Effect of Ultrasonic Vibration on Mechanical Properties of 3D Printing Non-Crystalline and Semi-Crystalline Polymers.

Science.gov (United States)

Li, Guiwei; Zhao, Ji; Wu, Wenzheng; Jiang, Jili; Wang, Bofan; Jiang, Hao; Fuh, Jerry Ying Hsi

2018-05-17

Fused deposition modeling 3D printing has become the most widely used additive manufacturing technology because of its low manufacturing cost and simple manufacturing process. However, the mechanical properties of the 3D printing parts are not satisfactory. Certain pressure and ultrasonic vibration were applied to 3D printed samples to study the effect on the mechanical properties of 3D printed non-crystalline and semi-crystalline polymers. The tensile strength of the semi-crystalline polymer polylactic acid was increased by 22.83% and the bending strength was increased by 49.05%, which were almost twice the percentage increase in the tensile strength and five times the percentage increase in the bending strength of the non-crystalline polymer acrylonitrile butadiene styrene with ultrasonic strengthening. The dynamic mechanical properties of the non-crystalline and semi-crystalline polymers were both improved after ultrasonic enhancement. Employing ultrasonic energy can significantly improve the mechanical properties of samples without modifying the 3D printed material or adjusting the forming process parameters.

Fiscal 1998 achievement report on regional consortium research and development project. Venture business fostering regional consortium in its 2nd year--Creation of key industries (Development of processing of new structure-designed high-performance polymer alloy); 1998 nendo shinkina kozo seigyo koseino kobunshi alloy no seikei kako ni kansuru kenkyu kaihatsu seika hokokusho. 2

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

Efforts are exerted to make novel recyclable polymer alloys excellent in material characteristic and to develop a technology for processing them, for which liquid crystalline polymers equipped with a self-alignment capability are combined with thermoplastic resins. In the research on the alloying of polyethylene terephthalate (PET) and liquid crystal polymers (LCP), studies are conducted about inorganic nucleating additives, thermostabilizers, and mold releasing lubricants, and a success is attained in the manufacture of excellent alloyed pellets. In the injection molding of alloys of PET and LCP, a product is obtained, among those produced with the rate of LCP varied, which behaves excellently even at a high resin temperature of 285 degrees C. It is found about PET/LCP alloys that improvement is achieved with additional LCP in terms of the warpage temperature under load, bending property, strength, and dimensional stability upon exposure to heat. In the study of the response of LCP-diffused PET to a process demanding distortion, an injection-molded product containing 10-20% of LCP is found to exhibit excellent ductility. It is also found that PET/LCP alloys may be cut and machined easily and that therefore their crushing for the recycling purpose will be easy. (NEDO)

Autophobicity and layering behavior of thin liquid-crystalline polymer films.

NARCIS (Netherlands)

Wielen, van der M.W.J.; Cohen Stuart, M.A.; Fleer, G.J.

1998-01-01

The stability against breaking-up of thin spin-coated films of liquid-crystalline polymers depends on the film thickness and annealing temperature. This study concerns side-chain liquid-crystalline polymers, based on alternating copolymers of maleic anhydride and mesogenic alkenes. The mesogenic

Thermomechanical and adhesive properties of radiation-modified polymer composites for thermosetting products

International Nuclear Information System (INIS)

Kalkis, V.; Maksimov, R.D.; Kalnins, M.; Zicans, J.; Bocoka, T.; Revjakin, O.

2000-01-01

The gamma-irradiated blends of polyethylene (PE) with ethylene / propylene / diene copolymer (Epdm) and thermotropic liquid crystalline polymer (LCP) are investigated. The radiation dose absorbed does not exceed 150 kGy (10 kGy=1 Mrad). It is shown that the even small amounts of LCP added to PE improve the mechanical and operational properties of composites and the thermosetting products made of them. The temperature dependences of the elastics modulus, tension diagrams at a temperature above the PE melting point, and recovery curves of the oriented specimens are presented. The kinetics of thermorelaxation and residual setting stresses upon isometric heating and cooling of the previously oriented composites is studied. The data on the influence of LCP on the adhesion interaction of the blend with steel are obtained. The features of thermomechanical and adhesive properties are discussed and the results of morphological and calorimetric tests are given. (author)

Electric properties of a liquid crystalline methacrylic polymer

International Nuclear Information System (INIS)

Gonzalez Henriquez, C.M.; Soto Bustamante, E.A.; Haase, W.

2009-01-01

The formation of a liquid crystalline polymer called PM6R8 is reported. The polymers were obtained with different concentration of AIBN as initiator (0.25, 0.50, 1 and 2mg in 5ml solution) and time of reaction (24, 36 and 48 hours). The compounds were characterized by 1 H-NMR, differential thermal analysis (DTA), X-ray diffractometer and pyroelectric measurements. For the polymer a smectic C 2 phase occurs over broad temperature range, which is a possible explanation for the electric signal. The arrangement of the molecules within of the crystalline lattice is related with the kinetic of precipitation. (author)

Reducing burn-in voltage loss in polymer solar cells by increasing the polymer crystallinity

KAUST Repository

Heumueller, Thomas

2014-08-01

In order to commercialize polymer solar cells, the fast initial performance losses present in many high efficiency materials will have to be managed. This burn-in degradation is caused by light-induced traps and its characteristics depend on which polymer is used. We show that the light-induced traps are in the bulk of the active layer and we find a direct correlation between their presence and the open-circuit voltage loss in devices made with amorphous polymers. Solar cells made with crystalline polymers do not show characteristic open circuit voltage losses, even though light-induced traps are also present in these devices. This indicates that crystalline materials are more resistant against the influence of traps on device performance. Recent work on crystalline materials has shown there is an energetic driving force for charge carriers to leave amorphous, mixed regions of bulk heterojunctions, and charges are dominantly transported in pure, ordered phases. This energetic landscape allows efficient charge generation as well as extraction and also may benefit the stability against light-induced traps. This journal is © the Partner Organisations 2014.

Crystalline morphology of the matrix of PEEK-carbon fiber aromatic polymer composites. I. Assessment of crystallinity

International Nuclear Information System (INIS)

Blundell, D.J.; Chalmers, J.M.; Mackenzie, M.W.; Gaskin, W.F.

1985-01-01

The crystallinity of the polyetheretherketone (PEEK) matrix polymer in the Aromatic Polymer Composite APC-2 has been estimated using a combination of techniques based on wide angle x-ray diffraction and infrared reflection spectroscopy. Crystallinity varies systematically with cooling rate and annealing time over the range 20 to 40%. The occurrence of oriented crystal growth of the PEEK relative to the carbon fiber can be monitored by x-ray diffraction. 8 references, 10 figures, 1 table

Miniaturized and Ferrite Based Tunable Bandpass Filters in LCP and LTCC Technologies for SoP Applications

KAUST Repository

Arabi, Eyad A.

2015-01-01

, namely low temperature co-fired ceramic (LTCC) and the liquid crystal polymers (LCP) is demonstrated. The miniaturized filter is based on a second order topology, which has been modified to improve the selectivity and out-of-band rejection without

Effect of MWNTs and SiC-Coated MWNTs on Properties of PEEK/LCP Blend

Directory of Open Access Journals (Sweden)

Ganesh Chandra Nayak

2009-01-01

Full Text Available Multiwall carbon nanotubes (MWNTs were modified with polycarbosilane-derived silicon carbide (SiC to improve its dispersion in the polymer matrix. PEEK/LCP/MWNTs nanocomposites were prepared by melt blending. TEM images show the improved dispersion of SiC-coated MWNTs against agglomerated structure of pure MWNTs in the blend. FESEM images shows better fibrillation of LCP in presence of SiC-coated MWNTs. TGA reveals that nanocomposites with SiC-coated MWNTs shows higher thermal stability than MWNTs filled blend system. Based on enhanced dispersion, storage modulus, tensile modulus and tensile strength were increased drastically with the incorporation of SiC-coated MWNTs. Glass transition temperature of the nanocomposites shows significant improvement with the incorporation of MWNTs.

LCP nanoparticle for tumor and lymph node metastasis imaging

Science.gov (United States)

Tseng, Yu-Cheng

A lipid/calcium/phosphate (LCP) nanoparticle formulation (particle diameter ˜25 nm) has previously been developed to delivery siRNA with superior efficiency. In this work, 111In was formulated into LCP nanoparticles to form 111In-LCP for SPECT/CT imaging. With necessary modifications and improvements of the LCP core-washing and surface-coating methods, 111In-LCP grafted with polyethylene glycol exhibited reduced uptake by the mononuclear phagocytic system. SPECT/CT imaging supported performed biodistribution studies, showing clear tumor images with accumulation of 8% or higher injected dose per gram tissue (ID/g) in subcutaneous, human-H460, lung-cancer xenograft and mouse-4T1, breast cancer metastasis models. Both the liver and the spleen accumulated ˜20% ID/g. Accumulation in the tumor was limited by the enhanced permeation and retention effect and was independent of the presence of a targeting ligand. A surprisingly high accumulation in the lymph nodes (˜70% ID/g) was observed. In the 4T1 lymph node metastasis model, the capability of intravenously injected 111In-LCP to visualize the size-enlarged and tumor-loaded sentinel lymph node was demonstrated. By analyzing the SPECT/CT images taken at different time points, the PK profiles of 111In-LCP in the blood and major organs were determined. The results indicated that the decrement of 111In-LCP blood concentration was not due to excretion, but to tissue penetration, leading to lymphatic accumulation. Larger LCP (diameter ˜65 nm) nanoparticles were also prepared for the purpose of comparison. Results indicated that larger LCP achieved slightly lower accumulation in the tumor and lymph nodes, but much higher accumulation in the liver and spleen; thus, larger nanoparticles might not be favorable for imaging purposes. We also demonstrated that LCP with a diameter of ˜25 nm were better able to penetrate into tissues, travel in the lymphatic system and preferentially accumulate in the lymph nodes due to 1) small

Damage characterization for particles filled semi-crystalline polymer

Directory of Open Access Journals (Sweden)

Lauro Franck

2015-01-01

Full Text Available Damage evolution and characterization in semi-crystalline polymer filled with particles under various loadings is still a challenge. A specific damage characterization method using Digital Image Correlation is proposed for a wide range of strain rates considering tensile tests with hydraulic jacks as well as Hopkinson's bars. This damage measurement is obtained by using and adapting the SEE method [1] which was developed to characterize the behaviour laws at constant strain rates of polymeric materials in dynamic. To validate the characterization process, various damage measurement techniques are used under quasi-static conditions before to apply the procedure in dynamic. So, the well-known damage characterization by loss of stiffness technique under quasi-static loading is applied to a polypropylene. In addition, an in-situ tensile test, carried out in a microtomograph, is used to observe the cavitation phenomenon in real time. A good correlation is obtained between all these techniques and consequently the proposed technique is supposed suitable for measuring the ductile damage observed in semi-crystalline polymers under dynamic loading. By applying it to the semi-crystalline polymer at moderate and high speed loadings, the damage evolution is measured and it is observed that the damage evolution is not strain rate dependent but the failure strain on the contrary is strain rate dependent.

Sensing of environmental pollutant by conductive composite from prepared from hyperbranched polymer-grafted carbon black and crystalline polymer

International Nuclear Information System (INIS)

Taniguchi, Y.; Chen, J.; Ogawa, M.; Yokoyama, K.; Shimizu, H.; Tsubokawa, N.; Maekawa, Y.; Yoshida, M.

2002-01-01

Complete text of publication follows. The hyperbranched (HB) polymer-grafted (PG) carbon blacks (CB) have the possibility of utilizing as a support of catalyst and enzyme, and a curing agent of epoxy resin, because they have much terminal amino or hydroxyl groups. The postgrafting of crystalline polymer onto HB PG CB and the sensing of environmental pollutant by the conductive composite prepared from the polymer-postgrafted CB was discussed. The grafting of poly(amidoamide) onto CB surface was achieved by repeating either Michael addition of methyl acrylate to amino group on the surface or the amidation of the resulting terminal methyl ester group with ethylene diamine. HB polyester onto CB surface was grafted by stepwise growth of 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) from surface carboxyl and hydroxyl groups on CB as a core in the presence of p-toluenesulfonic acid (p-TSA). The one-pot grafting of HB polyester onto CB as core was also achieved by the polycondensation of bis-MPA in the presence of p-TSA. Postgrafting of crystalline polymer onto HB polymer-grafted CB was achieved by the reaction of terminal amino or hydroxyl groups of grafted chain with COCl-terminated crystalline polymer. The electric resistance of the composite prepared from crystalline polymer-postgrafted CB was found to increase drastically in hexane, containing environmental pollutant, such as chloroform and trichloroethane, and returned immediately to the initial resistance when it was transferred into pure hexane. Based on the above results, it is concluded that the composite can be used as a novel sensor for environmental pollutant in solution

Comparison of filters: Inkjet printed on PEN substrate versus a laser-etched on LCP substrate

KAUST Repository

Arabi, Eyad A.

2014-10-01

In this paper, microstrip-based bandpass filters on polyethylene naphthalate (PEN) and liquid crystal polymers (LCP) are presented to investigate the performance of filters on ultra-thin substrates. PEN (with a thickness of 120 μm) has been characterized and used for a filter for the first time. In addition to being low cost and transparent, it demonstrates comparable RF performance to LCP. The conductor losses are compared by fabricating filters with inkjet printed lines as well as laser etched copper clad LCP sheets. With 5 layers of inkjet printing, and a curing temperature below 200°C, a final silver thickness of 2 μm and conductivity of 9.6 × 106 S/m are achieved. The designs are investigated at two frequencies, 24 GHz as well as 5 GHz to assess their performance at high and low frequencies respectively. The 24 GHz inkjet printed filter shows an insertion loss of 2 dB, while the 5 GHz design gives an insertion loss of 8 dB. We find that thin substrates have a strong effect on the insertion loss of filters especially as the frequency is reduced. The same design, realized on LCP (thickness of 100 μm) through laser etching, demonstrates a very similar performance, thus verifying this finding. © 2014 European Microwave Association.

Comparison of filters: Inkjet printed on PEN substrate versus a laser-etched on LCP substrate

KAUST Repository

Arabi, Eyad A.; McKerricher, Garret; Shamim, Atif

2014-01-01

In this paper, microstrip-based bandpass filters on polyethylene naphthalate (PEN) and liquid crystal polymers (LCP) are presented to investigate the performance of filters on ultra-thin substrates. PEN (with a thickness of 120 μm) has been characterized and used for a filter for the first time. In addition to being low cost and transparent, it demonstrates comparable RF performance to LCP. The conductor losses are compared by fabricating filters with inkjet printed lines as well as laser etched copper clad LCP sheets. With 5 layers of inkjet printing, and a curing temperature below 200°C, a final silver thickness of 2 μm and conductivity of 9.6 × 106 S/m are achieved. The designs are investigated at two frequencies, 24 GHz as well as 5 GHz to assess their performance at high and low frequencies respectively. The 24 GHz inkjet printed filter shows an insertion loss of 2 dB, while the 5 GHz design gives an insertion loss of 8 dB. We find that thin substrates have a strong effect on the insertion loss of filters especially as the frequency is reduced. The same design, realized on LCP (thickness of 100 μm) through laser etching, demonstrates a very similar performance, thus verifying this finding. © 2014 European Microwave Association.

Dielectric properties and conductivity of carbon nanofiber/semi-crystalline polymer composites

International Nuclear Information System (INIS)

Sui, G.; Jana, S.; Zhong, W.H.; Fuqua, M.A.; Ulven, C.A.

2008-01-01

The properties of semi-crystalline polymer nanocomposites are affected by the nanofillers directly and indirectly, as two phases, i.e., crystalline and amorphous, exist in the polymer. The effects of nanofillers on the two phases could be competitive. The dielectric properties and conductivity of carbon nanofibers (CNF)/semi-crystalline polymer nanocomposites are studied in this paper. CNF/polypropylene (PP) nanocomposites are prepared in experiment by melt blending. The resulting morphology and crystalline structure are characterized by means of differential scanning calorimetry, wide angle X-ray diffraction and scanning electron microscopy. The PP nanocomposite containing 5 wt.% CNF exhibits a surprisingly high dielectric constant under wide sweep frequencies attended by low dielectric loss. Its dielectric constant is >600 under lower frequency, and remains >200 at a frequency of 4000 Hz. The electrical and thermal conductivities of the nanocomposites are studied, and enhancements are seen with increased CNF content. Theoretical analyses on the physical properties are carried out by applying the existing models. Research results indicate that a common commercial plastic with good comprehensive performance, which exhibited the potential for applications in advanced electronics, was obtained by a simple industry benign technique

Liquid crystalline thermosetting polymers as protective coatings for aerospace

OpenAIRE

Guerriero, G.L.

2012-01-01

Environmental regulations are driving the development of new aerospace coating systems, mainly to eliminate chromates and reduce volatile organic compound (VOC) emissions. Among the various potential options for new coating materials, liquid crystalline polymers (LCPs) are attractive due to their unique combination of mechanical properties and chemical resistance. Their use, however, has been limited mainly due to poor adhesion properties. Thermotropic liquid crystalline thermosets displayed ...

Cross-Linked Liquid Crystalline Systems From Rigid Polymer Networks to Elastomers

CERN Document Server

Broer, Dirk

2011-01-01

With rapidly expanding interest in liquid crystalline polymers and elastomers among the liquid crystal community, researchers are currently exploring the wide range of possible application areas for these unique materials, including optical elements on displays, tunable lasers, strain gauges, micro-structures, and artificial muscles. Written by respected scientists from academia and industry around the world, who are not only active in the field but also well-known in more traditional areas of research, "Cross-Linked Liquid Crystalline Systems: From Rigid Polymer Networks to Elastomers&qu

Interest of neutron scattering for the investigation of liquid-crystalline polymers

International Nuclear Information System (INIS)

Noirez, L.

1994-01-01

Small-angle Neutron scattering is the unique method which allows the determination of polymer conformation in the bulk state. This method has been applied to several kinds of liquid crystalline polymers. Results concerning side-chain liquid-crystal polymer, main-chain liquid-crystal polymer and combined liquid-crystal polymers, are reported. It is shown that the polymer conformation is largely dependent on the insertion site of the liquid crystal molecule and of the structure of the meso-phase. (author). 11 refs

Liquid crystalline thermosetting polymers as protective coatings for aerospace

NARCIS (Netherlands)

Guerriero, G.L.

2012-01-01

Environmental regulations are driving the development of new aerospace coating systems, mainly to eliminate chromates and reduce volatile organic compound (VOC) emissions. Among the various potential options for new coating materials, liquid crystalline polymers (LCPs) are attractive due to their

Effect of molecular structure and thermal treatment on photooptical properties of photochromic azobenzene-containing polymers films

Czech Academy of Sciences Publication Activity Database

Bobrovsky, A.; Shibaev, V.; Bubnov, Alexej; Hamplová, Věra; Kašpar, Miroslav; Pociecha, D.; Glogarová, Milada

2011-01-01

Roč. 212, č. 4 (2011), s. 342-352 ISSN 1022-1352 R&D Projects: GA AV ČR IAA100100911; GA AV ČR(CZ) GA202/09/0047; GA MŠk(CZ) OC10006 Grant - others:Federal Agency for Science and Innovation , Russian Federation(RU) RFASI No 02.740.11.5166 Institutional research plan: CEZ:AV0Z10100520 Keywords : calorimetry * liquid-crystalline polymers (LCP) * monomers phase behavior * polysiloxanes Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.361, year: 2011 http://onlinelibrary.wiley.com/doi/10.1002/macp.201000534/pdf

Comparison of the Resistance to Bending Forces of the 4.5 LCP Plate-rod Construct and of 4.5 LCP Alone Applied to Segmental Femoral Defects in Miniature Pigs

Directory of Open Access Journals (Sweden)

Lucie Urbanová

2010-01-01

Full Text Available The study deals with the determination of mechanical properties, namely resistance to bending forces, of flexible buttress osteosynthesis using two different bone-implant constructs stabilizing experimental segmental femoral bone defects (segmental ostectomy in a miniature pig ex vivo model using 4.5 mm titanium LCP and a 3 mm intramedullary pin (“plate and rod” construct (PR-LCP, versus the 4.5 mm titanium LCP alone (A-LCP. The “plate and rod” fixation (PR-LCP of the segmental femoral defect is significantly more resistant (p in vivo experiments in the miniature pig to investigate bone defect healing after transplantation of mesenchymal stem cells in combination with biocompatible scaffolds.

Transient molecular orientation and rheology in flow aligning thermotropic liquid crystalline polymers

International Nuclear Information System (INIS)

Ugaz, Victor M.; Burghardt, Wesley R.; Zhou, Weijun; Kornfield, Julia A.

2001-01-01

Quantitative measurements of molecular orientation and rheology are reported for various transient shear flows of a nematic semiflexible copolyether. Unlike the case of lyotropic liquid crystalline polymers (LCPs), whose structure and rheology in shear are dominated by director tumbling, this material exhibits flow aligning behavior. The observed behavior is quite similar to that seen in a copolyester that we have recently studied [Ugaz and Burghardt (1998)], suggesting that flow aligning dynamics may predominate in main-chain thermotropes that incorporate significant chain flexibility. Since the flow aligning regime has received little attention in previous attempts to model the rheology of textured, polydomain LCPs, we attempt to determine whether available models are capable of predicting the orientation and stress response of this class of LCP. We first examine the predictions of the polydomain Ericksen model, an adaptation of Ericksen's transversely isotropic fluid model which accounts for the polydomain distribution of director orientation while neglecting distortional elasticity. This simple model captures a number of qualitative and quantitative features associated with the evolution of orientation and stress during shear flow inception, but cannot cope with reversing flows. To consider the possible role of distortional elasticity in the re-orientation dynamics upon reversal, we evaluate the mesoscopically averaged domain theory of Larson and Doi [Larson and Doi (1991)], which incorporates a phenomenological description of distortional elastic effects. To date, their approach to account for polydomain structure has only been applied to describe tumbling LCPs. We find that it captures the qualitative transient orientation response to flow reversals, but is less successful in describing the evolution of stresses. This is linked to the decoupling approximation adopted during the model's development. Finally, a modified polydomain Ericksen model is introduced

Helium leak testing the Westinghouse LCP coil

International Nuclear Information System (INIS)

Merritt, P.A.; Attaar, M.H.; Hordubay, T.D.

1983-01-01

The tests, equipment, and techniques used to check the Westinghouse LCP coil for coolant flow path integrity and helium leakage are unique in terms of test sensitivity and application. This paper will discuss the various types of helium leak testing done on the LCP coil as it enters different stages of manufacture. The emphasis will be on the degree of test sensitivity achieved under shop conditions, and what equipment, techniques and tooling are required to achieve this sensitivity (5.9 x 10 -8 scc/sec). Other topics that will be discussed are helium flow and pressure drop testing which is used to detect any restrictions in the flow paths, and the LCP final acceptance test which is the final leak test performed on the coil prior to its being sent for testing. The overall allowable leak rate for this coil is 5 x 10 -6 scc/sec. A general evaluation of helium leak testing experience are included

Roll-to-Roll printed large-area all-polymer solar cells with 5% efficiency based on a low crystallinity conjugated polymer blend

Science.gov (United States)

Gu, Xiaodan; Zhou, Yan; Gu, Kevin; Kurosawa, Tadanori; Yan, Hongping; Wang, Cheng; Toney, Micheal; Bao, Zhenan

The challenge of continuous printing in high efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution coated all-polymer bulk heterojunction (BHJ) solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, our results showed that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. We were able to continuously roll-to-roll slot die print large area all-polymer solar cells with power conversion efficiencies of 5%, with combined cell area up to 10 cm2. This is among the highest efficiencies realized with R2R coated active layer organic materials on flexible substrate. DOE BRIDGE sunshot program. Office of Naval Research.

Semi-crystalline photovoltaic polymers with siloxane-terminated hybrid side-chains

Institute of Scientific and Technical Information of China (English)

Yuxiang Li; Seyeong Song; Song Yi Park; Jin Young Kim; Han Young Woo

2017-01-01

Three types of semi-crystalline photovoltaic polymers were synthesized by incorporating a siloxane-terminated organic/inorganic hybrid side-chain and changing the number of fluorine substituents.A branch point away from a polymer main backbone in the siloxane-containing side-chains and the intra-and/or interchain noncovalent coulombic interactions enhance a chain planarity and facile interchain organization.The resulting polymers formed strongly agglomerated films with high roughness,suggesting strong intermolecular interactions.The optical band gap of ca.1.7 eV was measured for all polymers with a pronounced shoulder peak due to tight π-π stacking.With increasing the fluorine substituents,the frontier energy levels decreased and preferential face-on orientation was observed.The siloxane-terminated side-chains and fluorine substitution promoted the intermolecular packing,showing well resolved lamellar scatterings up to (300) for this series of polymers in the grazing incidence wide angle X-ray scattering measurements.The PPsiDTBT,PPsiDTFBT and PPsiDT2FBT devices showed a power conversion efficiency of 3.16％,4.40％ and 5.65％,respectively,by blending with PC71BM.Langevin-type bimolecular charge recombination was similar for three polymeric solar cells.The main loss in the photocurrent generation for PPsiDTBT:PC71BM was interpreted to originate from the trap assisted charge recombination by measuring light-intensity dependent short-circuit current density (Jsc) and open-circuit voltage (Voc).Our results provide a new insight into the rational selection of solubilizing substituents for optimizing crystalline interchain packing with appropriate miscibility with PC71BM for further optimizing polymer solar cells.

Liquid crystallinity in flexible and rigid rod polymers

International Nuclear Information System (INIS)

Pickett, Galen T.; Schweizer, Kenneth S.

2000-01-01

We apply an anisotropic version of the polymer reference interaction site model (PRISM) integral equation description of flexible polymers to analyze athermal liquid crystallinity. The polymers are characterized by a statistical segment length, σ o , and by a physical hard-core thickness, d, that prevents the overlap of monomers on different chains. At small segment densities, ρ, the microscopic length scale d is irrelevant (as it must be in the universal semidilute regime), but becomes important in concentrated solutions and melts. Under the influence of the excluded volume interactions alone, the chains undergo a lyotropic, first-order isotropic-nematic transition at a concentration dependent upon the dimensionless ''aspect ratio,'' σ o /d. The transition becomes weaker as d→0, becoming second order, as has been previously shown. We extend the theory to describe the transition of rigid, thin rods, and discuss the evolution of the anisotropic liquid structure in the ordered phase. (c) 2000 American Institute of Physics

Pathogenic Leptospira species acquire factor H and vitronectin via the surface protein LcpA.

Science.gov (United States)

da Silva, Ludmila Bezerra; Miragaia, Lidia Dos Santos; Breda, Leandro Carvalho Dantas; Abe, Cecilia Mari; Schmidt, Mariana Costa Braga; Moro, Ana Maria; Monaris, Denize; Conde, Jonas Nascimento; Józsi, Mihály; Isaac, Lourdes; Abreu, Patrícia Antônia Estima; Barbosa, Angela Silva

2015-03-01

Upon infection, pathogenic Leptospira species bind several complement regulators in order to overcome host innate immunity. We previously characterized a 20-kDa leptospiral surface protein which interacts with C4b binding protein (C4BP): leptospiral complement regulator-acquiring protein A (LcpA). Here we show that LcpA also interacts with human factor H (FH), which remains functionally active once bound to the protein. Antibodies directed against short consensus repeat 20 (SCR20) inhibited binding of FH to LcpA by approximately 90%, thus confirming that this particular domain is involved in the interaction. We have also shown for the first time that leptospires bind human vitronectin and that the interaction is mediated by LcpA. Coincubation with heparin blocked LcpA-vitronectin interaction in a dose-dependent manner, strongly suggesting that binding may occur through the heparin binding domains of vitronectin. LcpA also bound to the terminal pathway component C9 and inhibited Zn(2+)-induced polymerization and membrane attack complex (MAC) formation. Competitive binding assays indicated that LcpA interacts with C4BP, FH, and vitronectin through distinct sites. Taken together, our findings indicate that LcpA may play a role in leptospiral immune evasion. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Micromechanical modeling of the elasto-viscoplastic bahavior of semi-crystalline polymers

NARCIS (Netherlands)

Dommelen, van J.A.W.; Parks, D.M.; Boyce, M.C.; Brekelmans, W.A.M.; Baaijens, F.P.T.

2003-01-01

A micromechanically-based constitutive model for the elasto-viscoplastic deformationand texture evolution of semi-crystalline polymers is developed. The modelidealizes the microstructure to consist of an aggregate of two-phase layered compositeinclusions. A new framework for the composite inclusion

Temperature influence in crystallinity of polymer microspheres

International Nuclear Information System (INIS)

Rezende, Cristiane de P.; Novack, Katia M.

2011-01-01

Drug delivery technology is evolving through the creation of new techniques of drug delivery effectively. The new methods used in drugs administration are based in microencapsulation process. Microsphere encapsulation modifies drug delivery bringing benefits and efficiency. In this work has been evaluated the influence of temperature in microspheres preparation. Microspheres were obtained by PMMA-co-PEG (COP) copolymer with indomethacin inserted in polymer matrix. Samples were characterized by SEM, DSC and XRD. SEM micrographs confirmed the formation of different sizes of microspheres and it was verified that higher temperatures make more crystalline microspheres. (author)

The effect of calcining temperature on the properties of 0-3 piezoelectric composites of PZT and a liquid crystalline thermosetting polymer

NARCIS (Netherlands)

Ende, D.A. van den; Groen, W.A.; Zwaag, S. van der

2011-01-01

We report on the optimisation of a recently developed high performance 0-3 piezoelectric composite comprising of the piezoelectric Lead Zirconate Titanate (PZT) powder and a liquid crystalline thermosetting matrix polymer (LCT). The matrix polymer is a liquid crystalline polymer comprising of an

LCP- LIFETIME COST AND PERFORMANCE MODEL FOR DISTRIBUTED PHOTOVOLTAIC SYSTEMS

Science.gov (United States)

Borden, C. S.

1994-01-01

The Lifetime Cost and Performance (LCP) Model was developed to assist in the assessment of Photovoltaic (PV) system design options. LCP is a simulation of the performance, cost, and revenue streams associated with distributed PV power systems. LCP provides the user with substantial flexibility in specifying the technical and economic environment of the PV application. User-specified input parameters are available to describe PV system characteristics, site climatic conditions, utility purchase and sellback rate structures, discount and escalation rates, construction timing, and lifetime of the system. Such details as PV array orientation and tilt angle, PV module and balance-of-system performance attributes, and the mode of utility interconnection are user-specified. LCP assumes that the distributed PV system is utility grid interactive without dedicated electrical storage. In combination with a suitable economic model, LCP can provide an estimate of the expected net present worth of a PV system to the owner, as compared to electricity purchased from a utility grid. Similarly, LCP might be used to perform sensitivity analyses to identify those PV system parameters having significant impact on net worth. The user describes the PV system configuration to LCP via the basic electrical components. The module is the smallest entity in the PV system which is modeled. A PV module is defined in the simulation by its short circuit current, which varies over the system lifetime due to degradation and failure. Modules are wired in series to form a branch circuit. Bypass diodes are allowed between modules in the branch circuits. Branch circuits are then connected in parallel to form a bus. A collection of buses is connected in parallel to form an increment to capacity of the system. By choosing the appropriate series-parallel wiring design, the user can specify the current, voltage, and reliability characteristics of the system. LCP simulation of system performance is site

[Comparison of LCP and locked intramedullary nailing fixation in treatment of tibial diaphysis fractures].

Science.gov (United States)

Huang, Peng; Tang, Peifu; Yao, Qi

2007-11-01

To evaluate the treatment results of LCP and locked intramedullary nailing for tibial diaphysis fractures. From October 2003 to April 2006, 55 patients with tibial diaphysis fractures (58 fractures) were treated. Of them there were 39 males and 16 females with an average of 39 years years ( 14 to 62 years). The fractures were on the left side in 27 patients and on the right side in 31 patients (3 patients had bilateral involvement). Thirty-four fractures were treated by intramedullary nailing (intramedullary nailing group) and 24 fractures by LCP fixation (LCP group). The average disease course was 3 days (intramedullary nailing group) and 3.1 days (LCP group). The operation time, the range of motion of knee and ankle joints, fracture healing time, and complications were evaluated. The patients were followed up 8-26 months (13 months on average). The operation time was 84.0+/-9.2 min (intramedullary nailing group) and 69.0+/-8.4 min (LCP group); the average cost in hospital was yen 19,297.78 in the intramedullary nailing group and yen 14,116.55 in the LCP group respectively, showing significant differences (P 0.05). The doral flexion and plantar flexion of ankle joint were 13.0+/-1.7 degrees and 41.0+/-2.6 degrees in intramedullary nailing group, and 10.0+/-1.4 degrees and 44.0+/-2.3 degrees in LCP group, showing no significant differences (P>0.05). The mean healing time was 3.3 months in intramedullary nailing group, and 3. 1 months in LCP group. Length discrepancy occurred in 1 case (2.5 cm), delayed union in 1 case and nailing end trouble in 3 cases in intramedullary nailing group; moreover rotation deformity occurred 1 case and anterior knee pain occurred in 6 cases (17.1%). One angulation and open fracture developed osteomyelitis in 1 case 1 week postoperatively and angulation deformity occurred in 1 case of distal-third tibial fractures in LCP group. LCP and locked intramedullary nailing can achieve satisfactory results in treating tibial diaphysis fracture

Graphic Interface for LCP2 Optimization Program

DEFF Research Database (Denmark)

Nicolae, Taropa Laurentiu; Gaunholt, Hans

1998-01-01

This report provides information about the software interface that is programmed for the Optimization Program LCP2. The first part is about the general description of the program followed by a guide for using the interface. The last chapters contain a discussion about problems or futute extension...... of the project. The program is written in Visual C++5.0 on a Windows NT4.0 operating system.......This report provides information about the software interface that is programmed for the Optimization Program LCP2. The first part is about the general description of the program followed by a guide for using the interface. The last chapters contain a discussion about problems or futute extensions...

Selecting polymers for two-phase partitioning bioreactors (TPPBs): Consideration of thermodynamic affinity, crystallinity, and glass transition temperature.

Science.gov (United States)

Bacon, Stuart L; Peterson, Eric C; Daugulis, Andrew J; Parent, J Scott

2015-01-01

Two-phase partitioning bioreactor technology involves the use of a secondary immiscible phase to lower the concentration of cytotoxic solutes in the fermentation broth to subinhibitory levels. Although polymeric absorbents have attracted recent interest due to their low cost and biocompatibility, material selection requires the consideration of properties beyond those of small molecule absorbents (i.e., immiscible organic solvents). These include a polymer's (1) thermodynamic affinity for the target compound, (2) degree of crystallinity (wc ), and (3) glass transition temperature (Tg ). We have examined the capability of three thermodynamic models to predict the partition coefficient (PC) for n-butyric acid, a fermentation product, in 15 polymers. Whereas PC predictions for amorphous materials had an average absolute deviation (AAD) of ≥16%, predictions for semicrystalline polymers were less accurate (AAD ≥ 30%). Prediction errors were associated with uncertainties in determining the degree of crystallinity within a polymer and the effect of absorbed water on n-butyric acid partitioning. Further complications were found to arise for semicrystalline polymers, wherein strongly interacting solutes increased the polymer's absorptive capacity by actually dissolving the crystalline fraction. Finally, we determined that diffusion limitations may occur for polymers operating near their Tg , and that the Tg can be reduced by plasticization by water and/or solute. This study has demonstrated the impact of basic material properties that affects the performance of polymers as sequestering phases in TPPBs, and reflects the additional complexity of polymers that must be taken into account in material selection. © 2015 American Institute of Chemical Engineers.

Thermal degradation of polymer systems having liquid crystalline oligoester segment

Directory of Open Access Journals (Sweden)

Renato Matroniani

Full Text Available Abstract Block copolymers and blends comprised by liquid crystalline oligoester and polystyrene were prepared and their thermal stability were characterized by thermogravimetric analysis (TGA. The samples have shown three main decomposition temperatures due to (1 lost of flexible chain and decomposition of mesogenic segment, (2 decomposition of polystyrene and (3 final decomposition of oligoester rigid segment. Both copolymers and polymer blends presented lower thermal stability compared to polystyrene and oligoester. The residual mass after heating at 600 °C in copolymers and polymer blends were lower than those found in the oligoesters. A degradative process of aromatic segments of oligoester induced by decomposition of polystyrene is suggested.

A copper-based layered coordination polymer: synthesis, magnetic properties and electrochemical performance in supercapacitors.

Science.gov (United States)

Liu, Qi; Liu, Xiuxiu; Shi, Changdong; Zhang, Yanpeng; Feng, Xuejun; Cheng, Mei-Ling; Su, Seng; Gu, Jiande

2015-11-28

A copper-based layered coordination polymer ([Cu(hmt)(tfbdc)(H2O)]; hmt = hexamethylenetetramine, tfbdc = 2,3,5,6-tetrafluoroterephthalate; Cu-LCP) has been synthesized, and it has been structurally and magnetically characterized. The Cu-LCP shows ferromagnetic interactions between the adjacent copper(II) ions. Density functional theory calculations on the special model of Cu-LCP support the occurrence of ferromagnetic interactions. As an electrode material for supercapacitors, Cu-LCP exhibits a high specific capacitance of 1274 F g(-1) at a current density of 1 A g(-1) in 1 M LiOH electrolyte, and the capacitance retention is about 88% after 2000 cycles.

Properties analysis of tensile strength, crystallinity degree and microstructure of polymer composite polypropylene-sand

International Nuclear Information System (INIS)

Sudirman; Karo-Karo, Aloma; Ari-Handayani; Bambang-Sugeng; Rukihati; Mashuri

2004-01-01

Materials modification base on polymer toward polymer composite is needed by addition of filler. Mechanical properties such as tensile strength, crystallinity degree and microstructure of polymer composite based on polypropylene with sand filler have been investigated. In this work, the polymer composite has been made by mixing the matrix of polypropylene melt flow 2 (PP MF2) or polypropylene melt flow 10 (PP MF 10) with sand filler in a labo plastomill. The composition of sand filler was varied to 10, 30, 40 and 50 % v/v, a then the composite were casted to the film sheets form. The sheets were characterized mechanically i.e tensile strength, crystallinity degree and microstructure. The result showed that the tensile strength decreased by increasing the volume fraction of sand filler, in accordance with microstructure investigation that the matrix area under zone plastic deformation (more cracks), while the filler experienced elastic deformation, so that the strength mechanism of filler did not achieved with expectation (Danusso and Tieghi theory). For filler more than 30 % of volume fraction, the tensile strength of polypropylene melt flow 10 (PP MF 10) was greater than that polypropylene melt flow 2 (PP MF2). It was caused by plasticities in PP MF 10. The tensile strength of PP MF2 was greater than that PP MF 10 for volume fraction of sand filler less than 30 %. It was caused by PP MF2 to be have more degree of crystallinity

Effect of Polyamide 6 on Crystalline Structure of Polymer in PVDF-Nanoclay Nanocomposite

Directory of Open Access Journals (Sweden)

Ali Akbar Yousefi

2012-12-01

Full Text Available The  effect  of  nanocaly  on  crystalline  structure  of  poly(vinylidene  fuoride, PVDF, and the morphology of the resulting nano-composite were investigated using  different  characterization  techniques.  The  presence  of  3wt%  Cloisite 30B in PVDF matrix results in 11 fold increase in the percentage of beta crystalline content of the polymer. This was found to be attributed to the epitaxial effect of the clay  surface. The  beta  crystalline  content  of  the  pure  polymer  (6% was  raised  to 68% in the composite. Addition of 5wt% polyamide 6 (PA6 improved dispersion of nanoclay which led to augmentation of the viscosity and displacement of the crossover frequency of the compatibilized composite towards lower frequencies. However, due to stronger affnity of the PA6 towards organically modifed clay the epitaxial effect of  the  clay on  crystalline  structure of PVDF was  totally  eliminated. The  reduction of  viscosity  in  incompatibilized  nanocomposite was  attributed  to  reduced  number of PVDF chain entanglements  in  the presence of nanoclay. Meanwhile,  increase  in viscosity and displacement of crossover  frequency  towards  lower  frequencies were attributed to formation of clay-PA nanoparticles and PVDF-polyamide 6 interactions. It is expected that the presence of polyamide 6 promotes the formation of oriented-beta crystals in PVDF, which in turn improves the piezoelectric properties of the polymer.

Stilbene crystalline powder in polymer base as a new fast neutron detector

International Nuclear Information System (INIS)

Budakovsky, S.V.; Galunov, N.Z.; Grinyov, B.V.; Karavaeva, N.L.; Kyung Kim, Jong; Kim, Yong-Kyun; Pogorelova, N.V.; Tarasenko, O.A.

2007-01-01

A new organic scintillation material consisting of stilbene grains in a polymer glue base is presented. The crystalline grains of stilbene are obtained by mechanical grinding of stilbene single crystals. The resulting composite scintillators have been studied as detectors for fast neutrons

Histidine at Position 195 is Essential for Association of Heme-b in Lcp1VH2

Science.gov (United States)

Oetermann, Sylvia; Vivod, Robin; Hiessl, Sebastian; Hogeback, Jens; Holtkamp, Michael; Karst, Uwe; Steinbüchel, Alexander

2018-03-01

The latex clearing protein (Lcp) is the key enzyme of polyisoprene degradation in actinomycetes (Yikmis and Steinbüchel in Appl Environ Microbiol 78:4543-4551, https://doi.org/10.1128/AEM.00001-12, 2012). In this study it was shown that Lcp from Gordonia polyisoprenivorans VH2 (Lcp1VH2) harbors a non-covalently bound heme b as cofactor, which was identified by pyridine hemochrome spectra and confirmed by LC/ESI-ToF-MS. It contains iron, most likely in the Fe3+ state. We focused on the characterization of the heme-cofactor, its accessibility with respect to the conformation of Lcp1VH2, and the identification of putative histidine residues involved in the coordination of heme. A change was detectable in UV/Vis-spectra of reduced Lcp1VH2 when imidazole was added, showing that Lcp1VH2 "as isolated" occurs in an open state, directly being accessible for external ligands. In addition, three highly conserved histidines (H195, H200 and H228), presumably acting as ligands coordinating the heme within the heme pocket, were replaced with alanines by site-directed mutagenesis. The effect of these changes on in vivo rubber-mineralization was investigated. The lcp- deletion mutant complemented with the H195A variant of lcp1 VH2 was unable to mineralize poly(cis-1,4-isoprene). In vitro analyses of purified, recombinant Lcp1VH2H195A confirmed the loss of enzyme activity, which could be ascribed to the loss of heme. Hence, H195 is essential for the association of heme-b in the central region of Lcp1VH2.

Histidine at Position 195 is Essential for Association of Heme- b in Lcp1VH2

Science.gov (United States)

Oetermann, Sylvia; Vivod, Robin; Hiessl, Sebastian; Hogeback, Jens; Holtkamp, Michael; Karst, Uwe; Steinbüchel, Alexander

2018-05-01

The latex clearing protein (Lcp) is the key enzyme of polyisoprene degradation in actinomycetes (Yikmis and Steinbüchel in Appl Environ Microbiol 78:4543-4551, https://doi.org/10.1128/AEM.00001-12 , 2012). In this study it was shown that Lcp from Gordonia polyisoprenivorans VH2 (Lcp1VH2) harbors a non-covalently bound heme b as cofactor, which was identified by pyridine hemochrome spectra and confirmed by LC/ESI-ToF-MS. It contains iron, most likely in the Fe3+ state. We focused on the characterization of the heme-cofactor, its accessibility with respect to the conformation of Lcp1VH2, and the identification of putative histidine residues involved in the coordination of heme. A change was detectable in UV/Vis-spectra of reduced Lcp1VH2 when imidazole was added, showing that Lcp1VH2 "as isolated" occurs in an open state, directly being accessible for external ligands. In addition, three highly conserved histidines (H195, H200 and H228), presumably acting as ligands coordinating the heme within the heme pocket, were replaced with alanines by site-directed mutagenesis. The effect of these changes on in vivo rubber-mineralization was investigated. The lcp- deletion mutant complemented with the H195A variant of lcp1 VH2 was unable to mineralize poly( cis-1,4-isoprene). In vitro analyses of purified, recombinant Lcp1VH2H195A confirmed the loss of enzyme activity, which could be ascribed to the loss of heme. Hence, H195 is essential for the association of heme- b in the central region of Lcp1VH2.

Towards the understanding of the molecular weight dependence of essential work of fracture in semi-crystalline polymers: A study on poly(ε-caprolactone

Directory of Open Access Journals (Sweden)

F. Tuba

2014-11-01

Full Text Available The plane-stress ductile fracture of poly(#-caprolactone (PCL has been investigated as a function of molecular weight and related crystalline structure. Because of the interacting effects in semi-crystalline polymers a separate study of a given structural parameter is rather challenging. Nevertheless, this polymer seems to be a good model material to study the effect of molecular weight on the essential work of fracture, as the interactions between the separate parameters, at room temperature, are negligible. The molecular characteristics of PCL were determined by size exclusion chromatography. To confirm the entangled molecular structure of studied polymers rheological measurements were performed. The crystalline morphology has been characterized by differential scanning calorimetry and wide angle X-ray diffraction. Quasi-static tensile tests and essential work of fracture tests were performed to study the mechanical behavior. Based on the experimental observations an empirical model has been proposed to outline the molecular weight and crystallinity dependence of the essential work of fracture in this semi-crystalline polymer.

Liquid crystalline polymers IX Main chain thermotropic poly (azomethine – ethers containing thiazole moiety linked with polymethylene spacers

Directory of Open Access Journals (Sweden)

2007-04-01

Full Text Available A new homologous series of thermally stable thermotropic liquid crystalline poly(azomethine-ethers based on thiazole moiety were synthesized by solution polycondensation of 4,4`-diformyl-α,ω-diphenoxyalkanes, I–IV or 4,4`-diformyl-2,2`-dimethoxy-α,ω-diphenoxyalkanes V–VIII with the new bis(2-aminothiazole monomer X. A model compound XI was synthesized from X with benzaldehyde and characterized by elemental and spectral analyses. The inherent viscosities of the resulting polymers were in the range 0.43–1.34 dI/g. All the poly(azomethine-ethers were insoluble in common organic solvents but dissolved completely in concentrated H2SO4 and formic acid. The mesomorphic properties of these polymers were studied as a function of the diphenoxyalkane space length. Their thermotropic liquid crystalline properties were examined by DSC and optical polarizing microscopy and demonstrated that the resulting polymers form nematic mesophases over wide temperature ranges. The thermogravimetric analyses of those polymers were evaluated by TGA and DSC measurements and correlated to their structural units. X-ray analysis showed that polymers having some degree of crystallinity in the region 2θ = 5–60°. In addition, the morphological properties of selected examples were tested by scanning electron microscopy.

Demixing by a Nematic Mean Field: Coarse-Grained Simulations of Liquid Crystalline Polymers

Energy Technology Data Exchange (ETDEWEB)

Ramírez-Hernández, Abelardo; Hur, Su-Mi; Armas-Pérez, Julio; Cruz, Monica; de Pablo, Juan

2017-03-01

Liquid crystalline polymers exhibit a particular richness of behaviors that stems from their rigidity and their macromolecular nature. On the one hand, the orientational interaction between liquid-crystalline motifs promotes their alignment, thereby leading to the emergence of nematic phases. On the other hand, the large number of configurations associated with polymer chains favors formation of isotropic phases, with chain stiffness becoming the factor that tips the balance. In this work, a soft coarse-grained model is introduced to explore the interplay of chain stiffness, molecular weight and orientational coupling, and their role on the isotropic-nematic transition in homopolymer melts. We also study the structure of polymer mixtures composed of stiff and flexible polymeric molecules. We consider the effects of blend composition, persistence length, molecular weight and orientational coupling strength on the melt structure at the nano-and mesoscopic levels. Conditions are found where the systems separate into two phases, one isotropic and the other nematic. We confirm the existence of non-equilibrium states that exhibit sought-after percolating nematic domains, which are of interest for applications in organic photovoltaic and electronic devices.

Confined crystallization, crystalline phase deformation and their effects on the properties of crystalline polymers

Science.gov (United States)

Wang, Haopeng

With the recent advances in processing and catalyst technology, novel morphologies have been created in crystalline polymers and they are expected to substantially impact the properties. To reveal the structure-property relationships of some of these novel polymeric systems becomes the primary focus of this work. In the first part, using an innovative layer-multiplying coextrusion process to obtain assemblies with thousands of polymer nanolayers, dominating "in-plane" lamellar crystals were created when the confined poly(ethylene oxide) (PEO) layers were made progressively thinner. When the thickness was confined to 25 nanometers, the PEO crystallized as single, high-aspect-ratio lamellae that resembled single crystals. This crystallization habit imparted more than two orders of magnitude reduction in the gas permeability. The dramatic decrease in gas permeability was attributed to the reduced diffusion coefficient, because of the increase in gas diffusion path length through the in-plane lamellae. The temperature dependence of lamellar orientation and the crystallization kinetics in the confined nanolayers were also investigated. The novel olefinic block copolymer (OBC) studied in the second part consisted of long crystallizable sequences with low comonomer content alternating with rubbery amorphous blocks with high comonomer content. The crystallizable blocks formed lamellae that organized into space-filling spherulites even when the fraction of crystallizable block was so low that the crystallinity was only 7%. These unusual spherulites were highly elastic and recovered from strains as high as 300%. These "elastic spherulites" imparted higher strain recovery and temperature resistance than the conventional random copolymers that depend on isolated, fringed micellar-like crystals to provide the junctions for the elastomeric network. In the third part, positron annihilation lifetime spectroscopy (PALS) was used to obtain the temperature dependence of the free

Diffusion of Lithium Ions in Amorphous and Crystalline Poly(ethylene oxide)_3:LiCF_3SO_3 Polymer Electrolytes

International Nuclear Information System (INIS)

Xue, Sha; Liu, Yingdi; Li, Yaping; Teeters, Dale; Crunkleton, Daniel W.; Wang, Sanwu

2017-01-01

The PEO_3:LiCF_3SO_3 polymer electrolyte has attracted significant research due to high conductivity and enhanced stability in lithium polymer batteries. Most experimental studies have shown that amorphous PEO lithium salt electrolytes have higher conductivity than the crystalline ones. Other studies, however, have shown that crystalline PEO salt complexes can conduct ions. As a result, further theoretical investigations are warranted to help clarify the issue. In this work, we use density functional theory with the climbing image nudged elastic band method to investigate the atomic-scale mechanism of lithium ion transport in the polymer electrolytes. We also use density functional theory and ab initio molecular dynamics simulations to obtain the amorphous structure of PEO_3:LiCF_3SO_3. The diffusion pathways and activation energies of lithium ions in both crystalline and amorphous PEO_3:LiCF_3SO_3 are determined. In crystalline PEO_3:LiCF_3SO_3, the activation energy for the low-barrier diffusion pathway is approximately 1.0 eV. In the amorphous phase, the value is 0.6 eV. This result would support the experimental observation that amorphous PEO_3:LiCF_3SO_3 has higher ionic conductivity than the crystalline phase.

Study and modeling of heat transfer during the solidification of semi-crystalline polymers

Energy Technology Data Exchange (ETDEWEB)

Le Goff, R.; Poutot, G.; Delaunay, D. [Laboratoire de Thermocinetique de l' ecole polytechnique de l' universite de Nantes, UMR CNRS 6607, rue Christian Pauc, BP 50609 44306 Nantes cedex 3 (France); Fulchiron, R.; Koscher, E. [Laboratoire des Materiaux Polymeres et des Biomateriaux, IMP/UMR CNRS 5627, Universite Claude Bernard, Lyon 1, 69622 Villeurbanne Cedex (France)

2005-12-01

Semi-crystalline polymers are materials whose behavior during their cooling is difficult to model because of the strong coupling between the crystallization, heat transfer, pressure and shear. Thanks to two original apparatus we study solidification of such a polymer without shear. Firstly the comparison between experimental results and a numerical model will permit to validate crystallization kinetic for cooling rate reachable by DSC. The second experiment makes it possible to analyze solidification for high cooling rate, corresponding to some manufacturing processes. It appears that crystallization has an influence on the thermal contact resistance. (author)

Detection of radiation deformation in crystalline polymers using the speckle photography technique

International Nuclear Information System (INIS)

El-Ghandoor, H.; Hashem, A.A.; Sharaf, F.

1995-01-01

In order to measure the resulting deformation due to gamma irradiation of polymers, a new optical technique, namely speckle-photography, was established and used. Thin films of tetrafluoroethene, with constant thickness were irradiated by different doses of gamma rays and the diffraction patterns of a laser beam passing through these films were recorded using the speckle photography technique. This technique has been applied to detect the radiation deformation in (Teflon) TFE, which is a crystalline polymer. A diffraction pattern due to the TFE thin layer is obtained and superimposed on the interference pattern displaying the speckle pattern pairs recorded on the same emulsion. (author)

Langmuir-Blodgett films prepared from pre-formed cholestanic liquid-crystalline polymers

Energy Technology Data Exchange (ETDEWEB)

Tundo, P.; Hodge, P.; Valli, L.; Davis, F. (Venice Univ. (Italy). Dip. di Scienze Ambientali Lecce Univ. (Italy). Dip. di Scienza dei Materiali Manchester Univ. (United Kingdom). Dep. of Chemistry)

1992-01-01

A series of alternating copolymers of maleic anhydride and a-olefins functionalized through different alkyl chains with cholestanic groups were synthetised and derivatives prepared by reactions of the anhydride residues with methanol, water, dimethylamine and morpholine, respectively. The same starting functionalized a-olefins were used to prepare other suitable compounds in order to correlate the features of the liquid-crystalline behaviour of the mesogenic cholestanic group with the stability of the forthcoming polymeric or not polymeric Langmuir-Blodgett (LB) films. For some copolymers surface pressure against area per molecule isotherms are reported. In some multilayer (LB) films, the spacings between the layers were determined by the detection of BRAGG peaks by X-ray diffraction. The (LB) films of these polymers are closed packed, owing to either the polymeric skeleton or liquid-crystalline interaction.

Small Molecule Acceptor and Polymer Donor Crystallinity and Aggregation Effects on Microstructure Templating: Understanding Photovoltaic Response in Fullerene-Free Solar Cells

Energy Technology Data Exchange (ETDEWEB)

Eastham, Nicholas D.; Dudnik, Alexander S.; Aldrich, Thomas J.; Manley, Eric F.; Fauvell, Thomas J.; Hartnett, Patrick E.; Wasielewski, Michael R.; Chen, Lin X.; Melkonyan, Ferdinand S.; Facchetti, Antonio; Chang, Robert P. H.; Marks, Tobin J.

2017-05-10

Perylenediimide (PDI) small molecule acceptor (SMA) crystallinity and donor polymer aggregation and crystallinity effects on bulk-heterojunction microstructure and polymer solar cell (PSC) performance are systematically investigated. Two highperformance polymers, semicrystalline poly[5-(2-hexyldodecyl)-4Hthieno[3,4-c]pyrrole-4,6(5H)-dione-1,3-yl-alt-4,4''dodecyl-2,2':5',2''- terthiophene-5,5''-diyl] (PTPD3T or D1) and amorphous poly{4,8- bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene- 2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-2-carboxylate-2,6-diyl) (PBDTT-FTTE or D2), are paired with three PDI-based SMAs (A1-A3) of differing crystallinity (A1 is the most, A3 is the least crystalline). The resulting PSC performance trends are strikingly different from those of typical fullerene-based PSCs and are highly material-dependent. The present trends reflect synergistic aggregation propensities between the SMA and polymer components. Importantly, the active layer morphology is templated by the PDI in some blends and by the polymer in others, with the latter largely governed by the polymer aggregation. Thus, PTPD3T templating capacity increases as self-aggregation increases (greater Mn), optimizing PSC performance with A2, while A3-based cells exhibit an inverse relationship between polymer aggregation and performance, which is dramatically different from fullerene-based PSCs. For PBDTT-FTTE, A2-based cells again deliver the highest PCEs of ~5%, but here both A2 and PBDTT-FTTE (medium Mn) template the morphology. Overall, the present results underscore the importance of nonfullerene acceptor aggregation for optimizing PSC performance and offer guidelines for pairing SMAs with acceptable donor polymers.

Research and development activity in support of LCP

International Nuclear Information System (INIS)

Lubell, M.S.

1979-01-01

The research and development activity (RDAC) established in support of the Large Coil Program (LCP) at Oak Ridge National Laboratory (ORNL) is described. Some experimental results are presented and the importance of the RDAC to the magnet community is discussed

Semi-crystalline photovoltaic polymers with siloxane-terminated hybrid side-chains

Institute of Scientific and Technical Information of China (English)

Yuxiang Li; Seyeong Song; Song Yi Park; Jin Young Kim; Han Young Woo

2017-01-01

Three types of semi-cry stalline photovoltaic polymers were synthesized by incorporating a siloxane-terminated organic/inorganic hybrid side-chain and changing the number of fluorine substituents.A branch point away from a polymer main backbone in the siloxane-containing side-chains and the intra-and/or interchain noncovalent coulombic interactions enhance a chain planarity and facile interchain organization.The resulting polymers formed strongly agglomerated films with high roughness,suggesting strong intermolecular interactions.The optical band gap of ca.1.7 eV was measured for all polymers with a pronounced shoulder peak due to tight π-π stacking.With increasing the fluorine substituents,the frontier energy levels decreased and preferential face-on orientation was observed.The siloxane-terminated side-chains and fluorine substitution promoted the intermolecular packing,showing well resolved lamellar scatterings up to（300） for this series of polymers in the grazing incidence wide angle X-ray scattering measurements.The PPsiDTBT,PPsiDTFBT and PPsiDT2 FBT devices showed a power conversion efficiency of 3.16%,4.40%and 5.65%,respectively,by blending with PC71BM.Langevin-type bimolecular charge recombination was similar for three polymeric solar cells.The main loss in the photocurrent generation for PPsiDTBT:PC71BM was interpreted to originate from the trap assisted charge recombination by measuring light-intensity dependent short-circuit current density(JSC) and open-circuit voltage(VOc).Our results provide a new insight into the rational selection of solubilizing substituents for optimizing crystalline interchain packing with appropriate miscibility with PC71 BM for further optimizing polymer solar cells.

Effect of carbon derivatives in sulfonated poly(etherimide)-liquid crystal polymer composite for methanol vapor sensing

Science.gov (United States)

Bag, Souvik; Rathi, Keerti; Pal, Kaushik

2017-05-01

A class of highly sensitive chemiresistive sensors is developed for methanol (MeOH) vapor detection in ambient atmosphere by introducing conductive nanofillers like carbon black, multi-wall carbon nanotubes, and reduced graphene oxide into sulfonated poly(etherimide) (PEI)/liquid crystal polymer (LCP) composite (sPEI-LCP). Polar composites are prepared by a sulfonation process for instantaneous enhancement in adsorption capability of the sensing films to the target analyte (MeOH). Sensing properties exhibit that polymer composite-based fabricated sensors are efficient for the detection of different concentration of methanol vapor from 300-1200 parts-per-million (ppm) at room temperature. The incorporation of nanofiller induces the dramatic change in sensing behavior of base composite film (sPEI-LCP). Thus, less mass fraction of nanofillers (i.e. 2 wt%) influences the nonlinear sensing behavior for the entire range of methanol vapor. The simple method and low fabrication cost of the prepared sensor are compelling reasons that methanol vapor sensor is suitable for environmental monitoring.

Study of LCP based flexible patch antenna array

KAUST Repository

Ghaffar, Farhan A.; Shamim, Atif; Roy, Langis

2012-01-01

Wrapping of a two element LCP based patch antenna array is studied in this work. For the first time, the designed array is bent in both E and H planes to observe the effect on the radiation and impedance performance of the antenna. The 38 GHz

A new series of two-ring-based side chain liquid crystalline polymers: synthesis and mesophase characterization

CSIR Research Space (South Africa)

Reddy, GSM

2013-05-01

Full Text Available A new series of side chain liquid crystalline polymers containing a core, a butamethylenoxy spacer, ester groups, and terminal alkoxy groups were synthesised and their structures were confirmed. The core was constructed with two phenyl rings...

Pulse coil concepts for the LCP Facility

International Nuclear Information System (INIS)

Nelson, B.E.; Burn, P.B.

1977-01-01

The pulse coils described in this paper are resistive copper magnets driven by time-varying currents. They are included in the Large Coil Test Facility (LCTF) portion of the Large Coil Program (LCP) to simulate the pulsed field environment of the toroidal coils in a tokamak reactor. Since TNS (a 150 sec, 5MA, igniting tokamak) and the Oak Ridge EPR (Experimental Power Reactor) are representative of the first tokamaks to require the technology developed in LCP, the reference designs for these machines, especially TNS, are used to derive the magnetic criteria for the pulse coils. This criteria includes the magnitude, distribution, and rate of change of pulsed fields in the toroidal coil windings. Three pulse coil concepts are evaluated on the basis of magnetic criteria and factors such as versatility of design, ease of fabrication and cost of operation. The three concepts include (1) a pair of poloidal coils outside the LCTF torus, (2) a single poloidal coil threaded through the torus, and (3) a pair of vertical axis coil windings inside the bore of one or more of the toroidal test coils

Carbon/Liquid Crystal Polymer Prepreg for Cryogenic and High-Temp Applications, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — KaZaK Composites proposes to develop a pultrusion process to produce carbon fiber / liquid crystal polymer (LCP) prepreg, a first for this category of materials and...

Smectic order and backbone anisotropy of a side-chain liquid crystalline polymer by Small-Angle Neutron Scattering

Science.gov (United States)

Noirez, L.; Pépy, G.; Keller, P.; Benguigui, L.

1991-07-01

We have simultaneously measured, for the first time, the extension of the polymer backbone of a side-chain liquid crystalline polymer and the intensity of the 001 Bragg reflection, which gives the smectic order parameter Psi as a function of temperature in the smectic phase. We have qualitatively demonstrated that the more the smectic phase is ordered, the more the polymer backbone is localized between the mesogenic layers. It is shown that the Landau theory allows us to relate the radius of gyration parallel to the magnetic field of the polymer backbone to the smectic order parameter. We also show that the Renz-Warner theory is suitable at low temperatures.

Organic Field-Effect Transistors Based on a Liquid-Crystalline Polymeric Semiconductor using SU-8 Gate Dielectrics onFlexible Substrates.

Science.gov (United States)

Tetzner, Kornelius; Bose, Indranil R; Bock, Karlheinz

2014-10-29

In this work, the insulating properties of poly(4-vinylphenol) (PVP) and SU-8 (MicroChem, Westborough, MA, USA) dielectrics are analyzed and compared with each other. We further investigate the performance behavior of organic field-effect transistors based on a semiconducting liquid-crystal polymer (LCP) using both dielectric materials and evaluate the results regarding the processability. Due to the lower process temperature needed for the SU-8 deposition, the realization of organic transistors on flexible substrates is demonstrated showing comparable charge carrier mobilities to devices using PVP on glass. In addition, a µ-dispensing procedure of the LCP on SU-8 is presented, improving the switching behavior of the organic transistors, and the promising stability data of the SU-8/LCP stack are verified after storing the structures for 60 days in ambient air showing negligible irreversible degradation of the organic semiconductor.

3D lumped components and miniaturized bandpass filter in an ultra-thin M-LCP for SOP applications

KAUST Repository

Arabi, Eyad A.

