Breakdown of the Stokes-Einstein Relation for the Rotational Diffusivity of Polymer Grafted Nanoparticles in Polymer Melts.

Science.gov (United States)

Maldonado-Camargo, Lorena; Rinaldi, Carlos

2016-11-09

We report observations of breakdown of the Stokes-Einstein relation for the rotational diffusivity of polymer-grafted spherical nanoparticles in polymer melts. The rotational diffusivity of magnetic nanoparticles coated with poly(ethylene glycol) dispersed in poly(ethylene glycol) melts was determined through dynamic magnetic susceptibility measurements of the collective rotation of the magnetic nanoparticles due to imposed time-varying magnetic torques. These measurements clearly demonstrate the existence of a critical molecular weight for the melt polymer, below which the Stokes-Einstein relation accurately describes the rotational diffusivity of the polymer-grafted nanoparticles and above which the Stokes-Einstein relation ceases to apply. This critical molecular weight was found to correspond to a chain contour length that approximates the hydrodynamic diameter of the nanoparticles.

Infrared laser-induced chaos and conformational disorder in a model polymer crystal: Melting vs ablation

International Nuclear Information System (INIS)

Sumpter, B.G.; Noid, D.W.; Voth, G.A.; Wunderlich, B.

1990-01-01

Molecular dynamics-based computer simulations are presented for the interaction of one and two infrared (IR) laser beams with a model polymer surface. When a single laser beam system is studied over a wide range of intensities, only melting of the polymer, or melting followed by bond dissociation, is observed for up to 100 picoseconds. In contrast, the two-laser simulation results exhibit a marked difference in the energy absorption behavior of the irradiated polymer which, in turn, results in multiple bond dissociations. The results for the one- and two-laser cases studied can be divided into four different classes of physical behavior: (a) the polymer remains in the solid state; (b) the polymer crystal melts; (c) the polymer ablates, but with significant melting (charring); or (d) the polymer ablates with minimal melting. Damage to the model polymer crystal from absorption of energy from either one or two lasers occurs through a mechanism that involves the competition between the absorption of energy and internal energy redistribution. The rate of energy loss from the absorption site(s) relative to the rate of absorption of energy from the radiation field determines rather the polymer melts or ablates (low absorption rates lead to melting or no change and high rates lead to ablation). A sufficiently large rate of energy absorption is only obtainable through the use of two lasers. Two lasers also significantly decrease the total laser intensity required to cause polymer crystal melting. The differences between the one- and two-laser cases are studied by adapting novel signal/subspace techniques to analyze the dynamical changes in the mode spectrum of the polymer as it melts

On the burst of branched polymer melts during inflation

DEFF Research Database (Denmark)

Rasmussen, Henrik K.; Yu, Kaijia

2008-01-01

Two molten low-density polyethylene melts, shaped as plates, have been inflated into a circular cylinder during isothermal conditions. Lowering the inflation rates allow the plates to be inflated into a larger volume of the cylinder before bursting. Numerical simulations of the inflations have been...

Investigation of Thermal and Viscoelastic Properties of Polymers Relevant to Hot Melt Extrusion, IV: Affinisol™ HPMC HME Polymers.

Science.gov (United States)

