sun, Mingliang; Yang, Renqiang

2016-10-05

It is known that fluorination on π-conjugated donor-acceptor (D-A) polymers can significantly affect the optoelectronic properties and fluorination on A moiety has been well established for design of efficient photovoltaic materials. For example, polymers based on 4,7-dithienyl-5,6-difluorobenzothiadiazole (DTffBT) have been intensively investigated and exhibited excellent performance, but the corresponding DTBT-based polymers without fluorine often display an unfavorable efficiency. With the purpose of improving photovoltaic efficiency of DTBT-based D-A polymers, we design three polymers PDTBT-TxfBT (x = 0, 1, 2) with fluorination on D moiety (TxfBT) and systematically investigate fluorination on the photophysical/electrochemical and photovoltaic properties. The results show that polymer solar cells (PSCs) based on PDTBT-TBT exhibit moderate power conversion efficiency (PCE) of 5.84%. However, the bis-fluorination on TffBT moiety (PDTBT-TffBT) can greatly enhance the molecular planarity and intermolecular interaction, improve the charge transport and heterojunction morphology, and further suppress the charge recombination losses. PSCs based on PDTBT-TffBT demonstrate obviously improved photovoltaic efficiency with the best PCE up to 7.53% without any processing additives, which ranks among the top DTBT-based PSCs. However, it should be noted that unsymmetrical fluorination on TfBT moiety (PDTBT-TfBT) impairs the regularity of polymer backbone and intermolecular interaction, increases the recombination losses, and seriously reduces the short-circuit current density and efficiency (5.44%). The results exhibit that fluorination on D moiety is a helpful strategy for design high-performance photovoltaic materials and the regularity of fluorination is crucial to improving efficiencies.

Polymer composites containing nanotubes

NASA Technical Reports Server (NTRS)

Bley, Richard A. (Inventor)

2008-01-01

The present invention relates to polymer composite materials containing carbon nanotubes, particularly to those containing singled-walled nanotubes. The invention provides a polymer composite comprising one or more base polymers, one or more functionalized m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers and carbon nanotubes. The invention also relates to functionalized m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers, particularly to m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers having side chain functionalization, and more particularly to m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers having olefin side chains and alkyl epoxy side chains. The invention further relates to methods of making polymer composites comprising carbon nanotubes.

Polycyanurates and Polycarbonates Based on Eugenol: Alternatives to Thermosetting and Thermoplastic Polymers Based on Bisphenol A

DTIC Science & Technology

2014-08-14

to 5a. CONTRACT NUMBER In-House Thermosetting and Thermoplastic Polymers based on Bisphenol A 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6...Francisco, CA, 14 August 2014. PA#14389 14. ABSTRACT Polycyanurate thermosetting networks, polycarbonate thermoplastics, and homogenous polycarbonate...ON EUGENOL: ALTERNATIVES TO THERMOSETTING AND THERMOPLASTIC POLYMES BASED ON BISPHENOL A 14 August 2014 Andrew J. Guenthner1, Benjamin G. Harvey2

Inkjet-Printed Organic Transistors Based on Organic Semiconductor/Insulating Polymer Blends.

PubMed

Kwon, Yoon-Jung; Park, Yeong Don; Lee, Wi Hyoung

2016-08-02

Recent advances in inkjet-printed organic field-effect transistors (OFETs) based on organic semiconductor/insulating polymer blends are reviewed in this article. Organic semiconductor/insulating polymer blends are attractive ink candidates for enhancing the jetting properties, inducing uniform film morphologies, and/or controlling crystallization behaviors of organic semiconductors. Representative studies using soluble acene/insulating polymer blends as an inkjet-printed active layer in OFETs are introduced with special attention paid to the phase separation characteristics of such blended films. In addition, inkjet-printed semiconducting/insulating polymer blends for fabricating high performance printed OFETs are reviewed.