2013-01-01

In this work, a library of 3D lumped components completely embedded in the thinnest, multilayer LCP (M-LCP) stack- up with four metallization layers and 100 μm of total thickness, is reported for the first time. A vertically and horizontally interdigitated capacitor, realized in this stack-up, provides higher self resonant frequency as compared to a similarly sized conventional parallel plate capacitor. Based on the above mentioned library, a miniaturized bandpass filter is presented for the GPS application. It utilizes mutually coupled inductors and is the smallest reported in the literature with a size of (0.035×0.028×0.00089)λg. Finally, the same filter realized in a competing ceramic technology (LTCC) is compared in performance with the ultra-thin M-LCP design. The M-LCP module presented in this work is inherently exible and offers great potential for wearable and conformal applications.

Organic Field-Effect Transistors Based on a Liquid-Crystalline Polymeric Semiconductor using SU-8 Gate Dielectrics onFlexible Substrates

Directory of Open Access Journals (Sweden)

Kornelius Tetzner

2014-10-01

Full Text Available In this work, the insulating properties of poly(4-vinylphenol (PVP and SU-8 (MicroChem, Westborough, MA, USA dielectrics are analyzed and compared with each other. We further investigate the performance behavior of organic field-effect transistors based on a semiconducting liquid-crystal polymer (LCP using both dielectric materials and evaluate the results regarding the processability. Due to the lower process temperature needed for the SU-8 deposition, the realization of organic transistors on flexible substrates is demonstrated showing comparable charge carrier mobilities to devices using PVP on glass. In addition, a µ-dispensing procedure of the LCP on SU-8 is presented, improving the switching behavior of the organic transistors, and the promising stability data of the SU-8/LCP stack are verified after storing the structures for 60 days in ambient air showing negligible irreversible degradation of the organic semiconductor.

Organic Field-Effect Transistors Based on a Liquid-Crystalline Polymeric Semiconductor using SU-8 Gate Dielectrics on Flexible Substrates

Science.gov (United States)

Tetzner, Kornelius; Bose, Indranil R.; Bock, Karlheinz

2014-01-01

In this work, the insulating properties of poly(4-vinylphenol) (PVP) and SU-8 (MicroChem, Westborough, MA, USA) dielectrics are analyzed and compared with each other. We further investigate the performance behavior of organic field-effect transistors based on a semiconducting liquid-crystal polymer (LCP) using both dielectric materials and evaluate the results regarding the processability. Due to the lower process temperature needed for the SU-8 deposition, the realization of organic transistors on flexible substrates is demonstrated showing comparable charge carrier mobilities to devices using PVP on glass. In addition, a µ-dispensing procedure of the LCP on SU-8 is presented, improving the switching behavior of the organic transistors, and the promising stability data of the SU-8/LCP stack are verified after storing the structures for 60 days in ambient air showing negligible irreversible degradation of the organic semiconductor. PMID:28788243

Bio-based liquid crystalline polyesters

Science.gov (United States)

Wilsens, Carolus; Rastogi, Sanjay; Dutch Collaboration

2013-03-01

The reported thin-film polymerization has been used as a screening method in order to find bio-based liquid crystalline polyesters with convenient melting temperatures for melt-processing purposes. An in depth study of the structural, morphological and chemical changes occurring during the ongoing polycondensation reactions of these polymers have been performed. Structural and conformational changes during polymerization for different compositions have been followed by time resolved X-ray and Infrared spectroscopy. In this study, bio-based monomers such as vanillic acid and 2,5-furandicarboxylic acid are successfully incorporated in liquid crystalline polyesters and it is shown that bio-based liquid crystalline polymers with high aromatic content and convenient processing temperatures can be synthesized. Special thanks to the Dutch Polymer Institute for financial support

Synthesis and characterization of organic-inorganic hybrids formed between conducting polymers and crystalline antimonic acid

Directory of Open Access Journals (Sweden)

Beleze Fábio A.

2001-01-01

Full Text Available In this paper we report the synthesis and characterization of novel organic-inorganic hybrid materials between the crystalline antimonic acid (CAA and two conductive polymers: polypyrrole and polyaniline. The hybrids were obtained by in situ oxidative polymerization of monomers by the Sb(V present in the pyrochlore-like CAA structure. The materials were characterized by infrared and Raman spectroscopy, X-ray diffraction, cyclic voltammetry, CHN elemental analysis and electronic paramagnetic resonance spectroscopy. The results showed that both polymers were formed in their oxidized form, with the CAA structure acting as a counter anion.

New theories for smectic and nematic liquid crystalline polymers

International Nuclear Information System (INIS)

Dowell, F.

1987-01-01

A summary of results from new statistical-physics theories for both backbone and side-chain liquid crystalline polymers (LCPs) and for mixtures with LCPs is presented. Thermodynamic and molecular ordering properties (including odd-even effects) have been calculated as a function of pressure, density, temperature, and molecule chemical structures (including degree of polymerization and the following properties of the chemical structures of the repeat units: lengths and shapes, intra-chain rotation energies, dipole moments, site-site polarizabilities and Lennard-Jones potentials, etc.) in nematic and multiple smectic-A LC phases and in the isotropic liquid phase. These theories can also be applied to combined LCPs. Since these theories have no ad hoc or arbitrarily adjustable parameters, these theories have been used to design new LCPs and new solvents and to predict and explain properties

Formation process of hierarchical structures in crystalline polymers as analyzed by simultaneous measurements of small-angle X-ray scattering and other techniques

International Nuclear Information System (INIS)

Yamamoto, Katsuhiro; Sakurai, Shinichi

2006-01-01

Crystalline polymers spontaneously form hierarchical structures, which provide us a potential use as a specialty material. Recently, not only a crystalline homopolymer but also semi-crystalline block copolymers and crystalline polymer blends have been attracting interests for the study of a hierarchical structure. In order to analyze such hierarchical structures in a variety of length scales, a simultaneous measurement of small-(SAXS) and wide-angle (WAXS) X-ray scattering with differential scanning calorimetry (DSC), or with small-angle light scattering (Hv-SALS) are most suitable. In this review, we show some examples of the simultaneous measurements. With DSC, exothermic heat flow can be simultaneously measured with X-ray scattering. On the other hand, with Hv-SALS it is possible to analyze evolution of a spherulitic structure, which is the structure at the highest rank in the hierarchy. For both cases, one can realize that it is impossible to obtain good statistics for SAXS and WAXS measurements without synchrotron radiations. (author)

Studies on the Synthesis,Characterization and Properties of the Reactive Thermotropic Liquid Crystalline Polymer

Institute of Scientific and Technical Information of China (English)

无

2007-01-01

1 Introduction Four species of reactive thermotropic liquid crystalline polymer (LCMC) with different relative molecular weight were synthesized in this work (see scheme 1, n=2, 6, 10, ∞.n means number of repeat structure unit). Their structure, morphology and properties were investigated systemically by differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), Wide-angle X-ray diffraction (WAXD), polarizing opticalmicroscopy (POM) and ubb...

PVD Silicon Carbide as a Thin Film Packaging Technology for Antennas on LCP Substrates for Harsh Environments

Science.gov (United States)

Scardelletti, Maximilian C.; Stanton, John W.; Ponchak, George E.; Jordan, Jennifer L.; Zorman, Christian A.

2010-01-01

This paper describes an effort to develop a thin film packaging technology for microfabricated planar antennas on polymeric substrates based on silicon carbide (SiC) films deposited by physical vapor deposition (PVD). The antennas are coplanar waveguide fed dual frequency folded slot antennas fabricated on liquid crystal polymer (LCP) substrates. The PVD SiC thin films were deposited directly onto the antennas by RF sputtering at room temperature at a chamber pressure of 30 mTorr and a power level of 300 W. The SiC film thickness is 450 nm. The return loss and radiation patterns were measured before and after the SiC-coated antennas were submerged into perchloric acid for 1 hour. No degradation in RF performance or physical integrity of the antenna was observed.

Synthesis of Isothianaphthene (ITN and 3,4-Ethylenedioxy-Thiophene (EDOT-Based Low-Bandgap Liquid Crystalline Conjugated Polymers

Directory of Open Access Journals (Sweden)

Hiromasa Goto

2013-05-01

Full Text Available Copolymers, consisting of isothianaphthene and phenylene derivatives with liquid crystal groups, were synthesized via Migita-Kosugi-Stille polycondensation reaction. IR absorption, UV-vis optical absorption, and PL spectroscopy measurements were carried out. Thermotropic liquid crystallinity of the polymers with bandgap of ~2.5 eV was confirmed.

Cost-effective computational method for radiation heat transfer in semi-crystalline polymers

Science.gov (United States)

Boztepe, Sinan; Gilblas, Rémi; de Almeida, Olivier; Le Maoult, Yannick; Schmidt, Fabrice

2018-05-01

This paper introduces a cost-effective numerical model for infrared (IR) heating of semi-crystalline polymers. For the numerical and experimental studies presented here semi-crystalline polyethylene (PE) was used. The optical properties of PE were experimentally analyzed under varying temperature and the obtained results were used as input in the numerical studies. The model was built based on optically homogeneous medium assumption whereas the strong variation in the thermo-optical properties of semi-crystalline PE under heating was taken into account. Thus, the change in the amount radiative energy absorbed by the PE medium was introduced in the model induced by its temperature-dependent thermo-optical properties. The computational study was carried out considering an iterative closed-loop computation, where the absorbed radiation was computed using an in-house developed radiation heat transfer algorithm -RAYHEAT- and the computed results was transferred into the commercial software -COMSOL Multiphysics- for solving transient heat transfer problem to predict temperature field. The predicted temperature field was used to iterate the thermo-optical properties of PE that varies under heating. In order to analyze the accuracy of the numerical model experimental analyses were carried out performing IR-thermographic measurements during the heating of the PE plate. The applicability of the model in terms of computational cost, number of numerical input and accuracy was highlighted.

Users Manual for the Program LCP2 (Version 2.40)

DEFF Research Database (Denmark)

Gaunholt, Hans

1996-01-01

LCP2 (Linear Circuit Program) is developed as an analysis and optimization tool to be used in the design of passive, active and digital filters with arbitrary structures. By the aid of an optimization loop the program may be used to solve nonlinear design equations for active filter structures or...

Treatment of type 2 and 4 olecranon fractures with locking compression plate (LCP) osteosynthesis in horses: a prospective study (2002-2008)

OpenAIRE

Jackson, M; Kummer, M; Auer, J; Hagen, R; Fürst, A

2011-01-01

This prospective study describes a series of 18 olecranon fractures in 16 horses that were treated with locking compression plates (LCP). Twelve of the 18 fractures were simple (type 2), whereas six were comminuted (type 4). Six fractures were open and 12 were closed. Each horse underwent LCP osteosynthesis consisting of open reduction and application of one or two LCP. Complete fracture healing was achieved in 13 horses. Three horses had to be euthanatized: two because of severe infection an...

Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template

KAUST Repository

Zhu, Jie

2014-02-12

Mesoporous zeolites are useful solid catalysts for conversion of bulky molecules because they offer fast mass transfer along with size and shape selectivity. We report here the successful synthesis of mesoporous aluminosilicate zeolite Beta from a commercial cationic polymer that acts as a dual-function template to generate zeolitic micropores and mesopores simultaneously. This is the first demonstration of a single nonsurfactant polymer acting as such a template. Using high-resolution electron microscopy and tomography, we discovered that the resulting material (Beta-MS) has abundant and highly interconnected mesopores. More importantly, we demonstrated using a three-dimensional electron diffraction technique that each Beta-MS particle is a single crystal, whereas most previously reported mesoporous zeolites are comprised of nanosized zeolitic grains with random orientations. The use of nonsurfactant templates is essential to gaining single-crystalline mesoporous zeolites. The single-crystalline nature endows Beta-MS with better hydrothermal stability compared with surfactant-derived mesoporous zeolite Beta. Beta-MS also exhibited remarkably higher catalytic activity than did conventional zeolite Beta in acid-catalyzed reactions involving large molecules. © 2014 American Chemical Society.

Improved model of activation energy absorption for different electrical breakdowns in semi-crystalline insulating polymers

Science.gov (United States)

Sima, Wenxia; Jiang, Xiongwei; Peng, Qingjun; Sun, Potao

2018-05-01

Electrical breakdown is an important physical phenomenon in electrical equipment and electronic devices. Many related models and theories of electrical breakdown have been proposed. However, a widely recognized understanding on the following phenomenon is still lacking: impulse breakdown strength which varies with waveform parameters, decrease in the breakdown strength of AC voltage with increasing frequency, and higher impulse breakdown strength than that of AC. In this work, an improved model of activation energy absorption for different electrical breakdowns in semi-crystalline insulating polymers is proposed based on the Harmonic oscillator model. Simulation and experimental results show that, the energy of trapped charges obtained from AC stress is higher than that of impulse voltage, and the absorbed activation energy increases with the increase in the electric field frequency. Meanwhile, the frequency-dependent relative dielectric constant ε r and dielectric loss tanδ also affect the absorption of activation energy. The absorbed activation energy and modified trap level synergistically determine the breakdown strength. The mechanism analysis of breakdown strength under various voltage waveforms is consistent with the experimental results. Therefore, the proposed model of activation energy absorption in the present work may provide a new possible method for analyzing and explaining the breakdown phenomenon in semi-crystalline insulating polymers.

Fuzzy set implementation for controlling and evaluation of factors affecting melting, crystallinity and interaction in polymer blends

International Nuclear Information System (INIS)

Al-Rawajfeh, Aiman Eid; Mamlook, Rustom

2008-01-01

In this study, the factors (i.e. weight fractions, crystallization temperatures and interaction such as hydrogen bonding) affecting melting, crystallinity, interaction parameters and miscibility of polymer blends (PB) have been studied by implementation of a fuzzy set. The interaction parameters were calculated using the Nishi-Wang equation, which is based on the Flory-Huggins theory. The values of interaction parameters χ 12 were negative for all blend compositions suggesting that χ 12 depends on the volume fraction (Φ) of the polymer. The various characteristics for the case study was synthesized and converted into relative weights w.r.t fuzzy set method. The fuzzy set analysis for the case study reveal increase as confirmed by the experimental data. The application of the fuzzy set methodology offers reasonable prediction and assessment for detecting yield in polymer blends

Identification of three homologous latex-clearing protein (lcp) genes from the genome of Streptomyces sp. strain CFMR 7.

Science.gov (United States)

Nanthini, Jayaram; Ong, Su Yean; Sudesh, Kumar

2017-09-10

Rubber materials have greatly contributed to human civilization. However, being a polymeric material does not decompose easily, it has caused huge environmental problems. On the other hand, only few bacteria are known to degrade rubber, with studies pertaining them being intensively focusing on the mechanism involved in microbial rubber degradation. The Streptomyces sp. strain CFMR 7, which was previously confirmed to possess rubber-degrading ability, was subjected to whole genome sequencing using the single molecule sequencing technology of the PacBio® RS II system. The genome was further analyzed and compared with previously reported rubber-degrading bacteria in order to identify the potential genes involved in rubber degradation. This led to the interesting discovery of three homologues of latex-clearing protein (Lcp) on the chromosome of this strain, which are probably responsible for rubber degrading activities. Genes encoding oxidoreductase α-subunit (oxiA) and oxidoreductase β-subunit (oxiB) were also found downstream of two lcp genes which are located adjacent to each other. In silico analysis reveals genes that have been identified to be involved in the microbial degradation of rubber in the Streptomyces sp. strain CFMR 7. This is the first whole genome sequence of a clear-zone-forming natural rubber- degrading Streptomyces sp., which harbours three Lcp homologous genes with the presence of oxiA and oxiB genes compared to the previously reported Gordonia polyisoprenivorans strain VH2 (with two Lcp homologous genes) and Nocardia nova SH22a (with only one Lcp gene). Copyright © 2017 Elsevier B.V. All rights reserved.

Mean-field theory of photoinduced molecular reorientation in azobenzene liquid crystalline side-chain polymers

DEFF Research Database (Denmark)

Pedersen, T.G.; Johansen, P.M.

1997-01-01

. The theory provides an explanation for the high long-term stability of the photoinduced anisotropy as well as a theoretical prediction of the temporal behavior of photoinduced birefringence. The theoretical results agree favorably with measurements in the entire range of writing intensities used......A novel mean-field theory of photoinduced reorientation and optical anisotropy in liquid crystalline side-chain polymers is presented and compared with experiments, The reorientation mechanism is based on photoinduced trans cis isomerization and a multidomain model of the material is introduced...

Crystallinity of Electrospun and Centrifugal Spun Polycaprolactone Fibers: A Comparative Study

Directory of Open Access Journals (Sweden)

Eva Kuzelova Kostakova

2017-01-01

Full Text Available Crystalline properties of semicrystalline polymers are very important parameters that can influence the application area. The internal structure, like the mentioned crystalline properties, of polymers can be influenced by the production technology itself and by changing technology parameters. The present work is devoted to testing of electrospun and centrifugal spun fibrous and nanofibrous materials and compare them to foils and granules made from the same raw polymer. The test setup reveals the structural differences caused by the production technology. Effects of average molecular weight are also exhibited. The applied biodegradable and biocompatible polymer is polycaprolactone (PCL as it is a widespread material for medical purposes. The crystallinity of PCL has significant effect on rate of degradation that is an important parameter for a biodegradable material and determines the applicability. The results of differential scanning calorimetry (DSC showed that, at the degree of crystallinity, there is a minor difference between the electrospun and centrifugal spun fibrous materials. However, the significant influence of polymer molecular weight was exhibited. The morphology of the fibrous materials, represented by fiber diameter, also did not demonstrate any connection to final measured crystallinity degree of the tested materials.

On the “Tertiary Structure” of Poly-Carbenes; Self-Assembly of sp3-Carbon-Based Polymers into Liquid-Crystalline Aggregates

NARCIS (Netherlands)

Franssen, N.G.M.; Ensing, B.; Hegde, M.; Dingemans, T.J.; Norder, B.; Picken, S.J.; Alberda van Ekenstein, G.O.R.; van Eck, E.R.H.; Elemans, J.A.A.W; Vis, M.; Reek, J.N.H.; de Bruin, B.

2013-01-01

The self-assembly of poly(ethylidene acetate) (st-PEA) into van der Waals-stabilized liquid-crystalline (LC) aggregates is reported. The LC behavior of these materials is unexpected, and unusual for flexible sp(3)-carbon backbone polymers. Although the dense packing of polar ester functionalities

Temperature influence in crystallinity of polymer microspheres; Influencia da temperatura na cristalinidade de microesferas polimericas

Energy Technology Data Exchange (ETDEWEB)

Rezende, Cristiane de P.; Novack, Katia M., E-mail: knovack@iceb.ufop.br [Universidade Federal de Ouro Preto - UFOP, ICEB, DEQUI, Ouro Preto, MG (Brazil)

2011-07-01

Drug delivery technology is evolving through the creation of new techniques of drug delivery effectively. The new methods used in drugs administration are based in microencapsulation process. Microsphere encapsulation modifies drug delivery bringing benefits and efficiency. In this work has been evaluated the influence of temperature in microspheres preparation. Microspheres were obtained by PMMA-co-PEG (COP) copolymer with indomethacin inserted in polymer matrix. Samples were characterized by SEM, DSC and XRD. SEM micrographs confirmed the formation of different sizes of microspheres and it was verified that higher temperatures make more crystalline microspheres. (author)

Graphene based strain sensor with LCP substrate

Science.gov (United States)

Nie, M.; Yang, H. S.; Xia, Y. H.

2018-02-01

A flexible strain sensor constructed by an efficient, low-cost fabrication strategy is presented in this paper. It is assembled by adhering grid-like graphene on LCP substrate. Kinds of measurement setup have been designed to verify that the proposed flexible sensor device is suitable to be used in health monitoring system. From the experiment results, it can be proved that the sensor exhibits the following features: ultra-light, relatively good sensitivity, high reversibility, superior physical robustness, easy fabrication. With the great performance of this flexible strain sensor, it is considered to play an important role in body monitoring, structural health monitoring system, fatigue detection and healthcare systems in the near future.

Structure-Property Relationships in Polymer Derived Amorphous/Nano-Crystalline Silicon Carbide for Nuclear Applications

International Nuclear Information System (INIS)

Zunjarrao, Suraj C.; Singh, Abhishek K.; Singh, Raman P.

2006-01-01

Silicon carbide (SiC) is a promising candidate for several applications in nuclear reactors owing to its high thermal conductivity, high melting temperature, good chemical stability, and resistance to swelling under heavy ion bombardment. However, fabricating SiC by traditional powder processing route generally requires very high temperatures for pressureless sintering. Polymer derived ceramic materials offer unique advantages such as ability to fabricate net shaped components, incorporate reinforcements and relatively low processing temperatures. Furthermore, for SiC based ceramics fabricated using polymer infiltration process (PIP), the microstructure can be tailored by controlling the processing parameters, to get an amorphous, nanocrystalline or crystalline SiC. In this work, fabrication of polymer derived amorphous and nano-grained SiC is presented and its application as an in-core material is explored. Monolithic SiC samples are fabricated by controlled pyrolysis of allyl-hydrido-poly-carbo-silane (AHPCS) under inert atmosphere. Chemical changes, phase transformations and microstructural changes occurring during the pyrolysis process are studied as a function of the processing temperature. Polymer cross-linking and polymer to ceramic conversion is studied using infrared spectroscopy (FTIR). Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) are performed to monitor the mass loss and phase change as a function of temperature. X-ray diffraction studies are done to study the intermediate phases and microstructural changes. Variation in density is carefully monitored as a function of processing temperature. Owing to shrinkage and gas evolution during pyrolysis, precursor derived ceramics are inherently porous and composite fabrication typically involves repeated cycles of polymer re-infiltration and pyrolysis. However, there is a limit to the densification that can be achieved by this method and porosity in the final materials presents

Liquid crystallinity driven highly aligned large graphene oxide composites

Energy Technology Data Exchange (ETDEWEB)

Lee, Kyung Eun; Oh, Jung Jae; Yun, Taeyeong [Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Daejeon 305-701 (Korea, Republic of); Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea, Republic of); Kim, Sang Ouk, E-mail: sangouk.kim@kaist.ac.kr [Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Daejeon 305-701 (Korea, Republic of); Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea, Republic of)

2015-04-15

Graphene is an emerging graphitic carbon materials, consisting of sp{sup 2} hybridized two dimensinal honeycomb structure. It has been widely studied to incorporate graphene with polymer to utilize unique property of graphene and reinforce electrical, mechanical and thermal property of polymer. In composite materials, orientation control of graphene significantly influences the property of composite. Until now, a few method has been developed for orientation control of graphene within polymer matrix. Here, we demonstrate facile fabrication of high aligned large graphene oxide (LGO) composites in polydimethylsiloxane (PDMS) matrix exploiting liquid crystallinity. Liquid crystalline aqueous dispersion of LGO is parallel oriented within flat confinement geometry. Freeze-drying of the aligned LGO dispersion and subsequent infiltration with PDMS produce highly aligned LGO/PDMS composites. Owing to the large shape anisotropy of LGO, liquid crystalline alignment occurred at low concentration of 2 mg/ml in aqueous dispersion, which leads to the 0.2 wt% LGO loaded composites. - Graphical abstract: Liquid crystalline LGO aqueous dispersions are spontaneous parallel aligned between geometric confinement for highly aligned LGO/polymer composite fabrication. - Highlights: • A simple fabrication method for highly aligned LGO/PDMS composites is proposed. • LGO aqueous dispersion shows nematic liquid crystalline phase at 0.8 mg/ml. • In nematic phase, LGO flakes are highly aligned by geometric confinement. • Infiltration of PDMS into freeze-dried LGO allows highly aligned LGO/PDMS composites.

Mathematical model of mechanical testing of bone-implant (4.5 mm LCP construct

Directory of Open Access Journals (Sweden)

Lucie Urbanová

2012-01-01

Full Text Available The study deals with the possibility of substituting time- and material-demanding mechanical testing of a bone defect fixation by mathematical modelling. Based on the mechanical model, a mathematical model of bone-implant construct stabilizing experimental segmental femoral bone defect (segmental ostectomy in a miniature pig ex vivo model using 4.5 mm titanium LCP was created. It was subsequently computer-loaded by forces acting parallel to the long axis of the construct. By the effect of the acting forces the displacement vector sum of individual construct points occurred. The greatest displacement was noted in the end segments of the bone in close proximity to ostectomy and in the area of the empty central plate hole (without screw at the level of the segmental bone defect. By studying the equivalent von Mises stress σEQV on LCP as part of the tested construct we found that the greatest changes of stress occur in the place of the empty central plate hole. The distribution of this strain was relatively symmetrical along both sides of the hole. The exceeding of the yield stress value and irreversible plastic deformations in this segment of LCP occurred at the acting of the force of 360 N. These findings are in line with the character of damage of the same construct loaded during its mechanic testing. We succeeded in creating a mathematical model of the bone-implant construct which may be further used for computer modelling of real loading of similar constructs chosen for fixation of bone defects in both experimental and clinical practice.

The importance of orientation in proton transport of a polymer film based on an oriented self-organized columnar liquid-crystalline polyether

Energy Technology Data Exchange (ETDEWEB)

Tylkowski, Bartosz; Castelao, Nuria [Departament d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paiesos Catalans, 26, E-43007, Tarragona (Spain); Giamberini, Marta, E-mail: marta.giamberini@urv.net [Departament d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paiesos Catalans, 26, E-43007, Tarragona (Spain); Garcia-Valls, Ricard [Departament d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paiesos Catalans, 26, E-43007, Tarragona (Spain); Reina, Jose Antonio [Departament de Quimica Analitica i Quimica Organica, Universitat Rovira i Virgili, Carrer Marcel.li Domingo s/n, E-43007, Tarragona (Spain); Gumi, Tania [Departament d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paiesos Catalans, 26, E-43007, Tarragona (Spain)

2012-02-01

We prepared membranes based on a liquid-crystalline side-chain polyether obtained by chemical modification of commercial poly(epichlorohydrin) (PECH) with dendrons. This polymer exhibited a columnar structure, which could form an ion channel in the inner part. The columns were successfully oriented by taking advantage of surface interactions between the polymer and hydrophilic substrates, as confirmed by X-ray diffraction analysis (XRD), environmental scanning electron microscopy (ESEM) and optical microscopy between crossed polars (POM). Column orientation was found to be crucial for effective transport: the oriented membranes exhibited proton transport comparable to that of Nafion Registered-Sign N117 and no water uptake. An increase in sodium ion concentration in the feed phase suggested a proton/cation antiport. On the contrary, no proton transport was detected on unoriented membranes based on the same liquid-crystalline side-chain polyether or on unmodified PECH. - Highlights: Black-Right-Pointing-Pointer We prepared oriented membranes based on a liquid crystalline columnar polyether. Black-Right-Pointing-Pointer In this structure, the inner polyether chain could work as an ion channel. Black-Right-Pointing-Pointer We obtained membranes by casting a chloroform solution in the presence of water. Black-Right-Pointing-Pointer Membranes showed good proton permeability due to the presence of oriented channels.

The importance of orientation in proton transport of a polymer film based on an oriented self-organized columnar liquid-crystalline polyether

International Nuclear Information System (INIS)

Tylkowski, Bartosz; Castelao, Nuria; Giamberini, Marta; Garcia-Valls, Ricard; Reina, José Antonio; Gumí, Tània

2012-01-01

We prepared membranes based on a liquid-crystalline side-chain polyether obtained by chemical modification of commercial poly(epichlorohydrin) (PECH) with dendrons. This polymer exhibited a columnar structure, which could form an ion channel in the inner part. The columns were successfully oriented by taking advantage of surface interactions between the polymer and hydrophilic substrates, as confirmed by X-ray diffraction analysis (XRD), environmental scanning electron microscopy (ESEM) and optical microscopy between crossed polars (POM). Column orientation was found to be crucial for effective transport: the oriented membranes exhibited proton transport comparable to that of Nafion® N117 and no water uptake. An increase in sodium ion concentration in the feed phase suggested a proton/cation antiport. On the contrary, no proton transport was detected on unoriented membranes based on the same liquid-crystalline side-chain polyether or on unmodified PECH. - Highlights: ► We prepared oriented membranes based on a liquid crystalline columnar polyether. ► In this structure, the inner polyether chain could work as an ion channel. ► We obtained membranes by casting a chloroform solution in the presence of water. ► Membranes showed good proton permeability due to the presence of oriented channels.

Study of the Transformations of Micro/Nano-crystalline Acetaminophen Polymorphs in Drug-Polymer Binary Mixtures.

Science.gov (United States)

Maniruzzaman, Mohammed; Lam, Matthew; Molina, Carlos; Nokhodchi, Ali

2017-07-01

This study elucidates the physical properties of sono-crystallised micro/nano-sized acetaminophen/paracetamol (PMOL) and monitors its possible transformation from polymorphic form I (monoclinic) to form II (orthorhombic). Hydrophilic Plasdone® S630 copovidone (S630), N-vinyl-2-pyrrolidone and vinyl acetate copolymer, and methacrylate-based cationic copolymer, Eudragit® EPO (EPO), were used as polymeric carriers to prepare drug/polymer binary mixtures. Commercially available PMOL was crystallised under ultra sound sonication to produce micro/nano-sized (0.2-10 microns) crystals in monoclinic form. Homogeneous binary blends of drug-polymer mixtures at various drug concentrations were obtained via a thorough mixing. The analysis conducted via the single X-ray crystallography determined the detailed structure of the crystallised PMOL in its monoclinic form. The solid state and the morphology analyses of the PMOL in the binary blends evaluated via differential scanning calorimetry (DSC), modulated temperature DSC (MTDSC), scanning electron microscopy (SEM) and hot stage microscopy (HSM) revealed the crystalline existence of the drug within the amorphous polymeric matrices. The application of temperature controlled X-ray diffraction (VTXRPD) to study the polymorphism of PMOL showed that the most stable form I (monoclinic) was altered to its less stable form II (orthorhombic) at high temperature (>112°C) in the binary blends regardless of the drug amount. Thus, VTXRD was used as a useful tool to monitor polymorphic transformations of crystalline drug (e.g. PMOL) to assess their thermal stability in terms of pharmaceutical product development and research.

Short-term supplementation of low-dose gamma-linolenic acid (GLA), alpha-linolenic acid (ALA), or GLA plus ALA does not augment LCP omega 3 status of Dutch vegans to an appreciable extent

NARCIS (Netherlands)

Fokkema, M R; Brouwer, D A; Hasperhoven, M B; Martini, I A; Muskiet, F A

Vegans do not consume meat and fish and have therefore low intakes of long chain polyunsaturated fatty acids (LCP). They may consequently have little negative feedback inhibition from dietary LCP on conversion of alpha -linolenic acid (ALA) to the LCP omega 3 eicosapentaenoic (EPA) and

Neutron scattering studies of molecular conformations in liquid crystal polymers

Science.gov (United States)

Noirez, L.; Moussa, F.; Cotton, J. P.; Keller, P.; Pépy, G.

1991-03-01

A comblike liquid crystal polymer (LPC) is a polymer on which mesogenic molecules have been grafted. It exhibits a succession of liquid crystal phases. Usually the equilibrium conformation of an ordinary polymeric chain corresponds to a maximum entropy, i.e., to an isotropic spherical coil. How does the backbone of a LCP behave in the nematic and smectic field? Small-angle neutron scattering may answer this question. Such measurements are presented here on four different polymers as a function of temperature. An anisotropy of the backbone conformation is found in all these studied compounds, much more pronounced in the smectic phase than in the nematic phase: the backbone spreads more or less perpendicularly to its hanging cores. A comparison with existing theories and a discussion of these results is outlined.

CO2 Sparging Proof of Concept Test Report, Revision 1, LCP Chemicals Site, Brunswick, Georgia

Science.gov (United States)

April 2013 report to evaluate the feasibility of CO2 sparging to remediate a sub-surface caustic brine pool (CBP) at the LCP Chemicals Superfund Site, GA. Region ID : 04, DocID: 10940639 , DocDate: 2013-04-01

Development of orodispersible polymer films with focus on the solid state characterization of crystalline loperamide.

Science.gov (United States)

Woertz, Christina; Kleinebudde, Peter

2015-08-01

The formulation of active pharmaceutical ingredients (API) as orodispersible films is gaining interest among novel oral drug delivery systems due to their small size, enhanced flexibility and improved patient compliance. The aim of this work was the preparation and characterization of orodispersible films containing loperamide hydrochloride (LPH) as model drug. As loperamide hydrochloride is poorly soluble in water it was used in crystalline form with a loading of 2mg/6cm(2) film. Hydroxypropyl methylcellulose (HPMC) and different types of hydroxypropyl cellulose (HPC) in different concentrations were used as film forming polymers whereas arabic gum, xanthan gum and tragacanth served as thickening agents. Films were characterized with respect to the content uniformity, morphology, thermal behavior and crystallinity. Suspensions were investigated regarding their viscosity using a rotational rheometer and the crystal structure of the Active Pharmaceutical Ingredient (API) was analyzed using polarized light microscopy. The development of flexible, non-brittle and homogeneous films of LPH was feasible. Two polymorphic forms of LPH appeared in the film formulations dependent on the utilized polymer. While in presence of HPMC the original polymorphic form I remained stable in suspension and films, the polymorphic form II occurred in presence of HPC. Both polymorphic forms were prepared separately and a solid state characterization was performed. Polymorph I showed isometric crystals whereas polymorph II showed needle shaped crystals. Tragacanth was able to prevent the transformation to polymorph II, if it was dissolved first before HPC. When HPC was added first to the suspension, the conversion to form II occurred irreversibly also after further addition of tragacanth. Copyright © 2015 Elsevier B.V. All rights reserved.

LCP method for a planar passive dynamic walker based on an event-driven scheme

Science.gov (United States)

Zheng, Xu-Dong; Wang, Qi

2018-06-01

The main purpose of this paper is to present a linear complementarity problem (LCP) method for a planar passive dynamic walker with round feet based on an event-driven scheme. The passive dynamic walker is treated as a planar multi-rigid-body system. The dynamic equations of the passive dynamic walker are obtained by using Lagrange's equations of the second kind. The normal forces and frictional forces acting on the feet of the passive walker are described based on a modified Hertz contact model and Coulomb's law of dry friction. The state transition problem of stick-slip between feet and floor is formulated as an LCP, which is solved with an event-driven scheme. Finally, to validate the methodology, four gaits of the walker are simulated: the stance leg neither slips nor bounces; the stance leg slips without bouncing; the stance leg bounces without slipping; the walker stands after walking several steps.

A fast Linear Complementarity Problem (LCP) solver for separating fluid-solid wall boundary Conditions

DEFF Research Database (Denmark)

Andersen, Michael; Abel, Sarah Maria Niebe; Erleben, Kenny

2017-01-01

We address the task of computing solutions for a separating fluid-solid wall boundary condition model. We present an embarrassingly parallel, easy to implement, fluid LCP solver.We are able to use greater domain sizes than previous works have shown, due to our new solver. The solver exploits matr...

Influence of the nematic order on the rheology and conformation of stretched comb-like liquid crystalline polymers

Science.gov (United States)

Fourmaux-Demange, V.; Brûlet, A.; Boué, F.; Davidson, P.; Keller, P.; Cotton, J. P.

2000-04-01

We have studied the rheology and the conformation of stretched comb-like liquid-crystalline polymers. Both the influence of the comb-like structure and the specific effect of the nematic interaction on the dynamics are investigated. For this purpose, two isomers of a comb-like polymetacrylate polymer, of well-defined molecular weights, were synthesized: one displays a nematic phase over a wide range of temperature, the other one has only an isotropic phase. Even with high degrees of polymerization N, between 40 and 1000, the polymer chains studied were not entangled. The stress-strain curves during the stretching and relaxation processes show differences between the isotropic and nematic comb-like polymers. They suggest that, in the nematic phase, the chain dynamics is more cooperative than for a usual linear polymer. Small-angle neutron scattering has been used in order to determine the evolution of the chain conformation after stretching, as a function of the duration of relaxation t_r. The conformation can be described with two parameters only: λ_p, the global deformation of the polymer chain, and p, the number of statistical units of locally relaxed sub-chains. For the comb-like polymer, the chain deformation is pseudo-affine: λ_p is always smaller than λ (the deformation ratio of the whole sample). In the isotropic phase, λ_p has a constant value, while p increases as t_r. This latter behavior is not that expected for non-entangled chains, in which p varies as {t_r}^{1/2} (Rouse model). In the nematic phase, λ_p decreases as a stretched exponential function of t_r, while p remains constant. The dynamics of the comb-like polymers is discussed in terms of living clusters from which junctions are produced by interactions between side chains. The nematic interaction increases the lifetime of these junctions and, strikingly, the relaxation is the same at all scales of the whole polymer chain.

Study of LCP based flexible patch antenna array

KAUST Repository

Ghaffar, Farhan A.

2012-07-01

Wrapping of a two element LCP based patch antenna array is studied in this work. For the first time, the designed array is bent in both E and H planes to observe the effect on the radiation and impedance performance of the antenna. The 38 GHz simulation results reveal better performance for H plane bending as compared to E plane bending. A 100 um thick substrate is used for the design which is best suited for flexible antenna applications. Gain variations of 1.1 dB and 1.4 dB are observed for the two orientations while a significantly increased impedance bandwidth of 3 % is obtained with H plane wrapping. The design is highly suitable for broadband micro-cellular backhaul applications. © 2012 IEEE.

LCP crystallization and X-ray diffraction analysis of VcmN, a MATE transporter from Vibrio cholerae

Energy Technology Data Exchange (ETDEWEB)

Kusakizako, Tsukasa [Graduate School of Science, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan); Tanaka, Yoshiki [Graduate School of Biological Sciences, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192 (Japan); Hipolito, Christopher J. [Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan); University of Tsukuba, 1-1-1 Tennodai, Tsukuba 305-8575 (Japan); Kuroda, Teruo [Graduate School of Biomedical and Health Sciences, Hiroshima University, 1-2-3 Kasumi, Minami-ku, Hiroshima 734-8553 (Japan); Ishitani, Ryuichiro [Graduate School of Science, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan); Suga, Hiroaki [Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan); Nureki, Osamu, E-mail: nureki@bs.s.u-tokyo.ac.jp [Graduate School of Science, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan)

2016-06-22

A V. cholerae MATE transporter was crystallized using the lipidic cubic phase (LCP) method. X-ray diffraction data sets were collected from single crystals obtained in a sandwich plate and a sitting-drop plate to resolutions of 2.5 and 2.2 Å, respectively. Multidrug and toxic compound extrusion (MATE) transporters, one of the multidrug exporter families, efflux xenobiotics towards the extracellular side of the membrane. Since MATE transporters expressed in bacterial pathogens contribute to multidrug resistance, they are important therapeutic targets. Here, a MATE-transporter homologue from Vibrio cholerae, VcmN, was overexpressed in Escherichia coli, purified and crystallized in lipidic cubic phase (LCP). X-ray diffraction data were collected to 2.5 Å resolution from a single crystal obtained in a sandwich plate. The crystal belonged to space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 52.3, b = 93.7, c = 100.2 Å. As a result of further LCP crystallization trials, crystals of larger size were obtained using sitting-drop plates. X-ray diffraction data were collected to 2.2 Å resolution from a single crystal obtained in a sitting-drop plate. The crystal belonged to space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 61.9, b = 91.8, c = 100.9 Å. The present work provides valuable insights into the atomic resolution structure determination of membrane transporters.

VA-LCP anterior clavicle plate: the anatomically precontoured fixation system with angular stability for clavicle shaft.

Science.gov (United States)

van Olden, G D J

2014-12-01

The aim of this investigation was to evaluate the introduction of the VA-LCP anterior clavicle plate in the treatment of clavicle fractures. From March 2011 to March 2013, 42 clavicle fractures were treated; 40 were middle-third and 2 lateral-third, and 13/42 (31 %) patients were treated due to painful nonunion. Patient age ranged from 16 to 81 years. Complications were screw placement through the AC-joint, one superficial wound infection and one neuropraxia of the nervus radialis with dropping hand. We had some difficulties prebending both lateral to low and lateral to high but without clinical consequences. In all cases, the fracture healed with full functionality. After 1 year, 4 patients underwent a removal of the hardware. The VA-LCP anterior plate showed good reliability and sufficient stability with both middle-third, lateral and nonunion fractures of the clavicle.

Enhancing the piezoelectric properties of flexible hybrid AlN materials using semi-crystalline parylene

Science.gov (United States)

Jackson, Nathan; Mathewson, Alan

2017-04-01

Flexible piezoelectric materials are desired for numerous applications including biomedical, wearable, and flexible electronics. However, most flexible piezoelectric materials are not compatible with CMOS fabrication technology, which is desired for most MEMS applications. This paper reports on the development of a hybrid flexible piezoelectric material consisting of aluminium nitride (AlN) and a semi-crystalline polymer substrate. Various types of semi-crystalline parylene and polyimide materials were investigated as the polymer substrate. The crystallinity and surfaces of the polymer substrates were modified by micro-roughening and annealing in order to determine the effects on the AlN quality. The AlN crystallinity and piezoelectric properties decreased when the polymer surfaces were treated with O2 plasma. However, increasing the crystallinity of the parylene substrate prior to deposition of AlN caused enhanced c-axis (002) AlN crystallinity and piezoelectric response of the AlN. Piezoelectric properties of 200 °C annealed parylene-N substrate resulted in an AlN d 33 value of 4.87 pm V-1 compared to 2.17 pm V-1 for AlN on polyimide and 4.0 pm V-1 for unannealed AlN/parylene-N. The electrical response measurements to an applied force demonstrated that the parylene/AlN hybrid material had higher V pp (0.918 V) than commercial flexible piezoelectric material (PVDF) (V pp 0.36 V). The results in this paper demonstrate that the piezoelectric properties of a flexible AlN hybrid material can be enhanced by increasing the crystallinity of the polymer substrate, and the enhanced properties can function better than previous flexible piezoelectrics.

A liquid crystal polymer membrane MEMS sensor for flow rate and flow direction sensing applications

International Nuclear Information System (INIS)

Kottapalli, A G P; Tan, C W; Olfatnia, M; Miao, J M; Barbastathis, G; Triantafyllou, M

2011-01-01

The paper reports the design, fabrication and experimental results of a liquid crystal polymer (LCP) membrane-based pressure sensor for flow rate and flow direction sensing applications. Elaborate experimental testing results demonstrating the sensors' performance as an airflow sensor have been illustrated and validated with theory. MEMS sensors using LCP as a membrane structural material show higher sensitivity and reliability over silicon counterparts. The developed device is highly robust for harsh environment applications such as atmospheric wind flow monitoring and underwater flow sensing. A simple, low-cost and repeatable fabrication scheme has been developed employing low temperatures. The main features of the sensor developed in this work are a LCP membrane with integrated thin film gold piezoresistors deposited on it. The sensor developed demonstrates a good sensitivity of 3.695 mV (ms −1 ) −1 , large operating range (0.1 to >10 ms −1 ) and good accuracy in measuring airflow with an average error of only 3.6% full-scale in comparison with theory. Various feasible applications of the developed sensor have been demonstrated with experimental results. The sensor was tested for two other applications—in clinical diagnosis for breath rate, breath velocity monitoring, and in underwater applications for object detection by sensing near-field spatial flow pressure

A PROSPECTIVE STUDY OF DISTAL TIBIAL FRACTURES BY MIPO (LCP

Directory of Open Access Journals (Sweden)

Chandra Sekharam Naidu

2015-05-01

contact . 9 MIPO promoted by AO group emphasis on indirect reduction, axial alignment and s table fixation without disturbing the fracture environment and thus preserving most of the vascularization and fracture haematoma, containing all necessary growth factors for bony healing. Technique of closed reduction and MIPPO with LCP has emerged as an alternative treatment option for distal dia - metaphyseal tibia fracture. When applied subcutaneously, LCP does not endanger periosteal blood supply, respect fracture heamtoma and also provides biomechanically stable construct. Several clinical studies have established MIPO with LCP as a biologically friendly and technically sound method of fixation for distal meta - diaphyseal tibial fracture.

QbD based approach for optimization of Tenofovir disoproxil fumarate loaded liquid crystal precursor with improved permeability

Directory of Open Access Journals (Sweden)

Sharvil Patil

2017-11-01

Full Text Available BCS class III drugs suffer from a drawback of low permeability even though they have high aqueous solubility. The objective of current work was to screen the suitability of glyceryl monooleate (GMO/Pluronic F127 cubic phase liquid crystals precursors for permeation enhancement and in turn the bioavailability of tenofovir disoproxil fumarate (TDF, a BCS class III drug. Spray-drying method was used for preparation of TDF loaded liquid crystal precursors (LCP consisting of GMO/Pluronic F127 and lactose monohydrate with an ability to in situ transform into stable cubic phases upon hydration. The quality by design (QbD approach (Factorial design was used for batch optimization. Spherical TDF loaded LCP as revealed by scanning electron microscopy photographs when hydrated and analyzed by small angle X-ray scattering confirmed formation of cubic phase. Differential scanning calorimetry and X-ray diffraction studies confirmed the molecular dispersion of TDF in polymer matrix and also suggested the conversion of TDF from crystalline to amorphous form. In vitro TDF release from prepared LCP showed controlled drug release over a period of 10 h. Further ex vivo studies revealed permeation enhancing activity of prepared LCP, which was highest when tested in presence of digestive enzyme extract. Thus, formulation of stable liquid crystal powder precursor can serve as an alternative for designing oral delivery system for drugs with low permeability.

Molecular Design for Preparation of Hexagonal-Ordered Porous Films Based on Side-chain Type Liquid-Crystalline Star Polymer.

Science.gov (United States)

Naka, Yumiko; Takayama, Hiromu; Koyama, Teruhisa; Le, Khoa V; Sasaki, Takeo

2018-05-02

Fabrication of regularly porous films by the breath-figure method has attracted much attention. The simple, low-cost technique uses the condensation of water droplets to produce these structures, but the phenomenon itself is complex, requiring control over many interacting parameters that change throughout the process. Developing a unified understanding for the molecular design of polymers to prepare ordered porous films is challenging, but required for further advancements. In this article, the effects of the chemical structure of polymers in the breath-figure technique were systematically explored using side-chain type liquid-crystalline (LC) star polymers. The formation of porous films was affected by the structure of the polymers. Although the entire film surface of poly(11-[4-(4-cyanobiphenyl)oxy]undecyl methacrylate) (P11CB) had a hexagonal ordered porous structure over a certain Mn value, regularly arranged holes did not easily form in poly(methyl methacrylate) (PMMA), even though the main chain of PMMA is similar to that of P11CB. Comparing P11CB and poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11B) (P11CB without cyano groups) showed that the local polar groups in hydrophobic polymers promoted the formation of ordered porous films. No holes formed in poly(4-cyanobiphenyl methacrylate) (P0CB) (P11CB without alkyl spacers) films due to its hydrophilicity. The introduction of alkyl chains in P0CB allowed the preparation of honeycomb-structured films by increasing the internal tension. However, alkyl chains in the side chain alone did not result in a porous structure, as in the case of poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11). Aromatic rings are also required to increase the Tg and improve film formability. In the present study, suitable molecular designs of polymers were found, specifically hydrophobic polymers with local polar groups, to form a regularly porous structure. Development of clear guidelines for the molecular

Chain confinement, phase transitions, and lamellar structure in semicrystalline polymers, polymer blends and polymer nanocomposites

Science.gov (United States)

Chen, Huipeng

Recent studies suggest that there are three phase fractions in semicrystalline polymers, the crystalline, the mobile amorphous and the rigid amorphous phases. Due to the distinct properties of the rigid amorphous fraction, RAF, it has been investigated for more than twenty years. In this thesis, a general method using quasi-isothermal temperature-modulated differential scaning calorimetry, DSC, is provided for the first time to obtain the temperature dependent RAF and the other two fractions, crystalline fraction and mobile amorphous fraction, MAF. For poly(ethylene terephthalate), PET, our results show RAF was vitrified during quasi-isothermal cooling after crystallization had been completed and became totally devitrified during quasi-isothermal heating before the start of melting. Several years after people initially discovered the existence of RAF, another issue arose relating to the physical location of RAF and mobile amorphous fraction, MAF, within a lamellar stack model. Two very different models to describe the location of RAF were proposed. In the Heterogeneous Stack Model, HET, RAF is located outside the lamellar stacks. In the Homogeneous Stack Model, HSM, RAF was located inside the lamellar stacks. To determine the lamellar structure of semicrystalline polymers comprising three phase, a general method is given in this thesis by using a combination of the DSC and small angle X-ray scattering, SAXS techniques. It has been applied to Nylon 6, isotactic polystyrene, iPS, and PET. It was found for all of these materials, the HSM model is correct to describe the lamellar structure. In addition to the determination of lamellar structures, this method can also provide the exact fraction of MAF inside and outside lamellar stacks for binary polymer blends. For binary polymer blends, MAF, normally is located partially inside and partially outside the lamellar stacks. However, the quantification of the MAF inside and outside the lamellar stacks has now been provided

The effect of modified ijuk fibers to crystallinity of polypropylene composite

Science.gov (United States)

Prabowo, I.; Nur Pratama, J.; Chalid, M.

2017-07-01

Nowadays, plastics becomes concern associated with its degradation and environmental issues. It has led studies to develop an environmental-friendly material. To minimize the impact of those problems, recently the usage of natural fibers as a filler are introduced because of biodegradability and availability. The promising natural fiber is “ijuk” fiber from Arenga pinnata plant as a filler and polypropylene (PP) polymer as a matrix. Unfortunately, the natural fibers and polymers have the different properties on which polymers are polar while natural fibers are non-polar so that reducing the compatibility and resulting the poor crystallinity. To enhance the compatibility and crystallinity, ijuk fibers were prepared by multistage treatments including alkalinization with 5 and 10% sodium hydroxide (NaOH), oxidation with 3 and 6% sodium hypochlorite (NaClO) and hydrolysis with 20% sulphuric acid (H2SO4) in sequences. The purposes of multistage treatments are to remove the components such as lignin, wax, hemicellulose, to cause an oxidative fragmentation of remaining lignin and to annihilate the amorphous parts respectively. Fourier-Transform Infrared (FTIR) confirms the compatibility meanwhile Differential Scanning Calorimetry (DSC) reveals the crystallinity and Scanning Electron Microscope (SEM) displays surface morphology of polypropylene. The experiments were revealing that the effects of “ijuk” fibers by the multistage treatments of 5 and 10% NaOH resulting the crystallinity of polypropylene around 31.2 and 27.64% respectively compared to the crystallinity before adding the “ijuk” fibers for 16.8%. It indicates that the entire treatments increasing the compatibility and crystallinity of polypropylene. In addition, the use of 5% NaOH offers the better crystallinity than non-treated polypropylene. The experiments conclude that by adding alkalinized “ijuk” fibers of multistage treatments can increase the compatibility and crystallinity of polypropylene.

Radhard optical patchcords and packaging for satellites using liquid crystal polymers

Science.gov (United States)

O'Riorden, S.; Mahapatra, A.

2017-11-01

There are many advantages to employing fiber optics for high capacity satellite communication. However, optical cables can be susceptible to high radiation, temperature extremes and vacuum environment. Any hardware used in these systems must be rugged, durable and immune to the detrimental effects of the aforementioned conditions. Standard COTS optical fiber will darken when exposed to high levels of radiation limiting the effectiveness of the communications system. Of particular concern to satellites in GEO are energetic electrons, bursts of heavy particles due to solar storms which can cause total dose and single event effects (SEE). Conventional fiber optic cables have several issues performing in high radiation environments. Linden has patented and developed a novel cable using an extruded layer of Liquid Crystal Polymer (LCP) applied to commercially available fiber. Total dose effects are minimized by shielding with Liquid Crystal Polymer jacketing. It is a simple, inexpensive way to increase the radiation shielding and mechanical performance of cables in satellites while concomitantly providing hermeticity and thus increased fatigue factor for optical glass. • LCPs exposed to 5000 Mrad dose of gamma rays retain in excess of 90% of their mechanical properties. • LCPs exposed to 1 Mrad radiation dose with energetic protons retain almost 100% of their mechanical strength. Tensile modulus increases with exposure to the radiation. • Weight for weight the proton absorbing power of LCP is 25% better than that of aluminum. We will present experimental data on radhard optical patchcords.

Crystallinity evaluation of polyhydroxybutyrate and polycaprolactone blends

International Nuclear Information System (INIS)

Cavalcante, Maxwell P.; Rodrigues, Elton Jorge R.; Tavares, Maria Ines B.

2015-01-01

Polyhydroxybutyrate, PHB, is a polymer obtained through bacterial or synthetic pathways. It has been used in the biomedical field as a matrix for drug delivery, medical implants and as scaffold material for tissue engineering. PHB has high structural organization, which makes it highly crystalline and brittle, making biodegradation difficult, reducing its employability. In order to enhance the mechanical and biological properties of PHB, blends with other polymers, biocompatible or not, are researched and produced. In this regard, blends of PHB and polycaprolactone, PCL, another biopolymer widely used in the biomedical industry, were obtained via solution casting and were characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and low field nuclear magnetic resonance (LF-NMR). Results have shown a dependence between PHB's crystallinity index and PCL quantity employed to obtain the blends.(author)

A quantitative correlation between the mobility and crystallinity of photo-cross-linkable P3HT

KAUST Repository

Woo, Claire; Piliego, Claudia; Holcombe, Thomas W.; Toney, Michael F.; Frechet, Jean

2012-01-01

The performance of polymer field effect transistors (FETs) can vary by orders of magnitude by applying different processing conditions. Although it is generally believed that a higher degree of crystallinity results in a higher mobility, the correlation is not straightforward. In addition, the effect of cross-linking on polymer thin film microstructural order is relatively unknown. This study investigates the effect of thermal annealing and UV-initiated photo-cross-linking on the FET performance and microstructural order of a photo-cross-linkable P3HT derivative. Our results demonstrate that while cross-linking did not disrupt the overall crystallinity of the polymer thin film, the photo-cross-linking process likely induced doping in the semiconductor layer, leading to the absence of saturation behavior in the FET. Annealing after cross-linking slightly improved the FET performance but only minimally affected the microstructural order of the polymer film since the 3D morphology had been "locked in" during the first cross-linking step. Importantly, annealing and cross-linking simultaneously was a successful method to preserve polymer crystallinity while also achieving effective cross-linking. Using newly developed quantitative X-ray analysis techniques, our study established a quantitative correlation between FET charge mobility and thin film crystallinity. © 2012 American Chemical Society.

A quantitative correlation between the mobility and crystallinity of photo-cross-linkable P3HT

KAUST Repository

Woo, Claire

2012-04-10

The performance of polymer field effect transistors (FETs) can vary by orders of magnitude by applying different processing conditions. Although it is generally believed that a higher degree of crystallinity results in a higher mobility, the correlation is not straightforward. In addition, the effect of cross-linking on polymer thin film microstructural order is relatively unknown. This study investigates the effect of thermal annealing and UV-initiated photo-cross-linking on the FET performance and microstructural order of a photo-cross-linkable P3HT derivative. Our results demonstrate that while cross-linking did not disrupt the overall crystallinity of the polymer thin film, the photo-cross-linking process likely induced doping in the semiconductor layer, leading to the absence of saturation behavior in the FET. Annealing after cross-linking slightly improved the FET performance but only minimally affected the microstructural order of the polymer film since the 3D morphology had been "locked in" during the first cross-linking step. Importantly, annealing and cross-linking simultaneously was a successful method to preserve polymer crystallinity while also achieving effective cross-linking. Using newly developed quantitative X-ray analysis techniques, our study established a quantitative correlation between FET charge mobility and thin film crystallinity. © 2012 American Chemical Society.

Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

Energy Technology Data Exchange (ETDEWEB)

Liu, Baoxia [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Huang, Yankai [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Zhu, Xu; Hao, Yuanqiang [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Ding, Yujie [College of Biochemical Engineering, Anhui Polytechnic University, Wuhu 241000 (China); Wei, Wei; Wang, Qi [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Qu, Peng, E-mail: qupeng0212@163.com [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Xu, Maotian, E-mail: xumaotian@sqnc.edu.cn [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China)

2016-03-17

Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg{sup 2+} detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb{sup 3+} from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg{sup 2+} into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg{sup 2+}. As a kind of Hg{sup 2+} nanosensor, the probe exhibited excellent selectivity for Hg{sup 2+} and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg{sup 2+} in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg{sup 2+} was achieved based on time-resolved spectroscopy.

Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

International Nuclear Information System (INIS)

Liu, Baoxia; Huang, Yankai; Zhu, Xu; Hao, Yuanqiang; Ding, Yujie; Wei, Wei; Wang, Qi; Qu, Peng; Xu, Maotian

2016-01-01

Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg"2"+ detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb"3"+ from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg"2"+ into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg"2"+. As a kind of Hg"2"+ nanosensor, the probe exhibited excellent selectivity for Hg"2"+ and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg"2"+ in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg"2"+ was achieved based on time-resolved spectroscopy.

Thermal characterization of semiconducting polymer bulk heterojunctions

Science.gov (United States)

Remy, Roddel A.

Polymer semiconductors are intriguing due to their potential use in flexible electronics. Poly (3-hexylthiophene) (P3HT)--a very common polymer in this field--is semicrystalline and it is known that crystalline P3HT has a higher hole mobility than amorphous P3HT. Quantifying each fraction in the bulk and thin film states is therefore crucial to understanding its performance in transistor and other applications. In polymer solar cells, it acts as an electron donor and is typically mixed with the nanoparticle-like molecule, phenyl-C61-butyric acid methyl ester (PCBM)--an electron acceptor--in a thin film morphology termed a bulk heterojunction (BHJ). The structural hierarchy within the bulk heterojunction is complicated and its characterization, with a focus on P3HT morphology, is the topic of this dissertation. Calorimetry can play an important role in the elucidation of P3HT morphology with quantitative analysis of the crystalline and amorphous fractions present in the material. This was demonstrated by employing differential scanning calorimetry (DSC) to obtain the enthalpy of fusion of 100% crystalline P3HT (42.9 J/g) using oligomeric P3HT measurements. The more sensitive temperature modulated DSC (TMDSC) was then used to examine the glass transition of P3HT and the crystalline, mobile amorphous and rigid amorphous phases were quantified. The presence of these phases can play a large role in understanding the charge transfer process in polymer semiconductors. BHJ thin films of 50 wt.% PCBM were then analyzed and a polymer crystallinity of 30% was found after thermal annealing from initially non-crystalline polymer material. With assistance from previously acquired small angle neutron scattering data, a thorough analysis of the entire BHJ morphology was accomplished. A surprisingly large rigid amorphous polymer phase is present in the BHJ which could be located at the P3HT/PCBM interface, affecting charge transfer. Finally, interlayer diffusion of PCBM was

NATO Advanced Research Workshop on Computational Methods for Polymers and Liquid Crystalline Polymers

CERN Document Server

Pasini, Paolo; Žumer, Slobodan; Computer Simulations of Liquid Crystals and Polymers

2005-01-01

Liquid crystals, polymers and polymer liquid crystals are soft condensed matter systems of major technological and scientific interest. An understanding of the macroscopic properties of these complex systems and of their many and interesting peculiarities at the molecular level can nowadays only be attained using computer simulations and statistical mechanical theories. Both in the Liquid Crystal and Polymer fields a considerable amount of simulation work has been done in the last few years with various classes of models at different special resolutions, ranging from atomistic to molecular and coarse-grained lattice models. Each of the two fields has developed its own set of tools and specialized procedures and the book aims to provide a state of the art review of the computer simulation studies of polymers and liquid crystals. This is of great importance in view of a potential cross-fertilization between these connected areas which is particularly apparent for a number of experimental systems like, e.g. poly...

Electro-optics of novel polymer-liquid crystalline composites

International Nuclear Information System (INIS)

Ibragimov, T.D.; Bayramov, G.M.; Imamaliyev, A.R.; Bayramov, G.M.

2014-01-01

The polymer network liquid crystals based on the liquid crystals H37 and 5CB with PMVP and PEG have been developed. Mesogene substance HOBA is served for stabilization of obtaining composites. Kinetics of network formation is investigated by methods of polarization microscopy and integrated small-angle scattering. It is shown that gel-like states of the composite H-37+PMVP+HOBA and 5CB+PEG+HOBA are formed at polymer concentration above 7 percent and 9 percent, correspondingly. The basic electro-optic parameters of the obtained composites are determined at room temperature. Experimental results are explained by phase separation of the system, diminution of a working area of electro-optical effects and influence of areas with high polymer concentration on areas with their low concentration

Development of a simulation tool to analyze the orientation of LCPs during extrusion process

Science.gov (United States)

Ahmadzadegan, Arash

In this thesis, different aspects of the rheology and directionality of the liquid crystalline polymers (LCPs) are investigated. The rheology of LCPs are modeled with different rheological models in different die geometries. The final goal in modeling the rheology and directionality of LCPs is to have a better understanding of their rheology during extrusion processing methods inside extrusion dies and eventually produce more isotropic films of LCPs. An attempt to design a die geometry that produces more isotropic films was made and it was shown that it is possible to use the inertia of the polymer to generate a more isotropic velocity profile at the lip of the die. This isotropic velocity profile can lead to alignment of directors along the streamlines and produce an isotropic film of LCP. It is shown that the rheological properties of the LCP should be altered to have a very low viscosity for this type of die to work. To be able to investigate the effect of processing on directionality of LCPs, it is essential to develop a method to simulate the directionality based on processing conditions. As a result, a user defined function (UDF) code was added to ANSYSRTM ~FLUENTRTM~ to simulate the directionality of LCPs. The rheology of the LCP is modeled using power-law fluid model and the consistency index (K) and power-law index (n) were estimated based on the experimental measurements done with capillary rheometry. Three main phenomena that affect the directionality namely effects of Franks elastic energy, the effect of shear and the effect of movement of crystals with the bulk of polymer are investigated. The results of this simulation are close to physical phenomena seen in real LCPs. To quantify the directionality of the LCPs, the order parameter of the domain were calculated and compared for different flow and fluid conditions. All polymers including LCPs are viscoelastic fluids in molten state. To understand the rheology of LCPs, a die-swell experiment was carried

Effect of gamma radiation on the structural and optical properties of Polyethyleneterephthalate (PET) polymer

International Nuclear Information System (INIS)

Siddhartha; Aarya, Suveda; Dev, Kapil; Raghuvanshi, Suresh Kumar; Krishna, J.B.M.; Wahab, M.A.

2012-01-01

Effect of 1.25 MeV gamma radiation on the structural and optical properties of virgin and gamma irradiated (0–2000 kGy) Polyethyleneterephthalate (PET) polymer samples are analyzed using powder X-ray diffractometer and UV–vis spectrophotometer. Diffraction pattern of PET polymer indicates the semi-crystalline in nature whereas the crystallinity increases with increasing dose of irradiation. The remarkable variation in crystallite size is also observed. The absorption and activation energy increase and the optical band gap (E g ) decreases with increasing dose in UV–vis studies. The existence of the maximum absorption, their shifting and broadening due to gamma irradiation in PET polymer are also discussed. - Highlights: ► PET is the transparent polymer and semi- crystalline. ► Crystallinity increases with increasing dose of irradiation of polymer. ► The remarkable variation in crystallite sizes was also observed in polymer. ► The absorption and activation energy increase and where as the optical band gap (E g ) decrease with increasing dose.