Gupta, Simerdeep Singh; Solanki, Nayan; Serajuddin, Abu T M

2016-02-01

Most cellulosic polymers cannot be used as carriers for preparing solid dispersion of drugs by hot melt extrusion (HME) due to their high melt viscosity and thermal degradation at high processing temperatures. Three HME-grade hydroxypropyl methylcelluloses, namely Affinisol™ HPMC HME 15 cP, Affinisol™ HPMC HME 100 cP, and Affinisol™ HPMC HME 4 M, have recently been introduced by The Dow Chemical Co. to enable the preparation of solid dispersion at lower and more acceptable processing temperatures. In the present investigation, physicochemical properties of the new polymers relevant to HME were determined and compared with that of Kollidon(®) VA 64. Powder X-ray diffraction (PXRD), modulated differential scanning calorimetry (mDSC), thermogravimetric analysis (TGA), moisture sorption, rheology, and torque analysis by melt extrusion were applied. PXRD and mDSC showed that the Affinisol™ polymers were amorphous in nature. According to TGA, the onset of degradation for all polymers was >220°C. The Affinisol™ polymers exhibited less hygroscopicity than Kollidon(®) VA 64 and another HPMC polymer, Methocel™ K100LV. The complex viscosity profiles of the Affinisol™ polymers as a function of temperature were similar. The viscosity of the Affinisol™ polymers was highly sensitive to the shear rate applied, and unlike Kollidon(®) VA 64, the viscosity decreased drastically when the angular frequency was increased. Because of the very high shear rate encountered during melt extrusion, Affinisol™ polymers showed capability of being extruded at larger windows of processing temperatures as compared to that of Kollidon(®) VA 64.

Stress Relaxation in Entangled Polymer Melts

DEFF Research Database (Denmark)

Hou, Ji-Xuan; Svaneborg, Carsten; Everaers, Ralf

2010-01-01

We present an extensive set of simulation results for the stress relaxation in equilibrium and step-strained bead-spring polymer melts. The data allow us to explore the chain dynamics and the shear relaxation modulus, G(t), into the plateau regime for chains with Z=40 entanglements...... and into the terminal relaxation regime for Z=10. Using the known (Rouse) mobility of unentangled chains and the melt entanglement length determined via the primitive path analysis of the microscopic topological state of our systems, we have performed parameter-free tests of several different tube models. We find...

Numerical simulation of viscoelastic layer rearrangement in polymer melts using OpenFOAM®

Energy Technology Data Exchange (ETDEWEB)

Köpplmayr, Thomas, E-mail: tkoepplmayr@gmail.com; Mayrhofer, Elias [Institute of Polymer Extrusion and Compounding, Johannes Kepler University Linz, Altenberger Str. 69, 4040 Linz (Austria)

2015-05-22

In addition to their shear-thinning behavior, polymer melts are characterized by first and second normal stress differences, which cause secondary motions. Polymer coextrusion processes involve viscoelastic two-phase flows that influence layer formation. Using polymer melts with different pigmentation makes visible the layers deformed by second normal stress differences. We used a new solver for the OpenFOAM CFD toolbox which handles viscoelastic two-phase flows. A derivative of the volume-of-fluid (VoF) methodology was employed to describe the interface. Different types of polymer melt, such as polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) were investigated. In a coextrusion process, the less viscous phase usually tends to encapsulate the more viscous one. However, the different viscoelastic properties of the melts also influence interface deformation. The materials were characterized by small-amplitude oscillatory-shear rheometry, and a multimode Giesekus model was used to fit shear viscosity, storage and loss modulus. Our simulations also took interfacial tension into account. Experimental observations and corresponding numerical simulations were found to be in good accordance.

Numerical simulation of viscoelastic layer rearrangement in polymer melts using OpenFOAM®

International Nuclear Information System (INIS)

Köpplmayr, Thomas; Mayrhofer, Elias

2015-01-01

In addition to their shear-thinning behavior, polymer melts are characterized by first and second normal stress differences, which cause secondary motions. Polymer coextrusion processes involve viscoelastic two-phase flows that influence layer formation. Using polymer melts with different pigmentation makes visible the layers deformed by second normal stress differences. We used a new solver for the OpenFOAM CFD toolbox which handles viscoelastic two-phase flows. A derivative of the volume-of-fluid (VoF) methodology was employed to describe the interface. Different types of polymer melt, such as polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) were investigated. In a coextrusion process, the less viscous phase usually tends to encapsulate the more viscous one. However, the different viscoelastic properties of the melts also influence interface deformation. The materials were characterized by small-amplitude oscillatory-shear rheometry, and a multimode Giesekus model was used to fit shear viscosity, storage and loss modulus. Our simulations also took interfacial tension into account. Experimental observations and corresponding numerical simulations were found to be in good accordance

Catastrophic failure of polymer melts during extension

DEFF Research Database (Denmark)

Rasmussen, Henrik K.