Inkjet-Printed Organic Transistors Based on Organic Semiconductor/Insulating Polymer Blends

PubMed Central

Kwon, Yoon-Jung; Park, Yeong Don; Lee, Wi Hyoung

2016-01-01

Recent advances in inkjet-printed organic field-effect transistors (OFETs) based on organic semiconductor/insulating polymer blends are reviewed in this article. Organic semiconductor/insulating polymer blends are attractive ink candidates for enhancing the jetting properties, inducing uniform film morphologies, and/or controlling crystallization behaviors of organic semiconductors. Representative studies using soluble acene/insulating polymer blends as an inkjet-printed active layer in OFETs are introduced with special attention paid to the phase separation characteristics of such blended films. In addition, inkjet-printed semiconducting/insulating polymer blends for fabricating high performance printed OFETs are reviewed. PMID:28773772

An easy and effective method to modulate molecular energy level of the polymer based on benzodithiophene for the application in polymer solar cells.

PubMed

Zhang, Maojie; Guo, Xia; Ma, Wei; Zhang, Shaoqing; Huo, Lijun; Ade, Harald; Hou, Jianhui

2014-04-02

Attaching meta-alkoxy-phenyl groups as conjugated side chains is an easy and effective way to modulate the molecular energy level of D-A polymer for photovoltaic application, and the polymer solar cells based on the polymer consisting meta-alkoxy-phenyl groups as conjugated side chain, PBT-OP, shows an enhanced open circuit voltage and thus higher efficiency of 7.50%, under the illumination of AM 1.5G, 100 mW/cm(2) . © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Long-Life Self-Renewing Solar Reflector Stack

DOEpatents

Butler, Barry Lynn

1997-07-08

A long-life solar reflector includes a solar collector substrate and a base layer bonded to a solar collector substrate. The first layer includes a first reflective layer and a first acrylic or transparent polymer layer covering the first reflective layer to prevent exposure of the first reflective layer. The reflector also includes at least one upper layer removably bonded to the first acrylic or transparent polymer layer of the base layer. The upper layer includes a second reflective layer and a second acrylic or transparent polymer layer covering the second reflective layer to prevent exposure of the second reflective layer. The upper layer may be removed from the base reflective layer to expose the base layer, thereby lengthening the useful life of the solar reflector. A method of manufacturing a solar reflector includes the steps of bonding a base layer to a solar collector substrate, wherein the base reflective layer includes a first reflective layer and a first transparent polymer or acrylic layer covering the first reflective layer; and removably bonding a first upper layer to the first transparent polymer or acrylic layer of the base layer. The first upper layer includes a second reflective layer and a second transparent polymer or acrylic layer covering the second reflective layer to prevent exposure of the second reflective layer.

Dimensional modulation and magnetic properties of triazole- and bis(triazole)-based copper(II) coordination polymers tuned by aromatic polycarboxylates

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

Zhang, Ju-Wen; Zhao, Wei; Lu, Qi-Lin

2014-04-01

Five new metal–organic coordination polymers ([Cu{sub 3}(μ{sub 2}-OH){sub 2}(atrz){sub 2}(nph){sub 2}(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (1), ([Cu{sub 2}(μ{sub 3}-OH)(atrz)(1,2,4-btc)]·2H{sub 2}O){sub n} (2), ([Cu{sub 2}(μ{sub 3}-OH)(atrz)(1,2,4-btc)(H{sub 2}O)]·H{sub 2}O){sub n} (3), [Cu(dth){sub 0.5}(nph)(H{sub 2}O)]{sub n} (4) and [Cu(dth)(Hnip){sub 2}]{sub n} (5) [atrz=4-amino-1,2,4-triazole, dth=N,N'-di(4H-1,2,4-triazole)hexanamide, H{sub 2}nph=3-nitrophthalic acid, 1,2,4-H{sub 3}btc=1,2,4-benzenetricarboxylic acid and H{sub 2}nip=5-nitroisophthalic acid] were hydrothermally synthesized and structurally characterized. Polymer 1 shows a one-dimensional (1D) chain. Polymers 2 and 3 exhibit similar tetranuclear Cu{sup II}{sub 4} cluster-based three-dimensional (3D) frameworks with the same components. Polymer 4 possesses a 3D framework with a 4{sup 12}·6{sup 3}-pcu topology. Polymer 5 displays a 3D frameworkmore » with a 4{sup 4}·6{sup 10}·8-mab topology. The magnetic properties of 1–4 were investigated. - Graphical abstract: Five triazole-based copper(II) polymers modulated by polycarboxylates were synthesized. Bis-triazole-bis-amide ligand and polycarboxylates play important roles in tuning dimensionality of polymers. Magnetic properties of polymers were investigated. - Highlights: • Five triazole- and bis(triazole)-based copper(II) coordination polymers tuned by aromatic polycarboxylates were obtained. • The aromatic polycarboxylates have an important influence on the dimensionality of five polymers. • The magnetic properties of four polymers were investigated.« less