Elaboration of submicron structures on PEEK polymer by femtosecond laser

International Nuclear Information System (INIS)

Hammouti, S.; Beaugiraud, B.; Salvia, M.; Mauclair, C.; Pascale-Hamri, A.; Benayoun, S.; Valette, S.

2015-01-01

Highlights: • We compare PEEK polymer under two crystalline forms: semi-crystalline and amorphous. • We assess topographical modifications of surface morphologies after femtosecond laser irradiation. • At low laser energy regime, there is an influence of the crystallinity rate on topographical features of surface morphologies. • At high laser energy regime, the contribution of the crystallinity tends to disappear. - Abstract: In this work, laser parameters initiating the emergence of periodic structures, so-called ripples on poly (ether ether ketone) (PEEK) surfaces, are investigated. PEEK was used in its semi-crystalline and amorphous forms. Polymer surfaces were treated locally by performing a matrix of laser impacts to highlight the influence of the crystallinity in ultrashort laser interaction. Different surface morphologies or ripples were analyzed by atomic force microscopy and optical interferometry. A map of the presence of these different morphologies according to the laser fluence and the number of pulses was established. Analysis by optical interferometry was carried out and led to the calculations of ablation efficiency. Some significant differences were demonstrated between amorphous and semi-crystalline surfaces. This work revealed topographical information on the local behavior of the irradiated material. Finally, the crystallinity rate of polymer surface seems to be a determinant factor for the periodic nanostructured appearance

Elaboration of submicron structures on PEEK polymer by femtosecond laser

Energy Technology Data Exchange (ETDEWEB)

Hammouti, S., E-mail: sabrina.hammouti@ec-lyon.fr [LTDS, Ecole Centrale de Lyon, 36 Avenue Guy de Collongue, 69134 Ecully (France); Beaugiraud, B.; Salvia, M. [LTDS, Ecole Centrale de Lyon, 36 Avenue Guy de Collongue, 69134 Ecully (France); Mauclair, C. [LaHC, Université Jean Monnet, 18 rue du Professeur Benoît Lauras, 42000 Saint-Etienne (France); MANUTECH-USD, 20 rue du Professeur Benoît Lauras, 42000 Saint-Etienne (France); Pascale-Hamri, A. [MANUTECH-USD, 20 rue du Professeur Benoît Lauras, 42000 Saint-Etienne (France); Benayoun, S. [LTDS, Ecole Centrale de Lyon, 36 Avenue Guy de Collongue, 69134 Ecully (France); Valette, S. [LTDS, Ecole Centrale de Lyon, 36 Avenue Guy de Collongue, 69134 Ecully (France); MANUTECH-USD, 20 rue du Professeur Benoît Lauras, 42000 Saint-Etienne (France)

2015-02-01

Highlights: • We compare PEEK polymer under two crystalline forms: semi-crystalline and amorphous. • We assess topographical modifications of surface morphologies after femtosecond laser irradiation. • At low laser energy regime, there is an influence of the crystallinity rate on topographical features of surface morphologies. • At high laser energy regime, the contribution of the crystallinity tends to disappear. - Abstract: In this work, laser parameters initiating the emergence of periodic structures, so-called ripples on poly (ether ether ketone) (PEEK) surfaces, are investigated. PEEK was used in its semi-crystalline and amorphous forms. Polymer surfaces were treated locally by performing a matrix of laser impacts to highlight the influence of the crystallinity in ultrashort laser interaction. Different surface morphologies or ripples were analyzed by atomic force microscopy and optical interferometry. A map of the presence of these different morphologies according to the laser fluence and the number of pulses was established. Analysis by optical interferometry was carried out and led to the calculations of ablation efficiency. Some significant differences were demonstrated between amorphous and semi-crystalline surfaces. This work revealed topographical information on the local behavior of the irradiated material. Finally, the crystallinity rate of polymer surface seems to be a determinant factor for the periodic nanostructured appearance.

Biomass enzymatic saccharification is determined by the non-KOH-extractable wall polymer features that predominately affect cellulose crystallinity in corn.

Science.gov (United States)

Jia, Jun; Yu, Bin; Wu, Leiming; Wang, Hongwu; Wu, Zhiliang; Li, Ming; Huang, Pengyan; Feng, Shengqiu; Chen, Peng; Zheng, Yonglian; Peng, Liangcai

2014-01-01

Corn is a major food crop with enormous biomass residues for biofuel production. Due to cell wall recalcitrance, it becomes essential to identify the key factors of lignocellulose on biomass saccharification. In this study, we examined total 40 corn accessions that displayed a diverse cell wall composition. Correlation analysis showed that cellulose and lignin levels negatively affected biomass digestibility after NaOH pretreatments at pcorn samples indicated that cellulose and lignin should not be the major factors on biomass saccharification after pretreatments with NaOH and H2SO4 at three concentrations. Notably, despite that the non-KOH-extractable residues covered 12%-23% hemicelluloses and lignin of total biomass, their wall polymer features exhibited the predominant effects on biomass enzymatic hydrolysis including Ara substitution degree of xylan (reverse Xyl/Ara) and S/G ratio of lignin. Furthermore, the non-KOH-extractable polymer features could significantly affect lignocellulose crystallinity at pcorn.

A constitutive law for degrading bioresorbable polymers.

Science.gov (United States)

Samami, Hassan; Pan, Jingzhe

2016-06-01

This paper presents a constitutive law that predicts the changes in elastic moduli, Poisson's ratio and ultimate tensile strength of bioresorbable polymers due to biodegradation. During biodegradation, long polymer chains are cleaved by hydrolysis reaction. For semi-crystalline polymers, the chain scissions also lead to crystallisation. Treating each scission as a cavity and each new crystal as a solid inclusion, a degrading semi-crystalline polymer can be modelled as a continuum solid containing randomly distributed cavities and crystal inclusions. The effective elastic properties of a degrading polymer are calculated using existing theories for such solid and the tensile strength of the degrading polymer is predicted using scaling relations that were developed for porous materials. The theoretical model for elastic properties and the scaling law for strength form a complete constitutive relation for the degrading polymers. It is shown that the constitutive law can capture the trend of the experimental data in the literature for a range of biodegradable polymers fairly well. Copyright © 2016 Elsevier Ltd. All rights reserved.

New theories for smectic and nematic liquid-crystal polymers: Backbone LCPs [liquid crystalline polymers] and their mixtures and side-chain LCPs

International Nuclear Information System (INIS)

Dowell, F.

1987-01-01

A summary of predictions and explanations from statistical-physics theories for both backbone and side-chain liquid crystalline polymers (LCPs) and for mixtures with backbone LCPs are presented. Trends in the thermodynamic and molecular ordering properties have been calculated as a function of pressure, density, temperature, and molecule chemical structures (including degree of polymerization and the following properties of the chemical structures of the repeat units: lengths and shapes, intra-chain rotation energies, dipole moments, site-site polarizabilities and Lennard-Jones potentials, etc.) in nematic and multiple smectic-A LC phases and in the isotropic liquid phase. The theoretical results are found to be in good agreement with existing experimental data. These theories can also be applied to combined LCPs. Since these theories have no ad hoc or arbitrarily adjustable parameters, these theories can be used to design new LCPs and new solvents as well as to predict and explain properties. 27 refs., 4 tabs

Contact mechanics in glassy polymers

NARCIS (Netherlands)

Breemen, van L.C.A.

2009-01-01

Polymers, primarily semi-crystalline, are widely used in applications where low friction is required; examples are cups in artificial hip joints, bearings and gears. Until now there is no clear indication why some polymers display low friction and others don’t. In this thesis a systematic

Diketopyrrolopyrrole polymers for organic solar cells

NARCIS (Netherlands)

Li, Wei Wei; Hendriks, K.H.; Wienk, M.M.; Janssen, R.A.J.

2016-01-01

Conspectus 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

Structural Analysis of Aromatic Liquid Crystalline Polyesters

Directory of Open Access Journals (Sweden)

Arpad Somogyi

2011-01-01

Full Text Available Laboratory preparations of liquid crystalline prepolymers, distillates accompanying prepolymers, final polymers, and sublimates accompanying final polymers were examined. NaOD/D2O depolymerization of prepolymers and polymers back to monomers with integration of the 1H NMR spectra showed up to 6% excess of carboxyls over phenol groups, caused partly by loss of the low-boiling comonomer hydroquinone through distillation during prepolymerization and leaving anhydride units in the polymer chain. ESI− MS and MS/MS of hexafluoroisopropanol extracts of the prepolymer detected small molecules including some containing anhydride groups; ESI+ MS showed the presence of small cyclic oligomers. 1H NMR (including TOCSY spectra provided more quantitative analyses of these oligomers. The final polymerization increases the length of the polymer chains and sublimes out the small oligomers. Anhydride linkages remaining in the polymer must make LCP’s more susceptible to degradation by nucleophilic reagents such as water, alkalis, and amines.

Biomass Enzymatic Saccharification Is Determined by the Non-KOH-Extractable Wall Polymer Features That Predominately Affect Cellulose Crystallinity in Corn

Science.gov (United States)

Wu, Leiming; Wang, Hongwu; Wu, Zhiliang; Li, Ming; Huang, Pengyan; Feng, Shengqiu; Chen, Peng; Zheng, Yonglian; Peng, Liangcai

2014-01-01

Corn is a major food crop with enormous biomass residues for biofuel production. Due to cell wall recalcitrance, it becomes essential to identify the key factors of lignocellulose on biomass saccharification. In this study, we examined total 40 corn accessions that displayed a diverse cell wall composition. Correlation analysis showed that cellulose and lignin levels negatively affected biomass digestibility after NaOH pretreatments at pbiomass saccharification after pretreatments with NaOH and H2SO4 at three concentrations. Notably, despite that the non-KOH-extractable residues covered 12%–23% hemicelluloses and lignin of total biomass, their wall polymer features exhibited the predominant effects on biomass enzymatic hydrolysis including Ara substitution degree of xylan (reverse Xyl/Ara) and S/G ratio of lignin. Furthermore, the non-KOH-extractable polymer features could significantly affect lignocellulose crystallinity at pbiomass digestibility. Hence, this study could suggest an optimal approach for genetic modification of plant cell walls in bioenergy corn. PMID:25251456

Calcium carbonate interaction analysis in polypropylene compounds and their impact on the formation of beta crystalline phase of this polymer

International Nuclear Information System (INIS)

Sakahara, Rogerio M.; Hui, Wang S.

2011-01-01

The insertion of calcium carbonate (CaCO 3 ) in polypropylene compound is a thoroughly known technique widely studied in the academic area and in the industry. Its wide application is due, mainly, to increase mechanical properties with low manufacturing cost. These improvements in this polymer make it more versatile and competitive compared to other expensive polymers. In this study, the incorporation of four types of CaCO3 from the same manufacturer were compared and the focus was on the size of this mineral filler. Furthermore, it was analyzed the interaction of graphitized polypropylene with maleic anhydride (PP-g-MA) in the same samples. All these samples were analyzed by WAXS and SEM. The physical properties of tensile strength and impact were also analyzed. It was observed from this study that the smallest CaCO3 produced with PP-g-MA resulted in better physical properties with the formation of a crystalline phase beta, as originally studied by other authors using other raw materials. (author)

Ionic conductivity studies in crystalline PVA/NaAlg polymer blend electrolyte doped with alkali salt KCl

Science.gov (United States)

Sheela, T.; Bhajantri, R. F.; Ravindrachary, V.; Pujari, P. K.; Rathod, Sunil G.; Naik, Jagadish

2014-04-01

Potassium Chloride (KCl) doped poly(vinyl alcohol) (PVA)/sodium alginate (NaAlg) in 60:40 wt% polymer blend electrolytes were prepared by solution casting method. The complexation of KCl with host PVA/NaAlg blend is confirmed by FTIR and UV-Vis spectra. The XRD studies show that the crystallinity of the prepared blends increases with increase in doping. The dc conductivity increases with increase in dopant concentration. Temperature dependent dc conductivity shows an Arrhenius behavior. The dielectric properties show that both the dielectric constant and dielectric loss increases with increase in KCl doping concentration and decreases with frequency. The cole-cole plots show a decrease in bulk resistance, indicates the increase in ac conductivity, due to increase in charge carrier mobility. The doping of KCl enhances the mechanical properties of PVA/NaAlg, such as Young's modulus, tensile strength, stiffness.

Photo-responsive liquid crystalline epoxy networks with exchangeable disulfide bonds

Energy Technology Data Exchange (ETDEWEB)

Li, Yuzhan [Washington State Univ., Pullman, WA (United States); Zhang, Yuehong [Washington State Univ., Pullman, WA (United States); Rios, Orlando [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Keum, Jong K. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Kessler, Michael R. [Washington State Univ., Pullman, WA (United States); North Dakota State Univ., Fargo, ND (United States)

2017-07-27

The increasing demand for intelligent materials has driven the development of polymers with a variety of functionalities. However, combining multiple functionalities within one polymer is still challenging because of the difficulties encountered in coordinating different functional building blocks during fabrication. In this work, we demonstrate the fabrication of a multifunctional liquid crystalline epoxy network (LCEN) using the combination of thermotropic liquid crystals, photo-responsive azobenzene molecules, and exchangeable disulfide bonds. In addition to shape memory behavior enabled by the reversible liquid crystalline phase transition and photo-induced bending behavior resulting from the photo-responsive azobenzene molecules, the introduction of dynamic disulfide bonds into the LCEN resulted in a structurally dynamic network, allowing the reshaping, repairing, and recycling of the material.

The effect of the stretching of PLA extruded films on their crystallinity and gas barrier properties

Science.gov (United States)

Guinault, A.; Menary, G. H.; Courgneau, C.; Griffith, D.; Ducruet, V.; Miri, V.; Sollogoub, C.

2011-05-01

Driven by environmental concerns, new polymers based on renewable resources are arriving on the market to replace conventional polymers, obtained from petroleum, for different applications like food packaging. One of the most prominent polymers among these materials is poly(lactic acid) (PLA), a biodegradable, thermoplastic, aliphatic polyester derived from renewable resources, such as corn starch (in the USA) or sugarcanes (in the rest of the world). However this polymer presents different disadvantages and especially low gas barrier properties [1]. Thermal crystallization can be used to increase its gas barrier properties but long times are necessary [2] and are not compatible with an industrial process. Another way to increase the gas barrier properties consists in stretching the film in order to increase its crystallinity and so its diffusion coefficient. We have prepared stretched PLA films with different stretch ratio and we have studied the effect of the stretching parameters on the gas barrier properties of PLA films. Finally we compared this process with the isothermal crystallization process by taking into account the crystallinity degree and the crystalline morphology.

Strain hardening and anisotropy in solid polymers

NARCIS (Netherlands)

Senden, D.J.A.

2013-01-01

Mechanical properties of polymers strongly depend on the underlying microstructure. For instance, processing-induced molecular orientation may, in semi-crystalline polymers, lead to differences in lifetime up to a factor of 500 within a single injection molded product. Furthermore, enormous

Self-assembly of azobenzene based side-chain liquid crystalline ...

Indian Academy of Sciences (India)

The polymeric complexes acquitted as undivided liquid crystalline properties ... India) methanol and other solvents were purified by .... mixture was warmed to room temperature and stirred ... Polymer is soluble in DMF, CHCl3, CH2Cl2 and.

Absorbable and biodegradable polymers

CERN Document Server

Shalaby, Shalaby W

2003-01-01

INTRODUCTION NOTES: Absorbable/Biodegradable Polymers: Technology Evolution. DEVELOPMENT AND APPLICATIONOF NEW SYSTEMS: Segmented Copolyesters with Prolonged Strength Retention Profiles. Polyaxial Crystalline Fiber-Forming Copolyester. Polyethylene Glycol-Based Copolyesters. Cyanoacrylate-Based Systems as Tissue Adhesives. Chitosan-Based Systems. Hyaluronic Acid-Based Systems. DEVELOPMENTS IN PREPARATIVE, PROCESSING, AND EVALUATION METHODS: New Approaches to the Synthesis of Crystalline. Fiber-Forming Aliphatic Copolyesters. Advances in Morphological Development to Tailor the Performance of Me

A study of the effect of polystyrene sulfonation on the performance of terephthaloyl chloride-dihydroxydiphenyl sulfone copolymer/polystyrene system

Science.gov (United States)

Kahraman, R.; Kahn, K. A.; Ali, S. A.; Hamid, S. H.; Sahin, A. Z.

1998-12-01

Thermal, morphological, and mechanical properties of composites of a liquid crystalline copolymer (LCP) poly(terephthaloyl chloride)-co-(p,p’-dihydroxydiphenyl sulfone) with polystyrene (PS) and sulfonated polystyrene (SPS) are presented and discussed. Sulfonation of polystyrene was expected to improve the interfacial adhesion by introducing hydrogen bonding in the LCP/PS system. The degree of sulfonation was 11 %. The incompatibility (lack of proper interfacial adhesion) of the LCP/PS system resulted in sharp decrease in the composite tensile strength with LCP addition. The performance of the system did not change when processed at a higher temperature (270 °C instead of 225 °C). While a composite plate of 25% LCP/PS could not be fabricated, it was possible for LCP/SPS (processed at 215 °C), indicating some improvement in interfacial bonding by sulfonation. Sulfonation of PS resulted in fracture with some degree of plastic deformation for pure SPS matrix and also the LCP/SPS system with the lowest LCP content (1 wt%), whereas plastic deformation was not observed for PS used as received. The strength of the LCP/SPS system also decreased with increase in LCP content, indicating that 11% sulfonation is not sufficient to introduce significant compatibility, but it was not as dramatic as that for LCP/PS. The performance of the LCP/SPS system was not affected significantly by heat treatment at the process temperature.

Introduction of chemical, physical and mechanical coupling in the study of the blistering phenomena for semi-crystalline polymers; Une approche multiphysique de l'endommagement de polymeres en milieu petrolier: exemple du blistering

Energy Technology Data Exchange (ETDEWEB)

Cangemi, L.; Klopffer, M.H.; Martin, J. [Institut Francais du Petrole (IFP), 92 - Rueil-Malmaison (France); Grandidier, J.C. [Poitiers Univ., Lab. de Mecanique et de Physique des Materiaux, UMR 6617 CNRS, ENSMA, 86 (France)

2005-09-01

Polymer materials are used in numerous oil applications where the knowledge and the control of their barrier properties are required: thermosetting coatings, rubber seals, thermoplastic liners. In that case, thermoplastic materials are in contact with water, hydrocarbons, gases and all carried fluids at high temperature and high pressure (up to 13 deg C and to 100 MPa). Under these extreme conditions, gases contained in petroleum products (such as H{sub 2}S, CO{sub 2}) have a high tendency to dissolve into semi-crystalline polymers (polyolefins, fluorinated polymers). A decompression, i.e. a rupture of the thermodynamic equilibrium may eventually lead to gas concentration and temperature gradients in the polymer structures. The resulting damaging phenomenon is called blistering and can be really dramatic for the material because it is irreversible and may end the pipe leak-proofness. As a matter of fact, the condition of damage is mainly correlated to the temperature, the rate of decompression and the properties of the material. Thereby, it is important to have an accurate knowledge of all the involved phenomena in order to quantify and then predict the barrier properties of the materials in those aggressive conditions. The aim of this study is to identify the various mechanism involved in the blistering phenomena for semi-crystalline polymers (such as PVF2, PE), to establish some relations between the polymer microstructure (morphology), its mechanical properties and the damage and to build physicochemical models which will take into account some mechanical, thermal and diffusional aspects. (authors)

Perfluorinated polymer grafting: influence of preirradiation conditions

International Nuclear Information System (INIS)

Moura, E.; Somessari, E.S.R.; Silveira, C.G.; Paes, H.A.; Sousa, C.A.; Fernandes, W.; Manzoli, J.E; Geraldo, A.B.; Cardozo, P.

2009-01-01

The technological interest of perfluorinated polymers is related to its specific properties like low chemical reactivity and high mechanical and temperature resistance. The development of polymeric membranes for PEM fuel cell dispositives requires beyond these characteristics, a long-life time performance and low cost compared to Nafion membranes. By these material have high crystallinity, the radiation grafting indeed occurs but this process generate a low mechanical resistance aggregate. In this way, it is necessary to render the polymer with a low crystallinity or even amorphous. Generally, irradiation under polymer melt temperatures makes the crystallinity breaking and polymer crosslinking. The main objective of this work was promoting the crosslinking process into perfluorinated polymers by pre-irradiation method and to precede styrene grafting by electron beam irradiation in a second step. The experimental methodology consists in pre-irradiate perfluorinated polymers films like PTFE and PFA under high temperature (> 300 deg C) and vacuum conditions by electron beam irradiation at 5 kGy to 30 kGy doses and 2,85 kGy/s to 22,4 kGy/s dose rates. To obtain temperatures above 300 deg C, it was necessary construct a vacuum chamber with a heating system where temperature process could be follow up in real time. Some molecular alterations in polymeric matrix were analyzed by Mid-ATR-FTIR spectroscopy; macroscopic changes are verified by gravimetry. The styrene grafting onto these samples is realized by electron beam irradiation at doses between 30 and 100 kGy. These results are discussed. (author)

Molecular and supramolecular orientation in conducting polymers

International Nuclear Information System (INIS)

Aldissi, M.

1987-01-01

Intrinsic anisotropy in electrical and optical properties of conducting polymers constitutes a unique aspect that derives π-electron delocalization along the polymer backbone and from the weak inter-chain interaction. To acquire such an intrinsic property, conducting polymers have to be oriented macroscopically and microscopically (at the chain level). A review of the various techniques, including stretch-alignment of the polymer and of precursor polymers, polymerization in ordered media, i.e., in a liquid crystal solvent, and synthesis of liquid crystalline conducting polymers will be given. 29 refs

Synthesis and characterization of semi-crystalline polyarylene ether nitrile with AIEE feature

Science.gov (United States)

Wang, Pan; Li, Kui; Jia, Kun; Liu, Xiaobo

2017-12-01

An AIEgen 1, 2-di (4-hydroxyphenyl)-1, 2-diphenylethene (TPE-2OH) was introduced into the back bone of semi-crystalline poly arylene ether nitriles (PEN). The fluorescence spectra results indicated that the derived polymer displayed a typical aggregation-induced emission enhancement (AIEE) active with an emitting peak at ∼470 nm. Then the AIEE active PEN was prepared into films through casting method and realised strong fluorescence emission and excellent mechanics properties. Besides, the crystal AIEE active polymer shows sphere micro-morphology along with a strong blue emission. These findings will open a door for further research on the high performance semi-crystalline PEN at flexible display technology and optical sensors.

Microinjection molding of thermoplastic polymers: morphological comparison with conventional injection molding

International Nuclear Information System (INIS)

Giboz, Julien; Mélé, Patrice; Copponnex, Thierry

2009-01-01

The skin–core crystalline morphology of injection-molded semi-crystalline polymers is well documented in the scientific literature. The thermomechanical environment provokes temperature and shear gradients throughout the entire thickness of the part during molding, thus influencing the polymer crystallization. Crystalline morphologies of a high-density polyethylene (HDPE) micromolded part (μpart) and a classical part (macropart) are compared with optical, thermal and x-ray diffraction analyses. Results show that the crystalline morphologies with regard to thickness vary between the two parts. While a 'skin–core' morphology is present for the macropart, the μpart exhibits a specific 'core-free' morphology, i.e. no spherulite is present at the center of the thickness. This result seems to be generated under the specific conditions used in microinjection molding that lead to the formation of smaller and more oriented crystalline entities

Crystallization of Polymers Investigated by Temperature-Modulated DSC

Directory of Open Access Journals (Sweden)

Maria Cristina Righetti

2017-04-01

Full Text Available The aim of this review is to summarize studies conducted by temperature-modulated differential scanning calorimetry (TMDSC on polymer crystallization. This technique can provide several advantages for the analysis of polymers with respect to conventional differential scanning calorimetry. Crystallizations conducted by TMDSC in different experimental conditions are analysed and discussed, in order to illustrate the type of information that can be deduced. Isothermal and non-isothermal crystallizations upon heating and cooling are examined separately, together with the relevant mathematical treatments that allow the evolution of the crystalline, mobile amorphous and rigid amorphous fractions to be determined. The phenomena of ‘reversing’ and ‘reversible‘ melting are explicated through the analysis of the thermal response of various semi-crystalline polymers to temperature modulation.

Prediction and design of first super-strong liquid-crystalline polymers

International Nuclear Information System (INIS)

Dowell, F.

1989-01-01

This paper presents the details of the theoretical prediction and design (atom by atom, bond by bond) of the molecule chemical structures of the first candidate super-strong liquid-crystalline polymers (SS LCPs). These LCPs are the first LCPs designed to have good compressive strengths, as well as to have tensile strengths and tensile moduli significantly larger than those of existing strong LCPs (such as Kevlar). The key feature of this new class of LCPs is that the exceptional strength is three dimensional on a microscopic, molecular level (thus, on a macroscopic level), in contrast to present LCPs (such as Kevlar) with their one-dimensional exceptional strength. These SS LCPs also have some solubility and processing advantages over existing strong LCPs. These SS LCPs are specially-designed combined LCPs such that the side chains of a molecule interdigitate with the side chains of other molecules. This paper also presents other essential general and specific features required for SS LCPs. Considerations in the design of SS LCPs include the spacing distance between side chains along the backbone, the need for rigid sections in the backbone and side chains, the degree of polymerization, the length of the side chains, the regularity of spacing of the side chains along the backbone, the interdigitation of side chains in submolecular strips, the packing of the side chains on one or two sides of the backbone, the symmetry of the side chains, the points of attachment of the side chains to the backbone, the flexibility and size of the chemical group connecting each side chain to the backbone, the effect of semiflexible sections in the backbone and side chains, and the choice of types of dipolar and/or hydrogen bonding forces in the backbones and side chains for easy alignment

Growing perovskite into polymers for easy-processable optoelectronic devices

Science.gov (United States)

Masi, Sofia; Colella, Silvia; Listorti, Andrea; Roiati, Vittoria; Liscio, Andrea; Palermo, Vincenzo; Rizzo, Aurora; Gigli, Giuseppe

2015-01-01

Here we conceive an innovative nanocomposite to endow hybrid perovskites with the easy processability of polymers, providing a tool to control film quality and material crystallinity. We verify that the employed semiconducting polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), controls the self-assembly of CH3NH3PbI3 (MAPbI3) crystalline domains and favors the deposition of a very smooth and homogenous layer in one straightforward step. This idea offers a new paradigm for the implementation of polymer/perovskite nanocomposites towards versatile optoelectronic devices combined with the feasibility of mass production. As a proof-of-concept we propose the application of such nanocomposite in polymer solar cell architecture, demonstrating a power conversion efficiency up to 3%, to date the highest reported for MEH-PPV. On-purpose designed polymers are expected to suit the nanocomposite properties for the integration in diverse optoelectronic devices via facile processing condition.

Miniaturized and Ferrite Based Tunable Bandpass Filters in LCP and LTCC Technologies for SoP Applications

KAUST Repository

Arabi, Eyad A.

2015-04-01

Wireless systems with emerging applications are leaning towards small size, light-weight and low cost. Another trend for these wireless devices is that new applications and functionalities are being added without increasing the size of the device. To accomplish this, individual components must be miniaturized and the system should be designed to maximize the integration of the individual components. The high level of 3D integration feasible in system on package design (SoP) concept can fulfill the latter requirement. Bandpass filters are important components on all wireless systems to reject the unwanted signals and reduce interference. Being mostly implemented with passive and distributed components, bandpass filters take considerable space in a wireless system. Moreover, with emerging bands and multiple applications encompassed in a single device, many bandpass filters are required. The miniaturization related to bandpass filters can be approached by three main ways: (1) at the component level through the miniaturization of individual bandpass filters, (2) at the system level through the use of tunable filters to reduce the overall number of filters, and (3) at the system level through the high level of integration in a 3D SoP platform. In this work we have focused on all three aspects of miniaturization of band pass filters mentioned above. In the first part of this work, a low frequency (1.5 GHz global positioning system (GPS) band) filter implemented through 3D lumped components in two leading SoP technologies, namely low temperature co-fired ceramic (LTCC) and the liquid crystal polymers (LCP) is demonstrated. The miniaturized filter is based on a second order topology, which has been modified to improve the selectivity and out-of-band rejection without increasing the size. Moreover, for the case of LCP, the filter is realized in an ultra-thin stack up comprising four metallization layers with an overall thickness of only 100 _m. Due to its ultra

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

Science.gov (United States)

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

2014-05-01

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

Controlling the morphology of side chain liquid crystalline block copolymer thin films through variations in liquid crystalline content.

Science.gov (United States)

Verploegen, Eric; Zhang, Tejia; Jung, Yeon Sik; Ross, Caroline; Hammond, Paula T

2008-10-01

In this paper, we describe methods for manipulating the morphology of side-chain liquid crystalline block copolymers through variations in the liquid crystalline content. By systematically controlling the covalent attachment of side chain liquid crystals to a block copolymer (BCP) backbone, the morphology of both the liquid crystalline (LC) mesophase and the phase-segregated BCP microstructures can be precisely manipulated. Increases in LC functionalization lead to stronger preferences for the anchoring of the LC mesophase relative to the substrate and the intermaterial dividing surface. By manipulating the strength of these interactions, the arrangement and ordering of the ultrathin film block copolymer nanostructures can be controlled, yielding a range of morphologies that includes perpendicular and parallel cylinders, as well as both perpendicular and parallel lamellae. Additionally, we demonstrate the utilization of selective etching to create a nanoporous liquid crystalline polymer thin film. The unique control over the orientation and order of the self-assembled morphologies with respect to the substrate will allow for the custom design of thin films for specific nanopatterning applications without manipulation of the surface chemistry or the application of external fields.

Liquid crystal polyester-carbon fiber composites

Science.gov (United States)

Chung, T. S.

1984-01-01

Liquid crystal polymers (LCP) have been developed as a thermoplastic matrix for high performance composites. A successful melt impregnation method has been developed which results in the production of continuous carbon fiber (CF) reinforced LCP prepreg tape. Subsequent layup and molding of prepreg into laminates has yielded composites of good quality. Tensile and flexural properties of LCP/CF composites are comparable to those of epoxy/CF composites. The LCP/CF composites have better impact resistance than the latter, although epoxy/CF composites possess superior compression and shear strength. The LCP/CF composites have good property retention until 200 F (67 % of room temperature value). Above 200 F, mechanical properties decrease significantly. Experimental results indicate that the poor compression and shear strength may be due to the poor interfacial adhesion between the matrix and carbon fiber as adequate toughness of the LCP matrix. Low mechanical property retention at high temperatures may be attributable to the low beta-transition temperature (around 80 C) of the LCP matrix material.

Amorphous and Crystalline Particulates: Challenges and Perspectives in Drug Delivery.

Science.gov (United States)

Al-Obaidi, Hisham; Majumder, Mridul; Bari, Fiza

2017-01-01

Crystalline and amorphous dispersions have been the focus of academic and industrial research due to their potential role in formulating poorly water-soluble drugs. This review looks at the progress made starting with crystalline carriers in the form of eutectics moving towards more complex crystalline mixtures. It also covers using glassy polymers to maintain the drug as amorphous exhibiting higher energy and entropy. However, the amorphous form tends to recrystallize on storage, which limits the benefits of this approach. Specific interactions between the drug and the polymer may retard this spontaneous conversion of the amorphous drug. Some studies have shown that it is possible to maintain the drug in the amorphous form for extended periods of time. For the drug and the polymer to form a stable mixture they have to be miscible on a molecular basis. Another form of solid dispersions is pharmaceutical co-crystals, for which research has focused on understanding the chemistry, crystal engineering and physico-chemical properties. USFDA has issued a guidance in April 2013 suggesting that the co-crystals as a pharmaceutical product may be a reality; but just not yet! While some of the research is still oriented towards application of these carriers, understanding the mechanism by which drug-carrier miscibility occurs is also covered. Within this context is the use of thermodynamic models such as Flory-Huggins model with some examples of studies used to predict miscibility. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Synthesis and characterization of novel side-chain liquid crystalline polycarbonates, 4 - Synthesis of side-chain liquid crystalline polycarbonates with mesogenic groups having tails of different lengths

NARCIS (Netherlands)

Jansen, J.C.; Addink, R.; Nijenhuis, K.T.; Mijs, W.J.

1999-01-01

Side-chain liquid crystalline polycarbonates with alkoxyphenylbenzoate side groups, having a short spacer and tails ranging from 1 to 8 C-atoms, were synthesized. The polymers were prepared by an organo-zinc catalysed copolymerization of carbon dioxide and mesogenic 4-alkoxyphenyl

On the molecular anisotropy of liquid crystalline and flexible polymer systems

Science.gov (United States)

van Horn, Brett L.

The demand for products of ever increasing quality or for novel applications has required increasing attention to or manipulation of the anisotropy of manufactured parts. Oriented plastics are used everywhere from recording film to automotive body parts to monofilament fishing line. Liquid crystals are also used in a wide array of applications including their dominance in the flat panel display industry, color changing temperature sensors, and woven bullet resistant fabrics. Anisotropy can also be detrimental, for instance sometimes leading to poor fracture resistance or low yield stress along specific directions. Controlling and measuring anisotropy of materials has become increasingly important, but doing so is wrought with challenges. Measuring physical properties of isotropic liquids, such as water or most oils can be done in a straightforward fashion. Their viscosities and densities, for example, have unique values under a given set of conditions. With anisotropic fluids, like liquid crystals, the viscosity, for instance, will not only depend upon temperature, concentration, etc. but also upon the direction of observation, degree of anisotropy, source of anisotropy, and so forth. This added degree of complexity complicates our ability to define the state of the material at which the measurements are made and generally necessitates the use of more sophisticated measurement strategies or techniques. This work presents techniques and tools for investigating anisotropy in liquid crystalline and stretched polymeric systems. Included are the use of conoscopy for the determination of birefringence and orientation of nematic liquid crystals and stretched polymers, the shear response of flow aligning nematic liquid crystal monodomains, and the design of a novel linear rheometer that allows for in situ optical or scattering investigations.

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

International Nuclear Information System (INIS)

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

2014-01-01

In the present work, two-dimensional systems based on biodegradable polymers such as poly(ε-caprolactone) (PCL), poly(ethylene oxide) (PEO) and polylactic acid (PLA) are fabricated by means of a sustainable approach which consists in inducing phase separation in solutions of such polymers and “green” solvents, namely ethyl lactate (EL) and ethyl acetate (EA). The extraction of the solvent is promoted by a controlled drying process, which is performed in either air or supercritical CO 2 . The latter can indeed act as both an antisolvent, which favors the deposition of the polymer by forming a mixture with EL and EA, and a plasticizing agent, whose solvation and transport properties may considerably affect the microstructure and crystallinity of the polymer films. The morphological, topographical and crystalline properties of the films are tailored through a judicial selection of the materials and the processing conditions and assessed by means of thermal analyses, polarized optical microscopy, scanning electron microscopy and confocal interferometric microscopy. The results show that the morphological and crystalline properties of the films are strongly dependent on the choice of both the polymer/solvent system and the operating conditions during the drying step. In particular, the morphological, topographical and thermal properties of films prepared starting from highly crystalline polymers, namely PCL and PEO, are greatly affected by the crystallization of the material. Conversely, the less crystalline PLA forms almost completely amorphous films

Liquid crystal polymers: evidence of hairpin defects in nematic main chains, comparison with side chain polymers

Science.gov (United States)

Li, M. H.; Brûlet, A.; Keller, P.; Cotton, J. P.

1996-09-01

This article describes the conformation of two species of liquid crystalline polymers as revealed by small angle neutron scattering. The results obtained with side chain polymers are recalled. The procedure used to analyze the scattering data of main chains in the nematic phase is reported in this paper. It permits a demonstration of the existence of hairpins. Comparison of both polymer species shows that in the isotropic phase, the two polymers adopt a random coil conformation. In the nematic phase, the conformations are very different; the side chains behave as a melt of penetrable random coils whereas the main chains behave as a nematic phase of non penetrable cylinders.

Thermal Analysis, Mechanical and Rheological Behaviour of Melt Manufactured Polyethylene/Liquid Crystal Polymer Blends

Directory of Open Access Journals (Sweden)

Ilze ELKSNITE

2011-07-01

Full Text Available Modification of properties of conventional thermoplastics with thermotropic liquid crystal polymers, from one hand, allows decrease their viscosities, substantially facilitating processing conditions, and, from another hand, allows increase their exploitation properties. Orientation of the labile structure of liquid crystal polymer in extrusion or injection moulding causes specific reinforcement (so-called self-reinforcement to occur in the blends containing liquid crystal polymer. Up to now the effect of self-reinforcement is mostly investigated in the blends, containing considerable amount of liquid crystal polymer. In this research the effect of minor amounts of liquid crystalline co-polyester modifier on the properties of polyethylene is investigated. Various compositions of laboratory synthesized hydroxybenzoic acid /polyethylene terephtalate copolymer containing polyethylene composites have been manufactured by thermoplastic blending. It has been observed that 1 modulus of elasticity, yield strength and ultimate strength increase with raising the content of liquid crystalline modifier; 2 void content in the investigated polyethylene/liquid crystal copolymer composites is not greater that 1 %; 3 addition of liquid crystalline co-polyester modifier improves arrangement of PE crystalline phase.http://dx.doi.org/10.5755/j01.ms.17.2.483

Picosecond laser ablation of poly-L-lactide: Effect of crystallinity on the material response

International Nuclear Information System (INIS)

Ortiz, Rocio; Quintana, Iban; Etxarri, Jon; Lejardi, Ainhoa; Sarasua, Jose-Ramon

2011-01-01

The picosecond laser ablation of poly-L-lactide (PLLA) as a function of laser fluence and degree of crystallinity was examined. The ablation parameters and the surface modifications were analyzed under various irradiation conditions using laser wavelengths ranging from the ultraviolet through the visible. When processing the amorphous PLLA, both energy threshold and topography varied considerably depending on laser wavelength. Laser irradiation showed a reduction in the energy ablation threshold as the degree of crystallinity increased, probably related to photomechanical effects involved in laser ablation with ultra-short pulses and the lower stress accommodation behavior of semicrystalline polymers. In particular, cooperative chain motions are impeded by the higher degree of crystallinity, showing fragile mechanical behavior and lower energy dissipation. The experimental results on ablation rate versus laser energy showed that UV laser ablation on semicrystalline PLLA was more efficient than the visible ablation, i.e., it exhibits higher etch rates over a wide range of pulse energy conditions. These results were interpreted in terms of photo-thermal and photo-chemical response of polymers as a function of material micro-structure and incident laser wavelength. High quality micro-grooves were produced in amorphous PLLA, reveling the potential of ultra-fast laser processing technique in the field of micro-structuring biocompatible and biodegradable polymers for biomedical applications.

Picosecond laser ablation of poly-L-lactide: Effect of crystallinity on the material response

Energy Technology Data Exchange (ETDEWEB)

Ortiz, Rocio; Quintana, Iban; Etxarri, Jon [Manufacturing Processes Department, Fundacion TEKNIKER, Av. Otaola 20, 20600, Eibar, Guipuzcoa (Spain); Lejardi, Ainhoa; Sarasua, Jose-Ramon [Department of Mining and Metallurgy Engineering and Materials Science, School of Engineering, University of the Basque Country (EHU-UPV), Alameda de Urquijo s/n, 48013 Bilbao (Spain)

2011-11-01

The picosecond laser ablation of poly-L-lactide (PLLA) as a function of laser fluence and degree of crystallinity was examined. The ablation parameters and the surface modifications were analyzed under various irradiation conditions using laser wavelengths ranging from the ultraviolet through the visible. When processing the amorphous PLLA, both energy threshold and topography varied considerably depending on laser wavelength. Laser irradiation showed a reduction in the energy ablation threshold as the degree of crystallinity increased, probably related to photomechanical effects involved in laser ablation with ultra-short pulses and the lower stress accommodation behavior of semicrystalline polymers. In particular, cooperative chain motions are impeded by the higher degree of crystallinity, showing fragile mechanical behavior and lower energy dissipation. The experimental results on ablation rate versus laser energy showed that UV laser ablation on semicrystalline PLLA was more efficient than the visible ablation, i.e., it exhibits higher etch rates over a wide range of pulse energy conditions. These results were interpreted in terms of photo-thermal and photo-chemical response of polymers as a function of material micro-structure and incident laser wavelength. High quality micro-grooves were produced in amorphous PLLA, reveling the potential of ultra-fast laser processing technique in the field of micro-structuring biocompatible and biodegradable polymers for biomedical applications.

The negative piezoelectric effect of the ferroelectric polymer poly(vinylidene fluoride)

DEFF Research Database (Denmark)

Katsouras, Ilias; Asadi, Kamal; Li, Mengyuan

2016-01-01

with trifluoroethylene (P(VDF-TrFE)), which exhibit a negative longitudinal piezoelectric coefficient. Reported explanations exclusively consider contraction with applied electric field of either the crystalline or the amorphous part of these semi-crystalline polymers. To distinguish between these conflicting...

Composite Polymer Electrolytes: Nanoparticles Affect Structure and Properties

Directory of Open Access Journals (Sweden)

Wei Wang

2016-11-01

Full Text Available Composite polymer electrolytes (CPEs can significantly improve the performance in electrochemical devices such as lithium-ion batteries. This review summarizes property/performance relationships in the case where nanoparticles are introduced to polymer electrolytes. It is the aim of this review to provide a knowledge network that elucidates the role of nano-additives in the CPEs. Central to the discussion is the impact on the CPE performance of properties such as crystalline/amorphous structure, dielectric behavior, and interactions within the CPE. The amorphous domains of semi-crystalline polymer facilitate the ion transport, while an enhanced mobility of polymer chains contributes to high ionic conductivity. Dielectric properties reflect the relaxation behavior of polymer chains as an important factor in ion conduction. Further, the dielectric constant (ε determines the capability of the polymer to dissolve salt. The atom/ion/nanoparticle interactions within CPEs suggest ways to enhance the CPE conductivity by generating more free lithium ions. Certain properties can be improved simultaneously by nanoparticle addition in order to optimize the overall performance of the electrolyte. The effects of nano-additives on thermal and mechanical properties of CPEs are also presented in order to evaluate the electrolyte competence for lithium-ion battery applications.

Controlled synthesis of single-crystalline graphene

Directory of Open Access Journals (Sweden)

Wang Xueshen

2014-02-01

Full Text Available This paper reports the controlled synthesis of single-crystalline graphene on the back side of copper foil using CH4 as the precursor. The influence of growth time and the pressure ratio of CH4/H2 on the structure of graphene are examined. An optimized polymer-assisted method is used to transfer the synthesized graphene onto a SiO2/Si substrate. Scanning electron microscopy and Raman spectroscopy are used to characterize the graphene.

Impact of solvents and supercritical CO{sub 2} drying on the morphology and structure of polymer-based biofilms

Energy Technology Data Exchange (ETDEWEB)

Causa, Andrea; Acierno, Domenico; Filippone, Giovanni [Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, Università di Napoli Federico II, Piazzale V. Tecchio, 80, 80125 Napoli (Italy); Salerno, Aurelio; Domingo, Concepción [Instituto de Ciencia de Materiales de Barcelona (ICMAB-CSIC), Campus de la UAB, 08193 Bellaterra (Spain)

2014-05-15

In the present work, two-dimensional systems based on biodegradable polymers such as poly(ε-caprolactone) (PCL), poly(ethylene oxide) (PEO) and polylactic acid (PLA) are fabricated by means of a sustainable approach which consists in inducing phase separation in solutions of such polymers and “green” solvents, namely ethyl lactate (EL) and ethyl acetate (EA). The extraction of the solvent is promoted by a controlled drying process, which is performed in either air or supercritical CO{sub 2}. The latter can indeed act as both an antisolvent, which favors the deposition of the polymer by forming a mixture with EL and EA, and a plasticizing agent, whose solvation and transport properties may considerably affect the microstructure and crystallinity of the polymer films. The morphological, topographical and crystalline properties of the films are tailored through a judicial selection of the materials and the processing conditions and assessed by means of thermal analyses, polarized optical microscopy, scanning electron microscopy and confocal interferometric microscopy. The results show that the morphological and crystalline properties of the films are strongly dependent on the choice of both the polymer/solvent system and the operating conditions during the drying step. In particular, the morphological, topographical and thermal properties of films prepared starting from highly crystalline polymers, namely PCL and PEO, are greatly affected by the crystallization of the material. Conversely, the less crystalline PLA forms almost completely amorphous films.

Crystallinity of polyethylene in uni-axial extensional flow

DEFF Research Database (Denmark)

Wingstrand, Sara Lindeblad; van Drongelen, Martin; Mortensen, Kell

Flow history of polymer melts in processing greatly influences the crystallinity and hence the solid properties of the final material. A wide range of polymer processes involve extensional flows e.g. fiber spinning, blow moulding etc. However, due to instrumental difficulties, experimental studies...... on polymer crystallization in controlled uniaxial extension are quite rare compared to studies of crystallization in shear. Inherently uniaxial extensional flows are strong and simple relative to shear flows, in the sense that chain stretch is easily obtained and that the molecules experience no tumbling...... such that crystallization from a stretched state can take place. In this work we explore this feature in the attempt to link the nonlinear extensional rheology to the final morphology. We investigate polyethylenes (PE) of various chain architectures and observe that, even for complex architectures like long chain branched...

Biomass enzymatic saccharification is determined by the non-KOH-extractable wall polymer features that predominately affect cellulose crystallinity in corn.

Directory of Open Access Journals (Sweden)

Jun Jia

Full Text Available Corn is a major food crop with enormous biomass residues for biofuel production. Due to cell wall recalcitrance, it becomes essential to identify the key factors of lignocellulose on biomass saccharification. In this study, we examined total 40 corn accessions that displayed a diverse cell wall composition. Correlation analysis showed that cellulose and lignin levels negatively affected biomass digestibility after NaOH pretreatments at p<0.05 & 0.01, but hemicelluloses did not show any significant impact on hexoses yields. Comparative analysis of five standard pairs of corn samples indicated that cellulose and lignin should not be the major factors on biomass saccharification after pretreatments with NaOH and H2SO4 at three concentrations. Notably, despite that the non-KOH-extractable residues covered 12%-23% hemicelluloses and lignin of total biomass, their wall polymer features exhibited the predominant effects on biomass enzymatic hydrolysis including Ara substitution degree of xylan (reverse Xyl/Ara and S/G ratio of lignin. Furthermore, the non-KOH-extractable polymer features could significantly affect lignocellulose crystallinity at p<0.05, leading to a high biomass digestibility. Hence, this study could suggest an optimal approach for genetic modification of plant cell walls in bioenergy corn.

Synthesis of polymer nanostructures with conductance switching properties

Science.gov (United States)

Su, Kai; Nuraje, Nurxat; Zhang, Lingzhi; Matsui, Hiroshi; Yang, Nan Loh

2015-03-03

The present invention is directed to crystalline organic polymer nanoparticles comprising a conductive organic polymer; wherein the crystalline organic polymer nanoparticles have a size of from 10 nm to 200 nm and exhibits two current-voltage states: (1) a high resistance current-voltage state, and (2) a low resistance current-voltage state, wherein when a first positive threshold voltage (V.sub.th1) or higher positive voltage, or a second negative threshold voltage (V.sub.th2) or higher negative voltage is applied to the nanoparticle, the nanoparticle exhibits the low-resistance current-voltage state, and when a voltage less positive than the first positive threshold voltage or a voltage less negative than the second negative threshold voltage is applied to the nanoparticle, the nanoparticle exhibits the high-resistance current-voltage state. The present invention is also directed methods of manufacturing the nanoparticles using novel interfacial oxidative polymerization techniques.

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

KAUST Repository

Cates, Nichole C.; Gysel, Roman; Dahl, Jeremy E. P.; Sellinger, Alan; McGehee, Michael D.

2010-01-01

Fullerenes have been shown to intercalate between the side chains of many crystalline and semicrystalline polymers and to affect the properties of polymer:fullerene bulk heterojunction solar cells. Here we present the first in-depth study

Emission inventory for large combustion plants in France according to the 2001/80/CE European directive - LCP - February 2010

International Nuclear Information System (INIS)

Chang, Jean-Pierre; Fontelle, Jean-Pierre; Gavel, Antoine; Vincent, Julien; Matthias, Etienne; Druart, Ariane; Jacquier, Guillaume; Nicco, Laetitia

2010-02-01

After a recall of the methodological aspects of this inventory (scope of application, concept of existing or new installation, thermal power, fuels, considered pollutants, equipment, data acquisition and processing), this report presents the national results: typology of large combustion plant (LCP) installations, energy consumption, atmospheric emissions (sulphur dioxide, nitrogen dioxide, particles), emission distribution per energy type, sector-based distribution of LCPs. It also presents regional results (for 2008 and evolutions in 2009)

Enzymatic transesterification of soybean oil with ethanol using lipases immobilized on highly crystalline PVA microspheres

International Nuclear Information System (INIS)

Bergamasco, Juliana; Araujo, Marcelo V. de; Vasconcellos, Adriano de; Luizon Filho, Roberto A.; Hatanaka, Rafael R.; Giotto, Marcus V.; Aranda, Donato A.G.; Nery, José G.

2013-01-01

Polyvinyl alcohol (PVA) microspheres with different degree of crystallinity were used as solid supports for Rhizomucor miehei lipase immobilization, and the enzyme-PVA complexes were used as biocatalysts for the transesterification of soybean oil to fatty acid ethyl esters (FAEE). The amounts of immobilized enzyme on the polymeric supports were similar for both the amorphous microspheres (PVA4) and the high crystalline microspheres (PVA25). However, the enzymatic activity of the immobilized enzymes was depended on the crystallinity degree of the PVA microspheres: enzymes immobilized on the PVA4 microspheres have shown low enzymatic activity (6.13 U mg −1 ), in comparison with enzymes immobilized on the high crystalline PVA25 microspheres (149.15 U mg −1 ). A synergistic effect was observed for the enzyme-PVA25 complex during the transesterification reaction of soybean oil to FAEE: transesterification reactions with free enzyme with the equivalent amount of enzyme that were immobilized onto the PVA25 microspheres (5.4 U) have yielded only 20% of FAEE, reactions with the pure highly crystalline microsphere PVA25 have not yielded FAEE, however reactions with the enzyme-PVA25 complexes have yielded 66.3% of FAEE. This synergistic effect of an immobilized enzyme on a polymeric support has not been observed before for transesterification reaction of triacylglycerides into FAEE. Based on ATR-FTIR, 23 Na- and 13 C-NMR-MAS spectroscopic data and the interaction of the polymeric network intermolecular hydrogen bonds with the lipases residual amino acids a possible explanation for this synergistic effect is provided. Highlights: • Rhizomucor miehei lipase was immobilized on PVA microspheres (PVA4, PVA12, PVA25). • Polymer-enzyme complex was characterized by XDR, SEM, ATR-FTIR, 13 C-CPMAS-NMR, 23 Na-MAS-NMR. • Polymer-enzymes (PVA12 and PVA25) enzymes yielded considerable amount of ethyl esters. • Synergistic effect was observed for the polymer-enzyme complexes

Crystallinity and mechanical effects from annealing Parylene thin films

Energy Technology Data Exchange (ETDEWEB)

Jackson, Nathan, E-mail: Nathan.Jackson@tyndall.ie [Tyndall National Institute, University College Cork, Cork (Ireland); Stam, Frank; O' Brien, Joe [Tyndall National Institute, University College Cork, Cork (Ireland); Kailas, Lekshmi [University of Limerick, Limerick (Ireland); Mathewson, Alan; O' Murchu, Cian [Tyndall National Institute, University College Cork, Cork (Ireland)

2016-03-31

Parylene is commonly used as thin film polymer for MEMS devices and smart materials. This paper investigates the impact on bulk properties due to annealing various types of Parylene films. A thin film of Parylene N, C and a hybrid material consisting of Parylene N and C were deposited using a standard Gorham process. The thin film samples were annealed at varying temperatures from room temperature up to 300 °C. The films were analyzed to determine the mechanical and crystallinity effects due to different annealing temperatures. The results demonstrate that the percentage of crystallinity and the full-width-half-maximum value on the 2θ X-ray diffraction scan increases as the annealing temperature increases until the melting temperature of the Parylene films was achieved. Highly crystalline films of 85% and 92% crystallinity were achieved for Parylene C and N respectively. Investigation of the hybrid film showed that the individual Parylene films behave independently to each other, and the crystallinity of one film had no significant impact to the other film. Mechanical testing showed that the elastic modulus and yield strength increase as a function of annealing, whereas the elongation-to-break parameter decreases. The change in elastic modulus was more significant for Parylene C than Parylene N and this is attributed to the larger change in crystallinity that was observed. Parylene C had a 112% increase in crystallinity compared to a 61% increase for Parylene N, because the original Parylene N material was more crystalline than Parylene C so the change of crystallinity was greater for Parylene C. - Highlights: • A hybrid material consisting of Parylene N and C was developed. • Parylene N has greater crystallinity than Parylene C. • Phase transition of Parylene N due to annealing results in increased crystallinity. • Annealing caused increased crystallinity and elastic modulus in Parylene films. • Annealed hybrid Parylene films crystallinity behave

Characterization of the polymer energy landscape in polymer:fullerene bulk heterojunctions with pure and mixed phases

KAUST Repository

Sweetnam, Sean

2014-10-08

Theoretical and experimental studies suggest that energetic offsets between the charge transport energy levels in different morphological phases of polymer:fullerene bulk heterojunctions may improve charge separation and reduce recombination in polymer solar cells (PSCs). In this work, we use cyclic voltammetry, UV-vis absorption, and ultraviolet photoelectron spectroscopy to characterize hole energy levels in the polymer phases of polymer:fullerene bulk heterojunctions. We observe an energetic offset of up to 150 meV between amorphous and crystalline polymer due to bandgap widening associated primarily with changes in polymer conjugation length. We also observe an energetic offset of up to 350 meV associated with polymer:fullerene intermolecular interactions. The first effect has been widely observed, but the second effect is not always considered despite being larger in magnitude for some systems. These energy level shifts may play a major role in PSC performance and must be thoroughly characterized for a complete understanding of PSC function.

Gamma-irradiation effects to posttranslational modification and chaperon function of bovine α-crystalline

International Nuclear Information System (INIS)

Hiroki, K; Matsumoto, S.; Awakura, M.; Fujii, N.

2001-01-01

The formation of D-asparate (D-Asp) in αA-crystallin of the aged human eye and the cataract crystalline lens has been reported. Crystalline lens keeps the transparency by forming α-crystallin which consists of a high order association of αA-and αB-crystallin. Bovine α-crystallin for investigating a chaperone function which protects the crystalline lens from getting to opaque or disordered agglutination with heat or light, is irradiated by gamma-ray (Co-60) at 0, 1, 2, 3, and 4 kGy, respectively. The irradiated bovine α-crystallin are analyzed with electrophoresis, gel permeation chromatograph, and UV absorption spectrometer for checking on the agglutination and the isomerization of macromolecules. Oxidation of methionine residues (Met-1) and isomerization of asparagine residues (Asp-151) in the αA-crystallin are ascertained in molecular levels with reversed phase liquid chromatography. The Met-1 oxidation and the Asp-151 isomerization depend on gamma-irradiation doses. It is thought that OH radical and H radical in water generated by the irradiation lead to the oxidation and the isomerization. Stereoinversion in the α-crystallin following to such a chemical change are considered to lead to the agglutination of polymer and the reduction of chaperon function. (M. Suetake)

Full color camouflage in a printable photonic blue-colored polymer

NARCIS (Netherlands)

Moirangthem, M.; Schenning, A.P.H.J.

2018-01-01

A blue reflective photonic polymer coating which can be patterned in full color, from blue to red, by printing with an aqueous calcium nitrate solution has been fabricated. Color change in the cholesteric liquid-crystalline polymer network over the entire visible spectrum is obtained by the use of

Obtaining Highly Crystalline Barium Sulphate Nanoparticles via Chemical Precipitation and Quenching in Absence of Polymer Stabilizers

Directory of Open Access Journals (Sweden)

Ángela B. Sifontes

2015-01-01

Full Text Available Here we report the synthesis of barium sulphate (BaSO4 nanoparticles from Ba(OH2/BaCl2 solutions by a combined method of precipitation and quenching in absence of polymer stabilizers. Transmission electron microscopy (HRTEM, Fourier transforms infrared spectroscopy (FTIR, and X-ray diffraction (XRD were employed to characterize the particles. The Scherrer formula was applied to estimate the particle size using the width of the diffraction peaks. The obtained results indicate that the synthesized material is mainly composed of nanocrystalline barite, with nearly spherical morphology, and diameters ranging from 4 to 92 nm. The lattice images of nanoparticles were clearly observed by HRTEM, indicating a high degree of crystallinity and phase purity. In addition, agglomerates with diameters between 20 and 300 nm were observed in both lattice images and dynamic light scattering measurements. The latter allowed obtaining the particle size distribution, the evolution of the aggregate size in time of BaSO4 in aqueous solutions, and the sedimentation rate of these solutions from turbidimetry measurements. A short discussion on the possible medical applications is presented.

Styrene-Based Copolymer for Polymer Membrane Modifications

OpenAIRE

Harsha Srivastava; Harshad Lade; Diby Paul; G. Arthanareeswaran; Ji Hyang Kweon

2016-01-01

Poly(vinylidene fluoride) (PVDF) was modified with a styrene-based copolymer. The crystalline behavior, phase, thermal stability, and surface morphology of the modified membranes were analyzed. The membrane surface roughness showed a strong dependence on the styrene-acrylonitrile content and was reduced to 34% for a PVDF/styrene-acrylonitrile blend membrane with a 40/60 ratio. The thermal and crystalline behavior confirmed the blend miscibility of both polymers. It was observed in X-ray diffr...

The application of positron annihilation lifetime spectroscopy to the study of glassy and partially crystalline materials

International Nuclear Information System (INIS)

Zipper, M.D.; Hill, A.J.

1994-01-01

The use of positron annihilation lifetime spectroscopy (PALS) as a materials characterisation technique is discussed and is illustrated by examples from the authors' laboratory. A brief guide to interpretation of PALS results for metals, semiconductors, ionic solids and molecular solids is presented; however, the paper focuses on recent results for glassy and partially crystalline ionic and molecular solids. Case studies are presented in which the phenomena studied by PALS include miscibility of polymer blends, plasticization of solid polymer electrolytes, crystallinity in molecular and ionic solids, nanostructure of glass-ceramics, and refractivity of fluoride glasses. Future directions for PALS research of the electronic and defect structures of materials are discussed. 140 refs., 1 tab., 19 figs

Reducing burn-in voltage loss in polymer solar cells by increasing the polymer crystallinity

KAUST Repository

Heumueller, Thomas; Mateker, William R.; Sachs-Quintana, I. T.; Vandewal, Koen; Bartelt, Jonathan A.; Burke, Timothy M.; Ameri, Tayebeh; Brabec, Christoph J.; McGehee, Michael D.

2014-01-01

In order to commercialize polymer solar cells, the fast initial performance losses present in many high efficiency materials will have to be managed. This burn-in degradation is caused by light-induced traps and its characteristics depend on which

CLASSIFICATION OF BIODEGRADABLE POLYMERS

Directory of Open Access Journals (Sweden)

I. I. Karpunin

2015-01-01

Full Text Available The executed investigations have made it possible to ascertain that a morphological structure of starch granules mainly determine technological peculiarities of starch isolation from raw material, its modification and its later use. Morphological structure of starch granules primarily depends on type of plant starch-containing raw material which has been used for its isolation. Class of raw material exerts a strong impact on the shape and size of the granules. Linear “light” amylose chains and “heavy” amylopectin branch chains form a starch granule ultrastructure. X-ray research has proved that starch granules are characterized by presence of interlacing amorphous and crystalline regions. In this case polymer orientation using stretching of the obtained end product influences on its physical and mechanical  indices which are increasing due to polymer orientation. For the purpose of packaging orientation of polymer films can solve such important problems as significant improvement of operational properties, creation of  thermosetting film materials, improvement of qualitative indices of the recycled film.Results of the conducted research have proved the fact that it is necessary to make changes in technology in order to increase biological degradability of the recycled packaging made from polymers and improve physical and mechanical indices. In this regard film production technology presupposes usage of such substances as stark and others which are characterized by rather large presence of branch chains of molecules and interlacing amorphous and crystalline regions. Such approach makes it possible to obtain after-use package which is strong and quickly degradable by micro-organisms.

The effect of crystallinity on cell growth in semi-crystalline microcellular foams by solid-state process: modeling and numerical simulation

Science.gov (United States)

Rezvanpanah, Elham; Ghaffarian Anbaran, S. Reza

2017-11-01

This study establishes a model and simulation scheme to describe the effect of crystallinity as one of the most effective parameters on cell growth phenomena in a solid batch foaming process. The governing model of cell growth dynamics, based on the well-known ‘Cell model’, is attained in details. To include the effect of crystallinity in the model, the properties of the polymer/gas mixtures (i.e. solubility, diffusivity, surface tension and viscosity) are estimated by modifying relations to consider the effect of crystallinity. A finite element-finite difference (FEFD) method is employed to solve the highly nonlinear and coupled equations of cell growth dynamics. The proposed simulation is able to evaluate all properties of the system at the given process condition and uses them to calculate the cell size, pressure and gas concentration gradient with time. A high-density polyethylene/nitrogen (HDPE/N2) system is used herein as a case study. Comparing the simulation results with the others works and experimental results verify the accuracy of the simulation scheme. The cell growth is a complicated combination of several phenomena. This study attempted to reach a better understanding of cell growth trend, driving and retarding forces and the effect of crystallinity on them.

Synthesis of biocompatible polymers by plasma

International Nuclear Information System (INIS)

Colin O, E.

2007-01-01

the smallest contact angles. It has been demonstrated that the high energy of plasma in the polymers favors certain crystalline arrangement due to the reorganization of polymeric chains. In this work the crystallinity was calculated by means of areas under the curve of the amorphous and crystalline signals obtained by X-ray diffraction. The crystallinity in PPy/PEG increases from 8% to 9.5%. In Poly allylamine (PAl) the crystallinity was from 4% to 16%. The crystallinity in these materials increases when the increases synthesis energy. While in PPy the crystallinity diminishes from 16% to 12% when the synthesis energy increases, due to the fragmentation and/or possible ramifications of the pyrrole rings that reduce the formation of orderly regions with the energy increments. This characteristic is important, because they can be ended up forming conduction channels in the polymer that is reflected in the electric conductivity of the material. The electric conductivity is another important factor in this study, since due to the electric impulses generated among materials and cells it can stimulates the cellular growth. The electric response of the polymers was study in function of the relative humidity in the interval of 25-80% and in function of the volume of the solutions of NaCl, NaCl-MgSO 4 , and Krebs-Ringer. In the interval of 25-80% of relative humidity, the increment in the electric conductivity in PPy/PEG went from 10 -12 to 10 -10 S/cm at 25% and of 10 -12 to 10 -8 S/cm to 80% of relative humidity. The electric conductivity regarding the humidity in PAl increases from 10 -11 of 10 -9 S/cm to 25% and of 10 - 1 0 to 10 -8 S/cm at 80%. In Poly pyrrole (PPy) and doped poly pyrrole with Iodine (PPy/I) one observes that the electric conductivity in the interval 25% to 80% of relative humidity went from 10 -9 to 10 11 S/cm in PPy and 10 -8 and 10 -10 S/cm in PPy/I almost increases two magnitude orders when increasing the relative humidity. The polymers showed a

Impact of the Formulation Pathway on the Colloidal State and Crystallinity of Poly-ε-caprolactone Particles Prepared by Solvent Displacement.