2013-01-01

Numerical flow modeling has been applied to study the break of monodisperse polymer melts during extension. These continuum mechanical based computations are within the ideas of the microstructural ’interchain pressure’ theory. Calculated breaks, a result of small initial sample imperfections, ag...

Flow and Failure in Extension of Monodisperse Polymer Melts

DEFF Research Database (Denmark)

Rasmussen, Henrik K.

is commonly referred to be of either brittle (e.g. cohesive type) or of liquid (e.g. necking type) nature. Here the focus will be on monodisperse polymers, to study numerically the sample flow dynamics in dual wind-up extensional rheometers. The computations are within the ideas of the microstructural......It is well known that failure or rupture phenomenon appears in the extension of polymer melts. These appear not only as failure in extension rheometers, but also as sharkskin, developments of holes in thin polymeric films etc. Sometime these ruptures appear spontaneous as well. The rupture...... 'interchain pressure' theory based on the molecular stress function constitutive model for the polymer melt flow. The purpose is twofold. Primarily to present to what extend the experimentally observed failure, appearing during or after (e.g. as a spontaneous failure) extension, can be explained within...

Orientational cross correlations between entangled branch polymers in primitive chain network simulations

Science.gov (United States)

Masubuchi, Yuichi; Pandey, Ankita; Amamoto, Yoshifumi; Uneyama, Takashi

2017-11-01

Although it has not been frequently discussed, contributions of the orientational cross-correlation (OCC) between entangled polymers are not negligible in the relaxation modulus. In the present study, OCC contributions were investigated for 4- and 6-arm star-branched and H-branched polymers by means of multi-chain slip-link simulations. Owing to the molecular-level description of the simulation, the segment orientation was traced separately for each molecule as well as each subchain composing the molecules. Then, the OCC was calculated between different molecules and different subchains. The results revealed that the amount of OCC between different molecules is virtually identical to that of linear polymers regardless of the branching structure. The OCC between constituent subchains of the same molecule is significantly smaller than the OCC between different molecules, although its intensity and time-dependent behavior depend on the branching structure as well as the molecular weight. These results lend support to the single-chain models given that the OCC effects are embedded into the stress-optical coefficient, which is independent of the branching structure.

The effect of branching in a semiconducting polymer on the efficiency of organic photovoltaic cells

NARCIS (Netherlands)

Heintges, G.H.L.; van Franeker, J.J.; Wienk, M.M.; Janssen, R.A.J.

2016-01-01

The impact of branching in a diketopyrrolopyrrole polymer on the performance of polymer–fullerene photovoltaic cells is investigated. Compared to the linear polymer, the branched polymer affords a more finely dispersed fibrillar network in the photoactive layer and as a result a large enhancement of

How mechanical behavior of glassy polymers enables us to characterize melt deformation: elastic yielding in glassy state after melt stretching?

Science.gov (United States)

Wang, Shi-Qing; Zhao, Zhichen; Tsige, Mesfin; Zheng, Yexin

Fast melt deformation well above the glass transition temperature Tg is known to produce elastic stress in an entangled polymer due to the chain entropy loss at the length scale of the network mesh size. Here chains of high molecular weight are assumed to form an entanglement network so that such a polymer behaves transiently like vulcanized rubber capable of affine deformation. We consider quenching a melt-deformed glassy polymer to well below Tg to preserve the elastic stress. Upon heating such a sample to Tg, the sample can return to the shape it took before melt deformation. This is the basic principle behind the design of all polymer-based shape-memory materials. This work presents intriguing evidence based on both experiment and computer simulation that the chain network, deformed well above Tg, can drive the glassy polymer to undergo elastic yielding. Our experimental systems include polystyrene, poly(methyl methacrylate) and polycarbonate; the molecular dynamics simulation is based on Kremer-Grest bead-spring model. National Science Foundation (DMR-1444859 and DMR-1609977).