Symmetry Breaking in Side Chains Leading to Mixed Orientations and Improved Charge Transport in Isoindigo-alt-Bithiophene Based Polymer Thin Films.

PubMed

Xue, Guobiao; Zhao, Xikang; Qu, Ge; Xu, Tianbai; Gumyusenge, Aristide; Zhang, Zhuorui; Zhao, Yan; Diao, Ying; Li, Hanying; Mei, Jianguo

2017-08-02

The selection of side chains is important in design of conjugated polymers. It not only affects their intrinsic physical properties, but also has an impact on thin film morphologies. Recent reports suggested that a face-on/edge-on bimodal orientation observed in polymer thin films may be responsible for a three-dimensional (3D) charge transport and leads to dramatically improved mobility in donor-acceptor based conjugated polymers. To achieve a bimodal orientation in thin films has been seldom explored from the aspect of molecular design. Here, we demonstrate a design strategy involving the use of asymmetric side chains that enables an isoindigo-based polymer to adopt a distinct bimodal orientation, confirmed by the grazing incidence X-ray diffraction. As a result, the polymer presents an average high mobility of 3.8 ± 0.7 cm 2 V -1 s -1 with a maximum value of 5.1 cm 2 V -1 s -1 , in comparison with 0.47 and 0.51 cm 2 V -1 s -1 obtained from the two reference polymers. This study exemplifies a new strategy to develop the next generation polymers through understanding the property-structure relationship.

Processing and characterization of natural cellulose fibers/thermoset polymer composites.

PubMed

Thakur, Vijay Kumar; Thakur, Manju Kumari

2014-08-30

Recently natural cellulose fibers from different biorenewable resources have attracted the considerable attraction of research community all around the globe owing to their unique intrinsic properties such as biodegradability, easy availability, environmental friendliness, flexibility, easy processing and impressive physico-mechanical properties. Natural cellulose fibers based materials are finding their applications in a number of fields ranging from automotive to biomedical. Natural cellulose fibers have been frequently used as the reinforcement component in polymers to add the specific properties in the final product. A variety of cellulose fibers based polymer composite materials have been developed using various synthetic strategies. Seeing the immense advantages of cellulose fibers, in this article we discuss the processing of biorenewable natural cellulose fibers; chemical functionalization of cellulose fibers; synthesis of polymer resins; different strategies to prepare cellulose based green polymer composites, and diverse applications of natural cellulose fibers/polymer composite materials. The article provides an in depth analysis and comprehensive knowledge to the beginners in the field of natural cellulose fibers/polymer composites. The prime aim of this review article is to demonstrate the recent development and emerging applications of natural cellulose fibers and their polymer materials. Copyright © 2014 Elsevier Ltd. All rights reserved.

Green polymer chemistry: biocatalysis and biomaterials

USDA-ARS?s Scientific Manuscript database

This overview briefly surveys the practice of green chemistry in polymer science. Eight related themes can be discerned from the current research activities: 1) biocatalysis, 2) bio-based building blocks and agricultural products, 3) degradable polymers, 4) recycling of polymer products and catalys...