Science.gov (United States)

Pucci, Carlotta; Cousin, Fabrice; Dole, François; Chapel, Jean-Paul; Schatz, Christophe

2018-02-20

The formulation pathway and/or the mixing method are known to be relevant in many out-of-equilibrium processes. In this work, we studied the effect of the mixing conditions on the physicochemical properties of poly-ε-caprolactone (PCL) particles prepared by solvent displacement. More specifically, water was added in one shot (fast addition) or drop by drop to PCL solution in tetrahydrofuran (THF) to study the impact of the mixing process on particle properties including size, stability, and crystallinity. Two distinct composition maps representing the Ouzo domain characteristic of the presence of metastable nanoparticles have been established for each mixing method. Polymer nanoparticles are formed in the Ouzo domain according to a nucleation and growth (or aggregation) mechanism. The fast addition promotes a larger nucleation rate, thus favoring the formation of small and uniform particles. For the drop-by-drop addition, for which the polymer solubility gradually decreases, the composition trajectories systematically cross an intermediate unstable region between the solubility limit of the polymer and the Ouzo domain. This leads to heterogeneous nucleation as shown by the formation of larger and less stable particles. Particles formed in the Ouzo domain have semi-crystalline properties. The PCL melting point is decreased with the THF fraction trapped in particles in accordance with Flory's theory for melt crystallization. On the other hand, the degree of crystallinity is constant, around 20% regardless of the THF fraction. No difference between fast and slow addition could be detected on the semi-crystalline properties of the particles which emphasize that thermodynamic rather than kinetic factors drive the polymer crystallization in particles. The recovery of bulk PCL crystallinity after the removal of THF from particles tends to confirm this hypothesis.

Singlet Exciton Lifetimes in Conjugated Polymer Films for Organic Solar Cells

KAUST Repository

Dimitrov, Stoichko

2016-01-13

The lifetime of singlet excitons in conjugated polymer films is a key factor taken into account during organic solar cell device optimization. It determines the singlet exciton diffusion lengths in polymer films and has a direct impact on the photocurrent generation by organic solar cell devices. However, very little is known about the material properties controlling the lifetimes of singlet excitons, with most of our knowledge originating from studies of small organic molecules. Herein, we provide a brief summary of the nature of the excited states in conjugated polymer films and then present an analysis of the singlet exciton lifetimes of 16 semiconducting polymers. The exciton lifetimes of seven of the studied polymers were measured using ultrafast transient absorption spectroscopy and compared to the lifetimes of seven of the most common photoactive polymers found in the literature. A plot of the logarithm of the rate of exciton decay vs. the polymer optical bandgap reveals a medium correlation between lifetime and bandgap, thus suggesting that the Energy Gap Law may be valid for these systems. This therefore suggests that small bandgap polymers can suffer from short exciton lifetimes, which may limit their performance in organic solar cell devices. In addition, the impact of film crystallinity on the exciton lifetime was assessed for a small bandgap diketopyrrolopyrrole co-polymer. It is observed that the increase of polymer film crystallinity leads to reduction in exciton lifetime and optical bandgap again in agreement with the Energy Gap Law.

Low-Cost and Green Fabrication of Polymer Electronic Devices by Push-Coating of the Polymer Active Layers.

Science.gov (United States)

Vohra, Varun; Mróz, Wojciech; Inaba, Shusei; Porzio, William; Giovanella, Umberto; Galeotti, Francesco

2017-08-02

Because of both its easy processability and compatibility with roll-to-roll processes, polymer electronics is considered to be the most promising technology for the future generation of low-cost electronic devices such as light-emitting diodes and solar cells. However, the state-of-the-art deposition technique for polymer electronics (spin-coating) generates a high volume of chlorinated solution wastes during the active layer fabrication. Here, we demonstrate that devices with similar or higher performances can be manufactured using the push-coating technique in which a poly(dimethylsiloxane) (PDMS) layer is simply laid over a very small amount of solution (less than 1μL/covered cm 2 ), which is then left for drying. Using mm thick PDMS provides a means to control the solvent diffusion kinetics (sorption/retention) and removes the necessity for additional applied pressure to generate the desired active layer thickness. Unlike spin-coating, push-coating is a slow drying process that induces a higher degree of crystallinity in the polymer thin film without the necessity for a post-annealing step. The polymer light-emitting diodes and solar cells prepared by push-coating exhibit slightly higher performances with respect to the reference spin-coated devices, whereas at the same time reduce the amounts of active layer materials and chlorinated solvents by 50 and 20 times, respectively. These increased performances can be correlated to the higher polymer crystallinities obtained without applying a post-annealing treatment. As push-coating is a roll-to-roll compatible method, the results presented here open the path to low-cost and eco-friendly fabrication of a wide range of emerging devices based on conjugated polymer materials.

Impaired maternal glucose homeostasis during pregnancy is associated with low status of long-chain polyunsaturated fatty acids (LCP) and essential fatty acids (EFA) in the fetus

NARCIS (Netherlands)

Dijck-Brouwer, DAJ; Hadders-Algra, M; Bouwstra, H; Decsi, T; Boehm, G; Martini, IA; Boersma, ER; Muskiet, FAJ

Low status of long-chain polyunsaturated fatty acids (LCP) and essential fatty acids (EFA) in the fetus is associated with less favorable neonatal neurological condition. A 'relative', rather than 'absolute' EFA deficiency might explain this finding. A relative EFA deficiency may derive from

Novel polypyrrole films with excellent crystallinity and good thermal stability

International Nuclear Information System (INIS)

Jeeju, Pullarkat P.; Varma, Sreekanth J.; Francis Xavier, Puthampadath A.; Sajimol, Augustine M.; Jayalekshmi, Sankaran

2012-01-01

Polypyrrole has drawn a lot of interest due to its high thermal and environmental stability in addition to high electrical conductivity. The present work highlights the enhanced crystallinity of polypyrrole films prepared from the redoped sample solution. Initially hydrochloric acid doped polypyrrole was prepared by chemical oxidative polymerization of pyrrole using ammonium peroxidisulphate as oxidant. The doped polypyrrole was dedoped using ammonia solution and then redoped with camphor sulphonic acid. Films were coated on ultrasonically cleaned glass substrates from the redoped sample solution in meta-cresol. The enhanced crystallinity of the polypyrrole films has been established from X-ray diffraction (XRD) studies. The room temperature electrical conductivity of the redoped polypyrrole film is about 30 times higher than that of the hydrochloric acid doped pellet sample. The results of Raman spectroscopy, Differential scanning calorimetry (DSC) and Thermogravimetric analysis (TGA) of the samples support the enhancement in crystallinity. Percentage crystallinity of the samples is estimated from XRD and DSC data. The present work is significant, since crystallinity of films is an important parameter for selecting polymers for specific applications. - Highlights: ► Polypyrrole films redoped with CSA have been prepared from meta-cresol solution. ► The solution casted films exhibit semi-crystallinity and good thermal stability. ► Percentage crystallinity estimated using XRD and DSC analysis is about 65%. ► Raman studies support the enhancement in crystallinity based on XRD and DSC data. ► The conductivity of the film is 30 times higher than that of HCl doped sample.

Novel polypyrrole films with excellent crystallinity and good thermal stability

Energy Technology Data Exchange (ETDEWEB)

Jeeju, Pullarkat P., E-mail: jeejupp@gmail.com [Division for Research in Advanced Materials, Department of Physics, Cochin University of Science and Technology, Cochin-22, Kerala (India); Varma, Sreekanth J.; Francis Xavier, Puthampadath A.; Sajimol, Augustine M. [Division for Research in Advanced Materials, Department of Physics, Cochin University of Science and Technology, Cochin-22, Kerala (India); Jayalekshmi, Sankaran, E-mail: jayalekshmi@cusat.ac.in [Division for Research in Advanced Materials, Department of Physics, Cochin University of Science and Technology, Cochin-22, Kerala (India)

2012-06-15

Polypyrrole has drawn a lot of interest due to its high thermal and environmental stability in addition to high electrical conductivity. The present work highlights the enhanced crystallinity of polypyrrole films prepared from the redoped sample solution. Initially hydrochloric acid doped polypyrrole was prepared by chemical oxidative polymerization of pyrrole using ammonium peroxidisulphate as oxidant. The doped polypyrrole was dedoped using ammonia solution and then redoped with camphor sulphonic acid. Films were coated on ultrasonically cleaned glass substrates from the redoped sample solution in meta-cresol. The enhanced crystallinity of the polypyrrole films has been established from X-ray diffraction (XRD) studies. The room temperature electrical conductivity of the redoped polypyrrole film is about 30 times higher than that of the hydrochloric acid doped pellet sample. The results of Raman spectroscopy, Differential scanning calorimetry (DSC) and Thermogravimetric analysis (TGA) of the samples support the enhancement in crystallinity. Percentage crystallinity of the samples is estimated from XRD and DSC data. The present work is significant, since crystallinity of films is an important parameter for selecting polymers for specific applications. - Highlights: Black-Right-Pointing-Pointer Polypyrrole films redoped with CSA have been prepared from meta-cresol solution. Black-Right-Pointing-Pointer The solution casted films exhibit semi-crystallinity and good thermal stability. Black-Right-Pointing-Pointer Percentage crystallinity estimated using XRD and DSC analysis is about 65%. Black-Right-Pointing-Pointer Raman studies support the enhancement in crystallinity based on XRD and DSC data. Black-Right-Pointing-Pointer The conductivity of the film is 30 times higher than that of HCl doped sample.

Stress controlled gas-barrier oxide coatings on semi-crystalline polymers

International Nuclear Information System (INIS)

Rochat, G.; Leterrier, Y.; Fayet, P.; Manson, J.-A.E.

2005-01-01

Thin silicon oxide (SiO x ) barrier coatings formed by plasma enhanced chemical vapor deposition on poly(ethylene terephthalate) (PET) substrates were subjected to post-deposition annealing treatments in the temperature range for orientation relaxation of the polymer. The resulting change in coating internal stress state was measured by means of thermo-mechanical analyses, and its effect on the coating cohesive properties and coating/polymer adhesion was determined from the analysis of uniaxial fragmentation tests in situ in a scanning electron microscope, assuming a Weibull-type probability of failure and a perfectly plastic stress transfer at the SiO x /PET interface. The strain to failure and intrinsic fracture toughness of the ultrathin oxide coating were found to be as high as 5.7% and 10 J/m 2 , respectively, and its interfacial shear strength with PET was found to be close to 100 MPa. Annealing for 10 min at 150 deg. C did not modify the oxygen permeation properties of the SiO x /PET film, which suggests that the defect population of the oxide was not affected by the thermal treatment. In contrast, the coating internal compressive stress resulting from annealing was shown to increase by 40% the apparent coating cohesive properties and adhesion to the polymer

Effects of blending poly(D,L-lactide) with poly(ethylene glycol) on the higher-order crystalline structures of poly(ethylene glycol) as revealed by small-angle X-ray scattering

International Nuclear Information System (INIS)

Tien, N D; Kimura, G; Yamashiro, Y; Fujiwara, H; Sasaki, S; Sakurai, S; Hoa, T P; Mochizuki, M

2011-01-01

Effects of blending poly(lactic acid) (PLA) with poly(ethylene glycol) (PEG) on higher-order crystalline structures of PEG were examined using small-angle X-ray scattering (SAXS). For this purpose, the fact that two polymers are both crystalline makes situtation much complicated. To simplify, non-crystalline PLA is suitable. Thus, we used poly(D,L-lactic acid) (DLPLA), which is random copolymer comprising D- and L-lactic acid moieties. Multiple scattering peaks arising from the regular crystalline lamellar structure were observed for the PEG homopolymer and the blends. Surprisingly, the structure is much more regular for the blend DLPLA/PEG at composition of 20/80 wt.% than for the PEG homopolymer. Also for this blend sample as well as for a PEG homopolymer, very peculiar SAXS profiles were observed just 1 deg. C below T m of PEG. This is found to be a particle scattering of plate-like objects, which has never been reported for polymer blends or crystalline polymers. Futhermore, it was found that there was strong hysteresis of the higher-order structure formation.

Polymer-Assisted Hydrothermal Synthesis of Hierarchically Arranged Hydroxyapatite Nanoceramic

Directory of Open Access Journals (Sweden)

A. Joseph Nathanael

2013-01-01

Full Text Available Flower-like hydroxyapatite (HA nanostructures were synthesized by a polymer-assisted hydrothermal method. The thickness of the petals/plates decreased from 200 nm to 40 nm as the polymer concentration increased. The thickness also decreased as the hydrothermal treatment time increased from 6 to 12 hr. The HRTEM and SAED patterns suggest that the floral-like HA nanostructures are single crystalline in nature. Structural analysis based on XRD and Raman experiments implied that the produced nanostructure is a pure form of HA without any other impurities. The possible formation mechanism was discussed for the formation of flower-like HA nanostructures during polymer-assisted hydrothermal synthesis. Finally, in vitro cellular analysis revealed that the hierarchically arranged HA nanoceramic had improved cell viability relative to other structures. The cells were actively proliferated over these nanostructures due to lower cytotoxicity. Overall, the size and the crystallinity of the nanostructures played a role in improving the cell proliferation.

Potential of a newly developed high-speed near-infrared (NIR) camera (Compovision) in polymer industrial analyses: monitoring crystallinity and crystal evolution of polylactic acid (PLA) and concentration of PLA in PLA/Poly-(R)-3-hydroxybutyrate (PHB) blends.

Science.gov (United States)

Ishikawa, Daitaro; Nishii, Takashi; Mizuno, Fumiaki; Sato, Harumi; Kazarian, Sergei G; Ozaki, Yukihiro

2013-12-01

This study was carried out to evaluate a new high-speed hyperspectral near-infrared (NIR) camera named Compovision. Quantitative analyses of the crystallinity and crystal evolution of biodegradable polymer, polylactic acid (PLA), and its concentration in PLA/poly-(R)-3-hydroxybutyrate (PHB) blends were investigated using near-infrared (NIR) imaging. This NIR camera can measure two-dimensional NIR spectral data in the 1000-2350 nm region obtaining images with wide field of view of 150 × 250 mm(2) (approximately 100  000 pixels) at high speeds (in less than 5 s). PLA with differing crystallinities between 0 and 50% blended samples with PHB in ratios of 80/20, 60/40, 40/60, 20/80, and pure films of 100% PLA and PHB were prepared. Compovision was used to collect respective NIR spectra in the 1000-2350 nm region and investigate the crystallinity of PLA and its concentration in the blends. The partial least squares (PLS) regression models for the crystallinity of PLA were developed using absorbance, second derivative, and standard normal variate (SNV) spectra from the most informative region of the spectra, between 1600 and 2000 nm. The predicted results of PLS models achieved using the absorbance and second derivative spectra were fairly good with a root mean square error (RMSE) of less than 6.1% and a determination of coefficient (R(2)) of more than 0.88 for PLS factor 1. The results obtained using the SNV spectra yielded the best prediction with the smallest RMSE of 2.93% and the highest R(2) of 0.976. Moreover, PLS models developed for estimating the concentration of PLA in the blend polymers using SNV spectra gave good predicted results where the RMSE was 4.94% and R(2) was 0.98. The SNV-based models provided the best-predicted results, since it can reduce the effects of the spectral changes induced by the inhomogeneity and the thickness of the samples. Wide area crystal evolution of PLA on a plate where a temperature slope of 70-105 °C had occurred was also

Ericksen number and Deborah number cascade predictions of a model for liquid crystalline polymers for simple shear flow

Science.gov (United States)

Klein, D. Harley; Leal, L. Gary; García-Cervera, Carlos J.; Ceniceros, Hector D.

2007-02-01

We consider the behavior of the Doi-Marrucci-Greco (DMG) model for nematic liquid crystalline polymers in planar shear flow. We found the DMG model to exhibit dynamics in both qualitative and quantitative agreement with experimental observations reported by Larson and Mead [Liq. Cryst. 15, 151 (1993)] for the Ericksen number and Deborah number cascades. For increasing shear rates within the Ericksen number cascade, the DMG model displays three distinct regimes: stable simple shear, stable roll cells, and irregular structure accompanied by disclination formation. In accordance with experimental observations, the model predicts both ±1 and ±1/2 disclinations. Although ±1 defects form via the ridge-splitting mechanism first identified by Feng, Tao, and Leal [J. Fluid Mech. 449, 179 (2001)], a new mechanism is identified for the formation of ±1/2 defects. Within the Deborah number cascade, with increasing Deborah number, the DMG model exhibits a streamwise banded texture, in the absence of disclinations and roll cells, followed by a monodomain wherein the mean orientation lies within the shear plane throughout the domain.

Indolo-naphthyridine-6,13-dione Thiophene Building Block for Conjugated Polymer Electronics: Molecular Origin of Ultrahigh n-Type Mobility

KAUST Repository

Fallon, Kealan J.

2016-10-18

Herein, we present the synthesis and characterization of four conjugated polymers containing a novel chromophore for organic electronics based on an indigoid structure. These polymers exhibit extremely small band gaps of ∼1.2 eV, impressive crystallinity, and extremely high n-type mobility exceeding 3 cm V s. The n-type charge carrier mobility can be correlated with the remarkably high crystallinity along the polymer backbone having a correlation length in excess of 20 nm. Theoretical analysis reveals that the novel polymers have highly rigid nonplanar geometries demonstrating that backbone planarity is not a prerequisite for either narrow band gap materials or ultrahigh mobilities. Furthermore, the variation in backbone crystallinity is dependent on the choice of comonomer. OPV device efficiencies up to 4.1% and charge photogeneration up to 1000 nm are demonstrated, highlighting the potential of this novel chromophore class in high-performance organic electronics.

Indolo-naphthyridine-6,13-dione Thiophene Building Block for Conjugated Polymer Electronics: Molecular Origin of Ultrahigh n-Type Mobility

KAUST Repository

Fallon, Kealan J.; Wijeyasinghe, Nilushi; Manley, Eric F.; Dimitrov, Stoichko D.; Yousaf, Syeda A.; Ashraf, Raja S.; Duffy, Warren; Guilbert, Anne A. Y.; Freeman, David M. E.; Al-Hashimi, Mohammed; Nelson, Jenny; Durrant, James R.; Chen, Lin X.; McCulloch, Iain; Marks, Tobin J.; Clarke, Tracey M.; Anthopoulos, Thomas D.; Bronstein, Hugo

2016-01-01

Herein, we present the synthesis and characterization of four conjugated polymers containing a novel chromophore for organic electronics based on an indigoid structure. These polymers exhibit extremely small band gaps of ∼1.2 eV, impressive crystallinity, and extremely high n-type mobility exceeding 3 cm V s. The n-type charge carrier mobility can be correlated with the remarkably high crystallinity along the polymer backbone having a correlation length in excess of 20 nm. Theoretical analysis reveals that the novel polymers have highly rigid nonplanar geometries demonstrating that backbone planarity is not a prerequisite for either narrow band gap materials or ultrahigh mobilities. Furthermore, the variation in backbone crystallinity is dependent on the choice of comonomer. OPV device efficiencies up to 4.1% and charge photogeneration up to 1000 nm are demonstrated, highlighting the potential of this novel chromophore class in high-performance organic electronics.

Effect of irradiation on the properties of some shrinking polymer films

International Nuclear Information System (INIS)

Varsanyi, E.

1974-01-01

Shrinking polymer films (polyethylene, polyvinylidene chloride, polyester) suitable for use in the food industry were studied with the intention to determine the effect of radurizing doses (800 krad and below) on changes in the proportion of crystalline parts in the polymer, and on the tensile strength, elongation at break and shrinkage of the film. Changes in the crystalline/amorphous ratio in the polymer were determined by means of infra-red spectrophotometry. Calculations based on spectral data showed no significant changes in the ratio of crystalline fraction of any of the films, as a function of radurizing doses. Tensile strength and elongation at break tests were carried out by means of standardized instruments and methods. It was found that the tensile strength of the polyethylene film decreased by about 25% as an effect of irradiation, while the same treatment caused no significant changes in the elongation at break. The tensile strength of the polyvinylidene chloride film suffered a decrease of roughly 15%, its elongation at break an about 30% decrease when irradiated. Radiation treatment caused a decrease if less than 10% in tensile strength of the polyester film and a more than 10% change in elongation at break. The tests indicated no significant changes in the shrinkage of radiation treated polymers. The results of the tests led to the conclusion that radurizing doses caused no such change which would affect the applicability of polymer films to the wrapping and packaging of foods subjected to irradiation or would make the films unsuitable for the protection of the goods. (F.J.)

gamma. -relaxation process in crystallizable polymers

Energy Technology Data Exchange (ETDEWEB)

Mindiyarov, Kh G; Zelenev, Yu V; Bartenev, G M [Birskij Gosudarstvennyj Pedagogicheskij Inst. (USSR)

1975-07-01

In the present paper, with the aid of radiothermoluminescence technique ..gamma..-relaxation processes are investigated, which are conditioned by molecular mobility and are associated with defects in the crystalline structure of polymers PEh, PP, and elastomers PIB, NK, SKD, SKI exposed to ..gamma..-rays of Co/sup 60/ at a dose rate of 1 Mrad. The shape of the thermoluminescence curve, i.e. the luminescence intensity in the ..cap alpha.. - ..gamma..-maxima, their relationship, position with respect to temperature are strongly dependent on the degree of crystallinity, on the thermal and mechanical prehistory. In highly crystalline samples of PEh and PP ..cap alpha..-maximum may be absent. Dependence has been studied of the luminescence intensity in the ..cap alpha..- and ..gamma..-maxima (Isub(..cap alpha..)/Isub(..gamma..)) on the crystallization temperature; the curve passes through the minimum when the crystallization rate is maximum. The relationship Isub(..gamma..)re of crystallinity degree.

Clay intercalation and influence on crystallinity of EVA-based clay nanocomposites

International Nuclear Information System (INIS)

Chaudhary, D.S.; Prasad, R.; Gupta, R.K.; Bhattacharya, S.N.

2005-01-01

Various polymer clay nanocomposites (PCNs) were prepared from ethylene vinyl acetate copolymer (EVA) with 9, 18 and 28% vinyl acetate (VA) content filled with different wt.% (2.5, 5 and 7.5) of a Montmorillonite-based organo-modified clay (Cloisite[reg] C15A and C30B). The PCNs were prepared using melt blending techniques. Morphological information regarding intercalation and exfoliation were determined by using wide-angle X-ray scattering (WAXS) and transmission electron microscopy (TEM). WAXS and TEM confirmed that increasing the VA content was necessary to achieve greater clay-polymer interaction as seen from the comparatively higher intercalation of clay platelets with 28% VA. The effect of addition of clay on the development and the modification of crystalline morphology in EVA matrix was also studied using WAXS and temperature-modulated differential scanning calorimetry (MDSC). Results are presented showing that the addition of clay platelets does not increase the matrix crystallinity but the morphology was significantly modified such that there was an increase in the 'rigid' amorphous phase. Mechanical properties were also evaluated against the respective morphological information for each specimen and there are indications that the level of clay-polymer interaction plays a significant role in such morphological modification, and in such a way that affects the final PCN mechanical properties which has wide and significant applications in the packaging industries

Structure-property relationships for n-alkyl-isocyanate-containing polymers

Science.gov (United States)

Aronson, Carl Lawrence

Poly(n-hexyl isocyanate) (PHIC), poly(n-butyl-isocyanate) (PBIC), poly(n-butyl-co-cyclohexyl isocyanate) (PBCHIC), poly(n-hexyl isocyanate-b-isoprene) (HI), poly(n-butyl isocyanate-b-isoprene) (BI) and poly(n-hexyl isocyanate-b-isoprene- b-styrene) (MS) were synthesized and characterized with respect to composition, molecular Weight and polydispersity. PHIC, HI and HIS were found to be lyotropic liquid crystalline whereas PBIC, PBCHIC and BI were found to be non-lyotropic. A lyotropic-nematic liquid crystalline phase diagram was determined for the PHIC/xylene system. A novel and reversible electric-field-induced biphasic-paranematic phase transition was found for the PHIC/xylene system from the dynamics of topological defects. The electric-field-induced phase diagram for PHIC/xylene agreed with the theoretically predicted field-induced phase diagram of Khokhlov and Semenov for semiflexible-persistent polymers. The dielectric characteristics, steady-state electrically induced birefringence and steady-state electroheological (ER) activity of PHIC, PBIC and PBCHIC solutions were compared as a function of polymer concentration. The role of lyotropic liquid crystalline ordering in the functional ER mechanism of poly( n-hexyl isocyanate) solutions is presented. PBCHIC was found to thermally decompose by a first-order rate process which became slower with increasing cyclohexyl isocyanate content from thermal gravimetric analysis. Competition between monomer dissociation and degradative trimerization as well as a non-alternating sequence distribution were determined for PBCHIC from direct pyrolysis/mass spectrometry. The Arrhenius activation energy, pre-exponential factor and entropy for diffusion and evaporation of xylene from PHIC, were found to be functions of initial polymer concentration whereas the intrinsic diffusion coefficient of the solvent was found to be independent of initial polymer concentration. The cross polarized/magic angle spinning solid state 13C

Multilayer electronic component systems and methods of manufacture

Science.gov (United States)

Thompson, Dane (Inventor); Wang, Guoan (Inventor); Kingsley, Nickolas D. (Inventor); Papapolymerou, Ioannis (Inventor); Tentzeris, Emmanouil M. (Inventor); Bairavasubramanian, Ramanan (Inventor); DeJean, Gerald (Inventor); Li, RongLin (Inventor)

2010-01-01

Multilayer electronic component systems and methods of manufacture are provided. In this regard, an exemplary system comprises a first layer of liquid crystal polymer (LCP), first electronic components supported by the first layer, and a second layer of LCP. The first layer is attached to the second layer by thermal bonds. Additionally, at least a portion of the first electronic components are located between the first layer and the second layer.

Polymer blends

Energy Technology Data Exchange (ETDEWEB)

Allen, Scott D.; Naik, Sanjeev

2017-08-22

The present invention provides, among other things, extruded blends of aliphatic polycarbonates and polyolefins. In one aspect, provided blends comprise aliphatic polycarbonates such as poly(propylene carbonate) and a lesser amount of a crystalline or semicrystalline polymer. In certain embodiments, provided blends are characterized in that they exhibit unexpected improvements in their elongation properties. In another aspect, the invention provides methods of making such materials and applications of the materials in applications such as the manufacture of consumer packaging materials.

Structure-Property Relationships of Semiconducting Polymers for Flexible and Durable Polymer Field-Effect Transistors.

Science.gov (United States)

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.

Modification of the twist angle in chiral nematic polymer films by photoisomerization of the chiral dopant

NARCIS (Netherlands)

Witte, van de P.; Neuteboom, E.E.; Brehmer, M.; Lub, Johan

1999-01-01

A method for the production of polarization sensitive recordings in liquid crystalline polymers is presented. The system is based on local modification of the twist angle of chiral nematic polymer films. The twist angle of the polymer film is varied by modifying the chemical structure of the chiral

Homogeneous crystal nucleation in polymers.

Science.gov (United States)

Schick, C; Androsch, R; Schmelzer, J W P

2017-11-15

The pathway of crystal nucleation significantly influences the structure and properties of semi-crystalline polymers. Crystal nucleation is normally heterogeneous at low supercooling, and homogeneous at high supercooling, of the polymer melt. Homogeneous nucleation in bulk polymers has been, so far, hardly accessible experimentally, and was even doubted to occur at all. This topical review summarizes experimental findings on homogeneous crystal nucleation in polymers. Recently developed fast scanning calorimetry, with cooling and heating rates up to 10 6 K s -1 , allows for detailed investigations of nucleation near and even below the glass transition temperature, including analysis of nuclei stability. As for other materials, the maximum homogeneous nucleation rate for polymers is located close to the glass transition temperature. In the experiments discussed here, it is shown that polymer nucleation is homogeneous at such temperatures. Homogeneous nucleation in polymers is discussed in the framework of the classical nucleation theory. The majority of our observations are consistent with the theory. The discrepancies may guide further research, particularly experiments to progress theoretical development. Progress in the understanding of homogeneous nucleation is much needed, since most of the modelling approaches dealing with polymer crystallization exclusively consider homogeneous nucleation. This is also the basis for advancing theoretical approaches to the much more complex phenomena governing heterogeneous nucleation.

Implicit implementation and consistent tangent modulus of a viscoplastic model for polymers

OpenAIRE

ACHOUR-RENAULT, Nadia; CHATZIGEORGIOU, George; MERAGHNI, Fodil; CHEMISKY, Yves; FITOUSSI, Joseph

2015-01-01

In this work, the phenomenological viscoplastic DSGZ model[Duan, Y., Saigal, A., Greif, R., Zimmerman, M. A., 2001. A Uniform Phenomenological Constitutive Model for Glassy and Semicrystalline Polymers. Polymer Engineering and Science 41 (8), 1322-1328], developed for glassy or semi-crystalline polymers, is numerically implemented in a three dimensional framework, following an implicit formulation. The computational methodology is based on the radial return mapping algorithm. This implicit fo...

Terahertz spectroscopic analysis of crystal orientation in polymers

Science.gov (United States)

Azeyanagi, Chisato; Kaneko, Takuya; Ohki, Yoshimichi

2018-05-01

Terahertz time-domain spectroscopy (THz-TDS) is attracting keen attention as a new spectroscopic tool for characterizing various materials. In this research, the possibility of analyzing the crystal orientation in a crystalline polymer by THz-TDS is investigated by measuring angle-resolved THz absorption spectra for sheets of poly(ethylene terephthalate), poly(ethylene naphthalate), and poly(phenylene sulfide). The resultant angle dependence of the absorption intensity of each polymer is similar to that of the crystal orientation examined using pole figures of X-ray diffraction. More specifically, THz-TDS can indicate the alignment of molecules in polymers.

Welding behavior of semi-crystalline polymers 2. The effect of cocrystallisation on autoadhesion

NARCIS (Netherlands)

Xue, Y.-Q.; Tervoort, T.A.; Rastogi, S.; Lemstra, P.J.

2000-01-01

The effect of cocrystallization on the welding behavior of semicrystalline polymers was studied by means of T-peel testing at room temperature, using ultrahigh-molecular-weight polyethylene (UHMWPE) as a model polymer. Solution-cast films of UHMWPE have a very special morphology, consisting of

The influence of polymerization rate on conductivity and crystallinity of electropolymerized polypyrrole

DEFF Research Database (Denmark)

Dyreklev, P.; Granström, M.; Inganäs, O.

1996-01-01

We report studies on electronic conductivity and crystallinity in electropolymerized polypyrrole. Different growth rates during electropolymerization strongly influence and determine structural and electronic properties. Polymer films grown using low current density show higher electronic conduct...... a different coupling route in the polymerization, induced by the lower current density. Copyright (C) 1996 Elsevier Science Ltd....

Gas-phase synthesis of magnetic metal/polymer nanocomposites

Science.gov (United States)

Starsich, Fabian H. L.; Hirt, Ann M.; Stark, Wendelin J.; Grass, Robert N.

2014-12-01

Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

An insight into the mechanism of charge-transfer of hybrid polymer:ternary/quaternary chalcopyrite colloidal nanocrystals

Directory of Open Access Journals (Sweden)

Parul Chawla

2014-08-01

Full Text Available In this work, we have demonstrated the structural and optoelectronic properties of the surface of ternary/quaternary (CISe/CIGSe/CZTSe chalcopyrite nanocrystallites passivated by tri-n-octylphosphine-oxide (TOPO and tri-n-octylphosphine (TOP and compared their charge transfer characteristics in the respective polymer: chalcopyrite nanocomposites by dispersing them in poly(3-hexylthiophene polymer. It has been found that CZTSe nanocrystallites due to their high crystallinity and well-ordered 3-dimensional network in its pristine form exhibit a higher steric- and photo-stability, resistance against coagulation and homogeneity compared to the CISe and CIGSe counterparts. Moreover, CZTSe nanocrystallites display efficient photoluminescence quenching as evident from the high value of the Stern–Volmer quenching constant (KSV and eventually higher charge transfer efficiency in their respective polymer P3HT:CZTSe composites. We modelled the dependency of the charge transfer from the donor and the charge separation mechanism across the donor–acceptor interface from the extent of crystallinity of the chalcopyrite semiconductors (CISe/CIGSe/CZTSe. Quaternary CZTSe chalcopyrites with their high crystallinity and controlled morphology in conjunction with regioregular P3HT polymer is an attractive candidate for hybrid solar cells applications.

An insight into the mechanism of charge-transfer of hybrid polymer:ternary/quaternary chalcopyrite colloidal nanocrystals.

Science.gov (United States)

Chawla, Parul; Singh, Son; Sharma, Shailesh Narain

2014-01-01

In this work, we have demonstrated the structural and optoelectronic properties of the surface of ternary/quaternary (CISe/CIGSe/CZTSe) chalcopyrite nanocrystallites passivated by tri-n-octylphosphine-oxide (TOPO) and tri-n-octylphosphine (TOP) and compared their charge transfer characteristics in the respective polymer: chalcopyrite nanocomposites by dispersing them in poly(3-hexylthiophene) polymer. It has been found that CZTSe nanocrystallites due to their high crystallinity and well-ordered 3-dimensional network in its pristine form exhibit a higher steric- and photo-stability, resistance against coagulation and homogeneity compared to the CISe and CIGSe counterparts. Moreover, CZTSe nanocrystallites display efficient photoluminescence quenching as evident from the high value of the Stern-Volmer quenching constant (K SV) and eventually higher charge transfer efficiency in their respective polymer P3HT:CZTSe composites. We modelled the dependency of the charge transfer from the donor and the charge separation mechanism across the donor-acceptor interface from the extent of crystallinity of the chalcopyrite semiconductors (CISe/CIGSe/CZTSe). Quaternary CZTSe chalcopyrites with their high crystallinity and controlled morphology in conjunction with regioregular P3HT polymer is an attractive candidate for hybrid solar cells applications.

On γ-relaxation process in crystallizable polymers

International Nuclear Information System (INIS)

Mindiyarov, Kh.G.; Zelenev, Yu.V.; Bartenev, G.M.

1975-01-01

In the present paper, with the aid of radiothermoluminescence technique γ-relaxation processes are investigated, which are conditioned by molecular mobility and are associated with defects in the crystalline structure of polymers PEh, PP, and elastomers PIB, NK, SKD, SKI exposed to γ-rays of Co 60 at a dose rate of 1 Mrad. The shape of the thermoluminescence curve, i.e. the luminescence intensity in the α - γ-maxima, their relationship, position with respect to temperature are strongly dependent on the degree of crystallinity, on the thermal and mechanical prehistory. In highly crystalline samples of PEh and PP α-maximum may be absent. Dependence has been studied of the luminescence intensity in the α- and γ-maxima (Isub(α)/Isub(γ)) on the crystallization temperature; the curve passes through the minimum when the crystallization rate is maximum. The relationship Isub(γ)re of crystallinity degree

Effects on the Thermo-Mechanical and Crystallinity Properties of Nylon 6,6 Electrospun Fibres Reinforced with One Dimensional (1D and Two Dimensional (2D Carbon

Directory of Open Access Journals (Sweden)

Francisco Medellín-Rodríguez

2013-08-01

Full Text Available Electrospun one dimensional (1D and two dimensional (2D carbon based polymer nanocomposites are studied in order to determine the effect provided by the two differently structured nanofillers on crystallinity and thermo-mechanical properties of the nanofibres. The nanomaterials studied are pristine carbon nanotubes, oxidised carbon nanotubes, reduced graphene oxide and graphene oxide. Functional groups associated with the order structure of the polymers are analysed by infrared and Raman spectroscopies; the morphology is studied by scanning electron microscopy and the crystallinity properties are investigated by differential scanning calorimetry and X-ray diffraction. Differences in crystallisation behaviour between 1D and 2D carbon based nanofibres are shown by their crystallinity degree and their crystal sizes. The nanocomposite crystal sizes perpendicular to the plane (100 decrease with nanofiller content in all cases. The crystallinity trend and crystal sizes are in accordance with storage modulus response. The results also suggest that functionalisation favours interfacial bonding and dispersion of the nanomaterials within the polymer matrix. As a consequence the number of nucleating sites increases which in turn decreases the crystal size in the nanocomposites. These features explain the improved thermo-mechanical properties in the nanocomposites.

Melting point of polymers under high pressure Part I: Influence of the polymer properties

International Nuclear Information System (INIS)

Seeger, Andreas; Freitag, Detlef; Freidel, Frank; Luft, Gerhard

2004-01-01

The pressure dependence of the melting point of various polymers including homo- and copolymers (HDPE, LDPE, PP and ethylene vinyl acetate copolymers (EVA)) was investigated under nitrogen atmosphere up to 330 MPa within a high pressure differential thermal analysis cell designed by our group. The properties of the polymers (vinylacetate content, melt flow index, molecular weight, isotactic index, crystallinity, density, and frequency of branching) have been correlated with the change of the melting point under pressure (dT m /dp). It could be shown that the melting point always increases linearly with pressure up to 330 MPa. The pressure dependence was found to be in the range of 11-17 K/(100 MPa). From these results it is possible to approximate dT m /dp using the enthalpy of fusion of the polymers at ambient pressure

Comparison of the electronic structure of two polymers with strong dipole ordering

International Nuclear Information System (INIS)

Xiao Jie; Rosa, Luis G; Poulsen, Matt; Feng, D-Q; Reddy, D Sahadeva; Takacs, James M; Cai, Lei; Zhang, Jiandi; Ducharme, Stephen; Dowben, P A

2006-01-01

Two different polymers, with large local electric dipoles, are compared: copolymers of polyvinylidene fluoride with trifluoroethylene [P(VDF-TrFE, 70%:30%)] and polymethylvinylidenecyanide (PMVC). While the different local point group symmetries play a key role, both crystalline polymers exhibit intra-molecular band structure, though the Brillouin zone critical points differ. (letter to the editor)

On the relevance of the micromechanics approach for predicting the linear viscoelastic behavior of semi-crystalline poly(ethylene)terephtalates (PET)

International Nuclear Information System (INIS)

Diani, J.; Bedoui, F.; Regnier, G.

2008-01-01

The relevance of micromechanics modeling to the linear viscoelastic behavior of semi-crystalline polymers is studied. For this purpose, the linear viscoelastic behaviors of amorphous and semi-crystalline PETs are characterized. Then, two micromechanics modeling methods, which have been proven in a previous work to apply to the PET elastic behavior, are used to predict the viscoelastic behavior of three semi-crystalline PETs. The microstructures of the crystalline PETs are clearly defined using WAXS techniques. Since microstructures and mechanical properties of both constitutive phases (the crystalline and the amorphous) are defined, the simulations are run without adjustable parameters. Results show that the models are unable to reproduce the substantial decrease of viscosity induced by the increase of crystallinity. Unlike the real materials, for moderate crystallinity, both models show materials of viscosity nearly identical to the amorphous material

Crystallinity evaluation of polyhydroxybutyrate and polycaprolactone blends; Avaliacao da cristalinidade de blendas de polihidroxibutirato e policaprolactona

Energy Technology Data Exchange (ETDEWEB)

Cavalcante, Maxwell P.; Rodrigues, Elton Jorge R.; Tavares, Maria Ines B., E-mail: maxdpc@gmail.com [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil). Instituto de Macromoleculas

2015-07-01

Polyhydroxybutyrate, PHB, is a polymer obtained through bacterial or synthetic pathways. It has been used in the biomedical field as a matrix for drug delivery, medical implants and as scaffold material for tissue engineering. PHB has high structural organization, which makes it highly crystalline and brittle, making biodegradation difficult, reducing its employability. In order to enhance the mechanical and biological properties of PHB, blends with other polymers, biocompatible or not, are researched and produced. In this regard, blends of PHB and polycaprolactone, PCL, another biopolymer widely used in the biomedical industry, were obtained via solution casting and were characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and low field nuclear magnetic resonance (LF-NMR). Results have shown a dependence between PHB's crystallinity index and PCL quantity employed to obtain the blends.(author)

A two-dimensional conjugated aromatic polymer via C-C coupling reaction

Science.gov (United States)

Liu, Wei; Luo, Xin; Bao, Yang; Liu, Yan Peng; Ning, Guo-Hong; Abdelwahab, Ibrahim; Li, Linjun; Nai, Chang Tai; Hu, Zhi Gang; Zhao, Dan; Liu, Bin; Quek, Su Ying; Loh, Kian Ping

2017-06-01

The fabrication of crystalline 2D conjugated polymers with well-defined repeating units and in-built porosity presents a significant challenge to synthetic chemists. Yet they present an appealing target because of their desirable physical and electronic properties. Here we report the preparation of a 2D conjugated aromatic polymer synthesized via C-C coupling reactions between tetrabromopolyaromatic monomers. Pre-arranged monomers in the bulk crystal undergo C-C coupling driven by endogenous solid-state polymerization to produce a crystalline polymer, which can be mechanically exfoliated into micrometre-sized lamellar sheets with a thickness of 1 nm. Isothermal gas-sorption measurements of the bulk material reveal a dominant pore size of ~0.6 nm, which indicates uniform open channels from the eclipsed stacking of the sheets. When employed as an organic anode in an ambient-temperature sodium cell, the material allows a fast charge/discharge of sodium ions, with impressive reversible capacity, rate capability and stability metrics.

Inelastic neutron scattering from synthetic and biological polymers

International Nuclear Information System (INIS)

White, J.W.

1976-01-01

Neutron elastic and inelastic scattering measurements have provided many unique insights into structure, and by reviewing progress on synthetics, important differences likely to arise in biological systems are identified and a direction for studies of the latter is suggested. By neutron inelastic scattering it is possible to measure the frequency of thermally excited interatomic and intermolecular vibrations in crystals. With perfect organic and inorganic crystals the technique is now classical and has given great insight into the crystal forces responsible for the observed structures as well as the phase transitions they undergo. The study of polymer crystals immediately presents two problems of disorder: (1) Macroscopic disorder arises because the sample is a mixture of amorphous and crystalline fractions, and it may be acute enough to inhibit growth of a single crystal large enough for neutron studies. (2) Microscopic disorder in the packing of polymer chains in the ''crystalline'' regions is indicated by broadening of Bragg peaks. Both types of disorder problem arise in biological systems. The methods by which they were partially overcome to allow neutron measurements with synthetic polymers are described but first a classical example of the determination of interatomic forces by inelastic neutron scattering is given

Influence of miscibility phenomenon on crystalline polymorph transition in poly(vinylidene fluoride)/acrylic rubber/clay nanocomposite hybrid.

Science.gov (United States)

Abolhasani, Mohammad Mahdi; Naebe, Minoo; Jalali-Arani, Azam; Guo, Qipeng

2014-01-01

In this paper, intercalation of nanoclay in the miscible polymer blend of poly(vinylidene fluoride) (PVDF) and acrylic rubber(ACM) was studied. X-ray diffraction was used to investigate the formation of nanoscale polymer blend/clay hybrid. Infrared spectroscopy and X-ray analysis revealed the coexistence of β and γ crystalline forms in PVDF/Clay nanocomposite while α crystalline form was found to be dominant in PVDF/ACM/Clay miscible hybrids. Flory-Huggins interaction parameter (B) was used to further explain the miscibility phenomenon observed. The B parameter was determined by combining the melting point depression and the binary interaction model. The estimated B values for the ternary PVDF/ACM/Clay and PVDF/ACM pairs were all negative, showing both proper intercalation of the polymer melt into the nanoclay galleries and the good miscibility of PVDF and ACM blend. The B value for the PVDF/ACM blend was almost the same as that measured for the PVDF/ACM/Clay hybrid, suggesting that PVDF chains in nanocomposite hybrids interact with ACM chains and that nanoclay in hybrid systems is wrapped by ACM molecules.

ZnO Coatings with Controlled Pore Size, Crystallinity and Electrical Conductivity

Directory of Open Access Journals (Sweden)

Roman SCHMACK

2016-05-01

Full Text Available Zinc oxide is a wide bandgap semiconductor with unique optical, electrical and catalytic properties. Many of its practical applications rely on the materials pore structure, crystallinity and electrical conductivity. We report a synthesis method for ZnO films with ordered mesopore structure and tuneable crystallinity and electrical conductivity. The synthesis relies on dip-coating of solutions containing micelles of an amphiphilic block copolymer and complexes of Zn2+ ions with aliphatic ligands. A subsequent calcination at 400°C removes the template and induces crystallization of the pore walls. The pore structure is controlled by the template polymer, whereas the aliphatic ligands control the crystallinity of the pore walls. Complexes with a higher thermal stability result in ZnO films with a higher content of residual carbon, smaller ZnO crystals and therefore lower electrical conductivity. The paper discusses the ability of different types of ligands to assist in the synthesis of mesoporous ZnO and relates the structure and thermal stability of the precursor complexes to the crystallinity and electrical conductivity of the zinc oxide.DOI: http://dx.doi.org/10.5755/j01.ms.22.1.8634

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

KAUST Repository

Zhao, Kui

2015-09-07

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

Efficient tunable luminescence of SiGe alloy sheet polymers

International Nuclear Information System (INIS)

Vogg, G.; Meyer, A. J.-P.; Miesner, C.; Brandt, M. S.; Stutzmann, M.

2001-01-01

Crystalline SiGe alloy sheet polymers were topotactically prepared from epitaxially grown calcium germanosilicide Ca(Si 1-x Ge x ) 2 precursor films in the whole composition range. These polygermanosilynes are found to be a well-defined mixture of the known siloxene and polygermyne sheet polymers with the OH groups exclusively bonded to silicon. The optical properties determined by photoluminescence and optical reflection measurements identify the mixed SiGe sheet polymers as direct semiconductors with efficient luminescence tunable in the energy range between 2.4 and 1.3 eV. [copyright] 2001 American Institute of Physics

Selectivity of radiation-induced processes in hydrocarbons, related polymers and organized polymer systems

International Nuclear Information System (INIS)

Feldman, V.I.; Sukhov, F.F.; Zezin, A.A.; Orlov, A.Yu.

1999-01-01

Fundamental aspects of the selectivity of radiation-induced events in polymers and polymeric systems were considered: (1) The grounds of selectivity of the primary events were analyzed on the basis of the results of studies of model compounds (molecular aspect). Basic results were obtained for hydrocarbon molecules irradiated in low-temperature matrices. The effects of selective localization of the primary events on the radical formation were examined for several polymers irradiated at low and superlow temperatures (77 and 15 K). A remarkable correlation between the properties of prototype ionized molecules (radical cations) and selectivity of the primary bond rupture in the corresponding polymers were found for polyethylene, polystyrene and some other hydrocarbon polymers. The first direct indication of selective localization of primary events at conformational defects was obtained for oriented high-crystalline polyethylene irradiated at 15 K. The significance of dimeric ring association was proved for the radiation chemistry of polystyrene. Specific mechanisms of low-temperature radiation-induced degradation were also analyzed for polycarbonate and poly(alkylene terephthalates). (2) Specific features of the localization of primary radiation-induced events in microheterogeneous polymeric systems were investigated (microstructural aspect). It was found that the interphase processes played an important role in the radiation chemistry of such systems. The interphase electron migration may result in both positive and negative non-additive effects in the formation of radiolysis products. The effects of component diffusion and chemical reactions on the radiation-induced processes in microheterogeneous polymeric systems were studied with the example of polycarbonate - poly(alkylene terephthalate) blends. (3) The effects of restricted molecular motion on the development of the radiation-chemical processes in polymers were investigated (dynamic aspect). In particular, it

A preliminary assessment of the effects of radiation on polymer properties

International Nuclear Information System (INIS)

Dickson, L.W.

1988-01-01

The literature on the effects of radiation on the properties of various polymers and composites has been briefly reviewed for the purpose of identifying polymeric materials that could be irradiated to improve their performance. Radiation treatment of polymers may lead to cross-linking or chain scission reactions, depending on the chemical nature of the polymer. Cross-linking generally leads to an improvement in the mechanical properties of the polymer. Chain scission leads to deterioration in mechanical properties. The properties of irradiated polymers also depend on the degree of polymer crystallinity and the irradiation conditions, including dose rate and the presence of oxygen, cross-linking agents and other additives. A 30% increase in the tensile strength of many polymers may be obtained by radiation cross-linking under appropriate conditions. 40 refs

Hybrid ZnO:polymer bulk heterojunction solar cells from a ZnO precursor

NARCIS (Netherlands)

Beek, W.J.E.; Slooff, L.H.; Wienk, M.M.; Kroon, J.M.; Janssen, R.A.J.; Kafafi, Z.H.

2005-01-01

We describe a simple and new method to create hybrid bulk heterojunction solar cells consisting of ZnO and conjugated polymers. A gel-forming ZnO precursor, blended with conjugated polymers, is converted into crystalline ZnO at temperatures as low as 110 °C. In-situ formation of ZnO in MDMO-PPV

Drying of semicrystalline polymers: Mathematical modeling and experimental characterization of poly(vinyl alcohol) films

OpenAIRE

Wong, Sim-Siong; Altınkaya, Sacide; Mallapragada, Surya K.

2004-01-01

A mathematical model was developed to predict the drying mechanism of semicrystalline polymers involving multiple solvents. Since drying of semicrystalline polymers can be accompanied by changes in polymer degree of crystallinity, the model integrates crystallization kinetics and the Vrentas-Duda diffusion model to provide a better understanding of the mechanism. The model considers the effect of external conditions such as temperature, film shrinkage and diffusion and evaporation of multiple...

Electrical and mechanical properties of poly(ethylene oxide)/intercalated clay polymer electrolyte

International Nuclear Information System (INIS)

Moreno, Mabel; Quijada, Raúl; Santa Ana, María A.; Benavente, Eglantina; Gomez-Romero, Pedro; González, Guillermo

2011-01-01

Highlights: ► Poly(ethylene oxide)/intercalated clay nanocomposite as filler in solid poly(ethylene oxide) electrolytes. ► Nanocomposite filler improves mechanical properties, transparency, and conductivity of poly(ethylene oxide) electrolyte films. ► Nanocomposite is more effective than unmodified clay in improving polymer electrolyte properties. ► Low Li/polymer ratio avoids crystalline Li complexes, so effects mainly arise from the polymer. ► High nanocomposite/poly(ethylene oxide)-matrix affinity enhances microhomogeneity in the polyelectrolyte. - Abstract: Solvent-free solid polymer electrolytes (SPEs) based on two different poly(ethylene oxide), PEO Mw 600,000 and 4,000,000 and intercalated clays are reported. The inorganic additives used were lithiated bentonite and the nanocomposite PEO-bentonite with the same polymer used as matrix. SPE films, obtained in the scale of grams by mixing the components in a Brabender-type batch mixer and molding at 130 °C, were characterized by X-ray diffraction analysis, UV–vis spectroscopy, and thermal analysis. During the preparation of the films, the unmodified clay got intercalated in situ. Comparative analysis of ionic conductivity and mechanical properties of the films show that the conductivity increases with the inclusion of fillers, especially for the polymer with low molecular weight. This effect is more pronounced when using PEO-bentonite as additive. Under selected work conditions, avoiding the presence of crystalline lithium complexes, observed effects are mainly centered on the polymer. An explanation, considering the higher affinity between the modified clay and PEO matrix which leads to differences in the micro homogeneity degree between both types of polymer electrolytes is proposed.

Effects of Confinement on Microstructure and Charge Transport in High Performance Semicrystalline Polymer Semiconductors

KAUST Repository

Himmelberger, Scott

2012-11-23

The film thickness of one of the most crystalline and highest performing polymer semiconductors, poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b] thiophene) (PBTTT), is varied in order to determine the effects of interfaces and confinement on the microstructure and performance in organic field effect transistors (OFETs). Crystalline texture and overall film crystallinity are found to depend strongly on film thickness and thermal processing. The angular distribution of crystallites narrows upon both a decrease in film thickness and thermal annealing. These changes in the film microstructure are paired with thin-film transistor characterization and shown to be directly correlated with variations in charge carrier mobility. Charge transport is shown to be governed by film crystallinity in films below 20 nm and by crystalline orientation for thicker films. An optimal thickness is found for PBTTT at which the mobility is maximized in unannealed films and where mobility reaches a plateau at its highest value for annealed films. The effects of confinement on the morphology and charge transport properties of poly(2,5-bis(3-tetradecylthiophen-2-yl) thieno[3,2-b]thiophene) (PBTTT) are studied using quantitative X-ray diffraction and field-effect transistor measurements. Polymer crystallinity is found to limit charge transport in the thinnest films while crystalline texture and intergrain connectivity modulate carrier mobility in thicker films. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Confinement on Microstructure and Charge Transport in High Performance Semicrystalline Polymer Semiconductors

KAUST Repository

Himmelberger, Scott; Dacuñ a, Javier; Rivnay, Jonathan; Jimison, Leslie H.; McCarthy-Ward, Thomas; Heeney, Martin; McCulloch, Iain; Toney, Michael F.; Salleo, Alberto

2012-01-01

The film thickness of one of the most crystalline and highest performing polymer semiconductors, poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b] thiophene) (PBTTT), is varied in order to determine the effects of interfaces and confinement on the microstructure and performance in organic field effect transistors (OFETs). Crystalline texture and overall film crystallinity are found to depend strongly on film thickness and thermal processing. The angular distribution of crystallites narrows upon both a decrease in film thickness and thermal annealing. These changes in the film microstructure are paired with thin-film transistor characterization and shown to be directly correlated with variations in charge carrier mobility. Charge transport is shown to be governed by film crystallinity in films below 20 nm and by crystalline orientation for thicker films. An optimal thickness is found for PBTTT at which the mobility is maximized in unannealed films and where mobility reaches a plateau at its highest value for annealed films. The effects of confinement on the morphology and charge transport properties of poly(2,5-bis(3-tetradecylthiophen-2-yl) thieno[3,2-b]thiophene) (PBTTT) are studied using quantitative X-ray diffraction and field-effect transistor measurements. Polymer crystallinity is found to limit charge transport in the thinnest films while crystalline texture and intergrain connectivity modulate carrier mobility in thicker films. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Importance of crystallinity of anchoring block of semi-solid amphiphilic triblock copolymers in stabilization of silicone nanoemulsions.

Science.gov (United States)

Le Kim, Trang Huyen; Jun, Hwiseok; Nam, Yoon Sung

2017-10-01

Polymer emulsifiers solidified at the interface between oil and water can provide exceptional dispersion stability to emulsions due to the formation of unique semi-solid interphase. Our recent works showed that the structural stability of paraffin-in-water emulsions highly depends on the oil wettability of hydrophobic block of methoxy poly(ethylene glycol)-block-poly(ε-caprolactone) (mPEG-b-PCL). Here we investigate the effects of the crystallinity of hydrophobic block of triblock copolymer-based emulsifiers, PCLL-b-PEG-b-PCLL, on the colloidal properties of silicone oil-in-water nanoemulsions. The increased ratio of l-lactide to ε-caprolactone decreases the crystallinity of the hydrophobic block, which in turn reduces the droplet size of silicone oil nanoemulsions due to the increased chain mobility at the interface. All of the prepared nanoemulsions are very stable for a month at 37°C. However, the exposure to repeated freeze-thaw cycles quickly destabilizes the nanoemulsions prepared using the polymer with the reduced crystallinity. This work demonstrates that the anchoring chain crystallization in the semi-solid interphase is critically important for the structural robustness of nanoemulsions under harsh physical stresses. Copyright © 2017 Elsevier Inc. All rights reserved.

Direct Coupling of Electron Beam Irradiation and Polymer Extrusion for a Continuous Polymer Modification in Molten State

International Nuclear Information System (INIS)

Stephan, M.

2006-01-01

The new approach of an e-beam initiating of chemical reactions in polymers in molten state results in some innovative results. High temperature, intensive macromolecular mobility and the absence of any crystallinity are some reasons for achieving unexpected structures, processing behaviour and properties changes in such treated thermoplastics and rubbers. Examples are a much more effective crosslinking of polyethylene and special rubbers, long chain branching of polypropylene or a partial crosslinking of polysulfone. Additionally, most of these modification effects are also achievable by a direct coupling of electron beam irradiation and conventional polymer extrusion processing for a continuous polymer modification in molten state. For realizing this unique processing technique a special MOBILE RADIATION FACILITY (MOBRAD1/T) was designed, constructed and manufactured in the IPF Dresden at which a lab-scale single screw extruder was adapted direct to an electron beam accelerator to realize a prompt irradiation of extruded polymer melt profiles before there solidification. Surprisingly, as a result of these short-time-melt reactions some effective and new polymer modification effects were found and will be presented

Alpha B- and βA3-crystallins containing d-aspartic acids exist in a monomeric state.

Science.gov (United States)

Sakaue, Hiroaki; Takata, Takumi; Fujii, Norihiko; Sasaki, Hiroshi; Fujii, Noriko

2015-01-01

Crystallin stability and subunit-subunit interaction are essential for eye lens transparency. There are three types of crystallins in lens, designated as α-, β-, and γ-crystallins. Alpha-crystallin is a hetero-polymer of about 800kDa, consisting of 35-40 subunits of two different αA- and αB-subunits, each of 20kDa. The β/γ-crystallin superfamily comprises oligomeric β-crystallin (2-6 subunits) and monomeric γ-crystallin. Since lens proteins have very long half-lives, they undergo numerous post-translational modifications including racemization, isomerization, deamidation, oxidation, glycation, and truncation, which may decrease crystallin solubility and ultimately cause cataract formation. Racemization and isomerization of aspartyl (Asp) residues have been detected only in polymeric α- and oligomeric β-crystallin, while the situation in monomeric γ-crystallin has not been studied. Here, we investigated the racemization and isomerization of Asp in the γ-crystallin fraction of elderly donors. The results show that Asp residues of γS-, γD- and γC-crystallins were not racemized and isomerized. However, strikingly, we found that a portion of αB-crystallin and βA3-crystallin moved to the lower molecular weight fraction which is the same size of γ-crystallin. In those fractions, Asp-96 of αB-crystallin and Asp-37 of βA3-crystallin were highly inverted, which do not occur in the native lens higher molecular weight fraction. Our results indicate the possibility that the inversion of Asp residues may induce dissociation of αB- and βA3-crystallins from the polymeric and oligomeric states. This is the first report that stereoinversion of amino acids disturbs lens protein assembly in aged human lens. Copyright © 2014 Elsevier B.V. All rights reserved.

Comparative Community Proteomics Demonstrates the Unexpected Importance of Actinobacterial Glycoside Hydrolase Family 12 Protein for Crystalline Cellulose Hydrolysis

Energy Technology Data Exchange (ETDEWEB)

Hiras, Jennifer; Wu, Yu-Wei; Deng, Kai; Nicora, Carrie D.; Aldrich, Joshua T.; Frey, Dario; Kolinko, Sebastian; Robinson, Errol W.; Jacobs, Jon M.; Adams, Paul D.; Northen, Trent R.; Simmons, Blake A.; Singer, Steven W.

2016-08-23

Glycoside hydrolases (GHs) are key enzymes in the depolymerization of plant-derived cellulose, a process central to the global carbon cycle and the conversion of plant biomass to fuels and chemicals. A limited number of GH families hydrolyze crystalline cellulose, often by a processive mechanism along the cellulose chain. During cultivation of thermophilic cellulolytic microbial communities, substantial differences were observed in the crystalline cellulose saccharification activities of supernatants recovered from divergent lineages. Comparative community proteomics identified a set of cellulases from a population closely related to actinobacteriumThermobispora bisporathat were highly abundant in the most active consortium. Among the cellulases fromT. bispora, the abundance of a GH family 12 (GH12) protein correlated most closely with the changes in crystalline cellulose hydrolysis activity. This result was surprising since GH12 proteins have been predominantly characterized as enzymes active on soluble polysaccharide substrates. Heterologous expression and biochemical characterization of the suite ofT. bisporahydrolytic cellulases confirmed that the GH12 protein possessed the highest activity on multiple crystalline cellulose substrates and demonstrated that it hydrolyzes cellulose chains by a predominantly random mechanism. This work suggests that the role of GH12 proteins in crystalline cellulose hydrolysis by cellulolytic microbes should be reconsidered.

IMPORTANCECellulose is the most abundant organic polymer on earth, and its enzymatic hydrolysis is a key reaction in the global carbon cycle and the conversion of plant biomass to biofuels. The glycoside hydrolases that depolymerize crystalline cellulose have been primarily characterized from isolates. In this study, we demonstrate that adapting microbial consortia from compost to grow on crystalline cellulose

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

Science.gov (United States)

Crane, Deborah J.

2002-01-01

the material of choice in the production of acetabular cups for hip and tibial cradles for knee orthopeadic implant components for over 30 years. Although UHMWPE is used for more than 1.5 million implants a year in the United States alone and more than 3 million implant surgeries a year worldwide, problems with debris particle formation, pitting and fracture continue to induce premature failure of implant components. chains produced during polymerization are capable of packing into crystalline structures called lamellae, which are embedded within randomly oriented amorphous regions. Crosslinks, or tie molecules bridge the crystalline structures, which contribute to the materials' toughness and strength as a biomedical material. Research has been conducted providing evidence that a crosslinked gradient at the articulating surface of the polymer component provides resistance to surface degradation and subsequent debris formation. Recently, the introduction of highly crosslinked UHMWPE had proven to reduce some of the problems associated with the applications of this polymer as a biomedical material and was seen as the answer to solving the continuing problems associated with UHMWPE implant components. Yet current research into the fatigue characteristics of highly crosslinked UHMWPE has shown that subsurface crack propagation and subsequent delamination continues to produce problematic debris generation. Studies have shown that various sterilization and accelerated aging (to emulate natural oxidation rates) protocols adversely effects the material properties. Additional research has shown that alignment of the lamellae, caused by processing technique, fabrication or surface articulation may be the precursor to debris particle formation. Processing techniques performed under high pressure has proven to effect the width of the crystalline lamellae and therefore, the material's response to wear and fracture. UHMWP due to a microgravity environment, which could be

Efectos de la calidad de la caña semilla en los componentes del rendimiento cultural de las variedades CP65-357 y LCP85-384 (Saccharum spp. según diferentes edades de corte (Parte I Effects of seedcane quality on yielding components of varieties CP65-357 and LCP85-384 (Saccharum spp. in different crops (Part I

Directory of Open Access Journals (Sweden)

María I. Cuenya

2007-06-01

Full Text Available Las principales variedades de caña de azúcar cultivadas en Tucumán mostraron, hasta hace pocos años, una elevada infección con achaparramiento de la caña soca, enfermedad sistémica causada por Leifsonia xyli subsp. xyli, ampliamente reconocida por su efecto detrimental sobre el rendimiento cultural. Esta situación fue consecuencia de que los productores cañeros utilizaban caña semilla proveniente de lotes comerciales en lugar de caña semilla de semilleros saneados. El objetivo del presente trabajo fue evaluar el efecto de la calidad de la semilla en los componentes del rendimiento cultural en LCP85-384 y CP65-357, dos variedades ampliamente difundidas en Tucumán. Para cada variedad se evaluaron dos alternativas con respecto a la calidad de la semilla: Semilla de Alta Calidad (SAC proveniente de micropropagación in vitro y Semilla Comercial (SC proveniente de un cañaveral comercial. Se implantó un ensayo de acuerdo a un diseño en bloques completos al azar con seis repeticiones. En caña planta, soca 1 y soca 2 se evaluaron: número de tallos/parcela, peso, altura y diámetro del tallo y rendimiento de caña/ha. Se efectuaron análisis de la varianza y pruebas de comparación de medias (DLS de Fisher. En ambas variedades los componentes del rendimiento cultural más afectados por la calidad de la semilla utilizada fueron el peso y la altura de tallos a través de edades de corte. Para CP65-357 y LCP85-384 los tratamientos con SAC produjeron, en promedio, tallos más altos y más pesados en comparación con los tratamientos obtenidos a partir de SC. El diámetro de tallos no se afectó por la calidad de la semilla. Se detectaron importantes disminuciones en el rendimiento cultural (t caña/ha por la utilización de SC (10-25% en CP65-357 y 19-25% en LCP85-384 a través de las edades de corte. Estos resultados sustentan la utilización generalizada de semilleros saneados, sistema puesto en marcha por la EEAOC a partir del año 2000

Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

Science.gov (United States)

Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

2016-03-14

Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.

Location of radiation-induced grafted chains in polymers studied by solid-state NMR

International Nuclear Information System (INIS)

Whittacker, A.; Liu, H.

1998-01-01

In this study styrene and N-phenyl maleimide monomers were grafted onto poly(ethylene) (PE) chains using gamma radiation. Of main interest is the distribution of grafted chains within the polymer matrix, as this will determine the efficacy of mixing with the glassy polymers. It is expected that grafting will occur within the amorphous regions, and especially near the interface of the crystalline and amorphous regions. A suitable method for characterising the location of the grafted chains is solid-state 13 C NMR spectroscopy. The 13 C CPMAS spectrum of the blend of PE and N-phenyl maleimide mixed in the melt at 150 deg C , prior to reaction, is shown above. The spectrum shows the typical peaks for poly(ethylene) due to the amorphous and crystalline phase at 30.5 and 32.5 ppm, respectively. Peaks are also seen in the aromatic and carbonyl region due to the maleimide (not plotted). Experiments will be described where the NMR magnetisation is prepared in either the crystalline and amorphous regions of the poly(ethylene) prior to spin diffusion to the maleimide and styrene fractions. The location of the grafted monomers can then be determined by monitoring the changes in signal of polymer and graft with time

Thermal, crystallinity and morphological studies of the filled RBD palm kernel oil polyurethane foam

International Nuclear Information System (INIS)

Khairiah Badri; Sahrim Ahmad; Sarani Zakaria

2000-01-01

The synthesis of RBD palm kernel oil (PKO) polyurethane polyol and the polyurethane foam has well been documented. However, less study has been put in discovering the thermal properties and crystallinity of the foam. It is also an initiative to investigate the effect of oil palm empty fruit bunch (EFB) and sorbitol as fillers in the polyurethane (PU) foam to these properties. Thermogravimetric (TGA) investigation of the PKO PU foam was performed to study their decompositions. The semi-crystalline nature of EFB-filled PU was confirmed by x-ray diffratogram and DSC thermogram of glass transition temperature, T g . The x-ray diffraction (XRD) study of the unfilled PU showed a broad amorphous halo, indicative of absence of crystallinity in the polymer, which has been explained as due to strong hydrogen bonding in the hard phase. Overall crystallinity decreases with an increase in the polyester content in agreement with the XRD results. The crystallinity however, increases with the inclusion of EFB in the polyurethane system. This study was followed by the observation of the surface morphologies of the PKO PU foam with and without fillers. The scanning electron micrographs verified the finding on the improved k-factor values. (Author)

Novel Polymer Architectures for Optical Storage

DEFF Research Database (Denmark)

Hvilsted, Søren; Forcén, Patrica; Oriol, Luis

2007-01-01

Azobenzene containing polymers have been shown to have a large potential for high capacity olographic information storage. However, it has been difficult to fabricate thick films of the polymers with good op~ical quality so far. Liquid crystalline block copolymers prepared by Atom Transfer Radical...... Polymerization and based on azobenzene methacrylate and methyl methacrylate show some promise due to the observed block segregation. Thus, lamellar nanostructure was observed'when the azobenzene content was > 20% by weight, and both birefringence and dichroism can be induced by linearly polarized 488 nm light....... The formation of azo-aggregation inside the azo blocks is strongly,reduced when going from the homopolymer to the copolymers....

Influence of Miscibility Phenomenon on Crystalline Polymorph Transition in Poly(Vinylidene Fluoride)/Acrylic Rubber/Clay Nanocomposite Hybrid

Science.gov (United States)

Abolhasani, Mohammad Mahdi; Naebe, Minoo; Jalali-Arani, Azam; Guo, Qipeng

2014-01-01

In this paper, intercalation of nanoclay in the miscible polymer blend of poly(vinylidene fluoride) (PVDF) and acrylic rubber(ACM) was studied. X-ray diffraction was used to investigate the formation of nanoscale polymer blend/clay hybrid. Infrared spectroscopy and X-ray analysis revealed the coexistence of β and γ crystalline forms in PVDF/Clay nanocomposite while α crystalline form was found to be dominant in PVDF/ACM/Clay miscible hybrids. Flory-Huggins interaction parameter (B) was used to further explain the miscibility phenomenon observed. The B parameter was determined by combining the melting point depression and the binary interaction model. The estimated B values for the ternary PVDF/ACM/Clay and PVDF/ACM pairs were all negative, showing both proper intercalation of the polymer melt into the nanoclay galleries and the good miscibility of PVDF and ACM blend. The B value for the PVDF/ACM blend was almost the same as that measured for the PVDF/ACM/Clay hybrid, suggesting that PVDF chains in nanocomposite hybrids interact with ACM chains and that nanoclay in hybrid systems is wrapped by ACM molecules. PMID:24551141

Influence of miscibility phenomenon on crystalline polymorph transition in poly(vinylidene fluoride/acrylic rubber/clay nanocomposite hybrid.

Directory of Open Access Journals (Sweden)

Mohammad Mahdi Abolhasani

Full Text Available In this paper, intercalation of nanoclay in the miscible polymer blend of poly(vinylidene fluoride (PVDF and acrylic rubber(ACM was studied. X-ray diffraction was used to investigate the formation of nanoscale polymer blend/clay hybrid. Infrared spectroscopy and X-ray analysis revealed the coexistence of β and γ crystalline forms in PVDF/Clay nanocomposite while α crystalline form was found to be dominant in PVDF/ACM/Clay miscible hybrids. Flory-Huggins interaction parameter (B was used to further explain the miscibility phenomenon observed. The B parameter was determined by combining the melting point depression and the binary interaction model. The estimated B values for the ternary PVDF/ACM/Clay and PVDF/ACM pairs were all negative, showing both proper intercalation of the polymer melt into the nanoclay galleries and the good miscibility of PVDF and ACM blend. The B value for the PVDF/ACM blend was almost the same as that measured for the PVDF/ACM/Clay hybrid, suggesting that PVDF chains in nanocomposite hybrids interact with ACM chains and that nanoclay in hybrid systems is wrapped by ACM molecules.

Crystalline and Crystalline International Disposal Activities

Energy Technology Data Exchange (ETDEWEB)

Viswanathan, Hari S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chu, Shaoping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Dittrich, Timothy M. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hyman, Jeffrey De' Haven [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Karra, Satish [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Makedonska, Nataliia [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Reimus, Paul William [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2017-03-06

This report presents the results of work conducted between September 2015 and July 2016 at Los Alamos National Laboratory in the crystalline disposal and crystalline international disposal work packages of the Used Fuel Disposition Campaign (UFDC) for DOE-NE’s Fuel Cycle Research and Development program. Los Alamos focused on two main activities during this period: Discrete fracture network (DFN) modeling to describe flow and radionuclide transport in complex fracture networks that are typical of crystalline rock environments, and a comprehensive interpretation of three different colloid-facilitated radionuclide transport experiments conducted in a fractured granodiorite at the Grimsel Test Site in Switzerland between 2002 and 2013. Chapter 1 presents the results of the DFN work and is divided into three main sections: (1) we show results of our recent study on the correlation between fracture size and fracture transmissivity (2) we present an analysis and visualization prototype using the concept of a flow topology graph for characterization of discrete fracture networks, and (3) we describe the Crystalline International work in support of the Swedish Task Force. Chapter 2 presents interpretation of the colloidfacilitated radionuclide transport experiments in the crystalline rock at the Grimsel Test Site.

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

Directory of Open Access Journals (Sweden)

Omed Gh. Abdullah

Full Text Available 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. Keywords: Solid polymer electrolyte, XRD analysis, FTIR study, Optical band gap, Dielectric constant, Refractive index

How do polymers degrade?

Science.gov (United States)

Lyu, Suping

2011-03-01

Materials derived from agricultural products such as cellulose, starch, polylactide, etc. are more sustainable and environmentally benign than those derived from petroleum. However, applications of these polymers are limited by their processing properties, chemical and thermal stabilities. For example, polyethylene terephthalate fabrics last for many years under normal use conditions, but polylactide fabrics cannot due to chemical degradation. There are two primary mechanisms through which these polymers degrade: via hydrolysis and via oxidation. Both of these two mechanisms are related to combined factors such as monomer chemistry, chain configuration, chain mobility, crystallinity, and permeation to water and oxygen, and product geometry. In this talk, we will discuss how these materials degrade and how the degradation depends on these factors under application conditions. Both experimental studies and mathematical modeling will be presented.

White emission from liquid-crystalline copolymers containing oxadiazole moieties in the side chain

Science.gov (United States)

Kawamoto, Masuki; Tsukamoto, Takuji; Kinoshita, Motoi; Ikeda, Tomiki

2006-09-01

A liquid-crystalline polymer in the side chain was synthesized through copolymerization of a bipolar carrier-transporting monomer with a liquid-crystalline monomer containing oxadiazole moieties substituted with trifluoromethyl groups. A single-layer light-emitting diode of indium tin oxide (ITO)/copolymer/MgAg emitted white light with a maximum luminous efficiency of 0.1cd/A. The origin of the white emission in the copolymer is the electroplex between bipolar carrier-transporting moieties and strong electron-withdrawing moieties. Furthermore, a simple multilayer device with configuration of ITO/poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid)/copolymer/MgAg device showed white emission with CIE 1931 chromaticity coordinates (x,y): (0.30, 0.33).

Polarized Emission from Conjugated Polymer Chains Aligned by Epitaxial Growth during Off-Center Spin-Coating

Directory of Open Access Journals (Sweden)

Takuya Anzai

2017-01-01

Full Text Available Due to their macromolecular nature, conjugated polymers can be relatively easily aligned by applying a variety of processes resulting in either elongation or ordering of their conjugated backbones. Processes that induce chain alignment include electrospinning, mechanical rubbing, epitaxial growth, and nanoconfinement and unidirectional deposition techniques such as off-center spin-coating. In this study, we compare these deposition techniques by applying them to a green-emitting conjugated polymer material that exhibits liquid crystalline phase behavior. Our study reveals that while methods such as electrospinning and mechanical rubbing can be useful to locally generate polymer chain alignment, the combination of epitaxial growth using 1,3,5-trichlorobenzene as crystallizing agent with off-center spin-coating results in the formation of anisotropic nanofiber-like structures with enhanced crystallinity degree and polarized light-emission properties. The unidirectional epitaxial growth was also applied to a red-emitting polymer that exhibits polarization ratios up to 4.1. Our results emphasize that this simple solution formulation and process can be used for the fabrication of polarized thin films of a variety of conjugated polymers with potential applications in the advanced display technologies or analytical equipment fields.

STRUCTURAL AND MECHANICAL CHARACTERIZATION OF DEFORMED POLYMER USING CONFOCAL RAMAN MICROSCOPY AND DSC

Directory of Open Access Journals (Sweden)

Birgit Neitzel

2016-02-01

Full Text Available Polymers have various interesting properties, which depend largely on their inner structure. One way to influence the macroscopic behaviour is the deformation of the polymer chains, which effects the change in microstructure. For analyzing the microstructure of non-deformed and deformed polymer materials, Raman spectroscopy as well as differential scanning calorimetry (DSC were used. In the present study we compare the results for crystallinity measurements of deformed polymers using both methods in order to characterize the differences in micro-structure due to deformation. The study is ongoing, and we present the results of the first tests.

Tuning crystallization pathways through sequence engineering of biomimetic polymers

Science.gov (United States)

Ma, Xiang; Zhang, Shuai; Jiao, Fang; Newcomb, Christina J.; Zhang, Yuliang; Prakash, Arushi; Liao, Zhihao; Baer, Marcel D.; Mundy, Christopher J.; Pfaendtner, James; Noy, Aleksandr; Chen, Chun-Long; de Yoreo, James J.

2017-07-01

Two-step nucleation pathways in which disordered, amorphous, or dense liquid states precede the appearance of crystalline phases have been reported for a wide range of materials, but the dynamics of such pathways are poorly understood. Moreover, whether these pathways are general features of crystallizing systems or a consequence of system-specific structural details that select for direct versus two-step processes is unknown. Using atomic force microscopy to directly observe crystallization of sequence-defined polymers, we show that crystallization pathways are indeed sequence dependent. When a short hydrophobic region is added to a sequence that directly forms crystalline particles, crystallization instead follows a two-step pathway that begins with the creation of disordered clusters of 10-20 molecules and is characterized by highly non-linear crystallization kinetics in which clusters transform into ordered structures that then enter the growth phase. The results shed new light on non-classical crystallization mechanisms and have implications for the design of self-assembling polymer systems.

Tuning crystallization pathways through sequence engineering of biomimetic polymers

Energy Technology Data Exchange (ETDEWEB)

Ma, Xiang; Zhang, Shuai; Jiao, Fang; Newcomb, Christina J.; Zhang, Yuliang; Prakash, Arushi; Liao, Zhihao; Baer, Marcel D.; Mundy, Christopher J.; Pfaendtner, James; Noy, Aleksandr; Chen, Chun-Long; De Yoreo, James J.

2017-04-17

Two-step nucleation pathways in which disordered, amorphous, or dense liquid states precede appearance of crystalline phases have been reported for a wide range of materials, but the dynamics of such pathways are poorly understood. Moreover, whether these pathways are general features of crystallizing systems or a consequence of system-specific structural details that select for direct vs two-step processes is unknown. Using atomic force microscopy to directly observe crystallization of sequence-defined polymers, we show that crystallization pathways are indeed sequence dependent. When a short hydrophobic region is added to a sequence that directly forms crystalline particles, crystallization instead follows a two-step pathway that begins with creation of disordered clusters of 10-20 molecules and is characterized by highly non-linear crystallization kinetics in which clusters transform into ordered structures that then enter the growth phase. The results shed new light on non-classical crystallization mechanisms and have implications for design of self-assembling polymer systems.

Study of photoconductor polymers synthesized by plasma

International Nuclear Information System (INIS)

Enriquez P, M.A.

2007-01-01

In this work the photoconductivity in poly thiophene (PTh), poly pyrrole (PPy) and doped poly pyrrole with iodine (PPy/I) is studied, whose structures depend of the intensity of the electric field applied during the synthesis by plasma. The conjugated organic polymers possess double alternated bonds in its chemical structure that its allow the one movement of π electrons through the polymeric chains. The plasma is produced by means of splendor discharges to 13.5 MHz, resistive coupling, at one pressure that oscillates in the interval from 2 to 3x10 -1 mbar, 180 min and powers of 10, 24, 40, 60 , 80 and 100 W. Its were used heteroaromatic polymers like PTh and PPy/I, due to their potential applications in optoelectronics. The influence of the iodine is evaluated as dopant in PPy and it is compared with their similar one without doping in the light absorption/emission processes. The polymers synthesized by plasma can ramify or to intersect due to the energy applied during the synthesis. However, if the polymer intersects, the aromaticity can continue through the polymeric chains. The absorptions obtained by infrared spectroscopy, suggest that the polymer conserves the aromatic structure of the monomer fundamentally with substitutions that indicate inter crossing and partial fragmentation. The structure of most of the polymers spreads to be amorphous because they don't possess any classification. However, the PPy/I and PTh synthesized by this technique present crystalline segments whose intensity diminishes with the power of the discharge. In PTh, the average crystallinity diminishes from 19.8% to 9.9%, and in PPy/I of 15.9% to 13.3% in the interval of 10 to 100 W of power. In this work, however, its were crystalline arrangements in all the studied powers. The classification of the polymeric structure favors the formation of trajectories of transfer of electric loads among the chains, that which influences in the global electric conductivity of the material. In UV

Characterization of temperature-dependent optical material properties of polymer powders

Energy Technology Data Exchange (ETDEWEB)

Laumer, Tobias [Bayerisches Laserzentrum GmbH, 91052 Erlangen (Germany); SAOT Erlangen Graduate School in Advanced Optical Technologies, 91052 Erlangen (Germany); CRC Collaborative Research Center 814 - Additive Manufacturing, 91052 Erlangen (Germany); Stichel, Thomas; Bock, Thomas; Amend, Philipp [Bayerisches Laserzentrum GmbH, 91052 Erlangen (Germany); CRC Collaborative Research Center 814 - Additive Manufacturing, 91052 Erlangen (Germany); Schmidt, Michael [Bayerisches Laserzentrum GmbH, 91052 Erlangen (Germany); University of Erlangen-Nürnberg, Institute of Photonic Technologies, 91052 Erlangen (Germany); SAOT Erlangen Graduate School in Advanced Optical Technologies, 91052 Erlangen (Germany); CRC Collaborative Research Center 814 - Additive Manufacturing, 91052 Erlangen (Germany)

2015-05-22

In former works, the optical material properties of different polymer powders used for Laser Beam Melting (LBM) at room temperature have been analyzed. With a measurement setup using two integration spheres, it was shown that the optical material properties of polymer powders differ significantly due to multiple reflections within the powder compared to solid bodies of the same material. Additionally, the absorption behavior of the single particles shows an important influence on the overall optical material properties, especially the reflectance of the powder bed. Now the setup is modified to allow measurements at higher temperatures. Because crystalline areas of semi-crystalline thermoplastics are mainly responsible for the absorption of the laser radiation, the influence of the temperature increase on the overall optical material properties is analyzed. As material, conventional polyamide 12 and polypropylene as new polymer powder material, is used. By comparing results at room temperature and at higher temperatures towards the melting point, the temperature-dependent optical material properties and their influence on the beam-matter interaction during the process are discussed. It is shown that the phase transition during melting leads to significant changes of the optical material properties of the analyzed powders.

Silk fibroin as an organic polymer for controlled drug delivery

NARCIS (Netherlands)

Hofmann, S.; Foo, S.; Rossetti, F.; Textor, M.; Vunjak-Novakovic, G.; Kaplan, D.L.; Merkle, H.P.; Meinel, L.

2006-01-01

The pharmaceutical utility of silk fibroin (SF) materials for drug delivery was investigated. SF films were prepared from aqueous solutions of the fibroin protein polymer and crystallinity was induced and controlled by methanol treatment. Dextrans of different molecular weights, as well as proteins,

Crystalline and Crystalline International Disposal Activities

Energy Technology Data Exchange (ETDEWEB)

Viswanathan, Hari S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chu, Shaoping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Reimus, Paul William [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Makedonska, Nataliia [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hyman, Jeffrey De' Haven [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Karra, Satish [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Dittrich, Timothy M. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2015-12-21

This report presents the results of work conducted between September 2014 and July 2015 at Los Alamos National Laboratory in the crystalline disposal and crystalline international disposal work packages of the Used Fuel Disposition Campaign (UFDC) for DOE-NE’s Fuel Cycle Research and Development program.

Electrospun PVdF-based fibrous polymer electrolytes for lithium ion polymer batteries

International Nuclear Information System (INIS)

Kim, Jeong Rae; Choi, Sung Won; Jo, Seong Mu; Lee, Wha Seop; Kim, Byung Chul

2004-01-01

This paper discusses the preparation of microporous fibrous membranes from PVdF solutions with different polymer contents, using the electrospinning technique. Electrospun PVdF-based fibrous membranes with average fiber diameters (AFD's) of 0.45-1.38 μm have an apparent porosity and a mean pore size (MPS) of 80-89% and 1.1-4.3 μm, respectively. They exhibited a high uptake of the electrolyte solution (320-350%) and a high ionic conductivity of above 1 x 10 -3 s/cm at room temperature. Their ionic conductivity increased with the decrease in the AFD of the fibrous membrane due to its high electrolyte uptake. The interaction between the electrolyte molecules and the PVdF with a high crystalline content may have had a minor effect on the lithium ion transfer in the fibrous polymer electrolyte, unlike in a nanoporous gel polymer electrolyte. The fibrous polymer electrolyte that contained a 1 M LiPF 6 -EC/DMC/DEC (1/1/1 by weight) solution showed a high electrochemical stability of above 5.0 V, which increased with the decrease in the AFD The interfacial resistance (R i ) between the polymer electrolyte and the lithium electrode slightly increased with the storage time, compared with the higher increase in the interfacial resistance of other gel polymer electrolytes. The prototype cell (MCMB/PVdF-based fibrous electrolyte/LiCoO 2 ) showed a very stable charge-discharge behavior with a slight capacity loss under constant current and voltage conditions at the C/2-rate of 20 and 60 deg. C

A thermodynamic approach to model the caloric properties of semicrystalline polymers

Science.gov (United States)

Lion, Alexander; Johlitz, Michael

2016-05-01

It is well known that the crystallisation and melting behaviour of semicrystalline polymers depends in a pronounced manner on the temperature history. If the polymer is in the liquid state above the melting point, and the temperature is reduced to a level below the glass transition, the final degree of crystallinity, the amount of the rigid amorphous phase and the configurational state of the mobile amorphous phase strongly depend on the cooling rate. If the temperature is increased afterwards, the extents of cold crystallisation and melting are functions of the heating rate. Since crystalline and amorphous phases exhibit different densities, the specific volume depends also on the temperature history. In this article, a thermodynamically based phenomenological approach is developed which allows for the constitutive representation of these phenomena in the time domain. The degree of crystallinity and the configuration of the amorphous phase are represented by two internal state variables whose evolution equations are formulated under consideration of the second law of thermodynamics. The model for the specific Gibbs free energy takes the chemical potentials of the different phases and the mixture entropy into account. For simplification, it is assumed that the amount of the rigid amorphous phase is proportional to the degree of crystallinity. An essential outcome of the model is an equation in closed form for the equilibrium degree of crystallinity in dependence on pressure and temperature. Numerical simulations demonstrate that the process dependences of crystallisation and melting under consideration of the glass transition are represented.

Effect of time and temperature exposition in the crystallinity degree of sulfonated poly-(styrene acrylic acid) (PSAA-S)

International Nuclear Information System (INIS)

Duarte, G.W.; Becker, E.B.; Silva, L.; Naspolini, A.M.; Consenso, E.C.; Paula, M.M.S.; Fiori, M.A.; Silveira, F.Z.

2010-01-01

Polymers with special properties have been increasingly applied in the development of technological devices. For example, polymeric materials with special electric properties, such as sulfonated poly-(styrene-acrylic acid) - PSAA-S, are of great interest for showing different conductivities depending on the environment where they are applied. The special properties of PSAA are obtained only after sulfonation step in acidic media. The present work aimed to evaluate the effect of time and temperature exposition in the crystallinity degree of PSAA-S, through a statistical experimental factorial planning. The samples of PSAA-S were submitted to FT-IR and DRX tests. The results showed that the temperature and the time of exposition are significant factors in the crystallinity degree of PSAA-S, considering that the crystal lattices created during the polymerization are damaged by the action of time and temperature at which the polymer is exposed. (author)

Effect of time and temperature exposition in the crystallinity degree of sulfonated poly-(styrene acrylic acid) (PSAA-S)

Energy Technology Data Exchange (ETDEWEB)

Duarte, G.W.; Becker, E.B.; Silva, L.; Naspolini, A.M.; Consenso, E.C.; Paula, M.M.S.; Fiori, M.A., E-mail: glau_bn@hotmail.co [University of Extreme South of Santa Catarina Criciuma, SC (Brazil). Dept. of Materials Engineering; Silveira, F.Z. [Federal University of Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. of Chemical Engineering

2010-07-01

Polymers with special properties have been increasingly applied in the development of technological devices. For example, polymeric materials with special electric properties, such as sulfonated poly-(styrene-acrylic acid) - PSAA-S, are of great interest for showing different conductivities depending on the environment where they are applied. The special properties of PSAA are obtained only after sulfonation step in acidic media. The present work aimed to evaluate the effect of time and temperature exposition in the crystallinity degree of PSAA-S, through a statistical experimental factorial planning. The samples of PSAA-S were submitted to FT-IR and DRX tests. The results showed that the temperature and the time of exposition are significant factors in the crystallinity degree of PSAA-S, considering that the crystal lattices created during the polymerization are damaged by the action of time and temperature at which the polymer is exposed. (author)

Titanium carbide nanocube core induced interfacial growth of crystalline polypyrrole/polyvinyl alcohol lamellar shell for wide-temperature range supercapacitors

Science.gov (United States)

Weng, Yu-Ting; Pan, Hsiao-An; Wu, Nae-Lih; Chen, Geroge Zheng

2015-01-01

This is the first investigation on electrically conducting polymers-based supercapacitor electrodes over a wide temperature range, from -18 °C to 60 °C. A high-performance supercapacitor electrode material consisting of TiC nanocube core and conformal crystalline polypyrrole (PPy)/poly-vinyl-alcohol (PVA) lamellar shell has been synthesized by heterogeneous nucleation-induced interfacial crystallization. PPy is induced to crystallize on the negatively charged TiC nanocube surfaces via strong interfacial interactions. In this organic-inorganic hybrid nanocomposite, the long chain PVA enables enhanced cycle life due to improved mechanical properties, and the TiC nanocube not only contributes to electron conduction, but also dictates the PPy morphology/crystallinity for maximizing the charging-discharging performance. The crystalline PPy/PAV layer on the TiC nanocube offers unprecedented high capacity (>350 F g-1-PPy at 300 mV s-1 with ΔV = 1.6 V) and cycling stability in a temperature range from -18 °C to 60 °C. The presented hybrid-filler and interfacial crystallization strategies can be applied to the exploration of new-generation high-power conducting polymer-based supercapacitor materials.

The evolution of strength and crystalline phases for alkali-activated ground blast furnace slag and fly ash-based geopolymers

KAUST Repository

Oh, Jae Eun; Monteiro, Paulo J.M.; Jun, Ssang Sun; Choi, Sejin; Clark, Simon M.

2010-01-01

The increase in strength and evolution of crystalline phases in inorganic polymer cement, made by the alkali activation of slag, Class C and Class F fly ashes, was followed using compressive strength test and synchrotron X-ray diffraction. In order

Molecular origins of anisotropic shock propagation in crystalline and amorphous polyethylene

Science.gov (United States)

O'Connor, Thomas C.; Elder, Robert M.; Sliozberg, Yelena R.; Sirk, Timothy W.; Andzelm, Jan W.; Robbins, Mark O.

2018-03-01

Molecular dynamics simulations are used to analyze shock propagation in amorphous and crystalline polyethylene. Results for the shock velocity Us are compared to predictions from Pastine's equation of state and hydrostatic theory. The results agree with Pastine at high impact velocities. At low velocities the yield stress becomes important, increasing the shock velocity and leading to anisotropy in the crystalline response. Detailed analysis of changes in atomic order reveals the origin of the anisotropic response. For shock along the polymer backbone, an elastic front is followed by a plastic front where chains buckle with a characteristic wavelength. Shock perpendicular to the chain backbone can produce plastic deformation or transitions to different orthorhombic or monoclinic structures, depending on the impact speed and direction. Tensile loading does not produce stable shocks: Amorphous systems craze and fracture while for crystals the front broadens linearly with time.

Hybrid zinc oxide conjugated polymer bulk heterojunction solar cells

NARCIS (Netherlands)

Beek, W.J.E.; Wienk, M.M.; Kemerink, M.; Yang, X.N.; Janssen, R.A.J.

2005-01-01

Bulk heterojunction photovoltaic devices based on blends of a conjugated polymer poly[2-methoxy-5-(3‘,7‘-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) as electron donor and crystalline ZnO nanoparticles (nc-ZnO) as electron acceptor have been studied. Composite nc-ZnO:MDMO-PPV films were cast

Functionalized Nanoporous Polymer Membranes with Well-Defined Pore Architectures via Lyotropic Liquid-Crystalline Monomers

National Research Council Canada - National Science Library

Gin, Douglas

1997-01-01

.... Two lyotropic liquid-crystalline monomer platforms have been synthesized. The interchannel separations in the polymerizable materials can be varied in the 30-40 A range by the choice of counterion on the ionic headgroup of the monomers...

Full Color Camouflage in a Printable Photonic Blue-Colored Polymer

OpenAIRE

Moirangthem, Monali; Schenning, Albertus P. H. J.

2018-01-01

A blue reflective photonic polymer coating which can be patterned in full color, from blue to red, by printing with an aqueous calcium nitrate solution has been fabricated. Color change in the cholesteric liquid-crystalline polymer network over the entire visible spectrum is obtained by the use of nonreactive mesogen. The pattern in the coating is hidden in the blue color dry state and appears upon exposure to water or by exhaling breath onto it due to different degrees of swelling of the pol...

Multicomponent semiconducting polymer systems with low crystallization-induced percolation threshold

DEFF Research Database (Denmark)

Goffri, S.; Müller, C.; Stingelin-Stutzmann, N.

2006-01-01

of the two components, during which the semiconductor is predominantly expelled to the surfaces of cast films, we can obtain vertically stratified structures in a one-step process. Incorporating these as active layers in polymer field-effect transistors, we find that the concentration of the semiconductor......–crystalline/semiconducting–insulating multicomponent systems offer expanded flexibility for realizing high-performance semiconducting architectures at drastically reduced materials cost with improved mechanical properties and environmental stability, without the need to design all performance requirements into the active semiconducting polymer...

A Route for Polymer Nanocomposites with Engineered Electrical Conductivity and Percolation Threshold

Directory of Open Access Journals (Sweden)

Lawrence T. Drzal

2010-02-01

Full Text Available Polymer nanocomposites with engineered electrical properties can be made by tuning the fabrication method, processing conditions and filler’s geometric and physical properties. This work focuses on investigating the effect of filler’s geometry (aspect ratio and shape, intrinsic electrical conductivity, alignment and dispersion within the polymer, and polymer crystallinity, on the percolation threshold and electrical conductivity of polypropylene based nanocomposites. The conductive reinforcements used are exfoliated graphite nanoplatelets, carbon black, vapor grown carbon fibers and polyacrylonitrile carbon fibers. The composites are made using melt mixing followed by injection molding. A coating method is also employed to improve the nanofiller’s dispersion within the polymer and compression molding is used to alter the nanofiller’s alignment.

Oxygen transport as a structure probe for heterogeneous polymeric systems

Science.gov (United States)

Hu, Yushan

Although permeability of small molecules is often measured as an important performance property, deeper analysis of the transport characteristics provides insight into polymer structure, especially if used in combination with other characterization techniques. Transport of small gas molecules senses the permeable amorphous structure and probes the nature of free volume. This work focuses on oxygen transport, supplemented with other methods of physical analysis, as a probe for: (1) the nature of free volume and crystalline morphology in the crystallized glassy state, (2) the nature of free volume and hierarchical structure in liquid crystalline polymers, and (3) the role of dispersed polyamide phase geometry on oxygen barrier properties of poly(ethylene terephthalate) (PET)/polyamide blends. In the first part, the improvement in oxygen-barrier properties of glassy polyesters by crystallization was examined. Examples included poly(ethylene naphthalate) (PEN), and a copolymer based on PET in which 55 mol% terephthalate was replaced with 4,4'-bibenzoate. Explanation of the unexpectedly high solubility of crystallized PEN required a two-phase transport model consisting of an impermeable crystalline phase of constant density and a permeable amorphous phase of variable density. The resulting relationship between oxygen solubility and amorphous phase density was consistent with free volume concepts of gas sorption. In the second part, oxygen barrier properties of liquid crystalline (LC) polyesters based on poly(diethylene glycol 4,4'-bibenzoate) (PDEGBB) were studied. This study extended the 2-phase transport model for oxygen transport of non-LC crystalline polymers to a smectic LCP. It was possible to systematically vary the solid state structure of (PDEGBB) from LC glass to crystallized LC glass. The results were consistent with a liquid crystalline state intermediate between the permeable amorphous glass and the impermeable 3-dimensional crystal. In this interpretation

Crystalline Silica Primer

Science.gov (United States)

,

1992-01-01

Crystalline silica is the scientific name for a group of minerals composed of silicon and oxygen. The term crystalline refers to the fact that the oxygen and silicon atoms are arranged in a threedimensional repeating pattern. This group of minerals has shaped human history since the beginning of civilization. From the sand used for making glass to the piezoelectric quartz crystals used in advanced communication systems, crystalline silica has been a part of our technological development. Crystalline silica's pervasiveness in our technology is matched only by its abundance in nature. It's found in samples from every geologic era and from every location around the globe. Scientists have known for decades that prolonged and excessive exposure to crystalline silica dust in mining environments can cause silicosis, a noncancerous lung disease. During the 1980's, studies were conducted that suggested that crystalline silica also was a carcinogen. As a result of these findings, crystalline silica has been regulated under the Occupational Safety and Health Administration's (OSHA) Hazard Communication Standard (HCS). Under HCS, OSHAregulated businesses that use materials containing 0.1% or more crystalline silica must follow Federal guidelines concerning hazard communication and worker training. Although the HCS does not require that samples be analyzed for crystalline silica, mineral suppliers or OSHAregulated

The flow properties and presence of crystals in drug-polymer mixtures

DEFF Research Database (Denmark)

Aho, J; Van Renterghem, J; Arnfast, L

2017-01-01

and ibuprofen with polyethylene oxide and methacrylate copolymer (Eudragit(®) E PO) were observed by polarized microscopy simultaneously while measuring their rheological properties within temperature ranges relevant for melt processes, such as hot melt extrusion and fused deposition modeling 3D printing....... The dissolution of solid crystalline matter into the molten polymer and its effects on the rheological parameters showed that the plasticization effect of the drug was highly dependent on the temperature range, and at a temperature high enough, plasticization induced by the small-molecule drugs could enhance...... morphological changes in the drug-polymer and the flow behavior of the drug-polymer mixtures at different temperature ranges and deformation modes....

Correlations between structure and optoelectronic properties of conjugated polymers

International Nuclear Information System (INIS)

Sims, Marc

2002-01-01

An understanding of the fundamental processes that govern the electro-optical properties of conjugated polymers is essential for the improvement of polymer light-emitting diodes (PLEDs). The majority of the work in this thesis comprises a study on a group of sterically congested poly(para-phenylenevinylene)s (PPVs). It deals initially with the discovery and development of a highly ordered crystalline phase of a chloro-derived n-butyl analogue. A thorough structural characterisation of this phase is then made from the results of X-ray Diffraction, FT-IR and Raman scattering spectroscopies. The effective conjugation length of the chains that comprise the crystalline sample is longer than that found in two relatively disordered films, one that was prepared by spin-coating and the other by drop-casting. The spin-coated film was found to exhibit a higher photoluminescence quantum efficiency (PLQE) value than the drop-cast film, which has been attributed to the presence of lower density of aggregate states in the former. The PLQE of the crystalline sample is considerably lower than that of both of the films and this is ascribed to the rapid migration of excitons to defect sites e.g. grain boundaries. PLE measurements for all the samples strongly suggest that singlet exciton quenching is intimately related to energy migration processes. Through the study of a novel, reversible, light-induced photoluminescence quenching effect, it was concluded that photogenerated polaronic species can be trapped sufficiently deeply that they can stabilise for periods in excess of hours at low temperatures. Furthermore, it is demonstrated that the photogenerated polaronic species are less stable in the crystalline sample, yet most stable in the most disordered spin-cast film. It is shown by excitation into the tail states of the crystalline sample that the first vibronic feature in the quasi-resonantly excited PL spectrum undergoes gain. This phenomenon is not observed in the more

Polymerization and processing of organic polymers in a magnetic field

Energy Technology Data Exchange (ETDEWEB)

Douglas, E.P. [Los Alamos National Laboratory, NM (United States)

1995-05-01

The use of magnetic fields to affect the structure and properties of polymeric materials remains an area of great promise. Liquid crystalline polymers have been actively studied over the past 20 years for use in high performance structural applications. In particular, highly oriented fibers can exhibit remarkable increases in strength to weight performance compared to conventional materials. For example, the fibers marketed by DuPont under the tradename Kevlar are 20 times stronger than steel on an equivalent weight basis. However, larger bulk parts do not exhibit the same increases in strength due to a lack of orientation of the polymer molecules. Magnetic field processing of polymers remains an attractive solution to this problem.

Shape-memory effect of nanocomposites based on liquid-crystalline elastomers

Science.gov (United States)

Marotta, A.; Lama, G. C.; Gentile, G.; Cerruti, P.; Carfagna, C.; Ambrogi, V.

2016-05-01

In this work, nanocomposites based on liquid crystalline (LC) elastomers were prepared and characterized in their shape memory properties. For the synthesis of materials, p-bis(2,3-epoxypropoxy)-α-methylstilbene (DOMS) was used as mesogenic epoxy monomer, sebacic acid (SA) as curing agent and multi-walled carbon nanotubes (MWCNT) and graphene oxide (GO) as fillers. First, an effective compatibilization methodology was set up to improve the interfacial adhesion between the matrix and the carbonaceous nanofillers, thus obtaining homogeneous distribution and dispersion of the nanofillers within the polymer phase. Then, the obtained nanocomposite films were characterized in their morphological and thermal properties. In particular, the effect of the addition of the nanofillers on liquid crystalline behavior, as well as on shape-memory properties of the realized materials was investigated. It was found that both fillers were able to enhance the thermomechanical response of the LC elastomers, making them good candidates as shape memory materials.

Midterm Follow-up of Treating Volar Marginal Rim Fractures with Variable Angle Lcp Volar Rim Distal Radius Plates.

Science.gov (United States)

Goorens, Chul Ki; Geeurickx, Stijn; Wernaers, Pascal; Staelens, Barbara; Scheerlinck, Thierry; Goubau, Jean

2017-06-01

Specific treatment of the volar marginal rim fragment of distal radius fractures avoids occurance of volar radiocarpal dislocation. Although several fixation systems are available to capture this fragment, adequately maintaining internal fixation is difficult. We present our experience of the first 10 cases using the 2.4 mm variable angle LCP volar rim distal radius plate (Depuy Synthes®, West Chester, US), a low-profile volar rim-contouring plate designed for distal plate positioning and stable buttressing of the volar marginal fragment. Follow-up patient satisfaction, range of motion, grips strength, functional scoring with the QuickDASH and residual pain with a numeric rating scale were assessed. Radiological evaluation consisted in evaluating fracture consolidation, ulnar variance, volar angulation and maintenance of the volar rim fixation. The female to male ratio was 5:5 and the mean age was 52.2 (range, 17-80) years. The mean follow-up period was 11 (range, 5-19) months postoperatively. Patient satisfaction was high. The mean total flexion/extension range was 144° (range, 100-180°) compared to the contralateral uninjured side 160° (range, 95-180°). The mean total pronation/supination range was 153° (range, 140-180°) compared to the contralateral uninjured side 170° (range, 155-180°). Mean grip strength was 14 kg (range, 9-22), compared to the contralateral uninjured side 20 kg (range, 12-25 kg). Mean pre-injury level activity QuickDASH was 23 (range, 0-34.1), while post-recovery QuickDASH was 25 (range 0-43.2). Residual pain was 1.5 on the visual numerical pain rating scale. Radiological evaluation revealed in all cases fracture consolidation, satisfactory reconstruction of ulnar variance, volar angulation and volar rim. We encountered no flexor tendon complications, although plate removal was systematically performed after fracture consolidation. The 2.4 mm variable angle LCP volar rim distal radius plates is a valid treatment option for treating

Time dependent mechanical modeling for polymers based on network theory

Energy Technology Data Exchange (ETDEWEB)

Billon, Noëlle [MINES ParisTech, PSL-Research University, CEMEF – Centre de mise en forme des matériaux, CNRS UMR 7635, CS 10207 rue Claude Daunesse 06904 Sophia Antipolis Cedex (France)

2016-05-18

Despite of a lot of attempts during recent years, complex mechanical behaviour of polymers remains incompletely modelled, making industrial design of structures under complex, cyclic and hard loadings not totally reliable. The non linear and dissipative viscoelastic, viscoplastic behaviour of those materials impose to take into account non linear and combined effects of mechanical and thermal phenomena. In this view, a visco-hyperelastic, viscoplastic model, based on network description of the material has recently been developed and designed in a complete thermodynamic frame in order to take into account those main thermo-mechanical couplings. Also, a way to account for coupled effects of strain-rate and temperature was suggested. First experimental validations conducted in the 1D limit on amorphous rubbery like PMMA in isothermal conditions led to pretty goods results. In this paper a more complete formalism is presented and validated in the case of a semi crystalline polymer, a PA66 and a PET (either amorphous or semi crystalline) are used. Protocol for identification of constitutive parameters is described. It is concluded that this new approach should be the route to accurately model thermo-mechanical behaviour of polymers using a reduced number of parameters of some physical meaning.

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

KAUST Repository

Cates, Nichole C.

2010-06-08

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

Synthesis of biocompatible polymers by plasma; Sintesis de polimeros biocompatibles por plasma

Energy Technology Data Exchange (ETDEWEB)

Colin O, E

2007-07-01

Cl its produced the smallest contact angles. It has been demonstrated that the high energy of plasma in the polymers favors certain crystalline arrangement due to the reorganization of polymeric chains. In this work the crystallinity was calculated by means of areas under the curve of the amorphous and crystalline signals obtained by X-ray diffraction. The crystallinity in PPy/PEG increases from 8% to 9.5%. In Poly allylamine (PAl) the crystallinity was from 4% to 16%. The crystallinity in these materials increases when the increases synthesis energy. While in PPy the crystallinity diminishes from 16% to 12% when the synthesis energy increases, due to the fragmentation and/or possible ramifications of the pyrrole rings that reduce the formation of orderly regions with the energy increments. This characteristic is important, because they can be ended up forming conduction channels in the polymer that is reflected in the electric conductivity of the material. The electric conductivity is another important factor in this study, since due to the electric impulses generated among materials and cells it can stimulates the cellular growth. The electric response of the polymers was study in function of the relative humidity in the interval of 25-80% and in function of the volume of the solutions of NaCl, NaCl-MgSO{sub 4}, and Krebs-Ringer. In the interval of 25-80% of relative humidity, the increment in the electric conductivity in PPy/PEG went from 10{sup -12} to 10{sup -10} S/cm at 25% and of 10{sup -12} to 10{sup -8} S/cm to 80% of relative humidity. The electric conductivity regarding the humidity in PAl increases from 10{sup -11} of 10{sup -9} S/cm to 25% and of 10{sup -}1{sup 0} to 10{sup -8} S/cm at 80%. In Poly pyrrole (PPy) and doped poly pyrrole with Iodine (PPy/I) one observes that the electric conductivity in the interval 25% to 80% of relative humidity went from 10{sup -9} to 10{sup 11} S/cm in PPy and 10{sup -8} and 10{sup -10} S/cm in PPy/I almost increases two

Macromolecular crowding-assisted fabrication of liquid-crystalline imprinted polymers.

Science.gov (United States)

Zhang, Chen; Zhang, Jing; Huang, Yan-Ping; Liu, Zhao-Sheng

2015-04-01

A macromolecular crowding-assisted liquid-crystalline molecularly imprinted monolith (LC-MIM) was prepared successfully for the first time. The imprinted stationary phase was synthesized with polymethyl methacrylate (PMMA) or polystyrene (PS) as the crowding agent, 4-cyanophenyl dicyclohexyl propylene (CPCE) as the liquid-crystal monomer, and hydroquinidine as the pseudo-template for the chiral separation of cinchona alkaloids in HPLC. A low level of cross-linker (26%) has been found to be sufficient to achieve molecular recognition on the crowding-assisted LC-MIM due to the physical cross-linking of mesogenic groups in place of chemical cross-linking, and baseline separation of quinidine and quinine could be achieved with good resolution (R(s) = 2.96), selectivity factor (α = 2.16), and column efficiency (N = 2650 plates/m). In contrast, the LC-MIM prepared without crowding agents displayed the smallest diastereoselectivity (α = 1.90), while the crowding-assisted MIM with high level of cross-linker (80%) obtained the greatest selectivity factor (α = 7.65), but the lowest column efficiency (N = 177 plates/m).

Puncture Self-Healing Polymers for Aerospace Applications

Science.gov (United States)

Gordon, Keith L.; Penner, Ronald K.; Bogert, Phil B.; Yost, W. T.; Siochi, Emilie J.

2011-01-01

Space exploration launch costs on the order of $10K per pound provide ample incentive to seek innovative, cost-effective ways to reduce structural mass without sacrificing safety and reliability. Damage-tolerant structural systems can provide a route to avoiding weight penalty while enhancing vehicle safety and reliability. Self-healing polymers capable of spontaneous puncture repair show great promise to mitigate potentially catastrophic damage from events such as micrometeoroid penetration. Effective self-repair requires these materials to heal instantaneously following projectile penetration while retaining structural integrity. Poly(ethylene-co-methacrylic acid) (EMMA), also known as Surlyn is an ionomer-based copolymer that undergoes puncture reversal (self-healing) following high impact puncture at high velocities. However EMMA is not a structural engineering polymer, and will not meet the demands of aerospace applications requiring self-healing engineering materials. Current efforts to identify candidate self-healing polymer materials for structural engineering systems are reported. Rheology, high speed thermography, and high speed video for self-healing semi-crystalline and amorphous polymers will be reported.

The equilibrium theory of inhomogeneous polymers (international series of monographs on physics)

CERN Document Server

Fredrickson, Glenn

2013-01-01

The Equilibrium Theory of Inhomogeneous Polymers provides an introduction to the field-theoretic methods and computer simulation techniques that are used in the design of structured polymeric fluids. By such methods, the principles that dictate equilibrium self-assembly in systems ranging from block and graft copolymers, to polyelectrolytes, liquid crystalline polymers, and polymer nanocomposites can be established. Building on an introductory discussion of single-polymer statistical mechanics, the book provides a detailed treatment of analytical and numerical techniques for addressing the conformational properties of polymers subjected to spatially-varying potential fields. This problem is shown to be central to the field-theoretic description of interacting polymeric fluids, and models for a number of important polymer systems are elaborated. Chapter 5 serves to unify and expound the topic of self-consistent field theory, which is a collection of analytical and numerical techniques for obtaining solutions o...

Photodeformable polymer materials: towards light-driven spoke-type micromotor application

Science.gov (United States)

Zhu, Yutian; Zheng, Lihui; Liu, Zhao; Liu, Heng; Yu, Yanlei

2014-06-01

Using a photodeformable polymer material, liquid-crystalline polymer incorporated with azobenzene moieties, a spoke-type micromotor is designed, which could convert light energy directly into mechanical work. It consists of four driving belts, whose mechanical model is established and the driving moment of the micromotor upon irradiation with UV light and without photoirradiation is calculated, respectively. According to the calculated driving moment, the UV light and the visible light are arranged to irradiate from parallel and opposite direction of the micromotor simultaneously, which convert the bending deflection of the photodeformable polymer material belts to continuous rotation of the micromotor. As light is a green energy source that can be controlled remotely, instantly and without the aid of electric wires, the photodeformable polymer material has great potential to be utilized in micro-actuator and other relative applications.

A rechargeable Li-CO{sub 2} battery with a gel polymer electrolyte

Energy Technology Data Exchange (ETDEWEB)

Li, Chao; Guo, Ziyang; Yang, Bingchang; Liu, Yao; Wang, Yonggang; Xia, Yongyao [Dept. of Chemistry and Shanghai Key Lab. of Molecular Catalysis and Innovative Materials, Inst. of New Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Fudan Univ. (China)

2017-07-24

The utilization of CO{sub 2} in Li-CO{sub 2} batteries is attracting extensive attention. However, the poor rechargeability and low applied current density have remained the Achilles' heel of this energy device. The gel polymer electrolyte (GPE), which is composed of a polymer matrix filled with tetraglyme-based liquid electrolyte, was used to fabricate a rechargeable Li-CO{sub 2} battery with a carbon nanotube-based gas electrode. The discharge product of Li{sub 2}CO{sub 3} formed in the GPE-based Li-CO{sub 2} battery exhibits a particle-shaped morphology with poor crystallinity, which is different from the contiguous polymer-like and crystalline discharge product in conventional Li-CO{sub 2} battery using a liquid electrolyte. Accordingly, the GPE-based battery shows much improved electrochemical performance. The achieved cycle life (60 cycles) and rate capability (maximum applied current density of 500 mA g{sup -1}) are much higher than most of previous reports, which points a new way to develop high-performance Li-CO{sub 2} batteries. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Impact of morphology on polaron delocalization in a semicrystalline conjugated polymer

KAUST Repository

Steyrleuthner, Robert

2016-12-20

We investigate the delocalization of holes in the semicrystalline conjugated polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT) by directly measuring the hyperfine coupling between photogenerated polarons and bound nuclear spins using electron nuclear double resonance spectroscopy. An extrapolation of the corresponding oligomer spectra reveals that charges tend to delocalize over 4.0-4.8 nm with delocalization strongly dependent on molecular order and crystallinity of the PBTTT polymer thin films. Density functional theory calculations of hyperfine couplings confirm that long-range corrected functionals appropriately describe the change in coupling strength with increasing oligomer size and agree well with the experimentally measured polymer limit. Our discussion presents general guidelines illustrating the various pitfalls and opportunities when deducing polaron localization lengths from hyperfine coupling spectra of conjugated polymers.

Irradiation effects on perfluorinated polymers

International Nuclear Information System (INIS)

Lappan, U.; Geissler, U.; Haeussler, L.; Pompe, G.; Scheler, U.; Lunkwitz, K.

2002-01-01

Complete text of publication follows. High-energy radiation affects the properties of polymers by chain scission and crosslinking reactions. Both types of reaction occur simultaneously in irradiated polymers. However, one process will usually predominate, depending on the chemical structure of the polymer and the irradiation conditions such as temperature and atmosphere. Polytetrafluoroethylene (PTFE) undergoes predominantly chain scission, if the irradiation is performed at room temperature. This shortcoming is exploited by converting PTFE into low molecular weight micropowders. The use of PTFE micropowders functionalized with COOH groups as additive in polyamides to improve the sliding properties of the materials has been studied. During the compounding process in a twin screw extruder the COOH groups of the irradiated PTFE react with the polyamides. For these studies, it became necessary to investigate the content of end groups in irradiated PTFE by FTIR and 19 F solid-state NMR. These date were used to calculate number-average molecular weights. The ratios of COOH groups to CF 3 groups are discussed in terms of the mechanism of PTFE degradation. If PTFE is irradiated at temperatures above its crystalline melting point in an oxygen-free atmosphere, branching and crosslinking occur. The dependence of radiation effects on perfluorinated copolymers (FEP, PFA) on temperature has been studied. Melt flow index measurements have shown that branching and crosslinking predominate over chain scission with increasing irradiation temperature both in FEP and in PFA. Quantitative analysis of 19 F solid-state NMR data has shown that the content of branching groups (>CF-) exceeds the content of end groups in the case of PFA irradiated above its crystalline melting point. The formation of COF and COOH groups in the irradiated PFA is interpreted as a result of partial degradation of perfluorovinyl ether comonomer units

Dialkoxybithiazole: a new building block for head-to-head polymer semiconductors.

Science.gov (United States)

Guo, Xugang; Quinn, Jordan; Chen, Zhihua; Usta, Hakan; Zheng, Yan; Xia, Yu; Hennek, Jonathan W; Ortiz, Rocío Ponce; Marks, Tobin J; Facchetti, Antonio

2013-02-06

Polymer semiconductors have received great attention for organic electronics due to the low fabrication cost offered by solution-based printing techniques. To enable the desired solubility/processability and carrier mobility, polymers are functionalized with hydrocarbon chains by strategically manipulating the alkylation patterns. Note that head-to-head (HH) linkages have traditionally been avoided because the induced backbone torsion leads to poor π-π overlap and amorphous film microstructures, and hence to low carrier mobilities. We report here the synthesis of a new building block for HH linkages, 4,4'-dialkoxy-5,5'-bithiazole (BTzOR), and its incorporation into polymers for high performance organic thin-film transistors. The small oxygen van der Waals radius and intramolecular S(thiazolyl)···O(alkoxy) attraction promote HH macromolecular architectures with extensive π-conjugation, low bandgaps (1.40-1.63 eV), and high crystallinity. In comparison to previously reported 3,3'-dialkoxy-2,2'-bithiophene (BTOR), BTzOR is a promising building block in view of thiazole geometric and electronic properties: (a) replacing (thiophene)C-H with (thiazole)N reduces steric encumbrance in -BTzOR-Ar- dyads by eliminating repulsive C-H···H-C interactions with neighboring arene units, thereby enhancing π-π overlap and film crystallinity; and (b) thiazole electron-deficiency compensates alkoxy electron-donating characteristics, thereby lowering the BTzOR polymer HOMO versus that of the BTOR analogues. Thus, the new BTzOR polymers show substantial hole mobilities (0.06-0.25 cm(2)/(V s)) in organic thin-film transistors, as well as enhanced I(on):I(off) ratios and greater ambient stability than the BTOR analogues. These geometric and electronic properties make BTzOR a promising building block for new classes of polymer semiconductors, and the synthetic route to BTzOR reported here should be adaptable to many other bithiazole-based building blocks.

Morphology and structure of polymers in ultrathin films and constrained geometries

Science.gov (United States)

Gullerud, Steven Olaf

We have explored the organization of polycaprolactone (PCL) constrained in ultrathin films and nanometer-scale domains. Specifically, PCL functionalized with triethoxysilane functional groups was used to create tethered ultrathin films on silicon (100) substrates through silanization, and a sol-gel reaction was used to produce PCL/silsesquioxane composites with nanoscale phase-separated domains. In the first case, analysis by AFM and ellipsometry showed the existence of an amorphous sublayer up to 4 nm thick. Above this, physisorbed PCL formed heterogeneous surface features, up to 7 nm thick, with the morphology dependent on the polymer solution concentration during the deposition process. Low PCL solution concentration produced amorphous globular domains, while higher polymer concentrations allowed the growth of dendritic crystalline features. We report the results of in situ thermal analysis of grafted PCL by AFM, which show the melting of the surface structures at the film surface as well as growth of new dendritic structures upon recrystallization. High tapping forces applied by the AFM tip revealed the presence of crystalline lamellae buried below an amorphous layer in the dendritic structures, as well as in the PCL sublayer when the film was cooled below room temperature. PCL phase separation behavior and morphology in sol-gel organic/inorganic nanocomposites with methylsilsesquioxane (MSSQ) or phenylsilsesquioxane (PSSQ) was probed using TEM, FTIR, and fluorescence spectroscopy of dansyl and pyrene-labeled PCL. Star-like and linear PCL were used to study the effects of molecular weight, endgroup functionality, and polymer geometry on the phase separation behavior in these materials. PCL crystallinity, as detected through FTIR, served to detect the presence of macroscopic phase separation, as well as the critical PCL loading amount at which this occurs, for a given PCL/SSQ system. Fluorescence spectroscopy of dansyl-labeled PCL detected the presence of an

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

Institute of Scientific and Technical Information of China (English)

Fakhri Yousefi; Hajir Karimi; Maryam Gomar

2015-01-01

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

Approaches for Making High Performance Polymer Materials from Commodity Polymers

Institute of Scientific and Technical Information of China (English)

Xu Xi

2004-01-01

A brief surrey of ongoing research work done for improving and enhancing the properties of commodity polymers by the author and author's colleagues is given in this paper. A series of high performance polymers and polymer nanomaterials were successfully prepared through irradiation and stress-induced reactions of polymers and hydrogen bonding. The methods proposed are viable, easy in operation, clean and efficient.1. The effect of irradiation source (UV light, electron beam, γ -ray and microwave), irradiation dose, irradiation time and atmosphere etc. on molecular structure of polyolefine during irradiation was studied. The basic rules of dominating oxidation, degradation and cross-linking reactions were mastered. Under the controlled conditions, cross-linking reactions are prevented, some oxygen containing groups are introduced on the molecular chain of polyolefine to facilitate the interface compatibility of their blends. A series of high performance polymer materials: u-HDPE/PA6,u-HDPE/CaCO3, u-iPP/STC, γ-HDPE/STC, γ-LLDPE/ATH, e-HDPE, e-LLDPE and m-HDPEfilled system were prepared (u- ultraviolet light irradiated, γ- γ-ray irradiated, e- electron beam irradiated, m- microwave irradiated)2. The effect of ultrasonic irradiation, jet and pan-milling on structure and changes in properties of polymers were studied. Imposition of critical stress on polymer chain can cause the scission of bonds to form macroradicals. The macroradicals formed in this way may recombine or react with monomer or other radicals to form linear, branched or cross-linked polymers or copolymers. About 20 kinds of block/graft copolymers have been synthesized from polymer-polymer or polymer-monomer through ultrasonic irradiation.Through jet-milling, the molecular weight of PVC is decreased somewhat, the intensity of its crystalline absorption bonds becomes indistinct. The processability, the yield strength, strength at break and elongation at break of PVC get increased quite a lot after

Letter from Kirk Kessler, EPS to Galo Jackson, USEPA. Subject: Results of the July 2011 Sampling in the Former Brunswick-Altamaha Canal South of the LCP Chemicals Site, Brunswick, Ga, Revision Dated April 19, 2012

Science.gov (United States)

Results report of sediment and fish tissue samples collected from the former Brunswick-Altamaha Canal, in a segment of the canal south of the LCP Chemicals Site in Brunswick, Georgia in July 2010. Region ID: 04 DocID: 10843428, DocDate: 04-19-2012

Preparation and Characterization of PVA Alkaline Solid Polymer Electrolyte with Addition of Bamboo Charcoal

OpenAIRE

Lidan Fan; Mengyue Wang; Zhen Zhang; Gang Qin; Xiaoyi Hu; Qiang Chen

2018-01-01

Natural bamboo charcoal (BC) powder has been developed as a novel filler in order to further improve performances of the polyvinyl alcohol (PVA)-based alkaline solid polymer electrolyte (ASPE) by solution casting method. X-ray diffraction patterns of composite polymer electrolyte with BC revealed the decrease in the degree of crystallinity with increasing content of BC. Scanning electron microscopy images showed pores on a micrometer scale (average diameter about 2 μm) distributed inside a...

Hydrogen Bond Induces Hierarchical Self-Assembly in Liquid-Crystalline Block Copolymers.

Science.gov (United States)

Huang, Shuai; Pang, Linlin; Chen, Yuxuan; Zhou, Liming; Fang, Shaoming; Yu, Haifeng

2018-03-01

Microphase-separated structures of block copolymers (BCs) with a size of sub-10 nm are usually obtained by hydrogen-bond-induced self-assembly of BCs through doping with small molecules as functional additives. Here, fabrication of hierarchically self-assembled sub-10 nm structures upon microphase separation of amphiphilic liquid-crystalline BCs (LCBCs) at the existence of hydrogen bonds but without any dopants is reported. The newly introduced urethane groups in the side chain of the hydrophobic block of LCBCs interact with the ether groups of the hydrophilic poly(ethylene oxide) (PEO) block, leading to imperfect crystallization of the PEO blocks. Both crystalline and amorphous domains coexist in the separated PEO phase, enabling a lamellar structure to appear inside the PEO nanocylinders. This provides an elegant method to fabricate controllable sub-10 nm microstructures in well-defined polymer systems without the introduction of any dopants. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A transparent conductive oxide electrode with highly enhanced flexibility achieved by controlled crystallinity by incorporating Ag nanoparticles on substrates

Energy Technology Data Exchange (ETDEWEB)

Triambulo, Ross E.; Cheong, Hahn-Gil [Department of Materials Science and Engineering, Yonsei University, Seoul (Korea, Republic of); Lee, Gun-Hwan [Advanced Thin Film Research Group, Korea Institute of Materials Science (KIMS), Changwon (Korea, Republic of); Yi, In-Sook [R and D Center, InkTec Co., Ltd., Ansan (Korea, Republic of); Park, Jin-Woo, E-mail: jwpark09@yonsei.ac.kr [Department of Materials Science and Engineering, Yonsei University, Seoul (Korea, Republic of)

2015-01-25

Highlights: • We developed a composite transparent electrode with Ag nanoparticles and indium-tin-oxide. • Transmittance of AgNPs was improved by formation of oxide layers by O{sub 2} plasma treatment. • Ag nanoparticles became crystalline seeds to grow strong ITO with a uniform growth orientation. • The hybrid electrode is highly more conductive and stable under bending than ITO. - Abstract: We report the synthesis of highly flexible indium tin oxide (ITO) on a polymer substrate whose surface was engineered by oxide-coated Ag nanoparticles (AgNPs) smaller than 20 nm in diameter. Polyimide (PI) substrates were spin coated with Ag ion ink and were subsequently heat treated to form AgNP coatings. The Ag oxide was formed by O{sub 2} plasma treatment to reduce the light absorbance by AgNPs. ITO was dc magnetron sputter-deposited atop the AgNPs. The ITO on the AgNPs was crystalline grown primarily with (2 2 2) growth orientation. This contrasts to the typical microstructure of ITO grown on the polymer, which is that growing c-ITO nucleates are embedded in an amorphous ITO (a-ITO) matrix like a particulate composite. The surface roughness of ITO on AgNPs was as small as the ITO on PI without AgNPs. The crystalline nature of the ITO on the AgNP-coated polymer resulted in the decrease of electric resistivity (ρ) by 65% compared to that of ITO on the bare PI. Furthermore, an electric resistivity change (Δρ) of the ITO on the AgNPs was only 8% at a bending radius (r{sub b}) down to 4 mm, whereas the ITO on the non-coated polymer became almost insulating at an r{sub b} of 10 mm, owing to a drastic increase in the number of cracks. To validate the potential application in the displays, flexible organic light emitting diodes (f-OLEDs) were fabricated on the ITO on AgNPs and the performances was compared with the f-OLED on ITO on the bare PI.

A transparent conductive oxide electrode with highly enhanced flexibility achieved by controlled crystallinity by incorporating Ag nanoparticles on substrates

International Nuclear Information System (INIS)

Triambulo, Ross E.; Cheong, Hahn-Gil; Lee, Gun-Hwan; Yi, In-Sook; Park, Jin-Woo

2015-01-01

Highlights: • We developed a composite transparent electrode with Ag nanoparticles and indium-tin-oxide. • Transmittance of AgNPs was improved by formation of oxide layers by O 2 plasma treatment. • Ag nanoparticles became crystalline seeds to grow strong ITO with a uniform growth orientation. • The hybrid electrode is highly more conductive and stable under bending than ITO. - Abstract: We report the synthesis of highly flexible indium tin oxide (ITO) on a polymer substrate whose surface was engineered by oxide-coated Ag nanoparticles (AgNPs) smaller than 20 nm in diameter. Polyimide (PI) substrates were spin coated with Ag ion ink and were subsequently heat treated to form AgNP coatings. The Ag oxide was formed by O 2 plasma treatment to reduce the light absorbance by AgNPs. ITO was dc magnetron sputter-deposited atop the AgNPs. The ITO on the AgNPs was crystalline grown primarily with (2 2 2) growth orientation. This contrasts to the typical microstructure of ITO grown on the polymer, which is that growing c-ITO nucleates are embedded in an amorphous ITO (a-ITO) matrix like a particulate composite. The surface roughness of ITO on AgNPs was as small as the ITO on PI without AgNPs. The crystalline nature of the ITO on the AgNP-coated polymer resulted in the decrease of electric resistivity (ρ) by 65% compared to that of ITO on the bare PI. Furthermore, an electric resistivity change (Δρ) of the ITO on the AgNPs was only 8% at a bending radius (r b ) down to 4 mm, whereas the ITO on the non-coated polymer became almost insulating at an r b of 10 mm, owing to a drastic increase in the number of cracks. To validate the potential application in the displays, flexible organic light emitting diodes (f-OLEDs) were fabricated on the ITO on AgNPs and the performances was compared with the f-OLED on ITO on the bare PI

A New Method of Constructing a Drug-Polymer Temperature-Composition Phase Diagram Using Hot-Melt Extrusion.