Overcoming the efficiency limitations of SnS2 nanoparticle-based bulk heterojunction solar cells

NASA Astrophysics Data System (ADS)

Tam Nguyen Truong, Nguyen; Kieu Trinh, Thanh; Thanh Hau Pham, Viet; Smith, Ryan P.; Park, Chinho

2018-04-01

This study examined the effects of heat treatment, the electron transport layer, and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) incorporation on the performance of hybrid bulk heterojunction (BHJ) solar cells composed of tin disulfide (SnS2) nanoparticles (NPs) and low band gap energy polymers poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b3,4-b‧]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT) or poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b‧]dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}) (PBT7). Inserting an electron transport layer (ETL) (i.e., ZnO) on the top of the photoactive layer improved the surface morphology of the photoactive layer, which led to an improvement in charge transport. Moreover, adding a suitable amount of PCBM to the SnS2/polymer active layer enhanced the device performance, such as short circuit current density (J sc) and power conversion efficiency (PCE). In particular, adding 0.5 mg of PCBM to the composite solution led to a 25% and 1.5% improvement in the J sc value and PCE, respectively. The enhanced performance was due mainly to the improvements in the surface morphology of the photoactive layer, charge carrier mobility within the donor-acceptor interface, and carrier collection efficiency at the cathode.

Plant-derived cis-β-ocimene as a precursor for biocompatible, transparent, thermally-stable dielectric and encapsulating layers for organic electronics.

PubMed

Bazaka, Kateryna; Destefani, Ryan; Jacob, Mohan V

2016-12-09

This article presents low-temperature, one-step dry synthesis of optically transparent thermally-stable, biocompatible cis-β-ocimene-based thin films for applications as interlayer dielectric and encapsulating layer for flexible electronic devices, e.g. OLEDs. Morphological analysis of thin films shows uniform, very smooth (R q  < 1 nm) and defect-free moderately hydrophilic surfaces. The films are optically transparent, with a refractive index of ~1.58 at 600 nm, an optical band gap of ~2.85 eV, and dielectric constant of 3.5-3.6 at 1 kHz. Upon heating, thin films are chemically and optically stable up to at least 200 °C, where thermal stability increases for films manufactured at higher RF power as well as for films deposited away from the plasma glow. Heating of the sample increases the dielectric constant, from 3.7 (25 °C) to 4.7 (120 °C) at 1 kHz for polymer fabricated at 25 W. Polymers are biocompatible with non-adherent THP-1 cells and adherent mouse macrophage cells, including LPS-stimulated macrophages, and maintain their material properties after 48 h of immersion into simulated body fluid. The versatile nature of the films fabricated in this study may be exploited in next-generation consumer electronics and energy technologies.

Plant-derived cis-β-ocimene as a precursor for biocompatible, transparent, thermally-stable dielectric and encapsulating layers for organic electronics

PubMed Central

Bazaka, Kateryna; Destefani, Ryan; Jacob, Mohan V.

2016-01-01

This article presents low-temperature, one-step dry synthesis of optically transparent thermally-stable, biocompatible cis−β−ocimene-based thin films for applications as interlayer dielectric and encapsulating layer for flexible electronic devices, e.g. OLEDs. Morphological analysis of thin films shows uniform, very smooth (Rq < 1 nm) and defect-free moderately hydrophilic surfaces. The films are optically transparent, with a refractive index of ~1.58 at 600 nm, an optical band gap of ~2.85 eV, and dielectric constant of 3.5−3.6 at 1 kHz. Upon heating, thin films are chemically and optically stable up to at least 200 °C, where thermal stability increases for films manufactured at higher RF power as well as for films deposited away from the plasma glow. Heating of the sample increases the dielectric constant, from 3.7 (25 °C) to 4.7 (120 °C) at 1 kHz for polymer fabricated at 25 W. Polymers are biocompatible with non-adherent THP–1 cells and adherent mouse macrophage cells, including LPS-stimulated macrophages, and maintain their material properties after 48 h of immersion into simulated body fluid. The versatile nature of the films fabricated in this study may be exploited in next-generation consumer electronics and energy technologies. PMID:27934916

Interface properties between a low band gap conjugated polymer and a calcium metal electrode.