Science.gov (United States)

Tian, Yiwei; Jones, David S; Donnelly, Conor; Brannigan, Timothy; Li, Shu; Andrews, Gavin P

2018-04-02

Current experimental methodologies used to determine the thermodynamic solubility of an API within a polymer typically involves establishing the dissolution/melting end point of the crystalline API within a physical mixture or through the use of the glass transition temperature measurement of a demixed amorphous solid dispersion. The measurable "equilibrium" points for solubility are normally well above the glass transition temperature of the system, meaning extrapolation is required to predict the drug solubility at pharmaceutically relevant temperatures. In this manuscript, we argue that the presence of highly viscous polymers in these systems results in experimental data that exhibits an under or overestimated value relative to the true thermodynamic solubility. In previous work, we demonstrated the effects of experimental conditions and their impact on measured and predicted thermodynamic solubility points. In light of current understanding, we have developed a new method to limit error associated with viscosity effects for application in small-scale hot-melt extrusion (HME). In this study, HME was used to generate an intermediate (multiphase) system containing crystalline drug, amorphous drug/polymer-rich regions as well as drug that was molecularly dispersed in polymer. An extended annealing method was used together with high-speed differential scanning calorimetry to accurately determine the upper and lower boundaries of the thermodynamic solubility of a model drug-polymer system (felodipine and Soluplus). Compared to our previously published data, the current results confirmed our hypothesis that the prediction of the liquid-solid curve using dynamic determination of dissolution/melting end point of the crystalline API physical mixture presents an underestimation relative to the thermodynamic solubility point. With this proposed method, we were able to experimentally measure the upper and lower boundaries of the liquid-solid curve for the model system. The

Dip-pen nanopatterning of photosensitive conducting polymer using a monomer ink

Science.gov (United States)

Su, Ming; Aslam, Mohammed; Fu, Lei; Wu, Nianqiang; Dravid, Vinayak P.

2004-05-01

Controlled patterning of conducting polymers at a micro- or nanoscale is the first step towards the fabrication of miniaturized functional devices. Here, we introduce an approach for the nanopatterning of conducting polymers using an improved monomer "ink" in dip-pen nanolithography (DPN). The nominal monomer "ink" is converted, in situ, to its conducting solid-state polymeric form after patterned. Proof-of-concept experiments have been performed with acid-promoted polymerization of pyrrole in a less reactive environment (tetrahydrofuran). The ratios of reactants are optimized to give an appropriate rate to match the operation of DPN. A similar synthesis process for the same polymer in its bulk form shows a high conductance and crystalline structure. The miniaturized conducting polymer sensors with light detection ability are fabricated by DPN using the improved ink formula, and exhibit excellent response, recovery, and sensitivity parameters.

Dip-pen nanopatterning of photosensitive conducting polymer using a monomer ink

International Nuclear Information System (INIS)

Su Ming; Aslam, Mohammed; Fu Lei; Wu Nianqiang; Dravid, Vinayak P.

2004-01-01

Controlled patterning of conducting polymers at a micro- or nanoscale is the first step towards the fabrication of miniaturized functional devices. Here, we introduce an approach for the nanopatterning of conducting polymers using an improved monomer 'ink' in dip-pen nanolithography (DPN). The nominal monomer 'ink' is converted, in situ, to its conducting solid-state polymeric form after patterned. Proof-of-concept experiments have been performed with acid-promoted polymerization of pyrrole in a less reactive environment (tetrahydrofuran). The ratios of reactants are optimized to give an appropriate rate to match the operation of DPN. A similar synthesis process for the same polymer in its bulk form shows a high conductance and crystalline structure. The miniaturized conducting polymer sensors with light detection ability are fabricated by DPN using the improved ink formula, and exhibit excellent response, recovery, and sensitivity parameters

Growth of ZnSe nano-needles by pulsed laser deposition and their application in polymer/inorganic hybrid solar cells

International Nuclear Information System (INIS)

Chen, L.; Lai, J.S.; Fu, X.N.; Sun, J.; Ying, Z.F.; Wu, J.D.; Lu, H.; Xu, N.

2013-01-01

Using pulsed-laser deposition method, crystalline ZnSe nano-needles have been grown on catalyst-coated silicon (100) substrates. The crystalline ZnSe nano-needles with the middle diameters of about 20–80 nm, and the lengths ranging from 100 to 600 nm can be grown densely on 300–400 °C substrates. The as-grown ZnSe nano-needles were well crystalline and base-grown. They are potential electron-capturing materials in polymer/inorganic hybrid solar cells for their properties of good electron-conductance and high ratio surface area. Based on the ZnSe nano-needle cathode, a five-layer composite structure of polymer/inorganic hybrid solar cell has been designed and fabricated. The absorption spectra of the blend of regioregular poly(3-hexylthiophene-2,5-diyl) and phenyl-C61-butyric acid methyl ester (P3HT:PCBM), ZnSe nano-needles and the combination of P3HT:PCBM and ZnSe nano-needles were examined by ultraviolet–visible-infrared spectrophotometer, respectively. The absorption bands of the combination of P3HT:PCBM and ZnSe nano-needles fit well with the solar spectral distribution. - Highlights: ► Crystalline ZnSe nano-needles grown by pulsed laser deposition. ► A five-layer polymer/inorganic hybrid solar cell based on ZnSe nano-needles cathode. ► ZnSe nano-needles improve light absorption. ► Employment of ZnSe nano-needles increase the open-circuit voltage and fill factor

Fabrication and characterization of all-polymer, transparent ferroelectric capacitors on flexible substrates

KAUST Repository

Khan, Yasser

2011-12-01

All-polymer, transparent ferroelectric devices, based on the functional polymer poly(vinylidene fluoride trifluoroethylene) [P(VDF-TrFE)], have been fabricated on flexible substrates. The performance of the all-polymer devices was studied and compared to devices with metal electrodes. Specifically, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) [PEDOT:PSS] and platinum (Pt) electrode effects on the morphology, crystallinity and orientation of P(VDF-TrFE) films were investigated. The devices with PEDOT:PSS electrodes showed similar hysteresis and switching current response compared to Pt electrodes but with tremendously improved fatigue performance. Further, the devices with PEDOT:PSS electrodes showed lower coercive field and better fatigue performance than values reported for other polymer electrodes used with P(VDF-TrFE) on flexible substrates. © 2011 Elsevier B.V. All rights reserved.

A flexible liquid crystal polymer MEMS pressure sensor array for fish-like underwater sensing

International Nuclear Information System (INIS)

Kottapalli, A G P; Asadnia, M; Miao, J M; Barbastathis, G; Triantafyllou, M S

2012-01-01

In order to perform underwater surveillance, autonomous underwater vehicles (AUVs) require flexible, light-weight, reliable and robust sensing systems that are capable of flow sensing and detecting underwater objects. Underwater animals like fish perform a similar task using an efficient and ubiquitous sensory system called a lateral-line constituting of an array of pressure-gradient sensors. We demonstrate here the development of arrays of polymer microelectromechanical systems (MEMS) pressure sensors which are flexible and can be readily mounted on curved surfaces of AUV bodies. An array of ten sensors with a footprint of 60 (L) mm × 25 (W) mm × 0.4 (H) mm is fabricated using liquid crystal polymer (LCP) as the sensing membrane material. The flow sensing and object detection capabilities of the array are illustrated with proof-of-concept experiments conducted in a water tunnel. The sensors demonstrate a pressure sensitivity of 14.3 μV Pa −1 . A high resolution of 25 mm s −1 is achieved in water flow sensing. The sensors can passively sense underwater objects by transducing the pressure variations generated underwater by the movement of objects. The experimental results demonstrate the array’s ability to detect the velocity of underwater objects towed past by with high accuracy, and an average error of only 2.5%. (paper)

Green Approach To Synthesize Crystalline Nanoscale ZnII-Coordination Polymers: Cell Growth Inhibition and Immunofluorescence Study.

Science.gov (United States)

Mukherjee, Somali; Ganguly, Sumi; Manna, Krishnendu; Mondal, Sanchaita; Mahapatra, Supratim; Das, Debasis

2018-04-02

Five new coordination polymers (CPs) namely, [{Zn(μ 2 -H 2 O) 0.5 (5N 3 -IPA)(2,2'-bpe)}] ∞ (1), [{Zn(μ 2 -H 2 O) 0.5 (5N 3 -IPA)(1,10-phen)}] ∞ (2), [{Zn(5N 3 -IPA)(1,2-bpe)}] ∞ (3), [{Zn(5N 3 -IPA)(1,2-bpey)}] ∞ (4), and [{Zn(H 2 O)(5N 3 -IPA)(4,4'-tme)}(H 2 O) 0.5 ] ∞ (5) (5N 3 -H 2 IPA = 5-azidoisophthalic acid, 2,2'-bpe= 2,2'-bipyridine, 1,10-phen = 1,10-phenanthroline, 1,2-bpe = 1,2-bis(4-pyridyl)ethane, 1,2-bpey = 1,2-bis(4-pyridyl)ethylene, 4,4'-tme = 4,4'-trimethylenedipyridine), have been synthesized based on a mixed ligand approach adopting a solvothermal technique. Depending upon the intrinsic structural flexibility of the bis-pyridyl coligands, interesting structural topologies have also been observed in the resulting CPs: Sra SrAl2 type topology for 3 and a 3-fold interpenetrated dmp topology for 4. A green hand grinding technique has been implemented to reduce the particle size of the CPs to generate nanoscale CPs (NCPs). SEM studies of NCPs reveal the formation of square and spherical particles for NCP 1 and 2, respectively, and nano rod for NCP 3, 4, and 5. Remarkably, when scaled down to nano range all the NCPs retain their crystalline nature. The cytotoxic activity of the NCPs (1-5) has been studied using human colorectal carcinoma cells (HCT 116). Significant cell death is observed for NCP 2, which is further corroborated by cell growth inhibition study. The observed cell death is likely to be due to mitochondrial-assisted apoptosis as is evident from immunofluorescence study.

Vinyl Flanked Difluorobenzothiadiazole-Dithiophene Conjugated Polymer for High Performance Organic Field-Effect Transistors.

Energy Technology Data Exchange (ETDEWEB)

Liang, Xianfeng; Sun, Wandong; Chen, Yanlin; Tan, Luxi; Cai, Zheng-Xu; Liu, Zitong; Wang, Lin; Li, Jing; Chen, Wei; Dong, Lichun

2018-02-21

Fluorine containing conjugated polymers have been widely applied in high performance organic solar cells, but their use in field-effect transistors is still quite limited. In this work, a conjugated polymer PTFBTV based on difluorobenzothiadiazole (DFBT) and dithiophene was synthesized, utilizing multiple vinylene as linkers. The polymer exhibits a relatively high hole mobility up to 2.0 cm(2) V-1 s(-1) compared with the reported DFBT-oligothiophene based polymers, yet its structural complexity is much simpler. The polymer thin film exhibits a typical 'face on' molecular orientation. A single crystal of its monomer revealed a non-covalent intramolecular contact between fluorine and the neighbouring proton, which strengthens the backbone co-planarity. Meanwhile an intermolecular F...F contact was also observed, which might cause rather scattered lamellar crystallinity for PTFBTV in the solid state.

Molecular Orientation of Conjugated Polymer Chains in Nanostructures and Thin Films: Review of Processes and Application to Optoelectronics

Directory of Open Access Journals (Sweden)

Varun Vohra

2017-01-01

Full Text Available Semiconducting polymers are composed of elongated conjugated polymer backbones and side chains with high solubility and mechanical properties. The combination of these two features results in a high processability and a potential to orient the conjugated backbones in thin films and nanofibers. The thin films and nanofibers are usually composed of highly crystalline (high charge transport and amorphous parts. Orientation of conjugated polymer can result in enhanced charge transport or optical properties as it induces increased crystallinity or preferential orientation of the crystallites. After summarizing the potential strategies to exploit molecular order in conjugated polymer based optoelectronic devices, we will review some of the fabrication processes to induce molecular orientation. In particular, we will review the cases involving molecular and interfacial interactions, unidirectional deposition processes, electrospinning, and postdeposition mechanical treatments. The studies presented here clearly demonstrate that process-controlled molecular orientation of the conjugated polymer chains can result in high device performances (mobilities over 40 cm2·V−1·s−1 and solar cells with efficiencies over 10%. Furthermore, the peculiar interactions between molecularly oriented polymers and polarized light have the potential not only to generate low-cost and low energy consumption polarized light sources but also to fabricate innovative devices such as solar cell integrated LCDs or bipolarized LEDs.

Enhanced drug delivery capabilities from stents coated with absorbable polymer and crystalline drug

OpenAIRE

Carlyle, Wenda C.; McClain, James B.; Tzafriri, Abraham R.; Bailey, Lynn; Zani, Brett G.; Markham, Peter M.; Stanley, James R.L.; Edelman, Elazer R.

2012-01-01

Current drug eluting stent (DES) technology is not optimized with regard to the pharmacokinetics of drug delivery. A novel, absorbable-coating sirolimus-eluting stent (AC-SES) was evaluated for its capacity to deliver drug more evenly within the intimal area rather than concentrating drug around the stent struts and for its ability to match coating erosion with drug release. The coating consisted of absorbable poly-lactide-co-glycolic acid (PLGA) and crystalline sirolimus deposited by a dry-p...

Brush Polymer of Donor-Accepter Dyads via Adduct Formation between Lewis Base Polymer Donor and All Carbon Lewis Acid Acceptor

Directory of Open Access Journals (Sweden)

Yang Wang

2017-09-01

Full Text Available A synthetic method that taps into the facile Lewis base (LB→Lewis acid (LA adduct forming reaction between the semiconducting polymeric LB and all carbon LA C60 for the construction of covalently linked donor-acceptor dyads and brush polymer of dyads is reported. The polymeric LB is built on poly(3-hexylthiophene (P3HT macromers containing either an alkyl or vinyl imidazolium end group that can be readily converted into the N-heterocyclic carbene (NHC LB site, while the brush polymer architecture is conveniently constructed via radical polymerization of the macromer P3HT with the vinyl imidazolium chain end. Simply mixing of such donor polymeric LB with C60 rapidly creates linked P3HT-C60 dyads and brush polymer of dyads in which C60 is covalently linked to the NHC junction connecting the vinyl polymer main chain and the brush P3HT side chains. Thermal behaviors, electronic absorption and emission properties of the resulting P3HT-C60 dyads and brush polymer of dyads have been investigated. The results show that a change of the topology of the P3HT-C60 dyad from linear to brush architecture enhances the crystallinity and Tm of the P3HT domain and, along with other findings, they indicate that the brush polymer architecture of donor-acceptor domains provides a promising approach to improve performances of polymer-based solar cells.

Preparation and performance of a novel gel polymer electrolyte based on poly(vinylidene fluoride)/graphene separator for lithium ion battery

International Nuclear Information System (INIS)

Liu, Jiuqing; Wu, Xiufeng; He, Junying; Li, Jie; Lai, Yanqing

2017-01-01

Poly(vinylidenefluoride)/graphene (PVDF/graphene) gel polymer electrolyte is prepared via non-solvent induced phase separation (NIPS) technique for lithium ion battery application. The effect of graphene on the ion conductivity is investigated by AC impedance measurement. The relationship among the chemical structure, PVDF crystallinity, the graphene on macroporous formation and the ion conductivity are investigated. The results indicate that the graphene disperses homogenously in PVDF, and it also increases the porosity and decreases the crystallinity of the PVDF. At the same time, the unique structure increases the liquid uptake capability of PVDF/graphene polymer electrolyte. The ionic conductivity of the PVDF/graphene polymer electrolyte increases significantly from 1.85 mS cm"−"1 in pristine PVDF to 3.61 mS cm"−"1 with 0.002 wt% graphene. It is found that graphene not only increases the ionic conductivity but also markedly enhances the rate capability and the cycling performances of coin cell. This study shows that PVDF/graphene gel polymer electrolyte is a very promising material for lithium ion batteries.

Processing-microstructure relationships in thermotropic liquid crystalline polymers: Experimental and numerical modeling studies

Science.gov (United States)

Fang, Jun

Thermotropic liquid crystalline polymers (TLCPs) are a class of promising engineering materials for high-demanding structural applications. Their excellent mechanical properties are highly correlated to the underlying molecular orientation states, which may be affected by complex flow fields during melt processing. Thus, understanding and eventually predicting how processing flows impact molecular orientation is a critical step towards rational design work in order to achieve favorable, balanced physical properties in finished products. This thesis aims to develop deeper understanding of orientation development in commercial TLCPs during processing by coordinating extensive experimental measurements with numerical computations. In situ measurements of orientation development of LCPs during processing are a focal point of this thesis. An x-ray capable injection molding apparatus is enhanced and utilized for time-resolved measurements of orientation development in multiple commercial TLCPs during injection molding. Ex situ wide angle x-ray scattering is also employed for more thorough characterization of molecular orientation distributions in molded plaques. Incompletely injection molded plaques ("short shots") are studied to gain further insights into the intermediate orientation states during mold filling. Finally, two surface orientation characterization techniques, near edge x-ray absorption fine structure (NEXAFS) and infrared attenuated total reflectance (FTIR-ATR) are combined to investigate the surface orientation distribution of injection molded plaques. Surface orientation states are found to be vastly different from their bulk counterparts due to different kinematics involved in mold filling. In general, complex distributions of orientation in molded plaques reflect the spatially varying competition between shear and extension during mold filling. To complement these experimental measurements, numerical calculations based on the Larson-Doi polydomain model

Phase behaviour of macromolecular liquid crystalline materials. Computational studies at the molecular level

International Nuclear Information System (INIS)

Stimson, Lorna M.

2003-01-01

Molecular simulations provide an increasingly useful insight into the static and dynamic characteristics of materials. In this thesis molecular simulations of macro-molecular liquid crystalline materials are reported. The first liquid crystalline material that has been investigated is a side chain liquid crystal polymer (SCLCP). In this study semi-atomistic molecular dynamics simulations have been conducted at a range of temperatures and an aligning potential has been applied to mimic the effect of a magnetic field. In cooling the SCLCP from an isotropic melt, microphase separation was observed yielding a domain structure. The application of a magnetic field to this structure aligns the domains producing a stable smectic mesophase. This is the first study in which mesophases have been observed using an off-lattice model of a SCLCP. The second material that has been investigated is a dendrimer with terminal mesogenic functionalization. Here, a multi-scale approach has been taken with Monte Carlo studies of a single dendrimer molecule in the gas phase at the atomistic level, semi-atomistic molecular dynamics of a single molecule in liquid crystalline solvents and a coarse-grained molecular dynamics study of the dendrimer in the bulk. The coarse-grained model has been developed and parameterized using the results of the atomistic and semi-atomistic work. The single molecule studies showed that the liquid crystalline dendrimer was able to change its structure by conformational changes in the flexible chains that link the mesogenic groups to the core. Structural change was seen under the application of a mean field ordering potential in the gas phase, and in the presence of liquid crystalline solvents. No liquid crystalline phases were observed for the bulk phase studies of the coarse-grained model. However, when the length of the mesogenic units was increased there was some evidence for microphase separation in these systems. (author)

Novel electrical transport properties in conducting polymers such as polythiophene and Poly(3-Methylthiophene)

International Nuclear Information System (INIS)

Kazama, Shigeo; Masubuchi, Shin-ichi; Matsuyama, Tomochika; Matsushita, Rokuji.

1994-01-01

Electric transport properties in most of the conducting organic polymers have provided a riddle that prevents a thorough physical understanding of the conduction mechanism. Major difficulties for approaching the most substantial aspect in the electrical transport properties underlie in complicated higher order structure inherent to polymeric materials consisting of crystalline regions entangled with disordered amorphous regions. In order to clearly understand the origin of the metallic nature of conducting polymers, we have to extract the proper transport properties characteristics of the ordered crystalline regions. We have made a series of experimental studies of the transport properties in conductive polythiophene and poly(3-methylthiophene) obtained with the electrochemical polymerization. For polythiophene, we have investigated both the as-grown samples and the ones that contain controlled amount of dopant species exchanged after the neutralization aiming to see the effect of dopant concentration on the transport properties. (author)

Ortho-positronium annihilation parameters in polyvinyl alcohol films with various degrees of polymerization, saponification and crystallinity

International Nuclear Information System (INIS)

Muramatsu, Hisakazu; Matsumoto, Kuniyuki; Minekawa, Sachiko; Yagi, Yukiko; Sasai, Shigenori

2001-01-01

Positron annihilation lifetime (PAL) spectroscopy has been applied to polyvinyl alcohol (PVA) films prepared with commercially available PVA or from polyvinyl acetate (PVac). The variation of lifetimes of ortho-positronium (o-Ps) formed in the films was investigated as a function of the degrees of polymerization, saponification, or crystallinity. For the fully saponificated samples, no dependence was found to exist on the degrees of polymerization or of crystallinity. For the partially saponificated samples, however, the dependence of the o-Ps lifetime on the degree of saponification was clearly observed, and this is explained by both the formation of hydrogen bonds among the polymer chains and the existence of acetyl group strongly inhibiting the hydrogen-bond formation due to steric hindrance. (orig.)

Influence of Chemical Treatments Sequence on Morphology and Crystallinity of Sorghum Fibers

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Ismojo Ismojo

2018-05-01

Full Text Available Micro-fibrillated cellulose (MFC derived from natural fibre is continuously gaining interest to produce an environmentally-friendly material, due to economic and ecological reasons. In consequence, sorghum is one of the most-cultivated crops that usually remain the waste as by product of bioethanol production. Indeed, it will be a promising area to utilize sorghum waste to produce MFC for enhancing polymer performance, especially in terms of crystallinity. The objective of this study is to investigate the effect of a sequence of chemical modification was applied to sorghum fibres, i.e. alkalization using 4% sodium hydroxide followed by bleaching using 1.7% sodium chlorite plus acetic acid as a buffer. The treatment was purposed to unbundle the lignocellulose networks into microfibrils cellulose with less amorphous part and lower hydrophilic properties. Evaluation of the chemical treatments effect on internal microstructure, crystallinity index and chemical composition of sorghum fibre was measured via Field-Emission Scanning Electron microscope (FE-SEM, X-ray Diffraction (XRD and Fourier Transformation Infra-Red (FTIR Spectroscopy. The experiments show that treatments led to a removal of binding materials, such as amorphous parts hemicellulose and lignin, from the sorghum fibres, resulting MFC of sorghum fibres and enhanced crystallinity index from 41.12 % to 75.73%.

Photocatalytic Anatase TiO2 Thin Films on Polymer Optical Fiber Using Atmospheric-Pressure Plasma.

Science.gov (United States)

Baba, Kamal; Bulou, Simon; Choquet, Patrick; Boscher, Nicolas D

2017-04-19

Due to the undeniable industrial advantages of low-temperature atmospheric-pressure plasma processes, such as low cost, low temperature, easy implementation, and in-line process capabilities, they have become the most promising next-generation candidate system for replacing thermal chemical vapor deposition or wet chemical processes for the deposition of functional coatings. In the work detailed in this article, photocatalytic anatase TiO 2 thin films were deposited at a low temperature on polymer optical fibers using an atmospheric-pressure plasma process. This method overcomes the challenge of forming crystalline transition metal oxide coatings on polymer substrates by using a dry and up-scalable method. The careful selection of the plasma source and the titanium precursor, i.e., titanium ethoxide with a short alkoxy group, allowed the deposition of well-adherent, dense, and crystalline TiO 2 coatings at low substrate temperature. Raman and XRD investigations showed that the addition of oxygen to the precursor's carrier gas resulted in a further increase of the film's crystallinity. Furthermore, the films deposited in the presence of oxygen exhibited a better photocatalytic activity toward methylene blue degradation assumedly due to their higher amount of photoactive {101} facets.

The equation of state of polymers. Part III: Relation with the compensation law.

Science.gov (United States)

Rault, Jacques

2017-09-01

The properties of amorphous polymers and of organic compounds under pressure are interpreted in the framework of the modified Van der Walls Equation of State (mVW-EOS) the Vogel-Fulcher-Tamann (VFT) law and of the compensation law. We have shown recently that polymers and organic compounds in amorphous liquid and crystalline states verify the mVW-EOS which depends on three parameters, [Formula: see text] [Formula: see text] and [Formula: see text]. In this paper we compare the characteristic pressure [Formula: see text] of the mVW-EOS to the various pressures [Formula: see text] deduced from thermodynamic and kinetic properties of polymers in the liquid and solid states. [Formula: see text] and [Formula: see text] are: a) the enthalpy and volume change at the melting and glass transitions (the glass being isotropic or oriented and annealed below [Formula: see text] at various aging conditions); b) the activation parameters of individual [Formula: see text] and cooperative [Formula: see text] motions in crystalline liquid and amorphous polymers studied by dielectric or mechanical spectroscopy; and c) the activation parameters of amorphous (solid and liquid) polymers submitted to a deformation depending on the time frequency temperature and strain rate. For a same material, whatever its state and whatever the experimental properties analyzed (dielectric and mechanical relaxation, viscosity, auto-diffusion, yielding under hydrostatic pressure), we demonstrate that [Formula: see text], ([Formula: see text] Grüneisen parameter, [Formula: see text] compressibility). In all polymers and organic compounds (and water), these pressures, weakly dependent on T and P near [Formula: see text] and [Formula: see text] at low pressure are characteristic of the H-H inter-molecular interactions. It is shown that the two empirical Lawson and Keyes relations of the compensation law can be deduced from the mVW-EOS.

Dynamic mechanical analysis and crystalline analysis of hemp fiber reinforced cellulose filled epoxy composite

Energy Technology Data Exchange (ETDEWEB)

Palanivel, Anand; Duruvasalu, Rajesh; Iyyanar, Saranraj; Velumayil, Ramesh, E-mail: p.anand@ymail.com [Mechanical Engineering, Vel Tech Dr RR. & Dr. SR University, Avadi, Chennai, Tamilnadu (India); Veerabathiran, Anbumalar [Mechanical Engineering, Velammal College of Engineering & Technology, Madurai, TN (India)

2017-07-01

The Dynamic mechanical behavior of chemically treated and untreated hemp fiber reinforced composites was investigated. The morphology of the composites was studied to understand the interaction between the filler and polymer. A series of dynamic mechanical tests were performed by varying the fiber loading and test frequencies over a range of testing temperatures. It was found that the storage modulus (E') recorded above the glass transition temperature (Tg) decrease with increasing temperature. The loss modulus (E”) and damping peaks (Tan δ) values were found to be reduced with increasing matrix loading and temperature. Morphological changes and crystallinity of Composites were investigated using scanning electron microscope (SEM) and XRD techniques. The composites with Alkali and Benzoyl treated fibers has attributed enhanced DMA Results. In case of XRD studies, the composites with treated fibers with higher filler content show enhanced crystallinity. (author)

Dynamic mechanical analysis and crystalline analysis of hemp fiber reinforced cellulose filled epoxy composite

Directory of Open Access Journals (Sweden)

Anand Palanivel

Full Text Available Abstract The Dynamic mechanical behavior of chemically treated and untreated hemp fiber reinforced composites was investigated. The morphology of the composites was studied to understand the interaction between the filler and polymer. A series of dynamic mechanical tests were performed by varying the fiber loading and test frequencies over a range of testing temperatures. It was found that the storage modulus (E’ recorded above the glass transition temperature (Tg decrease with increasing temperature. The loss modulus (E” and damping peaks (Tan δ values were found to be reduced with increasing matrix loading and temperature. Morphological changes and crystallinity of Composites were investigated using scanning electron microscope (SEM and XRD techniques. The composites with Alkali and Benzoyl treated fibers has attributed enhanced DMA Results. In case of XRD studies, the composites with treated fibers with higher filler content show enhanced crystallinity.

Lightweight, Low-CTE Tubes Made From Biaxially Oriented LCPs

Science.gov (United States)

Rubin, Leslie; Federico, Frank; Formato, Richard; Larouco, John; Slager, William

2004-01-01

Tubes made from biaxially oriented liquid-crystal polymers (LCPs) have been developed for use as penetrations on cryogenic tanks. ( Penetrations in this context denotes feed lines, vent lines, and sensor tubes, all of which contribute to the undesired conduction of heat into the tanks.) In comparison with corresponding prior cryogenic-tank penetrations made from stainless steels and nickel alloys, the LCP penetrations offer advantages of less weight and less thermal conduction. An additional major advantage of LCP components is that one can tailor their coefficients of thermal expansion (CTEs). The estimated cost of continuous production of LCP tubes of typical sizes is about $1.27/ft ($4.17/m) [based on 1998 prices]. LCP tubes that are compatible with liquid oxygen and that feature tailored biaxial molecular orientation and quasi-isotropic properties (including quasi-isotropic CTE) have been fabricated by a combination of proprietary and patented techniques that involve the use of counterrotating dies (CRDs). Tailoring of the angle of molecular orientation is what makes it possible to tailor the CTE over a wide range to match the CTEs of adjacent penetrations of other tank components; this, in turn, makes it possible to minimize differential-thermal expansion stresses that arise during thermal cycling. The fabrication of biaxially oriented LCP tubes by use of CRDs is not new in itself. The novelty of the present development lies in tailoring the orientations and thus the CTEs and other mechanical properties of the LCPs for the intended cryogenic applications and in modifications of the CRDs for this purpose. The LCP tubes and the 304-stainless-steel tubes that the LCP tubes were intended to supplant were tested with respect to burst strength, permeability, thermal conductivity, and CTE.

Effect of ionizing and nonionizing radiations on the mechanical properties of cellulose tri acetate polymer

Energy Technology Data Exchange (ETDEWEB)

Sallam, M M; El-Fiki, S A; Nooh, S A [Physics Department, Faculty of Science, Ain Chams Univ, Cairo (Egypt); Eissa, H M [National Institute for Standard, Cairo (Egypt)

1997-12-31

Several quantities including modulus of elasticity, fracture stress, fracture strain, yield tress and yield strain, were calculated for cellulose tri acetate polymer. These samples were exposed to different gamma doses in the range from (32 kg y), and different energies of infrared pulsated laser of 5 watt power in the range (Zero to 9 j/cm 2). The changes in these parameters were found to be due to changes in degree of crystallinity of polymers.4 figs., 3 tabs.

Electron beam effects on gelatin polymer

Energy Technology Data Exchange (ETDEWEB)

Inamura, Patricia Y.; Shimazaki, Kleber; Souza, Clecia de M.; Moura, Esperidiana A.B.; Mastro, Nelida L. del, E-mail: patyoko@yahoo.co [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Colombo, Maria A., E-mail: mascolombo@yahoo.com.b [Faculdade de Tecnologia da Zona Leste, Sao Paulo, SP (Brazil)

2009-07-01

The main field of electron-beam radiation processing applications is the modification of polymeric material. Polymer development includes new pathways to produce natural polymers with better mechanical and barrier properties and thermal stability. The aim of this paper was to investigate the behavior of a gelatin/acrylamide polymer treated by electron-beam radiation. Gelatin is a heterogeneous mixture of water-soluble proteins of high average molecular mass derived by hydrolytic action from animal collagen, a fibrous insoluble protein, which is widely found in nature as the major constituent of skin, bones and connective tissue. Hydrolyzed collagen is composed of a unique sequence of amino acids, characterized particularly by the high content of glycine, proline and hydroxyproline. Among biomaterials, gelatin is an interesting material because is a partially crystalline polymer and has a relatively low melting point. Samples of gelatin together with glycerin as plasticizer and acrylamide as copolymer were irradiated with doses of 10 kGy and 40 kGy, using an electron beam accelerator, dose rate 22.41kGy/s, at room temperature in presence of air. After irradiation, some preliminary analyses were done like viscometry, texture analyses and colorimetry. The results of the diverse tests showed changes that can be ascribed to radiation-induced crosslinking. The electron-beam processed acrylamide-gelatin polymer using glycerin as plasticizer must be first extensively characterized before to be used for general applications. (author)

Electron beam effects on gelatin polymer

International Nuclear Information System (INIS)

Inamura, Patricia Y.; Shimazaki, Kleber; Souza, Clecia de M.; Moura, Esperidiana A.B.; Mastro, Nelida L. del; Colombo, Maria A.

2009-01-01

The main field of electron-beam radiation processing applications is the modification of polymeric material. Polymer development includes new pathways to produce natural polymers with better mechanical and barrier properties and thermal stability. The aim of this paper was to investigate the behavior of a gelatin/acrylamide polymer treated by electron-beam radiation. Gelatin is a heterogeneous mixture of water-soluble proteins of high average molecular mass derived by hydrolytic action from animal collagen, a fibrous insoluble protein, which is widely found in nature as the major constituent of skin, bones and connective tissue. Hydrolyzed collagen is composed of a unique sequence of amino acids, characterized particularly by the high content of glycine, proline and hydroxyproline. Among biomaterials, gelatin is an interesting material because is a partially crystalline polymer and has a relatively low melting point. Samples of gelatin together with glycerin as plasticizer and acrylamide as copolymer were irradiated with doses of 10 kGy and 40 kGy, using an electron beam accelerator, dose rate 22.41kGy/s, at room temperature in presence of air. After irradiation, some preliminary analyses were done like viscometry, texture analyses and colorimetry. The results of the diverse tests showed changes that can be ascribed to radiation-induced crosslinking. The electron-beam processed acrylamide-gelatin polymer using glycerin as plasticizer must be first extensively characterized before to be used for general applications. (author)

Characterization of biodegradable polymers irradiated with swift heavy ions

International Nuclear Information System (INIS)

Salguero, N.G.; Grosso, M.F. del; Durán, H.; Peruzzo, P.J.; Amalvy, J.I.

2012-01-01

In view of their application as biomaterials, there is an increasing interest in developing new methods to induce controlled cell adhesion onto polymeric materials. The critical step in all these methods involves the modification of polymer surfaces, to induce cell adhesion, without changing theirs degradation and biocompatibility properties. In this work two biodegradable polymers, polyhydroxybutyrate (PHB) and poly-L-lactide acid (PLLA) were irradiated using carbon and sulfur beams with different energies and fluences. Pristine and irradiated samples were degradated by immersion in a phosphate buffer at pH 7.0 and then characterized. The analysis after irradiation and degradation showed a decrease in the contact angle values and changes in their crystallinity properties.

Characterization of biodegradable polymers irradiated with swift heavy ions

Energy Technology Data Exchange (ETDEWEB)

Salguero, N.G. [Gerencia de Investigacion y Aplicaciones, TANDAR-CNEA, Av. Gral. Paz 1499 (B1650KNA) San Martin, Buenos Aires (Argentina); Grosso, M.F. del, E-mail: delgrosso@tandar.cnea.gov.ar [Gerencia de Investigacion y Aplicaciones, TANDAR-CNEA, Av. Gral. Paz 1499 (B1650KNA) San Martin, Buenos Aires (Argentina); CONICET, Av. Rivadavia 1917 C1033AAJ CABA (Argentina); Duran, H. [CONICET, Av. Rivadavia 1917 C1033AAJ CABA (Argentina); Gerencia de Desarrollo Tecnologico y Proyectos Especiales, CNEA, Av. Gral. Paz 1499 (B1650KNA) San Mart Latin-Small-Letter-Dotless-I Acute-Accent n, Buenos Aires (Argentina); Escuela de Ciencia y Tecnologia, H. Yrigoyen 3100, CP 1650, San Martin, UNSAM (Argentina); Peruzzo, P.J. [CICPBA - Grupo de Materiales y Nanomateriales Polimericos, Instituto de Investigaciones Fisicoquimicas Teoricas y Aplicadas (INIFTA), CCT La Plata CONICET - Universidad Nacional de La Plata, La Plata (Argentina); Amalvy, J.I. [CICPBA - Grupo de Materiales y Nanomateriales Polimericos, Instituto de Investigaciones Fisicoquimicas Teoricas y Aplicadas (INIFTA), CCT La Plata CONICET - Universidad Nacional de La Plata, La Plata (Argentina); Facultad de Ingenieria, Universidad Nacional de La Plata, Calle 116 y 48 (B1900TAG), La Plata (Argentina); Departamento de Ingenieria Quimica, Facultad Regional La Plata, Universidad Tecnologica Nacional, 60 y 124 (1900), La Plata (Argentina); and others

2012-02-15

In view of their application as biomaterials, there is an increasing interest in developing new methods to induce controlled cell adhesion onto polymeric materials. The critical step in all these methods involves the modification of polymer surfaces, to induce cell adhesion, without changing theirs degradation and biocompatibility properties. In this work two biodegradable polymers, polyhydroxybutyrate (PHB) and poly-L-lactide acid (PLLA) were irradiated using carbon and sulfur beams with different energies and fluences. Pristine and irradiated samples were degradated by immersion in a phosphate buffer at pH 7.0 and then characterized. The analysis after irradiation and degradation showed a decrease in the contact angle values and changes in their crystallinity properties.

[Calcaneal fractures treated by open reduction and internal fixation with a locking compression plate (LCP). A prospective study. part I: basic analysis of the group].

Science.gov (United States)

Svatoš, F; Bartoška, R; Skála-Rosenbaum, J; Douša, P; Pacovský, V; Krbec, M

2011-01-01

In a prospective study of patients with calcaneal fractures treated by open reduction from an extensile lateral approach and LCP osteosynthesis, the authors evaluated the basic epidemiological data, mechanism of injury, type of fracture, essential data on surgery, days of hospital stay and the number of complications. In the period from September 1, 2006 to July 31, 2010, a total of 230 patients with 243 calcaneal fractures were treated. The fractures were classified as either open or closed and according to the Essex-Lopresti system. Of the total number of patients, 135 (55.6 % of all fractures) were indicated for conservative treatment and 108 (44.4% of all fractures) for surgical intervention. Indications for surgery based on the generally accepted criteria enabled us to select 77 patients with 82 fractures (33.7 % of all fractures) for treatment by the method of open reduction and LCP osteosynthesis. These patients constituted the group evaluated here. The other patients were treated using other techniques (21 fractures, i.e., 8.6 % of all fractures, by the Stehlík-Štulík transfixation method and further five [2.1 %] by screw osteosynthesis). Six surgeons were involved in the treatment of this group. For the diagnosis of fractures, plain radiographs in lateral and axial projection and axial and coronal CT images were used. All fractures were treated after subsidence of oedema by the method of open reduction and LCP fixation from an extensile lateral approach, with the use of a tourniquet. The follow-up period for the evaluation of functional outcome and bone union was 3 to 48 months. Fifty patients were followed up for over one year. The group evaluated comprised 58 men (75.3 %) with 63 fractures (76.8 %) and 19 women (24.7 %) with 19 fractures (23.2 %). The average age of the group was 42 years, with 41 years (range, 22-61 years) in men and 47 years (range, 30-70 years) in women. The most frequent cause of injury was a fall from a height below 1 metre and

Polymer - (BEDT-TTF) polyiodide composites

Energy Technology Data Exchange (ETDEWEB)

Ulanski, J [Polymer Inst., Technical Univ. of Lodz (Poland); Glowacki, I [Polymer Inst., Technical Univ. of Lodz (Poland); Kryszewski, M [Polymer Inst., Technical Univ. of Lodz (Poland); Jeszka, J K [Center of Molecular and Macromolecular Studies, Lodz (Poland); Tracz, A [Center of Molecular and Macromolecular Studies, Lodz (Poland); Laukhina, E [Inst. of Chemical Physics, Chernogolovka (Russian Federation)

1993-03-29

Preparation and properties of reticulate doped polymers containing BEDT-TTF polyiodide crystalline network are discussed. The highly conducting films are obtained using different methods, including recently developed one in which oxidation of the donor with iodine and crystallization of the resulting salt take place simultaneously in situ, in the swollen polymer matrix. It was found that the temperature dependence of conductivity of the separated microcrystal grown in the film exhibits metallic character with a maximum around 100K. The conductivity of the as-obtained composite increases with temperature up to ca. 120K with an activation energy of ca. 50 meV, then levels off. Annealing of the composites in order to transform the BEDT-TTF polyiodide crystalites into superconducting [beta][sup *]-phase causes dramatic changes in the conductivity behaviour; the [sigma](T) dependence of the composite switches from semiconductor- to metal-like. Stability of the films at ambient conditions is good. (orig.)

Thermotropic liquid crystalline polyazomethine nanocomposites via in situ interlayer polymerization

International Nuclear Information System (INIS)

Min, Ungki; Chang, Jin-Hae

2011-01-01

Highlights: → Nanocomposites of polyazomethine with the organoclay C 12 -MMT were synthesized by using the in situ interlayer polymerization method. → The thermal properties of the polyazomethine hybrids increase with the addition of the organoclay up to a critical content and then decrease with further organoclay loading. → Liquid crystalline compositions with 0-9 wt% organoclay have threaded Schlieren nematic textures. - Abstract: Nanocomposites of polyazomethine (PAM) with the organoclay C 12 -MMT were synthesized by using the in situ interlayer polymerization method. The variations with organoclay content of the thermal properties, morphology, and liquid crystalline mesophases of the hybrids were determined for concentrations from 0 to 9 wt% C 12 -MMT. The thermal properties and the morphologies of the PAM nanocomposites were examined by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide angle X-ray diffractometry (XRD), transmission electron microscopy (TEM), and polarizing optical microscopy (POM). The XRD analysis and TEM micrographs show that the levels of nanosize dispersion can be controlled by varying the C 12 -MMT content. The clay particles are better dispersed in the matrix polymer at low clay contents than at high clay contents. With the exception of the glass transition temperature (T g ), the maximum enhancement in the thermal properties was found to arise at an organoclay content of 1 wt%. Further, the PAM hybrids were shown to exhibit a nematic liquid crystalline phase for organoclay contents in the range 0-9 wt%.

The local free volume and its correlation with the structural, chemical and dynamic properties of branched polymers, polymer electrolytes, highly oriented polyethylene fibres and other polymers

International Nuclear Information System (INIS)

Bamford, David

2002-01-01

The work described in this thesis is concerned with the study of the local free volume measured by Positron Annihilation Spectroscopy and its correlation with the physical, chemical and structural properties of polymers. The average size of the local free volume holes in branched poly(ethylene-co-olefin) and poly(propylene-co-olefin) copolymers is studied using Positron Annihilation Lifetime Spectroscopy PALS and correlated with the number and length of the branches and the physical properties determined from Differential Scanning Calorimetry DSC and density measurements. The presence of the n-alkyl branches were found to form sterical hindrances to an effective chain packing resulting in a linear increase in the average free volume hole sizes, an increase in the specific volume of the amorphous phase, a decrease in the sample crystallinity and a decrease in the glass transition and melting temperatures. A linear relation was found between the average size of the free volume holes and the glass transition temperature, allowing a method for estimating the glass transition temperature of a sample purely from room temperature PALS measurements. Evidence is presented to support the common assumption that the fractional free volume is directly proportional to the average free volume hole size and that the specific crystalline volume may accurately represent the value of the specific occupied volume. The number density of holes was found to be constant for each of the series of copolymers in agreement with the above findings. Poly((ethylene glycol) 23 dimethacrylate) and poly(ethylene oxide) based polymer electrolytes exhibiting single anion, single cation and mixed ion conduction are studied as a function of temperature using PALS, ionic conductivity and DSC measurements. The glass transition temperature, the thermal expansion of the free volume and the effects on the free volume due to the addition of the ions are discussed. In particular, an explanation for the

Matrix-assisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers using new ionic liquid matrices.

Science.gov (United States)

Serrano, Carlos A; Zhang, Yi; Yang, Jian; Schug, Kevin A

2011-05-15

In this study, two novel ionic liquid matrices (ILMs), N,N-diisopropylethylammonium 3-oxocoumarate and N,N-diisopropylethylammonium dihydroxymonooxoacetophenoate, were tested for the structural elucidation of recently developed aliphatic biodegradable polymers by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The polymers, formed by a condensation reaction of three components, citric acid, octane diol, and an amino acid, are fluorescent, but the exact mechanism behind their luminescent properties has not been fully elucidated. In the original studies, which introduced the polymer class (J. Yang et al., Proc. Natl. Acad. Sci. USA 2009, 106, 10086-10091), a hyper-conjugated cyclic structure was proposed as the source for the photoluminescent behavior. With the use of the two new ILMs, we present evidence that supports the presence of the proposed cyclization product. In addition, the new ILMs, when compared with a previously established ILM, N,N-diisopropylethylammonium α-cyano-3-hydroxycinnimate, provided similar signal intensities and maintained similar spectral profiles. This research also established that the new ILMs provided good spot-to-spot reproducibility and high ionization efficiency compared with corresponding crystalline matrix preparations. Many polymer features revealed through the use of the ILMs could not be observed with crystalline matrices. Ultimately, the new ILMs highlighted the composition of the synthetic polymers, as well as the loss of water that was expected for the formation of the proposed cyclic structure on the polymer backbone. Copyright © 2011 John Wiley & Sons, Ltd.

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

KAUST Repository

Zhao, Kui; Yu, Xinhong; Li, Ruipeng; Amassian, Aram; Han, Yanchun

2015-01-01

The mechanistic understanding of the intrinsic molecular self-assembly of conjugated polymers is of immense importance to controlling the microstructure development in organic semiconducting thin films, with meaningful impact on charge transport

Structure–property relationships of oligothiophene–isoindigo polymers for efficient bulk-heterojunction solar cells

DEFF Research Database (Denmark)

Ma, Zaifei; Sun, Wenjun; Himmelberger, Scott

2014-01-01

interfacial energy level offset ensures efficient exciton separation and charge generation. The structure–property relationship demonstrated in this work would be a valuable guideline for the design of high performance polymers with small energy losses during the charge generation process, allowing......) in the repeating unit alters both polymer crystallinity and polymer–fullerene interfacial energetics, which results in a decreasing open-circuit voltage (Voc) of the solar cells with increasing n. The short-circuit current density (Jsc) of P1TI:PCBM devices is limited by the absence of a significant driving force...

Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

KAUST Repository

Schroeder, Bob C.; Nielsen, Christian B.; Westacott, Paul; Smith, Jeremy; Rossbauer, Stephan; Anthopoulos, Thomas D.; Stingelin, Natalie; McCulloch, Iain

2015-01-01

Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and processability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors. Copyright © Materials Research Society 2015

Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

KAUST Repository

Schroeder, Bob C.

2015-07-02

Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and processability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors. Copyright © Materials Research Society 2015

Space resolved x-ray diffraction measurements of the supercooled state of polymers

International Nuclear Information System (INIS)

Asano, Tsutomu; Yoshida, Shinya; Nishida, Akira; Mina, M.F.

2002-01-01

In order to measure an ordering process of polymers, the supercooled state near the crystallizing surface was observed by a space resolved X-ray diffraction method at Photon Factory (PF). Using temperature slope crystallization, low density polyethylene and even-number paraffins were examined during crystallization from the melt state. The results indicate that polyethylene shows a sharp b-axis orientation where the lamellar normal and crystalline c-axis are perpendicular to the temperature slope. The crystalline lamellae are well-developed with lamellar thickness of 180 A. The supercooled melt state just above the crystallizing plane shows some diffraction in the small angle region without any crystalline reflection in the wide angle. This fact suggests that a long-range ordering (lamellar structure) appears prior to the short-range one (crystalline structure). The in-situ crystallizing surface was observed by an optical microscope connected to a TV system. The crystallizing surface of even-number paraffins moves to upwards in the temperature slope. In-situ X-ray measurements at PF revealed that the crystalline c-axis and lamellar normal of the even number paraffins are parallel to the temperature slope. From these results, the crystalline ordering and the surface movement of even number paraffins are explained using special nucleation mechanism including a screw dislocation. (author)

Deuteron NMR and modelling in solid polymers

International Nuclear Information System (INIS)

Hirschinger, J.

1992-01-01

Deuteron NMR techniques are described and some recent applications to the study of rotational motions in solid polymers are reviewed. The information content and the domain of applicability of each technique are presented. Ultra-slow motions are studied in real time without any motional model consideration. For very fast motions, computer molecular dynamics simulations are shown to complement the NMR results. Experimental examples deal with the chain motion in the crystalline α-phase of poly(vinylidenefluoride) and nylon 6,6

Electric poling-assisted additive manufacturing process for PVDF polymer-based piezoelectric device applications

International Nuclear Information System (INIS)

Lee, ChaBum; Tarbutton, Joshua A

2014-01-01

This paper presents a new additive manufacturing (AM) process to directly and continuously print piezoelectric devices from polyvinylidene fluoride (PVDF) polymeric filament rods under a strong electric field. This process, called ‘electric poling-assisted additive manufacturing or EPAM, combines AM and electric poling processes and is able to fabricate free-form shape piezoelectric devices continuously. In this process, the PVDF polymer dipoles remain well-aligned and uniform over a large area in a single design, production and fabrication step. During EPAM process, molten PVDF polymer is simultaneously mechanically stresses in-situ by the leading nozzle and electrically poled by applying high electric field under high temperature. The EPAM system was constructed to directly print piezoelectric structures from PVDF polymeric filament while applying high electric field between nozzle tip and printing bed in AM machine. Piezoelectric devices were successfully fabricated using the EPAM process. The crystalline phase transitions that occurred from the process were identified by using the Fourier transform infrared spectroscope. The results indicate that devices printed under a strong electric field become piezoelectric during the EPAM process and that stronger electric fields result in greater piezoelectricity as marked by the electrical response and the formation of sharper peaks at the polar β crystalline wavenumber of the PVDF polymer. Performing this process in the absence of an electric field does not result in dipole alignment of PVDF polymer. The EPAM process is expected to lead to the widespread use of AM to fabricate a variety of piezoelectric PVDF polymer-based devices for sensing, actuation and energy harvesting applications with simple, low cost, single processing and fabrication step. (paper)

Development of degradable renewable polymers and stimuli-responsive nanocomposites

Science.gov (United States)

Eyiler, Ersan

The overall goal of this research was to explore new living radical polymerization methods and the blending of renewable polymers. Towards this latter goal, polylactic acid (PLA) was blended with a new renewable polymer, poly(trimethylene-malonate) (PTM), with the aim of improving mechanical properties, imparting faster degradation, and examining the relationship between degradation and mechanical properties. Blend films of PLA and PTM with various ratios (5, 10, and 20 wt %) were cast from chloroform. Partially miscible blends exhibited Young's modulus and elongation-to-break values that significantly extend PLA's usefulness. Atomic force microscopy (AFM) data showed that incorporation of 10 wt% PTM into PLA matrix exhibited a Young's modulus of 4.61 GPa, which is significantly higher than that of neat PLA (1.69 GPa). The second part of the bioplastics study involved a one-week hydrolytic degradation study of PTM and another new bioplastic, poly(trimethylene itaconate) (PTI) using DI water (pH 5.4) at room temperature, and the effects of degradation on crystallinity and mechanical properties of these films were examined by differential scanning calorimetry (DSC) and AFM. PTI showed an increase in crystallinity with degradation, which was attributed to predominately degradation of free amorphous regions. Depending on the crystallinity, the elastic modulus increased at first, and decreased slightly. Both bulk and surface-tethered stimuli-responsive polymers were studied on amine functionalized magnetite (Fe3O4) nanoparticles. Stimuli-responsive polymers studied, including poly(N-isopropylacrylamide) (PNIPAM), poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), and poly(itaconic acid) (PIA), were grafted via surface-initiated aqueous atom transfer radical polymerization (SI-ATRP). Both Fourier transform infrared spectroscopy (FTIR) and x-ray photoelectron spectroscopy (XPS) spectroscopies showed the progression of the grafting. The change in particle size as a

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

Science.gov (United States)

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

2016-10-01

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

Efecto de la época de plantación en la dinámica de la emergencia de caña semilla de alta calidad (termotratada y micropropagada de las variedades CP 65-357 y LCP 85-384 Effect of planting date on emergence dynamics of high quality CP 65-357 and LCP 85-384 seed cane (hot-water treated and micropropagated

Directory of Open Access Journals (Sweden)

Patricia A. Digonzelli

2005-12-01

Full Text Available Se evalúa el efecto de la época de plantación en la dinámica de la emergencia de caña semilla de alta calidad (micropropagada y termotratada de las variedades CP 65-357 y LCP 85-384, en condiciones de disponibilidad hídrica adecuada. La caña semilla micropropagada y termotratada (50ºC, 2 hs se plantó, con una densidad de 15 yemas/m, en tres épocas contrastantes: otoño, invierno y primavera. El material empleado estaba libre de escaldadura de la hoja (Xanthomonas albilineans y achaparramiento (Leifsonia xyli subsp. xyli. La época de plantación afectó todas las variables de la dinámica de la emergencia en las dos variedades y en ambos orígenes de la semilla. El origen afectó significativamente el inicio y la duración de la emergencia (t e y t50, pero no tuvo efecto en el porcentaje final ni en la tasa media de emergencia. La emergencia (% fue mayor en la plantación de octubre, que en las de mayo y agosto (59%, 35% y 45%, respectivamente. El te y el t50 fueron mayores en mayo que en agosto y octubre. La semilla micropropagada presentó, en general, valores de t e y t50 menores que la termotratada. La época de plantación fue el principal factor que afectó la dinámica de la emergencia de caña semilla de alta calidad de CP 65-357 y LCP 85-384. La variedad y el origen de la semilla afectaron significativamente, aunque en menor magnitud que la época de plantación, el inicio y la duración de la fase de emergencia.Planting date influence on emergence dynamics of high quality CP 65-357 and LCP 85-384 seed cane (hot-water treated and micropropagated, without humidity constraints, was evaluated. Material used was free from leaf scald disease (Xanthomonas albilineans and ratoon stunting disease (Leifsonia xyli subsp. xyli. Seed cane, micropropagated and hot-water treated (50ºC, 2 hours, was planted with a 15 buds/m density in three contrasting dates: autumn, winter and spring. The material was irrigated during the trial. Planting

Unconventional Face-On Texture and Exceptional In-Plane Order of a High Mobility n-Type Polymer

KAUST Repository

Rivnay, Jonathan; Toney, Michael F.; Zheng, Yan; Kauvar, Isaac V.; Chen, Zhihua; Wagner, Veit; Facchetti, Antonio; Salleo, Alberto

2010-01-01

Substantial in-plane crystallinity and dominant face-on stacking are observed in thin films of a high-mobility n-type rylene-thiophene copolymer. Spun films of the polymer, previously thought to have little or no order are found to exhibit an ordered microstructure at both interfaces, and in the bulk. The implications of this type of packing and crystalline morphology are discussed as they relate to thin-film transistors. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unconventional Face-On Texture and Exceptional In-Plane Order of a High Mobility n-Type Polymer

KAUST Repository

Rivnay, Jonathan

2010-07-09

Substantial in-plane crystallinity and dominant face-on stacking are observed in thin films of a high-mobility n-type rylene-thiophene copolymer. Spun films of the polymer, previously thought to have little or no order are found to exhibit an ordered microstructure at both interfaces, and in the bulk. The implications of this type of packing and crystalline morphology are discussed as they relate to thin-film transistors. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic Field Alignment of PS-P4VP: a Non-Liquid Crystalline Coil-Coil Block Copolymer

Science.gov (United States)

Rokhlenko, Yekaterina; Zhang, Kai; Larson, Steven; Gopalan, Padma; O'Hern, Corey; Osuji, Chinedum

2015-03-01

Magnetic fields provide the ability to control alignment of self-assembled soft materials such as block copolymers. Most prior work in this area has relied on the presence of ordered assemblies of anisotropic liquid crystalline species to ensure sufficient magnetic anisotropy to drive alignment. Recent experiments with poly(styrene-b-4-vinylpyridine), a non-liquid crystalline BCP, however, show field-induced alignment of a lamellar microstructure during cooling across the order-disorder transition. Using in situ x-ray scattering, we examine the roles of field strength and cooling rate on the alignment response of this low MW coil-coil BCP. Alignment is first observed at field strengths as low as 1 Tesla and improves markedly with both increasing field strength and slower cooling. We present a geometric argument to illustrate the origin of a finite, non-trivial magnetic susceptibility anisotropy for highly stretched surface-tethered polymer chains and corroborate this using coarse-grained molecular dynamics simulations. We rationalize the magnetic field response of the system in terms of the mobility afforded by the absence of entanglements, the intrinsic anisotropy resulting from the stretched polymer chains and sterically constrained conjugated rings, and the large grain size in these low molecular weight materials.

Thermoresponsive Membrane Based on Thermotropic Liquid Crystalline Cholesteryl - (L-lacticacidn System: Study of Its Drug Permeability

Directory of Open Access Journals (Sweden)

Massoumeh Bagheri

2013-01-01

Full Text Available The rapidly increasing interest in functional materials with reversibly switchable physico- chemical properties has led to significant work on the development of stimuli responsive membranes. Thermotropic liquid crystals with their exceptional properties have potentials for drug-delivery applications. Thermoresponsive liquid-crystal-embedded membranes were investigated for the purpose of developing the drug delivery systems with thermal stimuli response. Drug release occurs at temperatures above the phase transition temperature of thermotropic liquid crystals. Therefore, they can control drug release in response to small temperature changes. In this work, the biocompatible and thermotropic liquid crystalline polymer cholesteryl-(L-lactic acidn ,CLAn (n=30, was synthesized with accurate control of molecular weight via ring opening polymerization method. Polymerization of L-lactide was carried out in the presence of cholesterol as an initiator and catalytic amount of tin (II octoate (Sn(Oct2 at 150°C in 5 h. The number-average degree of polymerization of CLA 30 was obtained from 1H NMR spectroscopy. The phase transition behavior of liquid crystalline CLA30 was established by differential scanning calorimetry and polarizing optical microscopy. The resulting liquid crystalline CLA30 was subsequently utilized to prepare CLA30 -embedded cellulose nitrate membrane by adsorption method. The CLA30-embedded cellulose nitrate membrane was used by an in-vitro drug penetration studies. Acetaminophen was used as a model drug. The permeation study was carried out at different temperatures around glass transition temperature of polymer CLA30 (37, 45 and 40°C, respectively. The results show that the CLA30 -embedded cellulose nitrate membranes exhibit thermo-responsive sensitivity with controlled drug permeation.

Hierarchically Ordered Supramolecular Protein-Polymer Composites with Thermoresponsive Properties

Directory of Open Access Journals (Sweden)

Salla Välimäki

2015-05-01

Full Text Available Synthetic macromolecules that can bind and co-assemble with proteins are important for the future development of biohybrid materials. Active systems are further required to create materials that can respond and change their behavior in response to external stimuli. Here we report that stimuli-responsive linear-branched diblock copolymers consisting of a cationic multivalent dendron with a linear thermoresponsive polymer tail at the focal point, can bind and complex Pyrococcus furiosus ferritin protein cages into crystalline arrays. The multivalent dendron structure utilizes cationic spermine units to bind electrostatically on the surface of the negatively charged ferritin cage and the in situ polymerized poly(di(ethylene glycol methyl ether methacrylate linear block enables control with temperature. Cloud point of the final product was determined with dynamic light scattering (DLS, and it was shown to be approximately 31 °C at a concentration of 150 mg/L. Complexation of the polymer binder and apoferritin was studied with DLS, small-angle X-ray scattering, and transmission electron microscopy, which showed the presence of crystalline arrays of ferritin cages with a face-centered cubic (fcc, \\( Fm\\overline{3}m \\ Bravais lattice where lattice parameter a = 18.6 nm. The complexation process was not temperature dependent but the final complexes had thermoresponsive characteristics with negative thermal expansion.

Photoluminescence studies on porous silicon/polymer heterostructure

International Nuclear Information System (INIS)

Mishra, J.K.; Bhunia, S.; Banerjee, S.; Banerji, P.

2008-01-01

Hybrid devices formed by filling porous silicon with MEH-PPV or poly [2-methoxy-5(2-ethylhexyloxy-p-phenylenevinylene)] have been investigated in this work. Analyses of the structures by scanning electron microscopy (SEM) demonstrated that the porous silicon layer was filled by the polymer with no significant change of the structures except that the polymer was infiltrated in the pores. The photoluminescence (PL) of the structures at 300 K showed that the emission intensity was very high as compared with that of the MEH-PPV films on different substrates such as crystalline silicon (c-Si) and indium tin oxide (ITO). The PL peak in the MEH-PPV/porous silicon composite structure is found to be shifted towards higher energy in comparison with porous silicon PL. A number of possibilities are discussed to explain the observations

Non-Fullerene Polymer Solar Cells Based on Alkylthio and Fluorine Substituted 2D-Conjugated Polymers Reach 9.5% Efficiency.

Science.gov (United States)

Bin, Haijun; Zhang, Zhi-Guo; Gao, Liang; Chen, Shanshan; Zhong, Lian; Xue, Lingwei; Yang, Changduk; Li, Yongfang

2016-04-06

Non-fullerene polymer solar cells (PSCs) with solution-processable n-type organic semiconductor (n-OS) as acceptor have seen rapid progress recently owing to the synthesis of new low bandgap n-OS, such as ITIC. To further increase power conversion efficiency (PCE) of the devices, it is of a great challenge to develop suitable polymer donor material that matches well with the low bandgap n-OS acceptors thus providing complementary absorption and nanoscaled blend morphology, as well as suppressed recombination and minimized energy loss. To address this challenge, we synthesized three medium bandgap 2D-conjugated bithienyl-benzodithiophene-alt-fluorobenzotriazole copolymers J52, J60, and J61 for the application as donor in the PSCs with low bandgap n-OS ITIC as acceptor. The three polymers were designed with branched alkyl (J52), branched alkylthio (J60), and linear alkylthio (J61) substituent on the thiophene conjugated side chain of the benzodithiophene (BDT) units for studying effect of the substituents on the photovoltaic performance of the polymers. The alkylthio side chain, red-shifted absorption down-shifted the highest occupied molecular orbital (HOMO) level and improved crystallinity of the 2D conjugated polymers. With linear alkylthio side chain, the tailored polymer J61 exhibits an enhanced JSC of 17.43 mA/cm(2), a high VOC of 0.89 V, and a PCE of 9.53% in the best non-fullerene PSCs with the polymer as donor and ITIC as acceptor. To the best of our knowledge, the PCE of 9.53% is one of the highest values reported in literature to date for the non-fullerene PSCs. The results indicate that J61 is a promising medium bandgap polymer donor in non-fullerene PSCs.

Design of porphyrin-based conjugated microporous polymers with enhanced singlet oxygen productivity

Czech Academy of Sciences Publication Activity Database

Hynek, Jan; Rathouský, Jiří; Demel, Jan; Lang, Kamil

2016-01-01

Roč. 6, č. 50 (2016), s. 44279-44287 ISSN 2046-2069 R&D Projects: GA ČR(CZ) GA16-15020S Institutional support: RVO:61388980 ; RVO:61388955 Keywords : Conjugated microporous polymers * Crystalline materials * Metal organic framework * biomimetic catalysis Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 3.108, year: 2016

Exceptionally crystalline and conducting acid doped polyaniline films by level surface assisted solution casting approach

Energy Technology Data Exchange (ETDEWEB)

Puthirath, Anand B.; Varma, Sreekanth J.; Jayalekshmi, S., E-mail: jayalekshmi@cusat.ac.in [Division for Research in Advanced Materials, Department of Physics, Cochin University of Science and Technology, Cochin, Kerala 682022 (India); Methattel Raman, Shijeesh [Nanophotonic and Optoelectronic Devices Laboratory, Department of Physics, Cochin University of Science and Technology, Cochin, Kerala 682022 (India)

2016-04-18

Emeraldine salt form of polyaniline (PANI) was synthesized by chemical oxidative polymerisation method using ammonium persulfate as oxidant. Resultant emeraldine salt form of PANI was dedoped using ammonia solution and then re-doped with camphor sulphonic acid (CSA), naphthaline sulphonic acid (NSA), hydrochloric acid (HCl), and m-cresol. Thin films of these doped PANI samples were deposited on glass substrates using solution casting method with m-cresol as solvent. A level surface was employed to get homogeneous thin films of uniform thickness. Detailed X-ray diffraction studies have shown that the films are exceptionally crystalline. The crystalline peaks observed in the XRD spectra can be indexed to simple monoclinic structure. FTIR and Raman spectroscopy studies provide convincing explanation for the exceptional crystallinity observed in these polymer films. FESEM and AFM images give better details of surface morphology of doped PANI films. The DC electrical conductivity of the samples was measured using four point probe technique. It is seen that the samples also exhibit quite high DC electrical conductivity, about 287 S/cm for CSA doped PANI, 67 S/cm for NSA doped PANI 65 S/cm for HCl doped PANI, and just below 1 S/cm for m-cresol doped PANI. Effect of using the level surface for solution casting is studied and correlated with the observed crystallinity.

Crystal structure and thin film morphology of BBL ladder polymer

Energy Technology Data Exchange (ETDEWEB)

Song, H H [Department of Macromolecular Science, Han Nam University, Taejon (Korea, Republic of); Fratini, A V [Department of Chemistry, University of Dayton, Dayton, OH (United States); Chabinyc, M [Department of Chemistry, University of Dayton, Dayton, OH (United States); Price, G E [University of Dayton Research, Dayton, OH (United States); Agrawal, A K [Systran Corporation, Dayton, OH (United States); Wang, C S [University of Dayton Research, Dayton, OH (United States); Burkette, J [University of Dayton Research, Dayton, OH (United States); Dudis, D S [Materials Directorate, Wright Laboratory, Wright-Patterson Air Force Base, OH (United States); Arnold, F E [Materials Directorate, Wright Laboratory, Wright-Patterson Air Force Base, OH (United States)

1995-03-01

Crystal structure and morphology of poly[7-oxo-7H-benz(d,e)imidazo(4`,5`:5,6)-benzimidazo(2,1-a)isoquinoline-3,4:10,11-tetrayl-10-carbonyl] (BBL) ladder-like polymer were studied. The polymer forms a two-dimensional lattice of nematic liquid crystalline structure. An orthorhombic unit cell with cell parameters of a=7.87 b=3.37 c=11.97A was determined from the fiber diffraction pattern. In thin films, the rigid chains spontaneously form a layered structure across the film thickness, but in a very unusual manner, i.e. the very large molecular plane is standing perpendicularly to the film surface plane. The results are identical to our recent results of poly(p-phenylene benzobisthiazole) (PBT) film [7]. The polymer, however, lost its anisotropic order upon extrusion into a film and resulted in a fiber-like structure. (orig.)

A Thieno[3,2-b][1]benzothiophene Isoindigo Building Block for Additive- and Annealing-Free High-Performance Polymer Solar Cells

KAUST Repository

Yue, Wan; Ashraf, Raja Shahid; Nielsen, Christian B.; Collado-Fregoso, Elisa; Niazi, Muhammad Rizwan; Yousaf, Syeda Amber; Kirkus, Mindaugas; Chen, Hung-Yang; Amassian, Aram; Durrant, James R.; McCulloch, Iain

2015-01-01

A novel photoactive polymer with two different molecular weights is reported, based on a new building block: thieno[3,2-b][1]benzothiophene isoindigo. Due to the improved crystallinity, optimal blend morphology, and higher charge mobility, solar-cell devices of the high-molecular-weight polymer exhibit a superior performance, affording efficiencies of 9.1% without the need for additives, annealing, or additional extraction layers during device fabrication.

A Thieno[3,2-b][1]benzothiophene Isoindigo Building Block for Additive- and Annealing-Free High-Performance Polymer Solar Cells

KAUST Repository

Yue, Wan

2015-08-20

A novel photoactive polymer with two different molecular weights is reported, based on a new building block: thieno[3,2-b][1]benzothiophene isoindigo. Due to the improved crystallinity, optimal blend morphology, and higher charge mobility, solar-cell devices of the high-molecular-weight polymer exhibit a superior performance, affording efficiencies of 9.1% without the need for additives, annealing, or additional extraction layers during device fabrication.

Multiscale Modeling of Thermal Conductivity of Polymer/Carbon Nanocomposites

Science.gov (United States)

Clancy, Thomas C.; Frankland, Sarah-Jane V.; Hinkley, Jeffrey A.; Gates, Thomas S.

2010-01-01

Molecular dynamics simulation was used to estimate the interfacial thermal (Kapitza) resistance between nanoparticles and amorphous and crystalline polymer matrices. Bulk thermal conductivities of the nanocomposites were then estimated using an established effective medium approach. To study functionalization, oligomeric ethylene-vinyl alcohol copolymers were chemically bonded to a single wall carbon nanotube. The results, in a poly(ethylene-vinyl acetate) matrix, are similar to those obtained previously for grafted linear hydrocarbon chains. To study the effect of noncovalent functionalization, two types of polyethylene matrices. -- aligned (extended-chain crystalline) vs. amorphous (random coils) were modeled. Both matrices produced the same interfacial thermal resistance values. Finally, functionalization of edges and faces of plate-like graphite nanoparticles was found to be only modestly effective in reducing the interfacial thermal resistance and improving the composite thermal conductivity

Influence of structures of polymer backbones on cooperative photoreorientation behavior of p-cyanoazobenzene side chains

DEFF Research Database (Denmark)

Han, Mina; Kidowaki, Masatoshi; Ichimura, Kunihiro

2001-01-01

Photoinduced orientational behavior of a polymethacrylate (CN6) and a polyester (p6a12) with p-cyanoazobenzene side chains was studied to reveal the structural effect of the liquid crystalline polymer backbones. Irradiation with linearly polarized W light resulted in the reorientation of the azob...

Effects of Alternating Hydrogenated and Protonated Segments in polymers on their Wettability.

Science.gov (United States)

Smith, Dennis; Traiphol, Rakchart; Cheng, Gang; Perahia, Dvora

2003-03-01

Polymers consisting of alternating hydrogenated and fluorinated segments exhibit unique interfacial characteristics governed by the components that dominate the interface. Presence of fluorine reduces the interfacial energy and is expected to decrease the adhesion to the polymer surface. Thin liquid crystalline (LC) layers of 4,4?-octyl-cyanobiphenyl, cast on top of a polymeric layer consisting of alternating methylstylbine protonated segments bridged by a fluorinated group was used as a mechanistic tool to study of interfacial effects on three parameters: wetting, interfacial alignment and surface induces structures. The liquid crystal cast on a low interfacial energy fluorinated polymeric film exhibits bulk homeotropic alignment as expected. However it fully wetted the polymer surface despite the incompatibility of the protonated LC and mainly fluorinated polymer interface. Further more, it was found to stabilize the interfacial Semitic layers to a higher temperature and induce different surface ordering that was not observed at the same temperature neither in the bulk nor at the interfaces with silicon or glass surface. These results indicate that the interfacial interactions of polymers with liquid crystals are a complex function of both surface energies and the interfacial structure of the polymer.

Influence of processing and intrinsic polymer parameters on photochemical stability of polythiophene thin films

DEFF Research Database (Denmark)

Vesterager Madsen, Morten; Tromholt, Thomas; Böttiger, Arvid P.L.

2012-01-01

shielding effects were shown to have a negligible effect on the photochemical degradation rate. The results obtained in this work advance the understanding of polymer stability and will help improve the design of materials used for polymer solar cells resulting in longer lifetimes, which will push......Intrinsic polymer parameters such as regio-regularity, molecular weight, and crystallinity play an important role when studying polymer stability. 18 different batches of poly-3-hexyl-thiophene (P3HT) were degraded in a solar simulator (AM1.5G, 1000 W/m2) and the degradation kinetics were monitored....... The results suggest that the radical reaction responsible for the photodegradation takes place at terminal thiophene rings exposed at points were the conjugation is broken. This proposed mechanism is supported by the fact that stability scales with regio-regularity following the ratio of head...

The evolution of strength and crystalline phases for alkali-activated ground blast furnace slag and fly ash-based geopolymers

KAUST Repository

Oh, Jae Eun

2010-02-01

The increase in strength and evolution of crystalline phases in inorganic polymer cement, made by the alkali activation of slag, Class C and Class F fly ashes, was followed using compressive strength test and synchrotron X-ray diffraction. In order to increase the crystallinity of the product the reactions were carried out at 80 °C. We found that hydrotalcite formed in both the alkali-activated slag cements and the fly ash-based geopolymers. Hydroxycancrinite, one member of the ABC-6 family of zeolites, was found only in the fly ash geopolymers. Assuming that the predominantly amorphous geopolymer formed under ambient conditions relates to the crystalline phases found when the mixture is cured at high temperature, we propose that the structure of this zeolitic precursor formed in Na-based high alkaline environment can be regarded as a disordered form of the basic building unit of the ABC-6 group of zeolites which includes poly-types such as hydroxycancrinite, hydroxysodalite and chabazite-Na. © 2009 Elsevier Ltd.

The evolution of strength and crystalline phases for alkali-activated ground blast furnace slag and fly ash-based geopolymers

International Nuclear Information System (INIS)

Oh, Jae Eun; Monteiro, Paulo J.M.; Jun, Ssang Sun; Choi, Sejin; Clark, Simon M.

2010-01-01

The increase in strength and evolution of crystalline phases in inorganic polymer cement, made by the alkali activation of slag, Class C and Class F fly ashes, was followed using compressive strength test and synchrotron X-ray diffraction. In order to increase the crystallinity of the product the reactions were carried out at 80 deg. C. We found that hydrotalcite formed in both the alkali-activated slag cements and the fly ash-based geopolymers. Hydroxycancrinite, one member of the ABC-6 family of zeolites, was found only in the fly ash geopolymers. Assuming that the predominantly amorphous geopolymer formed under ambient conditions relates to the crystalline phases found when the mixture is cured at high temperature, we propose that the structure of this zeolitic precursor formed in Na-based high alkaline environment can be regarded as a disordered form of the basic building unit of the ABC-6 group of zeolites which includes poly-types such as hydroxycancrinite, hydroxysodalite and chabazite-Na.

Conductivity enhancement induced by casting of polymer electrolytes under a magnetic field

International Nuclear Information System (INIS)

Kovarsky, R.; Golodnitsky, D.; Peled, E.; Khatun, S.; Stallworth, P.E.; Greenbaum, S.; Greenbaum, A.

2011-01-01

Highlights: ► Ordering of polymer electrolytes under applied magnetic field. ► Positive effect of nanosize ferromagnetic filler. ► Structure-ion conductivity interrelationship. - Abstract: We recently presented a procedure for orienting the polyethylene-oxide (PEO) helices in a direction perpendicular to the film plane by casting the polymer electrolytes (PE) under a magnetic field (MF). Here we study the influence of magnetic fields of different strengths and configurations on the structural properties and ionic conductivity of concentrated LiCF 3 SO 3 (LiTf) and LiAsF 6 :P(EO) pristine and composite polymer electrolytes containing γ-Fe 2 O 3 nanoparticles. Some data of LiI:P(EO) system are shown for comparison. We suggest that the effect of type of salt (LiI, LiTf and LiAsF 6 ) on the structure–conductivity relationship of the polymer electrolytes cast under magnetic field is closely connected to the crystallinity of the PEO–LiX system. It was found that the higher the content of the crystalline phase and the size of spherulites in the typically cast salt-polymer system, the stronger the influence of the magnetic field on the conductivity enhancement when the electrolyte is cast and dried under MF. Casting of the PE from a high-dielectric-constant solvent results in disentanglement of the PEO chains, which facilitates even more the perpendicular orientation of helices under applied MF. The enhancement of ionic conductivity was appreciably higher in the PEs cast under strong NdFeB magnets than under SmCo. Both bulk (intrachain) and grain-boundary conductivities increase when a MF is applied, but the improvement in the grain-boundary conductivity – associated with ion-hopping between polymer chains – is more pronounced. For LiAsF 6 :(PEO) 3 at 65 °C, the interchain conductivity increased by a factor of 75, while the intrachain conductivity increased by a factor of 11–14. At room temperature, the SEI resistance of these PEs, cast under NdFeB HMF

Electro-mechanical properties of free standing micro- and nano-scale polymer-ceramic composites for energy density capacitors

Energy Technology Data Exchange (ETDEWEB)

Singh, Paritosh; Borkar, Hitesh [CSIR-National Physical Laboratory, Dr. K. S. Krishnan Marg, New Delhi, 110012 (India); Academy of Scientific and Innovative Research (AcSIR), CSIR-National Physical Laboratory (CSIR-NPL) Campus, Dr. K. S. Krishnan Road, New Delhi, 110012 (India); Singh, B.P.; Singh, V.N. [CSIR-National Physical Laboratory, Dr. K. S. Krishnan Marg, New Delhi, 110012 (India); Kumar, Ashok, E-mail: ashok553@nplindia.org [CSIR-National Physical Laboratory, Dr. K. S. Krishnan Marg, New Delhi, 110012 (India); Academy of Scientific and Innovative Research (AcSIR), CSIR-National Physical Laboratory (CSIR-NPL) Campus, Dr. K. S. Krishnan Road, New Delhi, 110012 (India)

2015-11-05

The integration of inorganic fillers in polymer matrix is useful for superior mechanical strength and functional properties of polymer-ceramic composites. We report the fabrication and characterization of polyvinylidene fluoride-CoFe{sub 2}O{sub 4} (PVDF-CFO) (wt% 80:20, respectively) and PVDF-Pb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3}–CoFe{sub 2}O{sub 4} (PVDF-PZT-CFO) (wt% 80:10:10, respectively) free standing 50 μm thick ferroelectric-polymer-ceramic composites films. X-ray diffraction (XRD) patterns and Raman spectra revealed the presence of major semi-crystalline β-PVDF along with α-phase which is responsible for ferroelectric nature in both the composite systems. Ferroelectric, dielectric and mechanical strength measurements were performed in order to evaluate the effects of CFO and PZT inorganic fillers in PVDF matrix. The inclusion of CFO and PZT micro-/nano-particles in PVDF polymer matrix improved the polarization behavior, dielectric properties and mechanical strength. The energy density was calculated by polarization-electric field hysteresis loop and found in the range of 6–8 J/cm{sup 3} may be useful for microelectronics. - Graphical abstract: Large area PVDF-PZT-CFO nano- and micro-composite films have been fabricated for high energy density storage flexible capacitor. Presence of nanocrystalline PZT and CFO particles in polymer matrix significantly enhanced their energy density capacity. - Highlights: • Physical interaction of cobalt iron oxide with polymer matrix results β-PVDF phase. • Evidence of Micro and Nano crystalline CFO and PZT fillers in polymer matrix. • The CFO and PZT fillers provide better mechanical strength to composite films. • PVDF-ceramic nanocomposites show low leakage behavior for high electric field.

Dye-sensitized solar cell with natural gel polymer electrolytes and f-MWCNT as counter-electrode

Science.gov (United States)

Nwanya, A. C.; Amaechi, C. I.; Ekwealor, A. B. C.; Osuji, R. U.; Maaza, M.; Ezema, F. I.

2015-05-01

Samples of DSSCs were made with gel polymer electrolytes using agar, gelatin and DNA as the polymer hosts. Anthocyanine dye from Hildegardia barteri flower is used to sensitize the TiO2 electrode, and the spectrum of the dye indicates strong absorptions in the blue region of the solar spectrum. The XRD pattern of the TiO2 shows that the adsorption of the dye did not affect the crystallinity of the electrode. The f-MWCNT indicates graphite structure of the MWCNTs were acid oxidized without significant damage. Efficiencies of 3.38 and 0.1% were obtained using gelatin and DNA gel polymer electrolytes, respectively, for the fabricated dye-sensitized solar cells.

Detection of gaseous effluents from partly crystalline polymer tubes for chemicals

International Nuclear Information System (INIS)

Hessel, J.; Henkhaus, R.; Buss, R.

1980-01-01

In case of polymer tubes which lead aggressive, liquid media and additionally have to sustain a mechanical load possibly at clevated temperatures a leakage can occur in the gas phase due to the permeability of the material. The paper describes a detection method for a quantitative analysis of the medium which desorbes on the outside of the tube wall. As examples the systems polypropylene/acetic acid and polyethylene/acetic acid were chosen. An inert carrier gas leads the desorbed medium to a conductivity cell which registers the conductivity as a function of time. The measured conductivity is directly proportional to the quantity of medium desorbed by the examined part of the tube. (orig.) [de

Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity

Science.gov (United States)

Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

2015-12-01

The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies.

Crystalline color superconductivity

International Nuclear Information System (INIS)

Alford, Mark; Bowers, Jeffrey A.; Rajagopal, Krishna

2001-01-01

In any context in which color superconductivity arises in nature, it is likely to involve pairing between species of quarks with differing chemical potentials. For suitable values of the differences between chemical potentials, Cooper pairs with nonzero total momentum are favored, as was first realized by Larkin, Ovchinnikov, Fulde, and Ferrell (LOFF). Condensates of this sort spontaneously break translational and rotational invariance, leading to gaps which vary periodically in a crystalline pattern. Unlike the original LOFF state, these crystalline quark matter condensates include both spin-zero and spin-one Cooper pairs. We explore the range of parameters for which crystalline color superconductivity arises in the QCD phase diagram. If in some shell within the quark matter core of a neutron star (or within a strange quark star) the quark number densities are such that crystalline color superconductivity arises, rotational vortices may be pinned in this shell, making it a locus for glitch phenomena

Diketopyrrolopyrrole Polymers for Organic Solar Cells.

Science.gov (United States)

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

Molecular-weight dependence of interchain polaron delocalization and exciton bandwidth in high-mobility conjugated polymers

DEFF Research Database (Denmark)

Chang, J.F.; Clark, J.; Zhao, N.

2006-01-01

delocalization with increasing conjugation length and crystalline quality. From comparative studies of field-effect transistor characteristics, film morphology, and optical properties our study provides a microscopic understanding of the factors which limit the charge transport in P3HT to field-effect mobilities......Interchain interactions have a profound effect on the optical as well as charge transport properties of conjugated polymer thin films. In contrast to oligomeric model systems in solution-deposited polymer thin films the study of such effects is complicated by the complex microstructure. We present...

Processing and properties of ceramic matrix-polymer composites for dental applications

Science.gov (United States)

Huang, Hsuan Yao

The basic composite structure of natural hard tissue was used to guide the design and processing of dental restorative materials. The design incorporates the methodology of using inorganic minerals as the main structural phase reinforced with a more ductile but tougher organic phase. Ceramic-polymer composites were prepared by slip casting a porous ceramic structure, heating and chemical treating the porous preform, infiltrating with monomer and then curing. The three factors that determined the mechanical properties of alumina-polymer composites were the type of polymer used, the method of silane treatments, and the type of bond between particles in the porous preforms. Without the use of silane coupling agents, the composites were measured to have a lower strength. The composite with a more "flexible" porous alumina network had a greater ability to plastically dissipate the energy of propagating cracks. However, the aggressive nature of the alumina particles on opposing enamel requires that these alumina-polymer composites have a wear compatible coating for practical application. A route to dense bioactive apatite wollastonite glass ceramics (AWGC)-polymer composites was developed. The problems associated with glass dissolution into the aqueous medium for slip casting were overcome with the use of silane. The role of heating rate and development of ceramic compact microstructure on composite properties was explored. In general, if isothermal heating was not applied, decreasing heating rate increased glass crystallinity and particle-particle fusion, but decreased pore volume. Also composite strength and fracture toughness decreased while modulus and hardness increased with decreasing heating rate. If isothermal heating was applied, glass crystallinity, pore content, and composite mechanical properties showed relatively little change regardless of the initial heating rate. The potential of AWGC-polymer composites for dental and implant applications was explored

Injection molding of ceramic filled polypropylene: The effect of thermal conductivity and cooling rate on crystallinity

International Nuclear Information System (INIS)

Suplicz, A.; Szabo, F.; Kovacs, J.G.

2013-01-01

Highlights: • BN, talc and TiO 2 in 30 vol% were compounded with polypropylene matrix. • According to the DSC measurements, the fillers are good nucleating agents. • The thermal conductivity of the fillers influences the cooling rate of the melt. • The higher the cooling rate is, the lower the crystallinity in the polymer matrix. - Abstract: Three different nano- and micro-sized ceramic powders (boron-nitride (BN), talc and titanium-dioxide (TiO 2 )) in 30 vol% have been compounded with a polypropylene (PP) matrix. Scanning electron microscopy (SEM) shows that the particles are dispersed smoothly in the matrix and larger aggregates cannot be discovered. The cooling gradients and the cooling rate in the injection-molded samples were estimated with numerical simulations and finite element analysis software. It was proved with differential scanning calorimetry (DSC) measurements that the cooling rate has significant influence on the crystallinity of the compounds. At a low cooling rate BN works as a nucleating agent so the crystallinity of the compound is higher than that of unfilled PP. On the other hand, at a high cooling rate, the crystallinity of the compound is lower than that of unfilled PP because of its higher thermal conductivity. The higher the thermal conductivity is, the higher the real cooling rate in the material, which influences the crystallization kinetics significantly

A non-invasive experimental approach for surface temperature measurements on semi-crystalline thermoplastics

Science.gov (United States)

Boztepe, Sinan; Gilblas, Remi; de Almeida, Olivier; Le Maoult, Yannick; Schmidt, Fabrice

2017-10-01

Most of the thermoforming processes of thermoplastic polymers and their composites are performed adopting a combined heating and forming stages at which a precursor is heated prior to the forming. This step is done in order to improve formability by softening the thermoplastic polymer. Due to low thermal conductivity and semi-transparency of polymers, infrared (IR) heating is widely used for thermoforming of such materials. Predictive radiation heat transfer models for temperature distributions are therefore critical for optimizations of thermoforming process. One of the key challenges is to build a predictive model including the physical background of radiation heat transfer phenomenon in semi-crystalline thermoplastics as their microcrystalline structure introduces an optically heterogeneous medium. In addition, the accuracy of a predictive model is required to be validated experimentally where IR thermography is one of the suitable methods for such a validation as it provides a non-invasive, full-field surface temperature measurement. Although IR cameras provide a non-invasive measurement, a key issue for obtaining a reliable measurement depends on the optical characteristics of a heated material and the operating spectral band of IR camera. It is desired that the surface of a material to be measured has a spectral band where the material behaves opaque and an employed IR camera operates in the corresponding band. In this study, the optical characteristics of the PO-based polymer are discussed and, an experimental approach is proposed in order to measure the surface temperature of the PO-based polymer via IR thermography. The preliminary analyses showed that IR thermographic measurements may not be simply performed on PO-based polymers and require a correction method as their semi-transparent medium introduce a challenge to obtain reliable surface temperature measurements.

Discrepancy between different estimates of the hydrodynamic diameter of polymer-coated iron oxide nanoparticles in solution

International Nuclear Information System (INIS)

Regmi, R.; Gumber, V.; Subba Rao, V.; Kohli, I.; Black, C.; Sudakar, C.; Vaishnava, P.; Naik, V.; Naik, R.; Mukhopadhyay, A.; Lawes, G.

2011-01-01

We have synthesized iron oxide nanoparticles coated with a monolayer of dextran, with molecular weights of the polymer between 5 and 670 kDa. Transmission electron microscopy images confirm that the hard core has a crystalline diameter of approximately 12 nm. The hydrodynamic diameters of these coated nanoparticles in solution measured using dynamical light scattering and estimated from magnetic susceptibility studies vary from near 90 nm for the lightest polymer to 140 nm for the heaviest polymer. Conversely, fluorescence correlation spectroscopy measurements yield a diameter of approximately 55 nm for the 15–20 kDa dextran coated nanoparticles, which is consistent with the expected value estimated from the sum of the hard-core diameter and monolayer dextran coating. We discuss the implications of this discrepancy for applications involving polymer-coated magnetic nanoparticles.

Development of Novel Nano Polymer Composite Material for Solar Energy Conversion

International Nuclear Information System (INIS)

Sheha, E.; Elrasasi, T.Y.; El mansy, M.K.; Abdallah, B.

2014-01-01

PVA: Co 5 (OH) 8 (NO 3 ) 2 •2H 2 O polymer composite has been produced by casting of aqueous solution of mixed composite component. The nano polymer composites were characterized using structure techniques; XRD, SEM, FT-IR and TGA. The results indicated the formation composite without PVA degree of crystallinity variation. The measurements of electrical conductivity for the composites illustrated domination of ion conduction with activation energy (0.65-0.90) eV. The optical absorption illustrated an absorption peak around (530-540) nm which suggest electronic direct transition via energy gap width (1.90-2.16) eV. The electrochemical illustrated electrochemical band gap (1.97-3.26) eV

Self-healing polymers

Science.gov (United States)

Klein, Daniel J. (Inventor)

2011-01-01

A three dimensional structure fabricated from a self-healing polymeric material, comprising poly(ester amides) obtained from ethylene glycol, azelaic acid and 1,1-aminoundecanoic acid, wherein polymeric material has a melt index above 2.5 g/10 min. as determined by ASTM D1238 at 190.degree. C. and 2.16kg, impact resistance and ductility sufficient to resist cracking and brittle fracture upon impact by a 9 mm bullet fired at a temperature of about 29.degree. C. at subsonic speed in a range from about 800 feet/sec to about 1000 feet/sec. It has been determined that the important factors necessary for self-healing behavior of polymers include sufficient impact strength, control of the degree of crystallinity, low melting point and the ability to instantly melt at impacted area.

Rheological analysis of irradiated crosslinkable and scissionable polymers used for medical devices under different radiation conditions

Science.gov (United States)

Satti, A. J.; Ressia, J. A.; Cerrada, M. L.; Andreucetti, N. A.; Vallés, E. M.

2018-03-01

The effects on different synthetic polymers of distinct types of radiation, gamma rays and electron beam, under different atmospheres are followed by changes in their viscoelastic behavior. Taking into account the two main radioinduced reactions, crosslinking and scissioning of polymeric chains, liquid polydimethylsiloxane has been used as example of crosslinkable polymer and semi crystalline polypropylene as example of scissionable polymer. Propylene - 1-hexene copolymers have been also evaluated, and the effects of both reactions were clearly noticed. Accordingly, samples of those aforementioned polymers have been irradiated with 60Co gamma irradiation in air and under vacuum, and also with electron beam, at similar doses. Sinusoidal dynamic oscillation experiments showed a significant increase in branching and crosslinking reactions when specimens are irradiated under vacuum, while scissioning reactions were observed for the different polymers when irradiation takes place under air with either gamma irradiation or electron beam.

RNA aptamers targeted for human αA-crystallin do not bind αB-crystallin, and spare the α-crystallin domain.

Science.gov (United States)

Mallik, Prabhat K; Shi, Hua; Pande, Jayanti

2017-09-16

The molecular chaperones, α-crystallins, belong to the small heat shock protein (sHSP) family and prevent the aggregation and insolubilization of client proteins. Studies in vivo have shown that the chaperone activity of the α-crystallins is raised or lowered in various disease states. Therefore, the development of tools to control chaperone activity may provide avenues for therapeutic intervention, as well as enable a molecular understanding of chaperone function. The major human lens α-crystallins, αA- (HAA) and αB- (HAB), share 57% sequence identity and show similar activity towards some clients, but differing activities towards others. Notably, both crystallins contain the "α-crystallin domain" (ACD, the primary client binding site), like all other members of the sHSP family. Here we show that RNA aptamers selected for HAA, in vitro, exhibit specific affinity to HAA but do not bind HAB. Significantly, these aptamers also exclude the ACD. This study thus demonstrates that RNA aptamers against sHSPs can be designed that show high affinity and specificity - yet exclude the primary client binding region - thereby facilitating the development of RNA aptamer-based therapeutic intervention strategies. Copyright © 2017 Elsevier Inc. All rights reserved.

Entanglements in Conjugated Polymers

Science.gov (United States)

Xie, Renxuan; Lee, Youngmin; Aplan, Melissa; Caggiano, Nick; Gomez, Enrique; Colby, Ralph

Conjugated polymers, such as poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly-((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT), are widely used as hole and electron transport materials in a variety of electronic devices. However, fundamental knowledge regarding chain entanglements and nematic-to-isotropic transition is still lacking and are crucial to maximize charge transport properties. A systematic melt rheology study on P3HT with various molecular weights and regio regularities was performed. We find that the entanglement molecular weight Me is 5.0 kg/mol for regiorandom P3HT, but the apparent Me for regioregular P3HT is significantly higher. The difference is postulated to arise from the presence of a nematic phase only in regioregular P3HT. Analogously, PFTBT shows a clear rheological signature of the nematic-to-isotropic transition as a reversible sharp transition at 278 C. Shearing of this nematic phase leads to anisotropic crystalline order in PFTBT. We postulate that aligning the microstructure will impact charge transport and thereby advance the field of conducting polymers. National Science Foundation.

Stability and Degradation of Organic and Polymer Solar Cells

DEFF Research Database (Denmark)

Organic photovoltaics (OPV) are a new generation of solar cells with the potential to offer very short energy pay back times, mechanical flexibility and significantly lower production costs compared to traditional crystalline photovoltaic systems. A weakness of OPV is their comparative instability...... during operation and this is a critical area of research towards the successful development and commercialization of these 3rd generation solar cells. Covering both small molecule and polymer solar cells, Stability and Degradation of Organic and Polymer Solar Cells summarizes the state of the art...... understanding of stability and provides a detailed analysis of the mechanisms by which degradation occurs. Following an introductory chapter which compares different photovoltaic technologies, the book focuses on OPV degradation, discussing the origin and characterization of the instability and describing...

Alignment engineering in liquid crystalline elastomers: Free-form microstructures with multiple functionalities

Energy Technology Data Exchange (ETDEWEB)

Zeng, Hao; Cerretti, Giacomo; Wiersma, Diederik S., E-mail: camilla.parmeggiani@lens.unifi.it, E-mail: wiersma@lens.unifi.it [European Laboratory for Non Linear Spectroscopy (LENS), University of Florence, via Nello Carrara 1, 50019 Sesto Fiorentino (Italy); Wasylczyk, Piotr [European Laboratory for Non Linear Spectroscopy (LENS), University of Florence, via Nello Carrara 1, 50019 Sesto Fiorentino (Italy); Faculty of Physics, Institute of Experimental Physics, University of Warsaw, ul. Hoza 69, Warszawa 00-681 (Poland); Martella, Daniele [European Laboratory for Non Linear Spectroscopy (LENS), University of Florence, via Nello Carrara 1, 50019 Sesto Fiorentino (Italy); Dipartimento di Chimica “Ugo Schiff,” University of Florence, via della Lastruccia 3-13, 50019 Sesto Fiorentino (Italy); Parmeggiani, Camilla, E-mail: camilla.parmeggiani@lens.unifi.it, E-mail: wiersma@lens.unifi.it [European Laboratory for Non Linear Spectroscopy (LENS), University of Florence, via Nello Carrara 1, 50019 Sesto Fiorentino (Italy); CNR-INO, via Nello Carrara 1, 50019 Sesto Fiorentino (Italy)

2015-03-16

We report a method to fabricate polymer microstructures with local control over the molecular orientation. Alignment control is achieved on molecular level in a structure of arbitrary form that can be from 1 to 100 μm in size, by fixing the local boundary conditions with micro-grating patterns. The method makes use of two-photon polymerization (Direct Laser Writing) and is demonstrated specifically in liquid-crystalline elastomers. This concept allows for the realization of free-form polymeric structures with multiple functionalities which are not possible to realize with existing techniques and which can be locally controlled by light in the micrometer scale.

Irradiation effects on polymer-model compounds

International Nuclear Information System (INIS)

Seguchi, Tadao; Hayakawa, Naohiro; Tamura, Naoyuki; Katsumura, Yosuke; Hayashi, Nariyuki; Tabata, Yoneho

1991-01-01

Irradiation effects on n-paraffins and squalane, used as models of polymers, were investigated by product analysis. Four n-paraffins, C 20 H 42 , C 21 H 44 , C 23 H 48 and C 24 H 50 , and squalane (C 30 H 62 ) were γ-irradiated under vacuum in liquid, crystalline and glassy states. The evolved gases were analyzed by gas chromatography and changes in molecular weight were analyzed by liquid chromatography and mass spectroscopy. G-values for crosslinking of n-paraffins were 1.2 for crystalline states (at 25 0 C) and 1.7 for liquid states (at 55 0 C), and showed no difference between odd and even carbon numbers. The G-value of liquid squalane was 1.7; it was 1.3 for the glassy state at low temperature (-77 0 C). Double bonds were common in the crosslinked products, especially after liquid-phase irradiation. The probability of chain scission was estimated as being negligible, though a small number of chain-scission products (which were products of scission at chain-ends or side chains) were observed by gas analysis. (author)

Tuning crystalline ordering by annealing and additives to study its effect on exciton diffusion in a polyalkylthiophene copolymer.

Science.gov (United States)

Chowdhury, Mithun; Sajjad, Muhammad T; Savikhin, Victoria; Hergué, Noémie; Sutija, Karina B; Oosterhout, Stefan D; Toney, Michael F; Dubois, Philippe; Ruseckas, Arvydas; Samuel, Ifor D W

2017-05-17

The influence of various processing conditions on the singlet exciton diffusion is explored in films of a conjugated random copolymer poly-(3-hexylthiophene-co-3-dodecylthiophene) (P3HT-co-P3DDT) and correlated with the degree of crystallinity probed by grazing incidence X-ray scattering and with exciton bandwidth determined from absorption spectra. The exciton diffusion coefficient is deduced from exciton-exciton annihilation measurements and is found to increase by more than a factor of three when thin films are annealed using CS 2 solvent vapour. A doubling of exciton diffusion coefficient is observed upon melt annealing at 200 °C and the corresponding films show about 50% enhancement in the degree of crystallinity. In contrast, films fabricated from polymer solutions containing a small amount of either solvent additive or nucleating agent show a decrease in exciton diffusion coefficient possibly due to formation of traps for excitons. Our results suggest that the enhancement of exciton diffusivity occurs because of increased crystallinity of alkyl-stacking and longer conjugation of aggregated chains which reduces the exciton bandwidth.

Opposite photo-induced deformations in azobenzene-containing polymers with different molecular architecture: Molecular dynamics study

International Nuclear Information System (INIS)

Ilnytskyi, Jaroslav M.; Neher, Dieter; Saphiannikova, Marina

2011-01-01

Photo-induced deformations in azobenzene-containing polymers (azo-polymers) are central to a number of applications, such as optical storage and fabrication of diffractive elements. The microscopic nature of the underlying opto-mechanical coupling is yet not clear. In this study, we address the experimental finding that the scenario of the effects depends on molecular architecture of the used azo-polymer. Typically, opposite deformations in respect to the direction of light polarization are observed for liquid crystalline and amorphous azo-polymers. In this study, we undertake molecular dynamics simulations of two different models that mimic these two types of azo-polymers. We employ hybrid force field modeling and consider only trans-isomers of azobenzene, represented as Gay-Berne sites. The effect of illumination on the orientation of the chromophores is considered on the level of orientational hole burning and emphasis is given to the resulting deformation of the polymer matrix. We reproduce deformations of opposite sign for the two models being considered here and discuss the relevant microscopic mechanisms in both cases.

TCT-584 Nine Month Imaging and Twelve Month Clinical Results from the DESSOLVE II Randomized Trial of the MiStent® SES with Absorbable Polymer

OpenAIRE

Wijns, William; Vrolix, Mathias; Verheye, Stefan; Schoors, Danny; Slagboom, Ton; Gosselink, Marcel; Benit, Edouard; Desmet, Walter; Chowdhary, Saquib; Lansky, Alexandra; Bezerra, Hiram; Fitzgerald, Peter; Kandzari, David; Ormiston, John

2012-01-01

Background : The MiStent SES (Micell Technologies, Durham, NC) is an investigational drug-eluting stent (DES) developed to adress unfavorable late-term outcomes such as stent thrombosis. These events are hypothesized to be associated in part with durable polymers of current DES. The MiStent SES uses a unique combination of components, a crystalline formulation of sirolimus and a fully absorbable polymer on a thinstrut, cobalt chromium stent platform. The polymer coating is eliminated from the...

EFFECTS OF ULTRASOUND ON THE MORPHOLOGY, PARTICLE SIZE, CRYSTALLINITY, AND CRYSTALLITE SIZE OF CELLULOSE

Directory of Open Access Journals (Sweden)

SUMARI SUMARI

2014-05-01

Full Text Available The aim of this study is to optimize ultrasound treatment to produce fragment of cellulose that is low in particles size, crystallite size, and crystallinity. Slurry of 1 % (w/v the cellulose was sonicated at different time periods and temperatures. An ultrasonic reactor was operated at 300 Watts and 28 kHz to cut down the polymer into smaller particles. We proved that ultrasound damages and fragments the cellulose particles into shorter fibers. The fiber lengths were reduced from in the range of 80-120 µm to 30-50 µm due to an hour ultrasonication and became 20-30 µm after 5 hours. It was also found some signs of erosion on the surface and stringy. The acoustic cavitation also generated a decrease in particle size, crystallinity, and crystallite size of the cellulose along with increasing sonication time but it did not change d-spacing. However, the highest reduction of particle size, crystallite size, and crystallinity of the cellulose occurred within the first hour of ultrasonication, after which the efficiency was decreased. The particle diameter, crystallite size, and crystallinity were decreased from 19.88 µm to 15.96 µm, 5.81 Å to 2.98 Å, and 77.7% to 73.9% respectively due to an hour ultrasound treatment at 40 °C. The treatment that was conducted at 40 °C or 60 °C did not give a different effect significantly. Cellulose with a smaller particle and crystallite size as well as a more amorphous shape is preferred for further study.

Implicit implementation and consistent tangent modulus of a viscoplastic model for polymers

OpenAIRE

ACHOUR, Nadia; CHATZIGEORGIOU, George; MERAGHNI, Fodil; CHEMISKY, Yves; FITOUSSI, Joseph

2015-01-01

In this work, the phenomenological viscoplastic DSGZ model (Duan et al., 2001 [13]), developed for glassy or semi-crystalline polymers, is numerically implemented in a three-dimensional framework, following an implicit formulation. The computational methodology is based on the radial return mapping algorithm. This implicit formulation leads to the definition of the consistent tangent modulus which permits the implementation in incremental micromechanical scale transition analysis. The extende...

Polarized Emission of Wholly Aromatic Bio-Based Copolyesters of a Liquid Crystalline Nature

Directory of Open Access Journals (Sweden)

Daisaku Kaneko

2011-05-01

Full Text Available A novel thermotropic liquid crystalline polymers poly{3-benzylidene amino-4-hydroxybenzoic acid (3,4-BAHBA-co-trans-4-hydroxycinnamic acid (4HCA: trans-coumaric acid} (Poly(3,4-BAHBA-co-4HCA, was synthesized by the thermal polycondensation of 4HCA and 3,4-BAHBA, which was synthesized by a reaction of 3-amino-4-hydroxybenzoic acid (3,4-AHBA with benzaldehyde. When the 4HCA compositions of Poly(3,4-BAHBA-co-4HCAs were above 55 mol%, the copolymers showed a nematic, liquid crystalline phase. Differential scanning calorimetry (DSC measurements of the copolymers showed a high glass transition temperature of more than 100 °C, sufficient for use in engineering plastics. Furthermore, the copolymers showed photoluminescence in an N-methylpyrrolidone (NMP solution under ultraviolet (UV light with a wavelength of 365 nm. Oriented film of Poly(3,4-BAHBA-co-4HCA with a 4HCA composition of 75 mol% emitted polarized light, which was confirmed by fluorescent spectroscopy equipped with parallel and crossed polarizers.

Investigation of optical properties of aluminium oxide doped polystyrene polymer nanocomposite films

Science.gov (United States)

Bhavsar, Shilpa; Patel, Gnansagar B.; Singh, N. L.

2018-03-01

In the present work, a simple solution casting method was utilized to synthesize aluminium oxide (Al2O3) doped polystyrene (PS) polymer nanocomposite films. As synthesized films were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, ultra violet (UV)-visible spectroscopy, photoluminescence (PL) method and scanning electron microscopy (SEM). The crystalline nature of the films was found to decrease after incorporation of filler in the polymer matrix as revealed by XRD results. A new carbonyl group was appeared in the FTIR spectra and confirmed the charge transfer reaction between filler and polymer matrix. The decrease in the band gap was found with the filler concentration in the synthesized polymer nanocomposite films. Photoluminescence emission spectra of nanocomposites were observed at 411 nm, 435 nm and 462 nm, respectively in violet-blue region which indicates interaction between the dopant and the polymer matrix. The PL emission spectra of polymer nanocomposite films with 3 wt% of Al2O3 filler exhibited higher peak intensity. The Al2O3 filler dispersion is found to reduce band gap and promote luminescence property in polystyrene. SEM analysis indicates the agglomeration of Al2O3 nanoparticles into PS matrix at higher concentration.

Cellulose Nanocrystals vs. Cellulose Nanofibrils: A Comparative study on Their Microstructures and Effects as Polymer Reinforcing Agents

Science.gov (United States)

Xuezhu Xu; Fei Liu; Long Jiang; J.Y. Zhu; Darrin Haagenson; Dennis P. Wiesenborn

2013-01-01

Both cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) are nanoscale cellulose fibers that have shown reinforcing effects in polymer nanocomposites. CNCs and CNFs are different in shape, size and composition. This study systematically compared their morphologies, crystalline structure, dispersion properties in polyethylene oxide (PEO) matrix, interactions...

Temperature dependence of radiation chemistry of polymers

International Nuclear Information System (INIS)

Garrett, R.W.; Hill, D.J.T.; Le, T.T.; Milne, K.A.; O'Donnell, J.H.; Perera, S.M.C.; Pomery, P.J.

1990-01-01

Chemical reactions which occur during radiolysis of polymers usually show an increase in rate with increasing temperature that can be described by an Arrhenius relationship. The magnitude of the activation energy can vary widely and is affected by physical, as well as chemical, factors. Different reaction rates may be expected in crystalline and amorphous morphologies, and in glassy and rubbery regions. The temperature dependence of radiolysis reactions can be expected to show discontinuities at the glass and melting transitions, T g and T m . The ceiling temperature, T c , for polymerization/depolymerization will also affect the rate of degradation, especially for depropagation to monomer. The temperature for this effect depends on the molecular structure of the polymer. The temperature dependence of free radical reactions can be studied by cryogenic trapping and ESR spectroscopy during thermal profiling. Increased degradation rates at high dose rates can be due to increased temperatures resulting from energy absorption

Twinning of Polymer Crystals Suppressed by Entropy

Directory of Open Access Journals (Sweden)

Nikos Ch. Karayiannis

2014-09-01

Full Text Available We propose an entropic argument as partial explanation of the observed scarcity of twinned structures in crystalline samples of synthetic organic polymeric materials. Polymeric molecules possess a much larger number of conformational degrees of freedom than low molecular weight substances. The preferred conformations of polymer chains in the bulk of a single crystal are often incompatible with the conformations imposed by the symmetry of a growth twin, both at the composition surfaces and in the twin axis. We calculate the differences in conformational entropy between chains in single crystals and chains in twinned crystals, and find that the reduction in chain conformational entropy in the twin is sufficient to make the single crystal the stable thermodynamic phase. The formation of cyclic twins in molecular dynamics simulations of chains of hard spheres must thus be attributed to kinetic factors. In more realistic polymers this entropic contribution to the free energy can be canceled or dominated by nonbonded and torsional energetics.

Radiation crosslinking of polymers with segregated metallic particles. Final report, June 1, 1971--September 30, 1973

International Nuclear Information System (INIS)

Corneliussen, R.D.; Kamel, I.; Kusy, R.P.

1973-01-01

Through the past four years of research, a new approach to fabricating conductive polymer/metal composites has been developed. This approach consists of compacting mixtures of polymer and metal powders and then stabilizing the composite through radiation-induced crosslinking. The result is a mechanically strong, conductive materials consisting of two intertwining networks. One is a massive network consisting of fused crosslinked, large (greater than 100 μ) polymer particles while the other is a fine network of small, metallic particles (greater than 10 μ). Nine different systems including crystalline, amorphous, and rubbery polymers were studied. Processing at this time is limited to compression molding in a closed die because of network stability problems. Costs for processing were estimated at about $6.00/lb compared to $50.00 and up for commercial material based on random networks. (U.S.)

Tuning Fullerene Intercalation in a Poly (thiophene) derivative by Controlling the Polymer Degree of Self-Organisation

Science.gov (United States)

Paternò, G. M.; Skoda, M. W. A.; Dalgliesh, Robert; Cacialli, F.; Sakai, V. García

2016-10-01

Controlling the nanoscale arrangement in polymer-fullerene organic solar cells is of paramount importance to boost the performance of such promising class of photovoltaic diodes. In this work, we use a pseudo-bilayer system made of poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), to acquire a more complete understanding of the diffusion and intercalation of the fullerene-derivative within the polymer layer. By exploiting morphological and structural characterisation techniques, we observe that if we increase the film solidification time the polymer develops a higher crystalline order, and, as a result, it does not allow fullerene molecules to intercalate between the polymer side-chains. Gaining insight into the detailed fullerene intercalation mechanism is important for the development of organic photovoltaic diodes (PVDs).

Theoretical predictions of diffusion from Brownian motion in superstrong polymers

International Nuclear Information System (INIS)

Dowell, F.

1991-01-01

This paper presents a summary of unique highly nonlinear static and dynamic theories for chain molecules (actually, for almost any kind of organic molecule), including the first superstrong polymers. These theories have been used to predict and explain (1) the physical self-assembly (self-ordering) of specific kinds of molecules into liquid crystalline (LC) phases (i.e., partially ordered phases) and (2) the diffusion of these molecules in various LC phases and the isotropic (I) liquid phase

Superconductivity in a copper(II)-based coordination polymer with perfect kagome structure

Energy Technology Data Exchange (ETDEWEB)

Huang, Xing; Liu, Liyao; Xu, Wei; Zhu, Daoben [Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing (China); University of Chinese Academy of Sciences, Beijing (China); Zhang, Shuai [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing (China); Yu, Lei [Department of Chemistry, University of Kentucky, Lexington, KY (United States); Chen, Genfu [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing (China); University of Chinese Academy of Sciences, Beijing (China); Collaborative Innovation Center of Quantum Matter, Beijing (China)

2018-01-02

A highly crystalline copper(II) benzenehexathiolate coordination polymer (Cu-BHT) has been prepared. The two-dimensional kagome structure has been confirmed by powder X-ray diffraction, high-resolution transmission electron microscopy, and high-resolution scanning transmission electron microscopy. The as-prepared sample exhibits bulk superconductivity at about 0.25 K, which is confirmed by the zero resistivity, AC magnetic susceptibility, and specific heat measurements. Another diamagnetic transition at about 3 K suggests that there is a second superconducting phase that may be associated with a single layer or few layers of Cu-BHT. It is the first time that superconductivity has been observed in a coordination polymer. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Low-Frequency Internal Friction Study on the Structural Changes in Polymer Melts

International Nuclear Information System (INIS)

Xue-Bang, Wu; Qiao-Ling, Xu; Shu-Ying, Shang; Jia-Peng, Shui; Chang-Song, Liu; Zhen-Gang, Zhu

2008-01-01

With the help of the low-frequency internal friction method, we investigate the structural properties of polymer melts, such as amorphous polystyrene (PS), poly(methyl methacrylate) (PMMA), and semi-crystalline poly(ethylene oxide) (PEO). An obvious peak of relaxation type is found in each of the internal friction curves. The peak temperature T p follows the relation T p ≈ (1.15 – 1.18) T g for PS and PMMA melts, while it follows T p ≈ 1.22T m for PEO melt, with T g being the glass transition temperature and T m the melting temperature. Based on the analysis of the features of this peak, it is found that this peak is related to the liquid-liquid transition temperature T u of polymer melts. Mechanism of the liquid-liquid transition is suggested to be thermally-activated collective relaxation through cooperation. This finding may be helpful to understand the structural changes in polymer melts. In addition, the internal friction technique proves to be effective in studying dynamics in polymer melts

Radiation induced crystallinity damage in poly(L-lactic acid)

CERN Document Server

Kantoglu, O

2002-01-01

The radiation-induced crystallinity damage in poly(L-lactic acid) (PLLA) in the presence of air and in vacuum, is studied. From the heat of fusion enthalpy values of gamma irradiated samples, some changes on the thermal properties were determined. To identify these changes, first the glass transition temperature (T sub g) of L-lactic acid polymers irradiated to various doses in air and vacuum have been investigated and it is found that it is independent of irradiation atmosphere and dose. The fraction of damaged units of PLLA per unit of absorbed energy has been measured. For this purpose, SAXS and differential scanning calorimetry methods were used, and the radiation yield of number of damaged units (G(-u)) is found to be 0.74 and 0.58 for PLLA samples irradiated in vacuum and air, respectively.

Solid state nuclear magnetic resonance spectroscopy of polymer thin films: chain conformation, dynamics, and morphology

International Nuclear Information System (INIS)

Nasreddine, V.F.

2003-01-01

This dissertation presents solid-state NMR studies of the chain conformation, dynamics and morphology of three adsorbed polymer systems: two random semi-crystalline copolymers, poly(ethylene-co-acrylic acid) (PEA) and poly(propylene-co-acrylic acid) (PPA), and an amorphous homopolymer, poly(n-butyl methacrylate) (PnBMA). Zirconia (ZrO 2 ) was chosen as the substrate for all three polymers since the binding of carboxylic acids to this metal oxide is well understood. The choice of polymers was based on their particular bulk conformational and dynamic properties as well as their common use in polymer coatings. These studies are motivated by the general lack of a microscopic picture of adsorbed polymers, which can be provided by NMR, and the relevance of chain conformation and dynamics to important polymer film properties such as adhesion. First the chain conformation and surface binding of adsorbed PEA as a function of acrylic acid content are characterized by 13 C cross polarization - magic angle spinning (CP-MAS), 2D 1 H- 13 C wideline separation (WISE) and 1 H spin diffusion NMR experiments and FTIR-PAS (Fourier transform infrared photoacoustic spectroscopy) measurements. The most important finding is that the chain conformation of adsorbed PEA is determined primarily by the sticker group density rather than the surface coverage. The second study of PEA concerns the chain dynamics in the bulk and adsorbed states. Variable temperature NMR experiments provide evidence that ethylene segments of adsorbed PEA form partially folded loops rather than flat extended trains. Finally 129 Xe NMR studies, used to probe the morphology of adsorbed PEA, show a bulk-like signal only for the highest loadings. The second system investigated, PPA, is another semi-crystalline random copolymer which binds to zirconia via carboxylate linkages. The 13 C CP-MAS NMR spectra of adsorbed PPAC unexpectedly show splittings normally associated with chain-chain packing in the crystalline regions

Crystallinity and order of poly(ethylene oxide)/lithium triflate complex confined in nanoporous membranes

International Nuclear Information System (INIS)

Bishop, Christina; Teeters, Dale

2009-01-01

The confinement of poly(ethylene oxide), PEO, electrolyte in pores of 13, 35, 55 and 100 nm in diameter in nanoporous alumina membranes was seen to have effects on the ionic conduction properties. Specific conductivity values for the PEO/lithium triflate complex in the 13 and 35 nm pores, for temperatures below the melt temperatures, were increased by a factor of four compared to the non-confined polymer and the 55 and 100 nm pore systems. Thermal analysis data indicate the melting temperature for the PEO electrolyte in the pores is directly proportional to the pore size such that as the pore size of confinement is decreased, the T m decreases as well. The same behavior is seen for the amount of crystallinity, with less crystallinity being observed as the pores become smaller. Perhaps the observed conduction behavior could be attributed to less crystallinity. However, it is known that confinement of polyethers in pores results in stretching and ordering of the backbone and that such ordering can increase ion conduction. This ordering would seem to be the major factor involved in these results. The enhanced conduction only being seen in the 13 and 35 nm pores and not the 55 and 100 nm pores is attributed to the larger size for the latter which allows a more bulk-like behavior with less ordering.

Structure and size of ions electrochemically doped in conducting polymer

Science.gov (United States)

Kaneto, Keiichi; Hata, Fumito; Uto, Sadahito

2018-05-01

Among electroactive polymers (EAPs) for softactuators, conducting polymers have been intensively studied because of the large strain and stress caused by a low voltage operation. A larger deformation is desirable to extend their cycle life by reducing the operation voltage, and this is advantageous for their potential use in wider applications. The deformation is generated by the insertion of ions by electrochemical oxidation; hence, the magnitude of the strain depends on the bulkiness of the ions in the electrolytes. It is important, therefore, to clarify the structure and size of the ions during the electrochemical cycle, in order to achieve better performance of actuation. Anion and cation sizes (radii) in polypyrrole (PPy) film have been estimated using the precise measurement of strain against the amount of charge injected during the electrochemical cycles, assuming isotropic deformation of the film. The anion size was estimated using an anion-drive film, which was electrodeposited in TBABF4/methyl benzoate. The film was electrochemically cycled in sodium electrolytes, and the strain was measured simultaneously using a laser displacement meter. The cation size was obtained using a cation-drive film, being electropolymerized in aqueous dodecylbenzene sulfonic (DBS) acid. The cation-drive film was cycled in chloride electrolytes and measured the strain. The Cl-, Br-, NO3- , BF4- , and ClO4- radii were found to be approximately 235, 245, 250, 270 and 290 pm, respectively. The radii of K+, Na+ and Li+ were approximately 230, 237 and 274 pm, respectively. The results were discussed and took the crystalline ion radius and hydrated ion radius (Stokes radius) into consideration. It was found that the structure and size of the anions were slightly larger than the crystalline ion radius. Contrary to the anions, the cation radii were close to the hydrated ion radius, being larger than the crystalline ion radius.

A thermodynamic framework for the study of crystallization in polymers

Science.gov (United States)

Rao, I. J.; Rajagopal, K. R.

In this paper, we present a new thermodynamic framework within the context of continuum mechanics, to predict the behavior of crystallizing polymers. The constitutive models that are developed within this thermodynamic setting are able to describe the main features of the crystallization process. The model is capable of capturing the transition from a fluid like behavior to a solid like behavior in a rational manner without appealing to any adhoc transition criterion. The anisotropy of the crystalline phase is built into the model and the specific anisotropy of the crystalline phase depends on the deformation in the melt. These features are incorporated into a recent framework that associates different natural configurations and material symmetries with distinct microstructural features within the body that arise during the process under consideration. Specific models are generated by choosing particular forms for the internal energy, entropy and the rate of dissipation. Equations governing the evolution of the natural configurations and the rate of crystallization are obtained by maximizing the rate of dissipation, subject to appropriate constraints. The initiation criterion, marking the onset of crystallization, arises naturally in this setting in terms of the thermodynamic functions. The model generated within such a framework is used to simulate bi-axial extension of a polymer film that is undergoing crystallization. The predictions of the theory that has been proposed are consistent with the experimental results (see [28] and [7]).

Dialkylthio Substitution: An Effective Method to Modulate the Molecular Energy Levels of 2D-BDT Photovoltaic Polymers.

Science.gov (United States)

Yao, Huifeng; Zhang, Hao; Ye, Long; Zhao, Wenchao; Zhang, Shaoqing; Hou, Jianhui

2016-02-17

Dialkylthio-substituted thienyl-benzodithiophene (BDT-DST) was designed and synthesized as a building block to modulate the molecular levels of the conjugated polymers, and three copolymers named PDST-BDD, PDST-TT and PDST-DPP were prepared and applied in polymer solar cells (PSCs). Theoretical calculations and electrochemical cyclic voltammetry (CV) measurement suggested that the dialkylthio group could decrease the molecular energy levels of the resulting polymers distinctly. The open-circuit voltage (VOC) of PSC devices based on PDST-BDD, PDST-TT, and PDST-DPP are as high as 1.0, 0.98, and 0.88 V, respectively, which are ∼0.15 V higher than those of the corresponding alky-substituted analogues. Moreover, the influence of the dialkylthio group on the absorption spectra, crystalline properties, hole mobilities, and blend morphologies of the polymers was also investigated. The results indicate that the dialkythio substitution is an effective method to modulate the molecular energy levels and that the BDT-DST unit has potential for constructing high-efficiency photovoltaic polymers.

Sorption and permeation of gaseous molecules in amorphous and crystalline PPX C membranes: molecular dynamics and grand canonical Monte Carlo simulation studies

International Nuclear Information System (INIS)

Bian Liang; Shu Yuan-Jie; Wang Xin-Feng

2012-01-01

Amorphous and crystalline poly (chloro-p-xylylene) (PPX C) membranes are constructed by using a novel computational technique, that is, a combined method of NVT+NPT-molecular dynamics (MD) and gradually reducing the size (GRS) methods. The related free volumes are defined as homology clusters. Then the sorption and the permeation of gases in PPX C polymers are studied using grand canonical Monte Carlo (GCMC) and NVT-MD methods. The results show that the crystalline PPX C membranes provide smaller free volumes for absorbing or transferring gases relative to the amorphous PPX C area. The gas sorption in PPX C membranes mainly belongs to the physical one, and H bonds can appear obviously in the amorphous area. By cluster analyzing on the mean square displacement of gases, we find that gases walk along the x axis in the crystalline area and walk randomly in the amorphous area. The calculated permeability coefficients are close to the experimental data. (electromagnetism, optics, acoustics, heat transfer, classical mechanics, and fluid dynamics)

Thermally induced texture flip in semiconducting polymer stabilized by epitaxial relationship

Science.gov (United States)

O'Hara, Kathryn A.; Pokuri, Balaji S. S.; Takacs, Christopher J.; Beaujuge, Pierre M.; Ganapathysubramanian, Baskar; Chabinyc, Michael L.

The morphology of semiconducting polymer films has a large effect on the charge transport properties. Charges can move easily along the conjugated backbone and in the pi-pi stacking direction. However, transport through the film is determined by the connectivity between domains, which is not well understood. We previously observed quadrites in the polymer, PSBTBT, and proposed that the preferential overlap between lamellae may improve connectivity and provide an additional conduction pathway. Now, the presence of quadrites is revealed in another successful donor polymer, PBDTTPD, using high resolution transmission electron microscopy (HRTEM). A study of how side-chain substitution affects the epitaxial crossing is conducted by examining several PBDTTPD derivatives. The stability of the film texture with annealing is also examined as a function of quadrite formation. It has been shown that heating some semicrystalline polymers above the melting temperature and slow cooling can flip the lamellar texture from face-on to edge-on. We hypothesize that the orientation of lamellar crystallites in PBDTTPD films is stabilized by the epitaxial overlap between adjacent crystalline domains. This may have important implications for the electronic transport properties.

Structural, microstructural and electrochemical properties of dispersed-type polymer nanocomposite films

Science.gov (United States)

Arya, Anil; Sharma, A. L.

2018-01-01

Free-standing solid polymer nanocomposite (PEO-PVC)  +  LiPF6-TiO2 films have been prepared through a standard solution-cast technique. The improvement in structural, microstructural and electrochemical properties has been observed on the dispersion of nanofiller in polymer salt complex. X-ray diffraction studies clearly reflect the formation of complex formation, as no corresponding salt peak appeared in the diffractograms. The Fourier transform infrared analysis suggested clear and convincing evidence of polymer-ion, ion-ion and polymer-ion-nanofiller interaction. The highest ionic conductivity of the prepared solid polymer electrolyte (SPE) films is ~5  ×  10-5 S cm-1 for 7 wt.% TiO2. The linear sweep voltammetry provides the electrochemical stability window of the prepared SPE films, about ~3.5 V. The ion transference number has been estimated, t ion  =  0.99 through the DC polarization technique. Dielectric spectroscopic studies were performed to understand the ion transport process in polymer electrolytes. All solid polymer electrolytes possess good thermal stability up to 300 °C. Differential scanning calorimetry analysis confirms the decrease of the melting temperature and signal of glass transition temperature with the addition of nanofiller, which indicates the decrease of crystallinity of the polymer matrix. An absolute correlation between diffusion coefficient (D), ion mobility (µ), number density (n), double-layer capacitance (C dl), glass transition temperature, melting temperature (T m), free ion area (%) and conductivity (σ) has been observed. A convincing model to study the role of nanofiller in a polymer salt complex has been proposed, which supports the experimental findings. The prepared polymer electrolyte system with significant ionic conductivity, high ionic transference number, and good thermal and voltage stability could be suggested as a potential candidate as electrolyte cum separator for the fabrication of a

Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties

Directory of Open Access Journals (Sweden)

Matasebia T. Munie

2011-10-01

Full Text Available Supramolecular coordination polymers with wavelike structures have been synthesized by self-assembly and their structures analyzed using the sine trigonometric function. Slow evaporation of a methylene chloride-methanol solution of a 1:1 molar mixture of [M(tmhd2], where M = Co or Ni, and quinoxaline; a 1:2:1 molar mixture of [M(acac2], where M = Co or Ni, 2,2,6,6-tetramethyl-3,5-heptadione and quinoxaline; or a 1:2:1 molar mixture of [Co(acac2], dibenzoylmethane, and quinoxaline, yielded the crystalline coordination polymers. In the presence of the nitrogenous base, ligand scrambling occurs yielding the most insoluble product. The synthesis and structures of the following wavelike polymers are reported: trans-[Co(DBM2(qox]n·nH2O (2, trans-[Co(tmhd2(qox]n (3, trans-[Ni(tmhd2(qox]n (4, where DBM− = dibenzoylmethanate, tmhd− = 2,2,6,6-tetramethyl-3,5-heptadionate, and qox = quinoxaline. The wavelike structures are generated by intramolecular steric interactions and crystal packing forces between the chains. Some of the tert-butyl groups show a two-fold disorder. The sine function, φ = A sin 2πx/λ, where φ = distance (Ǻ along the polymer backbone, λ = wavelength (Ǻ, A = amplitude (Ǻ, x = distance (Ǻ along the polymer axis, provides a method to approximate and visualize the polymer structures.

Understanding the Effects of Defect Modification on the Structure and Properties of Fluorinated Polymers and Implications for Capacitive Energy Storage Technologies

Science.gov (United States)

Gadinski, Matthew R.