PubMed

Zhang, Wei; Pan, Xiao; Feng, Xuefei; Wang, Chia-Hsin; Yang, Yaw-Wen; Ju, Huanxin; Zhu, Junfa

2016-04-14

Interfaces between metal electrodes and π-conjugated polymers play an important role in the organic optoelectronic devices. In this paper, the molecular orientation of the pristine poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (APFO3) films, chemical reactions and the electronic structure during the interface formation of Ca/APFO3 have been investigated in detail using synchrotron radiation photoemission spectroscopy (SRPES), X-ray photoemission spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. It is shown that the APFO3 film has a high degree of orientational ordering with its aromatic ring tilted at an angle of 43° from the substrate, and the 9,9-dioctyl fluorene unit (F8) is almost in the same plane as the benzothiazole unit (BT). Upon vapor-deposition of Ca onto APFO3 at room temperature, Ca dopes electrons into APFO3 and induces the downward band bending of APFO3. Moreover, Ca can diffuse into the APFO3 subsurface and react with N, S and C atoms of APFO3. Finally, the barrier of electron injection at the Ca/APFO3 interface is derived by the energy level alignment diagram. These results enable us to gain comprehensive insights into APFO3 and will facilitate the reasonable design of high performance devices based on APFO3.

Gd2O3:Eu3+/PPO/POPOP/PS composites for digital imaging radiation detectors

NASA Astrophysics Data System (ADS)

Oliveira, J.; Martins, P. M.; Martins, P.; Correia, V.; Rocha, J. G.; Lanceros-Mendez, S.

2015-11-01

Polymer-based scintillator composites have been produced by combining polystyrene (PS) and Gd2O3:Eu3+ scintillator nanoparticles. Polystyrene has been used since it is a flexible and stable binder matrix, resistant to thermal and light deterioration and with suitable optical properties. Gd2O3:Eu3+ has been selected as scintillator material due to its wide band gap, high density and visible light yield. The optical, thermal and electrical characteristics of the composites were studied as a function of filler content, together with their performance as scintillator material. Additionally 1 wt.% of 2,5-diphenyloxazole (PPO) and 0.01 wt.% of 1,4 di[2-(5phenyloxazolyl)]benzene (POPOP) were introduced in the polymer matrix in order to strongly improve light yield, i.e., the measured intensity of the output visible radiation, under X-ray irradiation. Increasing scintillator filler concentration (from 0.25 to 7.5 wt.%) increases scintillator light yield and decreases the optical transparency of the composite. The addition of PPO and POPOP strongly increased the overall transduction performance of the composite due to specific absorption and re-emission processes. It is thus shown that Gd2O3:Eu3+/PPO/POPOP/PS composites with 0.25 wt.% of scintillator content with fluorescence molecules are suitable for the development of innovative large-area X-ray radiation detectors with huge demand from the industries.

Plant-derived cis-β-ocimene as a precursor for biocompatible, transparent, thermally-stable dielectric and encapsulating layers for organic electronics

NASA Astrophysics Data System (ADS)

Bazaka, Kateryna; Destefani, Ryan; Jacob, Mohan V.