As the world begins to turn to alternative energy technologies and our electronic devices have become more both mobile and integral to everyday life, increasing interest has been focused on energy storage technologies. Capacitors are one of these energy storage technologies that utilize the polarization of an insulating material sandwiched by two electrodes as a means to store electric charge. Polymers are a preferred dielectric material for capacitors because of both their performance and practicality. However, polymer dielectrics are limited in energy density by low dielectric constant, and high loss at elevated temperature. This work aims to address these issues in order to enable polymer dielectrics for future applications and demands. As most polymer tend to have low dielectric constants (˜2-3), but impressive breakdown strengths, only a moderate improvement in dielectric constant has the potential to vastly improve the energy density of polymer capacitors. As such tremendous interest has been placed on poly(vinylidene fluoride) (PVDF) which has a dielectric of 10+ due to the highly polar C-F bonds of its backbone. To improve PVDF's performance defect monomers have been introduced to tailor the polymorphic crystalline phase to tune its properties. Additionally, this defect modification has implications for piezoelectric, electrocaloric, and thermoelectric applications of PVDF. In Chapter 2 a copolymer of VDF and bromotrifluoroethylene (BTFE) was produced. The effect of BTFE on the structure and dielectric properties of the resulting copolymer had not been previously evaluated, and its synthesis allowed for the comparison to previously reported VDF based copolymers including P(VDF-CTFE) and P(VDF-HFP). Through 19F NMR it was determined due to reactivity ratio differences of BTFE in comparison to previously explored copolymers, BTFE during synthesis is much more likely to link with itself. This results in long runs of BTFE-BTFE defects along with isolated

High performance all polymer solar cells fabricated via non-halogenated solvents (Presentation Recording)

Science.gov (United States)

Zhou, Yan; Bao, Zhenan

2015-10-01

The performance of organic solar cells consisting of a donor/acceptor bulk heterojunction (BHJ) has rapidly improved over the past few years.1. Major efforts have been focused on developing a variety of donor materials to gain access to different regions of the solar spectrum as well as to improve carrier transport properties.2 On the other hand, the most utilized acceptors are still restricted to the fullerene family, which includes PC61BM, PC71BM and ICBA.2b, 3 All-polymer solar cells, consisting of polymers for both the donor and acceptor, gained significantly increased interests recently, because of their ease of solution processing, potentially low cost, versatility in molecular design, and their potential for good chemical and morphological stability due to entanglement of polymers. Unlike small molecular fullerene acceptors, polymer acceptors can benefit from the high mobility of intra-chain charge transport and exciton generation by both donor and acceptor. Despite extensive efforts on all-polymer solar cells in the past decade, the fundamental understanding of all-polymer solar cells is still in its inceptive stage regarding both the materials chemistry and structure physics.4 Thus, rational design rules must be utilized to enable fundamental materials understanding of the all polymer solar cells. We report high performance all-polymer solar cells employing polymeric donors based on isoindigo and acceptor based on perylenedicarboximide. The phase separation domain length scale correlates well with the JSC and is found to be highly sensitive to the aromatic co-monomer structures used in the crystalline donor polymers. With the PS polymer side chain engineering, the phase separation domain length scale decreased by more than 45%. The PCE and JSC of the devices increased accordingly by more than 20%. A JSC as high as 10.0 mA cm-2 is obtained with the donor-acceptor pair despite of a low LUMO-LUMO energy offset of less than 0.1 eV. All the factors such as

Characterization and properties of acetylated nanocrystalline cellulose (aNC) reinforced polylactic acid (PLA) polymer

Science.gov (United States)

Kasa, Siti Norbaya; Omar, Mohd Firdaus; Ismail, Ismarul Nizam

2017-12-01

Nanocrystalline cellulose (NCC) was synthesized from banana stem through strong acid hydrolysis with measured length of approximately 287.0 ± 56.4 nm and diameter of 26.6 ± 4.8 nm. Modification of NCC was carried by acetylation reaction in order to increase the compatibility during reinforcement with polylactic acid (PLA) polymer. The reinforcing effect towards morphology, crystallinity, mechanical and thermal properties of bio-nanocomposites was investigated. Scanning Electron Microscope (SEM) micrograph reveals the uniform dispersion achieved at 1 %, 3 % and 5% aNC loading while agglomeration was found at 7 % aNC loading. Disappearance of crystallinity peak at 2θ = 22.7⁰ for low aNC loading during elemental analysis using X-Ray Diffraction (XRD) indicates the proper dispersion of aNC in PLA polymer. From the tensile test, 1 % aNC loading gives the highest mechanical properties of bio-nanocomposite film with 82.71 %, 118.7 % and 24.18 % increment in tensile strength, tensile modulus and elongation at break. However, 7 % aNC loading gives the highest increment in TGA of aNC-PLA nanocomposites which is from 310 °C to 320 °C.

Strength of Drug–Polymer Interactions: Implications for Crystallization in Dispersions

Energy Technology Data Exchange (ETDEWEB)

Mistry, Pinal; Suryanarayanan, Raj

2016-09-07

We investigated the influence of the strength of drug–polymer interactions on the crystallization behavior of a model drug in amorphous solid dispersions (ASDs). Ketoconazole ASDs were prepared with each poly(acrylic acid), poly(2-hydroxyethyl methacrylate), and polyvinylpyrrolidone. Over a wide temperature range in the supercooled region, the α-relaxation time was obtained, which provided a measure of molecular mobility. Isothermal crystallization studies were performed in the same temperature interval using either a synchrotron (for low levels of crystallinity) or a laboratory X-ray (for crystallization kinetics) source. The stronger the drug–polymer interaction, the longer was the delay in crystallization onset time, indicating an increase in physical stability. Stronger drug–polymer interactions also translated to a decrease in the magnitude of the crystallization rate constant. In amorphous ketoconazole as well as in the dispersions, the coupling coefficient, a measure of the extent of coupling between relaxation and crystallization times was ~0.5. This value was unaffected by the strength of drug–polymer interactions. On the basis of these results, the crystallization times in ASDs were predicted at temperatures very close to Tg, using the coupling coefficient experimentally determined for amorphous ketoconazole. The predicted and experimental crystallization times were in good agreement, indicating the usefulness of the model.

Calcium carbonate interaction analysis in polypropylene compounds and their impact on the formation of beta crystalline phase of this polymer; Analise da interacao de diferentes tipos de carbonato de calcio em compositos de polipropileno e suas consequencias na formacao da fase cristalina beta do PP

Energy Technology Data Exchange (ETDEWEB)

NONE

2011-07-01

The insertion of calcium carbonate (CaCO{sub 3}) in polypropylene compound is a thoroughly known technique widely studied in the academic area and in the industry. Its wide application is due, mainly, to increase mechanical properties with low manufacturing cost. These improvements in this polymer make it more versatile and competitive compared to other expensive polymers. In this study, the incorporation of four types of CaCO3 from the same manufacturer were compared and the focus was on the size of this mineral filler. Furthermore, it was analyzed the interaction of graphitized polypropylene with maleic anhydride (PP-g-MA) in the same samples. All these samples were analyzed by WAXS and SEM. The physical properties of tensile strength and impact were also analyzed. It was observed from this study that the smallest CaCO3 produced with PP-g-MA resulted in better physical properties with the formation of a crystalline phase beta, as originally studied by other authors using other raw materials. (author)

Study of photoconductor polymers synthesized by plasma; Estudio de polimeros fotoconductores sintetizados por plasma

Energy Technology Data Exchange (ETDEWEB)

Enriquez P, M.A

2007-07-01

In this work the photoconductivity in poly thiophene (PTh), poly pyrrole (PPy) and doped poly pyrrole with iodine (PPy/I) is studied, whose structures depend of the intensity of the electric field applied during the synthesis by plasma. The conjugated organic polymers possess double alternated bonds in its chemical structure that its allow the one movement of {pi} electrons through the polymeric chains. The plasma is produced by means of splendor discharges to 13.5 MHz, resistive coupling, at one pressure that oscillates in the interval from 2 to 3x10{sup -1} mbar, 180 min and powers of 10, 24, 40, {sup 60}, 80 and 100 W. Its were used heteroaromatic polymers like PTh and PPy/I, due to their potential applications in optoelectronics. The influence of the iodine is evaluated as dopant in PPy and it is compared with their similar one without doping in the light absorption/emission processes. The polymers synthesized by plasma can ramify or to intersect due to the energy applied during the synthesis. However, if the polymer intersects, the aromaticity can continue through the polymeric chains. The absorptions obtained by infrared spectroscopy, suggest that the polymer conserves the aromatic structure of the monomer fundamentally with substitutions that indicate inter crossing and partial fragmentation. The structure of most of the polymers spreads to be amorphous because they don't possess any classification. However, the PPy/I and PTh synthesized by this technique present crystalline segments whose intensity diminishes with the power of the discharge. In PTh, the average crystallinity diminishes from 19.8% to 9.9%, and in PPy/I of 15.9% to 13.3% in the interval of 10 to 100 W of power. In this work, however, its were crystalline arrangements in all the studied powers. The classification of the polymeric structure favors the formation of trajectories of transfer of electric loads among the chains, that which influences in the global electric conductivity of the

Blending crystalline/liquid crystalline small molecule semiconductors: A strategy towards high performance organic thin film transistors

Science.gov (United States)

He, Chao; He, Yaowu; Li, Aiyuan; Zhang, Dongwei; Meng, Hong

2016-10-01

Solution processed small molecule polycrystalline thin films often suffer from the problems of inhomogeneity and discontinuity. Here, we describe a strategy to solve these problems through deposition of the active layer from a blended solution of crystalline (2-phenyl[1]benzothieno[3,2-b][1]benzothiophene, Ph-BTBT) and liquid crystalline (2-(4-dodecylphenyl) [1]benzothieno[3,2-b]benzothiophene, C12-Ph-BTBT) small molecule semiconductors with the hot spin-coating method. Organic thin film transistors with average hole mobility approaching 1 cm2/V s, much higher than that of single component devices, have been demonstrated, mainly due to the improved uniformity, continuity, crystallinity, and stronger intermolecular π-π stacking in blend thin films. Our results indicate that the crystalline/liquid crystalline semiconductor blend method is an effective way to enhance the performance of organic transistors.

The Effect of Irradiation on Mechanical and Thermal Properties of Selected Types of Polymers

Directory of Open Access Journals (Sweden)

David Manas

2018-02-01

Full Text Available This article deals with the influence of electron-beam radiation on the micro-mechanical, thermo-mechanical, and structural properties of selected polymers. In the search for the desired improvement of polymers, it is possible to use, inter alia, one particular possible modification—Namely, crosslinking—Which is a process during which macromolecular chains start to connect to each other and, thus, create the spatial network in the structure. In the course of the treatment of the ionizing radiation, two actions can occur: crosslinking and scission of macromolecules, or degradation. Both these processes run in parallel. Using the crosslinking technology, standard and technical polymers can acquire the more “expensive” high-tech polymeric material properties and, thus, replace these materials in many applications. The polymers that were tested were selected from across the whole spectra of thermoplastics, ranging from commodity polymers, technical polymers, as well as high-performance polymers. These polymers were irradiated by different doses of beta radiation (33, 66, 99, 132, 165, and 198 kGy. The micro-mechanical and thermo-mechanical properties of these polymers were measured. When considering the results, it is obvious that irradiation acts on each polymer differently but, always when the optimal dose was found, the mechanical properties increased by up to 36%. The changes of micro-mechanical and thermo-mechanical properties were confirmed by structural measurement when the change of the micro-hardness and modulus corresponded to the crystalline phase change as determined by X-ray and gel content.

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

Science.gov (United States)

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.

Ultra-fast solid state electro-optical modulator based on liquid crystal polymer and liquid crystal composites

Energy Technology Data Exchange (ETDEWEB)

Ouskova, Elena; Sio, Luciano De, E-mail: luciano@beamco.com; Vergara, Rafael; Tabiryan, Nelson [Beam Engineering for Advanced Measurements Company, Winter Park, Florida 32789 (United States); White, Timothy J.; Bunning, Timothy J. [Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio 45433-7707 (United States)

2014-12-08

A different generation of polymer-dispersed liquid crystals (PDLCs) based on a liquid crystalline polymer host is reported wherein the fluid behavior of the reactive mesogenic monomer is an enabler to concentration windows (liquid crystal polymer/liquid crystal) (and subsequent morphologies) not previously explored. These liquid crystal (LC) polymer/LC composites, LCPDLCs, exhibit excellent optical and electro-optical properties with negligible scattering losses in both the ON and OFF states. These systems thus have application in systems where fast phase modulation of optical signal instead of amplitude control is needed. Polarized optical microscopy and high resolution scanning electron microscopy confirm a bicontinuous morphology composed of aligned LC polymer coexisting with a phase separated LC fluid. Operating voltages, switching times, and spectra of LCPDLCs compare favourably to conventional PDLC films. The LCPDLCs exhibit a low switching voltage (4–5 V/μm), symmetric and submillisecond (200 μs) on/off response times, and high transmission in both the as formed and switched state in a phase modulation geometry.

X-ray diffraction studies of chitosan acetate-based polymer electrolytes

International Nuclear Information System (INIS)

Osman, Z.; Ibrahim, Z.A.; Abdul Kariem Arof

2002-01-01

Chitosan is the product when partially deacetylated chitin dissolves in dilute acetic acid. This paper presents the x-ray diffraction patterns of chitosan acetate, plasticised chitosan acetate and plasticised-salted chitosan acetate films. The results show that the chitosan acetate based polymer electrolyte films are not completely amorphous but it is partially crystalline. X-ray diffraction study also confirms the occurrence of the complexation between chitosan and the salt and the interaction between salt and plasticizer. The salt-chitosan interaction is clearly justified by infrared spectroscopy. (Author)

Fabrication of an Electrically-Resistive, Varistor-Polymer Composite

Directory of Open Access Journals (Sweden)

Sanaz A. Mohammadi

2012-11-01

Full Text Available This study focuses on the fabrication and electrical characterization of a polymer composite based on nano-sized varistor powder. The polymer composite was fabricated by the melt-blending method. The developed nano-composite was characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, field emission scanning electron microscopy (FeSEM, and energy-dispersive X-ray spectroscopy (EDAX. The XRD pattern revealed the crystallinity of the composite. The XRD study also showed the presence of secondary phases due to the substitution of zinc by other cations, such as bismuth and manganese. The TEM picture of the sample revealed the distribution of the spherical, nano-sized, filler particles throughout the matrix, which were in the 10–50 nm range with an average of approximately 11 nm. The presence of a bismuth-rich phase and a ZnO matrix phase in the ZnO-based varistor powder was confirmed by FeSEM images and EDX spectra. From the current-voltage curves, the non-linear coefficient of the varistor polymer composite with 70 wt% of nano filler was 3.57, and its electrical resistivity after the onset point was 861 KΩ. The non-linear coefficient was 1.11 in the sample with 100 wt% polymer content. Thus, it was concluded that the composites established a better electrical non-linearity at higher filler amounts due to the nano-metric structure and closer particle linkages.

Enhancement of the optical, thermal and electrical properties of PEO/PAM:Li polymer electrolyte films doped with Ag nanoparticles

Science.gov (United States)

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.

LIQUID CRYSTALLINE BEHAVIOR OF HYDROXYPROPYL CELLULOSE ESTERIFIED WITH 4-ALKOXYBENZOIC ACID.

Directory of Open Access Journals (Sweden)

Yehia Fahmy

2010-07-01

Full Text Available A series of 4- alkyoxybenzoyloxypropyl cellulose (ABPC-n samples was synthesized via the esterification of hydroxypropyl cellulose (HPC with 4-alkoxybenzoic acid bearing different numbers of carbon atoms. The molecular structure of the ABPC-n was confirmed by Fourier transform infrared (FT-IR spectroscopy and 1H NMR spectroscopy. The liquid crystalline (LC phases and transitions behaviors were investigated using differential scanning calorimetry (DSC, polarized light microscopy (PLM, and refractometry. It was found that the glass transition (Tg and clearing (Tc temperatures decrease with increase of the alkoxy chain length. It was observed that the derivatives with an odd number of carbon atoms are non-mesomorphic. This series of ABPC-n polymers exhibit characteristic features of cholesteric LC phases between their glass transition and isotropization temperatures.

Hierarchical Structure in Semicrystalline Polymers Tethered to Nanospheres

KAUST Repository

Kim, Sung A

2014-01-28

We report on structural and dynamic transitions of polymers tethered to nanoparticles. In particular, we use X-ray diffraction, vibrational spectroscopy, and thermal measurements to investigate multiscale structure and dynamic transitions of poly(ethylene glycol) (PEG) chains densely grafted to SiO2 nanoparticles. The approach used for synthesizing these hybrid particles leads to homogeneous SiO2-PEG composites with polymer grafting densities as high as 1.5 chains/nm2, which allows the hybrid materials to exist as self-suspended suspensions with distinct hierarchical structure and thermal properties. On angstrom and nanometer length scales, the tethered PEG chains exhibit more dominant TTG conformations and helix unit cell structure, in comparison to the untethered polymer. The nanoparticle tethered PEG chains are also reported to form extended crystallites on tens of nanometers length scales and to exhibit more stable crystalline structure on small dimensions. On length scales comparable to the size of each hybrid SiO 2-PEG unit, the materials are amorphous presumably as a result of the difficulty fitting the nanoparticle anchors into the PEG crystal lattice. This structural change produces large effects on the thermal transitions of PEG molecules tethered to nanoparticles. © 2014 American Chemical Society.

Fabrication of ferroelectric polymer nanostructures on flexible substrates by soft-mold reverse nanoimprint lithography

International Nuclear Information System (INIS)

Song, Jingfeng; Lu, Haidong; Gruverman, Alexei; Ducharme, Stephen; Li, Shumin; Tan, Li

2016-01-01

Conventional nanoimprint lithography with expensive rigid molds is used to pattern ferroelectric polymer nanostructures on hard substrate for use in, e.g., organic electronics. The main innovation here is the use of inexpensive soft polycarbonate molds derived from recordable DVDs and reverse nanoimprint lithography at low pressure, which is compatible with flexible substrates. This approach was implemented to produce regular stripe arrays with a spacing of 700 nm from vinylidene fluoride co trifluoroethylene ferroelectric copolymer on flexible polyethylene terephthalate substrates. The nanostructures have very stable and switchable piezoelectric response and good crystallinity, and are highly promising for use in organic electronics enhanced or complemented by the unique properties of the ferroelectric polymer, such as bistable polarization, piezoelectric response, pyroelectric response, or electrocaloric function. The soft-mold reverse nanoimprint lithography also leaves little or no residual layer, affording good isolation of the nanostructures. This approach reduces the cost and facilitates large-area, high-throughput production of isolated functional polymer nanostructures on flexible substrates for the increasing application of ferroelectric polymers in flexible electronics. (paper)

Fabrication of ferroelectric polymer nanostructures on flexible substrates by soft-mold reverse nanoimprint lithography.

Science.gov (United States)

Song, Jingfeng; Lu, Haidong; Li, Shumin; Tan, Li; Gruverman, Alexei; Ducharme, Stephen

2016-01-08

Conventional nanoimprint lithography with expensive rigid molds is used to pattern ferroelectric polymer nanostructures on hard substrate for use in, e.g., organic electronics. The main innovation here is the use of inexpensive soft polycarbonate molds derived from recordable DVDs and reverse nanoimprint lithography at low pressure, which is compatible with flexible substrates. This approach was implemented to produce regular stripe arrays with a spacing of 700 nm from vinylidene fluoride co trifluoroethylene ferroelectric copolymer on flexible polyethylene terephthalate substrates. The nanostructures have very stable and switchable piezoelectric response and good crystallinity, and are highly promising for use in organic electronics enhanced or complemented by the unique properties of the ferroelectric polymer, such as bistable polarization, piezoelectric response, pyroelectric response, or electrocaloric function. The soft-mold reverse nanoimprint lithography also leaves little or no residual layer, affording good isolation of the nanostructures. This approach reduces the cost and facilitates large-area, high-throughput production of isolated functional polymer nanostructures on flexible substrates for the increasing application of ferroelectric polymers in flexible electronics.

Dissolution of crystalline ceramics

International Nuclear Information System (INIS)

White, W.B.

1982-01-01

The present program objectives are to lay out the fundamentals of crystalline waste form dissolution. Nuclear waste ceramics are polycrystalline. An assumption of the work is that to the first order, the release rate of a particular radionuclide is the surface-weighted sum of the release rates of the radionuclide from each crystalline form that contains it. In the second order, of course, there will be synergistic effects. There will be also grain boundary and other microstructural influences. As a first approximation, we have selected crystalline phases one at a time. The sequence of investigations and measurements is: (i) Identification of the actual chemical reactions of dissolution including identification of the solid reaction products if such occur. (ii) The rates of these reactions are then determined empirically to give what may be called macroscopic kinetics. (iii) Determination of the rate-controlling mechanisms. (iv) If the rate is controlled by surface reactions, the final step would be to determine the atomic kinetics, that is the specific atomic reactions that occur at the dissolving interface. Our concern with the crystalline forms are in two areas: The crystalline components of the reference ceramic waste form and related ceramics and the alumino-silicate phases that appear in some experimental waste forms and as waste-rock interaction products. Specific compounds are: (1) Reference Ceramic Phases (zirconolite, magnetoplumbite, spinel, Tc-bearing spinel and perovskite); (2) Aluminosilicate phases (nepheline, pollucite, CsAlSi 5 O 12 , Sr-feldspar). 5 figures, 1 table

Introduction of Functional Structures in Nano-Scales into Engineering Polymer Films Using Radiation Technique

Energy Technology Data Exchange (ETDEWEB)

Maekawa, Y., E-mail: maekawa.yasunari@jaea.go.jp [Japan Atomic Energy Agency (JAEA), Quantum Beam Science Directorate, High Performance Polymer Group, 1233 Watanuki-Machi, Takasaki, Gunma-ken 370-1292 (Japan)

2010-07-01

Introduction of functional regions in nanometer scale in polymeric films using γ-rays, EB, and ion beams are proposed. Two approaches to build nano-scale functional domains in polymer substrates are proposed: 1) Radiation-induced grafting to transfer nano-scale polymer crystalline structures (morphology), acting as a nano-template, to nano-scale graft polymer regions. The obtained polymers with nano structures can be applied to high performance polymer membranes. 2) Fabrication of nanopores and functional domains in engineering plastic films using ion beams, which deposit the energy in very narrow region of polymer films. Hydrophilic grafting polymers are introduced into hydrophobic fluorinated polymers, cross-linked PTFE (cPTFE) and aromatic hydrocarbon polymer, poly(ether ether ketone (PEEK), which is known to have lamella and crystallite in the polymer films. Then, the hierarchical structures of graft domains are analyzed by a small angle neutron scattering (SANS) experiment. From these analyses, the different structures and the different formation of graft domains were observed in fluorinated and hydrocarbon polymer substrates. the grafted domains in the cPTFE film, working as an ion channel, grew as covering the crystallite and the size of domain seems to be similar to that of crystallite. On the other hand, the PEEK-based PEM has a smaller domain size and it seems to grow independently on the crystallites of PEEK substrate. For nano-fabrication of polymer films using heavy ion beams, the energy distribution in radial direction, which is perpendicular to ion trajectory, is mainly concerned. For penumbra, we re-estimated effective radius of penumbra, in which radiation induced grafting took place, for several different ion beams. We observed the different diameters of the ion channels consisting of graft polymers. The channel sizes were quite in good agreement with the effective penumbra which possess the absorption doses more than 1 kGy. (author)

Introduction of Functional Structures in Nano-Scales into Engineering Polymer Films Using Radiation Technique

International Nuclear Information System (INIS)

Maekawa, Y.

2010-01-01

Introduction of functional regions in nanometer scale in polymeric films using γ-rays, EB, and ion beams are proposed. Two approaches to build nano-scale functional domains in polymer substrates are proposed: 1) Radiation-induced grafting to transfer nano-scale polymer crystalline structures (morphology), acting as a nano-template, to nano-scale graft polymer regions. The obtained polymers with nano structures can be applied to high performance polymer membranes. 2) Fabrication of nanopores and functional domains in engineering plastic films using ion beams, which deposit the energy in very narrow region of polymer films. Hydrophilic grafting polymers are introduced into hydrophobic fluorinated polymers, cross-linked PTFE (cPTFE) and aromatic hydrocarbon polymer, poly(ether ether ketone (PEEK), which is known to have lamella and crystallite in the polymer films. Then, the hierarchical structures of graft domains are analyzed by a small angle neutron scattering (SANS) experiment. From these analyses, the different structures and the different formation of graft domains were observed in fluorinated and hydrocarbon polymer substrates. the grafted domains in the cPTFE film, working as an ion channel, grew as covering the crystallite and the size of domain seems to be similar to that of crystallite. On the other hand, the PEEK-based PEM has a smaller domain size and it seems to grow independently on the crystallites of PEEK substrate. For nano-fabrication of polymer films using heavy ion beams, the energy distribution in radial direction, which is perpendicular to ion trajectory, is mainly concerned. For penumbra, we re-estimated effective radius of penumbra, in which radiation induced grafting took place, for several different ion beams. We observed the different diameters of the ion channels consisting of graft polymers. The channel sizes were quite in good agreement with the effective penumbra which possess the absorption doses more than 1 kGy. (author)

Physical characterization and in silico modeling of inulin polymer conformation during vaccine adjuvant particle formation.

Science.gov (United States)

Barclay, Thomas G; Rajapaksha, Harinda; Thilagam, Alagu; Qian, Gujie; Ginic-Markovic, Milena; Cooper, Peter D; Gerson, Andrea; Petrovsky, Nikolai

2016-06-05

This study combined physical data from synchrotron SAXS, FTIR and microscopy with in-silico molecular structure predictions and mathematical modeling to examine inulin adjuvant particle formation and structure. The results show that inulin polymer chains adopt swollen random coil in solution. As precipitation occurs from solution, interactions between the glucose end group of one chain and a fructose group of an adjacent chain help drive organized assembly, initially forming inulin ribbons with helical organization of the chains orthogonal to the long-axis of the ribbon. Subsequent aggregation of the ribbons results in the layered semicrystalline particles previously shown to act as potent vaccine adjuvants. γ-Inulin adjuvant particles consist of crystalline layers 8.5 nm thick comprising helically organized inulin chains orthogonal to the plane of the layer. These crystalline layers alternate with amorphous layers 2.4 nm thick, to give overall particle crystallinity of 78%. Copyright © 2016 Elsevier Ltd. All rights reserved.

Nanoparticle-based capillary electroseparation of proteins in polymer capillaries under physiological conditions

DEFF Research Database (Denmark)

Nilsson, C.; Harwigsson, I.; Becker, K.

2010-01-01

Totally porous lipid-based liquid crystalline nanoparticles were used as pseudostationary phase for capillary electroseparation with LIF detection of proteins at physiological conditions using unmodified cyclic olefin copolymer capillaries (Topas (R), 6.7 cm effective length). In the absence of n...... at protein friendly conditions. The developed capillary-based method facilitates future electrochromatography of proteins on polymer-based microchips under physiological conditions and enables the initial optimization of separation conditions in parallel to the chip development....

Novel Shape-Memory Polymer with Two Transition Temperature Based on Two Different Memory Mechanism

Institute of Scientific and Technical Information of China (English)

Liu Guoqin; Ding Xiaobing; Cao Yiping; Zheng Zhaohui; Peng Yuxing

2004-01-01

at room temperature and did not deform at all under a given stress. However, if upon cooling; even after unloading, it did not recover the initial shape. When the polymer was ratio reach 90%. This observation illustrates that the shape memory phenomenon with 90%recovery ratio was found to be archived by changing the operation temperature below and above of Tm of crystalline PEG, which is based on a reversible order-disorder transition of crystalline aggregates. Similarly, the investigation on the shape memory transitin at Tg that when the sample (above Tg of the semi-IPN), the polymer showed second shape memory behavior, and quickly recovered to initial shape in 45s with shape recovery ratio more than 99%.

Novel fluorinated polymer materials based on 2,3,5,6-tetrafluoro-4-methoxystyrene

DEFF Research Database (Denmark)

Hvilsted, Søren; Borkar, Sachin; Siesler, HW

2003-01-01

2,3,5,6-Tetrafluoro-4-methoxystyrene (TFMS) has been polymerized in bulk and in xylene solution by Atom Transfer Radical Polymerization (ATRP) in a conventional protocol at 110 degreesC. Relatively good control has been achieved with number-average molecular mass (M) up to 17,000 and correspondin...... with different azobenzene side chains. The azobenzene derivatized polymer has additionally been copolymerized with St. Both homo- and block copolymers with azobenzene side chains form materials exhibiting liquid crystallinity.......) resulting in block copolymers with controlled characteristics. TFMS homo- and block copolymers with PS have better thermal stability than PS. The solubility of the PTFMS containing polymers is lower than that of PS. Furthermore, PTFMS has been demethylated and the resulting hydroxyl sites alkylated...

Diverse topics in crystalline beams

International Nuclear Information System (INIS)

Wei, Jie; Draeseke, A.; Sessler, A.M.; Li, Xiao-Ping

1995-01-01

Equations of motion are presented, appropriate to interacting charged particles of diverse charge and mass, subject to the external forces produced by various kinds of magnetic fields and radio-frequency (rf) electric fields in storage rings. These equations are employed in the molecular dynamics simulations to study the properties of crystalline beams. The two necessary conditions for the formation and maintenance of crystalline beams are summarized. The transition from ID to 2D, and from 2D to 3D is explored, and the scaling behavior of the heating rates is discussed especially in the high temperature limit. The effectiveness of various cooling techniques in achieving crystalline states has been investigated. Crystalline beams made of two different species of ions via sympathetic cooling are presented, as well as circulating ''crystal balls'' bunched in all directions by magnetic focusing and rf field. By numerically reconstructing the original experimental conditions of the NAP-M ring, it is found that only at extremely low beam intensities, outside of the range of the original measurement, proton particles can form occasionally-passing disks. The proposed New ASTRID ring is shown to be suitable for the formation and maintenance of crystalline beams of all dimensions

Synthesis of inorganic polymers using fly ash and primary lead slag.

Science.gov (United States)

Onisei, S; Pontikes, Y; Van Gerven, T; Angelopoulos, G N; Velea, T; Predica, V; Moldovan, P

2012-02-29

The present work reports on the synthesis and properties of inorganic polymers ("geopolymers") made of 100% fly ash from lignite's combustion, 100% primary lead slag and mixtures of the two. In the inorganic polymers with both fly ash and lead slag the main crystalline phases detected are wüstite, magnetite, sodium zinc silicate, quartz, anorthite, and gehlenite; litharge partially dissolves. FTIR analysis in these samples revealed that the main peaks and bands of end members also exist, along with a new amorphous reaction product. In terms of microstructure, both fly ash and lead slag dissolve and contribute in the binding phase whereas the larger particles act as aggregates. For an increasing lead slag in the composition, the binding phase is changing in chemistry and reaches PbO values higher than 50 wt.% for the 100% lead slag inorganic polymer. Regarding the properties of fly ash and lead slag inorganic polymers, compressive strength is higher than 35 MPa in all cases and water absorption diminishes as the lead slag content increases. A comparison of leaching results before and after polymerisation reveals that pH is an important factor as Pb is immobilised in the binding phase, unlike Zn and As. Copyright © 2011 Elsevier B.V. All rights reserved.

The Relationship between the Monomer Chain Length and the Electro-Optical Properties of Polymer Dispersed Liquid Crystals

Directory of Open Access Journals (Sweden)

Liu J.

2016-03-01

Full Text Available Five polymers dispersed liquid crystalline (LC films were fabricated using photo-polymerizable monomers with different lengths of carbon chains. These LC films have shown different electro-optical (EO properties. Through their SEM pictures, the relationship between the linear electro-optical effect and the mesh size of the polymer network was explored. With the increase of number of photo-polymerizable monomers, the mesh size of the polymer network would become larger. So the liquid crystal molecules would be easily oriented in the electric field and therefore, the threshold voltage and saturation voltage would decrease. The open state response times were also reduced and the off state response times would be extended. The DFT simulations have shown principal role of the ground state dipole moments in the observed electro-optical efficiency.

Molecular reorientations in a substance with liquid-crystalline and plastic-crystalline phases

International Nuclear Information System (INIS)

Nguyen, Xuan Phuc.

1986-05-01

Results of dielectric relaxation (DR), quasielastic neutron scattering (QNS), far infrared absorption (FIR), proton magnetic resonance (PMR), differential scanning calorimetry (DSC) and preliminary X-ray diffraction measurements on the di-n-pentyloxyazoxybenzene (5.OAOB) are presented. The measurements carried out by all these methods showed that 5.OAOB exhibits a nontypical for liquid-crystalline materials phase diagram. It has two mesophases: a nematic (N) and an ''intermediate'' crystalline phase just below it. A complex interpretation of results obtained is given. All suggestions concerning the character of reorientational motions of the molecule as a whole as well as of its segments in mesomorphic phases are analyzed. From comparison of the DR and QNS studies one can conclude that in the N phase the molecule as a whole performs rotational diffusion around the long axis (τ DR ∼ 100 ps) and at the same time the two moieties perform faster independent reorientations around N - benzene rings bonds withτ QNS ∼ 5 ps. On the basis of various experimental data it is shown that the CrI phase is a plastic-crystalline phase for which the molecule and its segments perform fast stochastic unaxial reorientations. This is the first case where the existence of such a phase in liquid-crystalline materials has been experimentally confirmed. (author)

Neutron transmission through crystalline Fe

International Nuclear Information System (INIS)

Adib, M.; Habib, N.; Kilany, M.; El-Mesiry, M.S.

2004-01-01

The neutron transmission through crystalline Fe has been calculated for neutron energies in the range 10 4 < E<10 eV using an additive formula. The formula permits calculation of the nuclear capture, thermal diffuse and Bragg scattering cross-section as a function of temperature and crystalline form. The obtained agreement between the calculated values and available experimental ones justifies the applicability of the used formula. A feasibility study on using poly-crystalline Fe as a cold neutron filter and a large Fe single crystal as a thermal one is given

Effect of carbon nanofillers on the microstructure and electromechanical properties of electroactive polymers

Science.gov (United States)

Sigamani, Nirmal Shankar

electroactive polymers, the relatively high electrical conductivity and low breakdown limits their use for practical applications. So next step was to exploit the advantages of a conductive carbon nanostructure while controlling its network to better impact its electrical properties which could also lead to higher breakdown strength. Based on the promising impact of hybrid nanofillers on the ferroelectric polymer PVDF, a similar polymer with a relaxor ferroelectric character is considered owing to its higher inherent electroactive response and higher breakdown strength. Given that it is not broadly studied, there was a need to understand structure-property relationship of the PVDF TrFE CTFE terpolymer. Hence, the effect of processing conditions (such as annealing times and isothermal crystallization temperatures) on the microstructure and the subsequent electromechanical properties were analyzed. This structure-property analysis helped to understand the relation between the different types of crystalline phases and the degrees of crystallinity as well as to observe crystal sizes as they relate to the electric field induced strain. As a final step, the effect of the hybrid SWNT/GO on both microstructure and electromechanical properties of the terpolymer were studied. The hybrid nanofillers were chemically modified to form a covalent bond between them to improve their interaction. The morphology of the hybrid nanofillers after the chemical modification was studied for two different chemical modification routes: one using thionyl chloride, other using NHS and EDAC as catalysts. Of the two methods, the NHS and EDAC catalyst method showed a strong uniform interaction, confirmed by SEM images and FTIR results, with a shift in the peak to 1630 cm-1. Finally, the effect of hybrid SWNT and GO on the electromechanical properties were studied and, interestingly, the hybrid terpolymer nanocomposite film showed a lower electroactive strain compared to pure terpolymer at the same applied

Highly efficient polymer solar cells with printed photoactive layer: rational process transfer from spin-coating

KAUST Repository

Zhao, Kui

2016-09-05

Scalable and continuous roll-to-roll manufacturing is at the heart of the promise of low-cost and high throughput manufacturing of solution-processed photovoltaics. Yet, to date the vast majority of champion organic solar cells reported in the literature rely on spin-coating of the photoactive bulk heterojunction (BHJ) layer, with the performance of printed solar cells lagging behind in most instances. Here, we investigate the performance gap between polymer solar cells prepared by spin-coating and blade-coating the BHJ layer for the important class of modern polymers exhibiting no long range crystalline order. We find that thickness parity does not always yield performance parity even when using identical formulations. Significant differences in the drying kinetics between the processes are found to be responsible for BHJ nanomorphology differences. We propose an approach which benchmarks the film drying kinetics and associated BHJ nanomorphology development against those of the champion laboratory devices prepared by spin-coating the BHJ layer by adjusting the process temperature. If the optimization requires the solution concentration to be changed, then it is crucial to maintain the additive-to-solute volume ratio. Emulating the drying kinetics of spin-coating is also shown to help achieve morphological and performance parities. We put this approach to the test and demonstrate printed PTB7:PC71BM polymer solar cells with efficiency of 9% and 6.5% PCEs on glass and flexible PET substrates, respectively. We further demonstrate performance parity for two other popular donor polymer systems exhibiting rigid backbones and absence of a long range crystalline order, achieving a PCE of 9.7%, the highest efficiency reported to date for a blade coated organic solar cell. The rational process transfer illustrated in this study should help the broader and successful adoption of scalable printing methods for these material systems.

Ionic conduction in 70-MeV C5+-ion-irradiated poly(vinylidenefluoride- co-hexafluoropropylene)-based gel polymer electrolytes

International Nuclear Information System (INIS)

Saikia, D.; Kumar, A.; Singh, F.; Avasthi, D.K.; Mishra, N.C.

2005-01-01

In an attempt to increase the Li + -ion diffusivity, poly(vinylidenefluoride-co-hexafluoropropylene)-(propylene carbonate+diethyl carbonate)-lithium perchlorate gel polymer electrolyte system has been irradiated with 70-MeV C 5+ -ion beam of nine different fluences. Swift heavy-ion irradiation shows enhancement in ionic conductivity at lower fluences and decrease in ionic conductivity at higher fluences with respect to unirradiated gel polymer electrolyte films. Maximum room-temperature (303 K) ionic conductivity is found to be 2x10 -2 S/cm after irradiation with a fluence of 10 11 ions/cm 2 . This interesting result could be attributed to the fact that for a particular ion beam with a given energy, a higher fluence provides critical activation energy for cross linking and crystallization to occur, which results in the decrease in ionic conductivity. X-ray-diffraction results show decrease in the degree of crystallinity upon ion irradiation at low fluences (≤10 11 ions/cm 2 ) and increase in crystallinity at higher fluences (>10 11 ions/cm 2 ). Analysis of Fourier-transform infrared spectroscopy results suggests the bond breaking at a fluence of 5x10 9 ions/cm 2 and cross linking at a fluence of 10 12 ions/cm 2 and corroborate conductivity and x-ray-diffraction results. Scanning electron micrographs exhibit increased porosity of the polymer electrolyte after ion irradiation

The make up of crystalline bedrock - crystalline body and blocks

International Nuclear Information System (INIS)

Huber, M.; Huber, A.

1986-01-01

Statements of a geological nature can be made on the basis of investigations of the bedrock exposed in southern Black Forest and these can, in the form of prognoses, be applied to the crystalline Basement of northern Switzerland. Such statements relate to the average proportions of the main lithological groups at the bedrock surface and the surface area of the granite body. Some of the prognoses can be compared and checked with the results from the deep drilling programme in northern Switzerland. Further, analogical interferences from the situation in the southern Black Forest allow predictions to be made on the anticipated block structure of the crystalline Basement. (author)

Piezoelectric Flexible LCP-PZT Composites for Sensor Applications at Elevated Temperatures

Science.gov (United States)

Tolvanen, Jarkko; Hannu, Jari; Juuti, Jari; Jantunen, Heli

2018-03-01

In this paper fabrication of piezoelectric ceramic-polymer composites is demonstrated via filament extrusion enabling cost-efficient large-scale production of highly bendable pressure sensors feasible for elevated temperatures. These composites are fabricated by utilizing environmentally resistant and stable liquid crystal polymer matrix with addition of lead zirconate titanate at loading levels of 30 vol%. These composites, of approximately 0.99 mm thick and length of > 50 cm, achieved excellent bendability with minimum bending radius of 6.6 cm. The maximum piezoelectric coefficients d33 and g33 of the composites were > 14 pC/N and > 108 mVm/N at pressure < 10 kPa. In all cases, the piezoelectric charge coefficient (d33) of the composites decreased as a function of pressure. Also, piezoelectric coefficient (d33) further decreased in the case of increased frequency press-release cycle sand pre-stress levels by approximately 37-50%. However, the obtained results provide tools for fabricating novel piezoelectric sensors in highly efficient way for environments with elevated temperatures.

Conductivity of oriented bis-azo polymer films

DEFF Research Database (Denmark)

Apitz, D.; Bertram, R.P.; Benter, N.

2006-01-01

The conductivity properties of electro-optic photoaddressable, dense bis-ozo chromophore polymer films are investigated by using samples corona poled at various temperatures. A dielectric spectrometer is applied to measure the frequency dependence of the conductivity at different temperatures...... before and after heating the material to above the glass transition temperature. The results show that the orientation of the chromophores changes the charge-carrier mobility. Ionic conductivity dominates in a more disordered configuration of the material, while the competing process of hole hopping...... takes over as a transition to a liquid-crystalline phase occurs when the material is heated to much higher than the gloss transition temperature. Such micro-crystallization strongly enhances the conductivity....

Self-assembly of perylenediimide based semiconductor on polymer substrate

Energy Technology Data Exchange (ETDEWEB)

Wiatrowski, Michal, E-mail: Michal.Wiatrowski@p.lodz.p [Department of Molecular Physics, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz (Poland); Dobruchowska, Ewa [Department of Molecular Physics, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz (Poland); Maniukiewicz, Waldemar [Institute of General and Ecological Chemistry, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz (Poland); Pietsch, Ulrich [FB7- Physik , Universitaet Siegen, 57068 Siegen (Germany); Kowalski, Jacek [Division of Non-Metallic Materials, Faculty of Mechanical Engineering, Technical University of Lodz, Stefanowskiego1/15, 90-924 Lodz (Poland); Szamel, Zbigniew; Ulanski, Jacek [Department of Molecular Physics, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz (Poland)

2010-02-01

The continuous bi-layer composites consisting of top, ordered crystalline layer of perylenediimide derivative (2,9-di(pent-3-yl)-anthra[,1,9-def:6,5,10-d'e'f'] diisoquinoline-1,3,8,10-tetrone) - PTCDI-C5(3) and bottom poly(3-hexylthiophene-2,5-diyl) (P3HT) support were obtained from one solution, with a use of so called 'two-step reticulate doping' method. Optical, atomic force and scanning electron microscopy images show that the top crystalline layer is made of relatively large, anisotropic domains composed of long, parallel crystals. The crystalline character of the surface layer of PTCDI-C5(3) grown on the P3HT film was confirmed by wide angle X-ray scattering measurements. Furthermore, the grazing-incidence angle X-ray diffraction experiments revealed that the self-assembly of PTCDI-C5(3) molecules on P3HT is dominated by {pi}-{pi} interaction between the conjugated perylene cores, and the stacks are parallel to the long axis of the crystals and to the polymer surface. The surface conductivity, measured along the long axis of the crystals was estimated to be ca. 2.4 10{sup -8} {Omega}{sup -1} square{sup -}1 at 285 K. Temperature dependence of the conductivity in the range 140-285 K reveal semiconductor-like behaviour with activation energy ca. 150 meV.

The scanning probe microscopy study of thin polymer films

International Nuclear Information System (INIS)

Harron, H.R.

1995-08-01

Scanning Tunnelling Microscopy and Atomic Force Microscopy were used systematically to investigate the morphology, uniformity, coverage and structure of the thin films of several commercially important insulating polymers. Despite the poorly conducting nature of the polymer sample, detailed and convincing images of this class of materials were achieved by STM without the need to coat the samples with a conductive layer. The polymer regions of the sample were further investigated by the use of surface profiling with 'line scans'. The fluctuations of the amplitude therein enabled important film characteristics to be assessed. An environmental stage was designed for the STM to enable the effect of various vapour-sample interactions to be observed during the imaging process. Using the data from the environmental stage in addition to the surface profiling with line scans, an insight into the conduction mechanism and image interpretation was gained. Results suggest that the water content of the sample and its immediate surroundings is an important factor in achieving reliable STM images in air. The initial study culminated with the observation by STM alone of the plasticizer induced crystallization of uncoated PC thin films. The 'amorphous' PC films were observed before crystallization and small ordered regions in roughly the same proportion as that predicted by diffraction studies [Prietschk, 1959 and Schnell, 1964] were imaged. This has never been observed by a microscopy technique. Furthermore, images of the crystalline film contained elongated units that were attributed to the lamellae formations that form the basic building blocks of polymer spherulites. The study continued with the AFM imaging of the growth of crystalline entities in a PC film, without the need for harsh sample treatment or metal coating. A method of casting and crystallizing the films was developed such that the growth was predominantly in two dimensions and consequently ideal for observation by

The quest for crystalline ion beams

CERN Document Server

Schramm, U; Bussmann, M; Habs, D

2002-01-01

The phase transition of an ion beam into its crystalline state has long been expected to dramatically influence beam dynamics beyond the limitations of standard accelerator physics. Yet, although considerable improvement in beam cooling techniques has been made, strong heating mechanisms inherent to existing high-energy storage rings have prohibited the formation of the crystalline state in these machines up to now. Only recently, laser cooling of low-energy beams in the table-top rf quadrupole storage ring PAaul Laser cooLing Acceleration System (PALLAS) has lead to the experimental realization of crystalline beams. In this article, the quest for crystalline beams as well as their unique properties as experienced in PALLAS will be reviewed.

Differential scanning calorimetry (DSC) of semicrystalline polymers.

Science.gov (United States)

Schick, C

2009-11-01

Differential scanning calorimetry (DSC) is an effective analytical tool to characterize the physical properties of a polymer. DSC enables determination of melting, crystallization, and mesomorphic transition temperatures, and the corresponding enthalpy and entropy changes, and characterization of glass transition and other effects that show either changes in heat capacity or a latent heat. Calorimetry takes a special place among other methods. In addition to its simplicity and universality, the energy characteristics (heat capacity C(P) and its integral over temperature T--enthalpy H), measured via calorimetry, have a clear physical meaning even though sometimes interpretation may be difficult. With introduction of differential scanning calorimeters (DSC) in the early 1960s calorimetry became a standard tool in polymer science. The advantage of DSC compared with other calorimetric techniques lies in the broad dynamic range regarding heating and cooling rates, including isothermal and temperature-modulated operation. Today 12 orders of magnitude in scanning rate can be covered by combining different types of DSCs. Rates as low as 1 microK s(-1) are possible and at the other extreme heating and cooling at 1 MK s(-1) and higher is possible. The broad dynamic range is especially of interest for semicrystalline polymers because they are commonly far from equilibrium and phase transitions are strongly time (rate) dependent. Nevertheless, there are still several unsolved problems regarding calorimetry of polymers. I try to address a few of these, for example determination of baseline heat capacity, which is related to the problem of crystallinity determination by DSC, or the occurrence of multiple melting peaks. Possible solutions by using advanced calorimetric techniques, for example fast scanning and high frequency AC (temperature-modulated) calorimetry are discussed.

Hierarchical self-assembly, coassembly, and self-organization of novel liquid crystalline lattices and superlattices from a twin-tapered dendritic benzamide and its four-cylinder-bundle supramolecular polymer.

Science.gov (United States)

Percec, Virgil; Bera, Tushar K; Glodde, Martin; Fu, Qiongying; Balagurusamy, Venkatachalapathy S K; Heiney, Paul A

2003-02-17

The synthesis and structural analysis of the twin-dendritic benzamide 10, based on the first-generation, self-assembling, tapered dendrons 3,4,5-tris(4'-dodecyloxybenzyloxy)benzoic acid and 3,4,5-tris(4'-dodecyloxybenzyloxy)-1-aminobenzene, and the polymethacrylate, 20, which contains 10 as side groups, are presented. Benzamide 10 self-assembles into a supramolecular cylindrical dendrimer that self-organizes into a columnar hexagonal (Phi(h)) liquid crystalline (LC) phase. Polymer 20 self-assembles into an imperfect four-cylinder-bundle supramolecular dendrimer, and creates a giant vesicular supercylinder that self-organizes into a columnar nematic (N(c)) LC phase which displays short-range hexagonal order. In mixtures of 20 and 10, 10 acts as a guest and 20 as a host to create a perfect four-cylinder-bundle host-guest supramolecular dendrimer that coorganizes with 10. A diversity of Phi(h), simple rectangular columnar (Phi(r-s)) and centered rectangular columnar (Phi(r-c)), superlattices are produced at different ratios between 20 and 10. This diversity of LC lattices and superlattices is facilitated by the architecture of the twin-dendritic building block, polymethacrylate, the host-guest supramolecular assembly, and by hydrogen bonding along the center of the supramolecular cylinders generated from 10 and 20.

Miscibility Studies on Polymer Blends Modified with Phytochemicals

Science.gov (United States)

Chandrasekaran, Neelakandan; Kyu, Thein

2009-03-01

The miscibility studies related to an amorphous poly(amide)/poly(vinyl pyrrolidone) [PA/PVP] blend with a crystalline phytochemical called ``Mangiferin'' is presented. Phytochemicals are plant derived chemicals which intrinsically possess multiple salubrious properties that are associated with prevention of diseases such as cancer, diabetes, cardiovascular disease, and hypertension. Incorporation of phytochemicals into polymers has shown to have very promising applications in wound healing, drug delivery, etc. The morphology of these materials is crucial to applications like hemodialysis, which is governed by thermodynamics and kinetics of the phase separation process. Hence, miscibility studies of PA/PVP blends with and without mangiferin have been carried out using dimethyl sulfoxide as a common solvent. Differential scanning calorimetry studies revealed that the binary PA/PVP blends were completely miscible at all compositions. However, the addition of mangiferin has led to liquid-liquid phase separation and liquid-solid phase transition in a composition dependent manner. Fourier transformed infrared spectroscopy was undertaken to determine specific interaction between the polymer constituents and the role of possible hydrogen bonding among three constituents will be discussed.

Liquid crystalline dihydroazulene photoswitches

DEFF Research Database (Denmark)

Petersen, Anne Ugleholdt; Jevric, Martyn; Mandle, Richard J.

2015-01-01

A large selection of photochromic dihydroazulene (DHA) molecules incorporating various substituents at position 2 of the DHA core was prepared and investigated for their ability to form liquid crystalline phases. Incorporation of an octyloxy-substituted biphenyl substituent resulted in nematic...... phase behavior and it was possible to convert one such compound partly into its vinylheptafulvene (VHF) isomer upon irradiation with light when in the liquid crystalline phase. This conversion resulted in an increase in the molecular alignment of the phase. In time, the meta-stable VHF returns...... to the DHA where the alignment is maintained. The systematic structural variation has revealed that a biaryl spacer between the DHA and the alkyl chain is needed for liquid crystallinity and that the one aromatic ring in the spacer cannot be substituted by a triazole. This work presents an important step...

Structural Studies of dielectric HDPE+ZrO2 polymer nanocomposites: filler concentration dependences

Science.gov (United States)

Nabiyev, A. A.; Islamov, A. Kh; Maharramov, A. M.; Nuriyev, M. A.; Ismayilova, R. S.; Doroshkevic, A. S.; Pawlukojc, A.; Turchenko, V. A.; Olejniczak, A.; Rulev, M. İ.; Almasan, V.; Kuklin, A. I.

2018-03-01

Structural properties of HDPE+ZrO2 polymer nanocomposites thin films of 80-100μm thicknesses were investigated using SANS, XRD, Laser Raman and FTIR spectroscopy. The mass fraction of the filler was 1, 3, 10, and 20%. Results of XRD analysis showed that ZrO2 powder was crystallized both in monoclinic and in cubic phase under normal conditions. The percentages of monoclinic and cubic phase were found to be 99.8% and 0.2%, respectively. It was found that ZrO2 nanoparticles did not affect the main crystal and chemical structure of HDPE, but the degree of crystallinity of the polymer decreases with increasing concentration of zirconium oxide. SANS experiments showed that at ambient conditions ZrO2 nanoparticles mainly distributed like mono-particles in the polymer matrix at all concentrations of filler.The structure of HDPE+ZrO2 does not changes up to 132°C at 1-3% of filler, excepting changing of the polymer structure at temperatures upper 82°C. At high concentrations of filler 10-20% the aggregation of ZrO2 nanoparticles occurs, forming domains of 2.5μm. The results of Raman and FTIR spectroscopy did not show additional specific chemical bonds between the filler and the polymer matrix. New peaks formation was not observed. These results suggest that core-shell structure does not exist in the polymer nanocomposite system.

Coupled effects of director orientations and boundary conditions on light induced bending of monodomain nematic liquid crystalline polymer plates

International Nuclear Information System (INIS)

You, Yue; Ding, Shurong; Huo, Yongzhong; Xu, Changwei

2012-01-01

A photo-chromic liquid crystal polymers (LCPs) is a smart material for large light-activated variation or bending to transfer luminous energy into mechanical energy. We study the light induced behavior by modeling planar and homeotropic nematic network polymer plates. We effectively illustrate some reported experimental outcomes and theoretically predict some possible bending patterns. This paper constructs an understanding between the bending behaviors and interactions among the alignments, aspect ratios and boundary conditions, etc. Our work provides information on optimizing light induced bending in the process of micro-opto-mechanical system (MOMS) design. (paper)

Cross-Linked Solid Polymer Electrolyte for All-Solid-State Rechargeable Lithium Batteries

International Nuclear Information System (INIS)

Ben youcef, Hicham; Garcia-Calvo, Oihane; Lago, Nerea; Devaraj, Shanmukaraj; Armand, Michel

2016-01-01

Semi-interpenetrated network Solid Polymer Electrolytes (SPEs) were fabricated by UV-induced cross-linking of poly(ethyleneglycol) diacrylate (PEGDA) and divinylbenzene (DVB) within a poly(ethyleneoxide) (PEO) matrix (M v = 5 × 10 6 g mol −1 ), comprising lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI), at a molar ratio of EO:Li ∼ 30:1. The influence of the DVB content on the final SPE properties was investigated in detail. An increase of DVB concentration resulted in self-standing polymer electrolytes. The DVB cross-linker incorporation was found to decrease the crystallinity of the PEO matrix from 34% to 23%, with a decrease in the melting temperature (T m ) of the membrane from 50 °C to 34 °C. Moreover, the influence of the DVB concentration on the ionic conductivity was determined for polymer electrolytes with 0, 10, 20 and 45% DVB from room temperature (RT) to 80 °C. The resulting SPEs showed a high electrochemical stability of 4.3 V as well as practical conductivity values exceeding 10 −4 S cm −1 at 70 °C. Cycling performance of these semi-interpenetrated SPE’s have been shown with a Li metal polymer battery and all solid -state Li sulphur battery.

Thermally Stable Bulk Heterojunction Prepared by Sequential Deposition of Nanostructured Polymer and Fullerene

Directory of Open Access Journals (Sweden)

Heewon Hwang

2017-09-01

Full Text Available A morphologically-stable polymer/fullerene heterojunction has been prepared by minimizing the intermixing between polymer and fullerene via sequential deposition (SqD of a polymer and a fullerene solution. A low crystalline conjugated polymer of PCPDTBT (poly[2,6-(4,4-bis-(2-ethylhexyl-4H-cyclopenta [2,1-b;3,4-b′]dithiophene-alt-4,7(2,1,3-benzothiadiazole] has been utilized for the polymer layer and PC71BM (phenyl-C71-butyric-acid-methyl ester for the fullerene layer, respectively. Firstly, a nanostructured PCPDTBT bottom layer was developed by utilizing various additives to increase the surface area of the polymer film. The PC71BM solution was prepared by dissolving it in the 1,2-dichloroethane (DCE, exhibiting a lower vapor pressure and slower diffusion into the polymer layer. The deposition of the PC71BM solution on the nanostructured PCPDTBT layer forms an inter-digitated bulk heterojunction (ID-BHJ with minimized intermixing. The organic photovoltaic (OPV device utilizing the ID-BHJ photoactive layer exhibits a highly reproducible solar cell performance. In spite of restricted intermixing between the PC71BM and the PCPDTBT, the efficiency of ID-BHJ OPVs (3.36% is comparable to that of OPVs (3.87% prepared by the conventional method (deposition of a blended solution of polymer:fullerene. The thermal stability of the ID-BHJ is superior to the bulk heterojunction (BHJ prepared by the conventional method. The ID-BHJ OPV maintains 70% of its initial efficiency after thermal stress application for twelve days at 80 °C, whereas the conventional BHJ OPV maintains only 40% of its initial efficiency.

Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

Energy Technology Data Exchange (ETDEWEB)

Nazir, Khuzaimah; Aziz, Ahmad Fairoz [Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor (Malaysia); Adam, Nurul Ilham [Faculty of Applied Sciences, Universiti Teknologi MARA, KampusTapah, 35400 Tapah Road, Tapah, Perak (Malaysia); Yahya, Muhd Zu Azhan [Faculty of Defence Sciences and Technology, Universiti Pertahanan Nasional Malaysia, Kem Sungai Besi, 57000 Kuala Lumpur (Malaysia); Ali, Ab Malik Marwan [Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Selangor (Malaysia)

2015-08-28

Epoxidized 30% poly(methyl methacrylate)-grafted natural rubber (EMG 30) as a polymer host in solid polymer electrolytes (SPEs) has been investigated. EMG30 was synthesized via performicepoxidation method onto 30% poly(methyl methacrylate)-grafted natural rubber (MG30) and the formations of epoxy group were discussed. The EMG30 were characterized by proton nuclear magnetic resonance ({sup 1}HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in {sup 1}HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF{sub 3}SO{sub 3} show the highest conductivity. The complexation between EMG30 and LiCF{sub 3}SO{sub 3} were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR)

Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

International Nuclear Information System (INIS)

Nazir, Khuzaimah; Aziz, Ahmad Fairoz; Adam, Nurul Ilham; Yahya, Muhd Zu Azhan; Ali, Ab Malik Marwan

2015-01-01

Epoxidized 30% poly(methyl methacrylate)-grafted natural rubber (EMG 30) as a polymer host in solid polymer electrolytes (SPEs) has been investigated. EMG30 was synthesized via performicepoxidation method onto 30% poly(methyl methacrylate)-grafted natural rubber (MG30) and the formations of epoxy group were discussed. The EMG30 were characterized by proton nuclear magnetic resonance ( 1 HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in 1 HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF 3 SO 3 show the highest conductivity. The complexation between EMG30 and LiCF 3 SO 3 were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR)

Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

Science.gov (United States)

Nazir, Khuzaimah; Aziz, Ahmad Fairoz; Adam, Nurul Ilham; Yahya, Muhd Zu Azhan; Ali, Ab Malik Marwan

2015-08-01

Epoxidized 30% poly(methyl methacrylate)-grafted natural rubber (EMG 30) as a polymer host in solid polymer electrolytes (SPEs) has been investigated. EMG30 was synthesized via performicepoxidation method onto 30% poly(methyl methacrylate)-grafted natural rubber (MG30) and the formations of epoxy group were discussed. The EMG30 were characterized by proton nuclear magnetic resonance (1HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in 1HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF3SO3 show the highest conductivity. The complexation between EMG30 and LiCF3SO3 were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR).

SULFUR POLYMER ENCAPSULATION

International Nuclear Information System (INIS)

KALB, P.

2001-01-01

Sulfur polymer cement (SPC) is a thermoplastic polymer consisting of 95 wt% elemental sulfur and 5 wt% organic modifiers to enhance long-term durability. SPC was originally developed by the U.S. Bureau of Mines as an alternative to hydraulic cement for construction applications. Previous attempts to use elemental sulfur as a construction material in the chemical industry failed due to premature degradation. These failures were caused by the internal stresses that result from changes in crystalline structure upon cooling of the material. By reacting elemental sulfur with organic polymers, the Bureau of Mines developed a product that successfully suppresses the solid phase transition and significantly improves the stability of the product. SPC, originally named modified sulfur cement, is produced from readily available, inexpensive waste sulfur derived from desulfurization of both flue gases and petroleum. The commercial production of SPC is licensed in the United States by Martin Resources (Odessa, Texas) and is marketed under the trade name Chement 2000. It is sold in granular form and is relatively inexpensive ((approx)$0.10 to 0.12/lb). Application of SPC for the treatment of radioactive, hazardous, and mixed wastes was initially developed and patented by Brookhaven National Laboratory (BNL) in the mid-1980s (Kalb and Colombo, 1985; Colombo et al., 1997). The process was subsequently investigated by the Commission of the European Communities (Van Dalen and Rijpkema, 1989), Idaho National Engineering Laboratory (Darnell, 1991), and Oak Ridge National Laboratory (Mattus and Mattus, 1994). SPC has been used primarily in microencapsulation applications but can also be used for macroencapsulation of waste. SPC microencapsulation has been demonstrated to be an effective treatment for a wide variety of wastes, including incinerator hearth and fly ash; aqueous concentrates such as sulfates, borates, and chlorides; blowdown solutions; soils; and sludges. It is not

Effects of thermal ageing on HMS-PP crystallinity

International Nuclear Information System (INIS)

Oliani, Washington L.; Parra, Duclerc F.; Lima, Luis F.C.P.; Lugao, Ademar B.

2009-01-01

The isotactic polypropylene is a linear polymer which exhibits low melt strength. Irradiation of PP under inert atmosphere causes a combination of chain scissioning and long-chain branching, and results in a material with significant enhanced melt strength. This process, which is sometimes termed visbreaking, thus provides improvement of rheological properties. HMS-PP (High Melt Strength Polypropylene) was obtained by the irradiation in atmosphere of acetylene as crosslinker agent. It was employed doses of 12.5 and 20 kGy of gamma radiation. The objective of this study is to investigate the effects of thermal ageing on the crystallinity level and chemical structure of HMS-PP. The thermal stability of the HMS-PP was evaluated after thermal ageing of samples using a stove at temperature of 90 deg C, in presence of air at different periods of time. The samples submitted to the thermal ageing were characterized by: thermogravimetry (TGA), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Since the long-term engineering properties of HMS-PP are intrinsically linked with the polymer microstructure, there is significant interest in understanding the effects of ageing, particularly due to prolonged exposure at service temperatures. In thermo-oxidative conditions, the formation of the oxidation products essentially involves a hydrogen abstraction by the peroxyl radicals, leading to hydroperoxides as primary products and chemical degradation in the immediate crack tips. Oxidative degradation on the network of HMS-PP, created by radiation process of PP, was revealed by the analytical results showing the susceptibility of HMS-PP to thermal oxidative degradation. Yellowing of the samples surface and oxidative products of degradation among other evidences were observed. (author)

Thermodynamics of Crystalline States

CERN Document Server

Fujimoto, Minoru

2010-01-01

Thermodynamics is a well-established discipline of physics for properties of matter in thermal equilibrium surroundings. Applying to crystals, however, the laws encounter undefined properties of crystal lattices, which therefore need to be determined for a clear and well-defined description of crystalline states. Thermodynamics of Crystalline States explores the roles played by order variables and dynamic lattices in crystals in a wholly new way. This book is divided into three parts. The book begins by clarifying basic concepts for stable crystals. Next, binary phase transitions are discussed to study collective motion of order variables, as described mostly as classical phenomena. In the third part, the multi-electron system is discussed theoretically, as a quantum-mechanical example, for the superconducting state in metallic crystals. Throughout the book, the role played by the lattice is emphasized and examined in-depth. Thermodynamics of Crystalline States is an introductory treatise and textbook on meso...