2016-12-01

This article presents low-temperature, one-step dry synthesis of optically transparent thermally-stable, biocompatible cis-β-ocimene-based thin films for applications as interlayer dielectric and encapsulating layer for flexible electronic devices, e.g. OLEDs. Morphological analysis of thin films shows uniform, very smooth (Rq < 1 nm) and defect-free moderately hydrophilic surfaces. The films are optically transparent, with a refractive index of ~1.58 at 600 nm, an optical band gap of ~2.85 eV, and dielectric constant of 3.5-3.6 at 1 kHz. Upon heating, thin films are chemically and optically stable up to at least 200 °C, where thermal stability increases for films manufactured at higher RF power as well as for films deposited away from the plasma glow. Heating of the sample increases the dielectric constant, from 3.7 (25 °C) to 4.7 (120 °C) at 1 kHz for polymer fabricated at 25 W. Polymers are biocompatible with non-adherent THP-1 cells and adherent mouse macrophage cells, including LPS-stimulated macrophages, and maintain their material properties after 48 h of immersion into simulated body fluid. The versatile nature of the films fabricated in this study may be exploited in next-generation consumer electronics and energy technologies.

Tuning the Electrical Memory Behavior from Nonvolatile to Volatile in Functional Copolyimides Bearing Varied Fluorene and Pyrene Moieties

NASA Astrophysics Data System (ADS)

Jia, Nanfang; Qi, Shengli; Tian, Guofeng; Wang, Xiaodong; Wu, Dezhen

2017-04-01

For producing polymer based electronics with good memory behavior, a series of functional copolyimides were designed and synthesized in this work by copolymerizing 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA) with (9,9'-bis(4-aminophenyl)fluorene) (BAPF) and N, N-bis(4-aminophenyl) aminopyrene (DAPAP) diamines. The synthesized copolyimides DSDA/(DAPAP/BAPF) were denoted as coPI-DAPAP x ( x = 100, 50, 20, 10, 5, 1, 0), where x% represents the molar fraction of the DAPAP unit in the diamines. Characterization results indicate that the coPI-DAPAP x exhibits tunable electrical switching behaviors from write once read many times (WORM, nonvolatile, coPI-DAPAP100, coPI-DAPAP50, coPI-DAPAP20, coPI-DAPAP10) to the static random access memory (SRAM, volatile, coPI-DAPAP5, coPI-DAPAP1) with the variation of the DAPAP content. Optical and electrochemical characterization show gradually decreasing highest occupied molecular orbital levels and enlarged energy gap with the decrease of the DAPAP moiety, suggesting decreasing charge-transfer effect in the copolyimides, which can account for the observed WORM-SRAM memory conversion. Meanwhile, the charge transfer process was elucidated by quantum chemical calculation at B3LYP/6-31G(d) theory level. This work shows the effect of electron donor content on the memory behavior of polymer electronic materials.

Synthesis, Characterization and Biological Studies of New Linear Thermally Stable Schiff Base Polymers with Flexible Spacers.

PubMed

Qureshi, Farah; Khuhawar, Muhammad Yar; Jahangir, Taj Muhammad; Channar, Abdul Hamid

2016-01-01

Five new linear Schiff base polymers having azomethine structures, ether linkages and extended aliphatic chain lengths with flexible spacers were synthesized by polycondensation of dialdehyde (monomer) with aliphatic and aromatic diamines. The formation yields of monomer and polymers were obtained within 75-92%. The polymers with flexible spacers of n-hexane were somewhat soluble in acetone, chloroform, THF, DMF and DMSO on heating. The monomer and polymers were characterized by melting point, elemental microanalysis, FT-IR, (1)HNMR, UV-Vis spectroscopy, thermogravimetry (TG), differential thermal analysis (DTA), fluorescence emission, scanning electron microscopy (SEM) and viscosities and thermodynamic parameters measurements of their dilute solutions. The studies supported formation of the monomer and polymers and on the basis of these studies their structures have been assigned. The synthesized polymers were tested for their antibacterial and antifungal activities.

Recent progress in nanocomposites based on conducting polymer: application as electrochemical sensors

NASA Astrophysics Data System (ADS)

El Rhazi, Mama; Majid, Sanaa; Elbasri, Miloud; Salih, Fatima Ezzahra; Oularbi, Larbi; Lafdi, Khalid

2018-06-01

Over the years, intensive research works have been devoted to conducting polymers due to their potential application in many fields such as fuel cell, sensors, and capacitors. To improve the properties of these compounds, several new approaches have been developed which consist in combining conducting polymers and nanoparticles. Then, this review intends to give a clear overview on nanocomposites based on conducting polymers, synthesis, characterization, and their application as electrochemical sensors. For this, the paper is divided into two parts: the first part will highlight the nanocomposites synthesized by combination of carbon nanomaterials (CNMs) and conducting polymers. The preparation of polymer/CNMs such as graphene and carbon nanotube modified electrode is presented coupled with relevant applications. The second part consists of a review of nanocomposites synthesized by combination of metal nanoparticles and conducting polymers.

Highly sensitive current sensor based on an optical microfiber loop resonator incorporating low index polymer

NASA Astrophysics Data System (ADS)

Yoon, Min-Seok; Han, Young-Geun

2014-05-01

A highly sensitive current sensor based on an optical microfiber loop resonator (MLR) incorporating low index polymer is proposed and experimentally demonstrated. The microfiber with a waist diameter of 1 μm is wrapped around the nicrhrome wire with low index polymer coating and the optical MLR is realized. The use of the microfiber and low index polymer with high thermal property can effectively improve the current sensitivity of the proposed MLR-based sensing probe to be 437.9 pm/A2, which is ~10 times higher than the previous result.

Lipid-absorbing Polymers

NASA Technical Reports Server (NTRS)

Marsh, H. E., Jr.; Wallace, C. J.

1973-01-01

The removal of bile acids and cholesterol by polymeric absorption is discussed in terms of micelle-polymer interaction. The results obtained with a polymer composed of 75 parts PEO and 25 parts PB plus curing ingredients show an absorption of 305 to 309%, based on original polymer weight. Particle size effects on absorption rate are analyzed. It is concluded that crosslinked polyethylene oxide polymers will absorb water, crosslinked polybutadiene polymers will absorb lipids; neither polymer will absorb appreciable amounts of lipids from micellar solutions of lipids in water.

ESR spectrometer with a loop-gap resonator for cw and time resolved studies in a superconducting magnet.

PubMed

Simon, Ferenc; Murányi, Ferenc

2005-04-01

The design and performance of an electron spin resonance spectrometer operating at 3 and 9 GHz microwave frequencies combined with a 9-T superconducting magnet are described. The probehead contains a compact two-loop, one gap resonator, and is inside the variable temperature insert of the magnet enabling measurements in the 0-9T magnetic field and 1.5-400 K temperature range. The spectrometer allows studies on systems where resonance occurs at fields far above the g approximately 2 paramagnetic condition such as in antiferromagnets. The low quality factor of the resonator allows time resolved experiments such as, e.g., longitudinally detected ESR. We demonstrate the performance of the spectrometer on the NaNiO2 antiferromagnet, the MgB2 superconductor, and the RbC60 conducting alkaline fulleride polymer.

Search for the Universal Ancestors

NASA Technical Reports Server (NTRS)

Hartman, H. (Editor); Lawless, J. G. (Editor); Morrison, P. (Editor)

1985-01-01

By its nature, the study of the origins of life is multidisciplinary, requiring contributions from astronomers, biologists, chemists, geologists, physicists, and many others. Partial answers are provided to many questions about organic chemical evolution and the origin of life. It is observed that the gaps in our knowledge concerning the steps from the nonliving to the living are numerous. Among these gaps are: (1) a solar system formation with its accumulation of raw materials; (2) the synthesis of the life forming monomers, such as the amino acids, nucleotides, and lipids; (3) the condensation of these monomers into useful polymers, such as proteins and nucleic acids; (4) the sequestering of these materials into droplets of proteinoid or membrane-like structures; and (5) the development of a chemical memory (the genetic code) to pass on to the progeny the information acquired.