Synthesis and characterization of a hyper-branched water-soluble β-cyclodextrin polymer

Directory of Open Access Journals (Sweden)

Francesco Trotta

2014-11-01

Full Text Available A new hyper-branched water-soluble polymer was synthesized by reacting β-cyclodextrin with pyromellitic dianhydride beyond the critical conditions that allow the phenomenon of gelation to occur. The molar ratio between the monomers is a crucial parameter that rules the gelation process. Nevertheless, the concentration of monomers in the solvent phase plays a key role as well. Hyper-branched β-cyclodextrin-based polymers were obtained performing the syntheses with excess of solvent and cross-linking agent, and the conditions for critical dilution were determined experimentally. A hyper-branched polymer with very high water solubility was obtained and fully characterized both as for its chemical structure and for its capability to encapsulate substances. Fluorescein was used as probe molecule to test the complexation properties of the new material.

Post polymerization cure shape memory polymers

Energy Technology Data Exchange (ETDEWEB)

Wilson, Thomas S.; Hearon, II, Michael Keith; Bearinger, Jane P.

2017-01-10

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Post polymerization cure shape memory polymers

Science.gov (United States)

Wilson, Thomas S; Hearon, Michael Keith; Bearinger, Jane P

2014-11-11

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

All solid-state polymer electrolytes prepared from a hyper-branched graft polymer using atom transfer radical polymerization

International Nuclear Information System (INIS)

Higa, Mitsuru; Fujino, Yukiko; Koumoto, Taihei; Kitani, Ryousuke; Egashira, Satsuki

2005-01-01

We propose an all solid-state (liquid free) polymer electrolyte (SPE) prepared from a hyper-branched graft copolymer. The graft copolymer consisting of a poly(methyl methacrylate) main chain and poly(ethylene glycol) methyl ether methacrylate side chains was synthesized by atom transfer radical polymerization changing the average chain distance between side chains, side chain length and branched chain length of the proposed structure of the graft copolymer. The ionic conductivity of the SPEs increases with increasing the side chain length, branched chain length and/or average distance between the side chains. The ionic conductivity of the SPE prepared from POEM 9 whose POEM content = 51 wt% shows 2 x 10 -5 S/cm at 30 deg. C. The tensile strength of the SPEs decreases with increases the side chain length, branched chain length and/or average distance between the side chains. These results indicate that a SPE prepared from the hyper-branched graft copolymer has potential to be applied to an all-solid polymer electrolyte

Investigations of model polymers: Dynamics of melts and statics of a long chain in a dilute melt of shorter chains

International Nuclear Information System (INIS)

Bishop, M.; Ceperley, D.; Frisch, H.L.; Kalos, M.H.

1982-01-01

We report additional results on a simple model of polymers, namely the diffusion in concentrated polymer systems and the static properties of one long chain in a dilute melt of shorter chains. It is found, for the polymer sizes and time scales amenable to our computer calculations, that there is as yet no evidence for a ''reptation'' regime in a melt. There is some indication of reptation in the case of a single chain moving through fixed obstacles. No statistically significant effect of the change, from excluded volume behavior of the long chain to ideal behavior as the shorter chains grow, is observed

Influence of Flame Retardants on the Melt Dripping Behaviour of Thermoplastic Polymers

Directory of Open Access Journals (Sweden)

Melissa Matzen

2015-08-01

Full Text Available Melt flow and dripping of the pyrolysing polymer melt can be both a benefit and a detriment during a fire. In several small-scale fire tests addressing the ignition of a defined specimen with a small ignition source, well-adjusted melt flow and dripping are usually beneficial to pass the test. The presence of flame retardants often changes the melt viscosity crucially. The influence of certain flame retardants on the dripping behaviour of four commercial polymers, poly(butylene terephthalate (PBT, polypropylene (PP, polypropylene modified with ethylene-propylene rubber (PP-EP and polyamide 6 (PA 6, is analysed based on an experimental monitoring of the mass loss due to melt dripping, drop size and drop temperature as a function of the furnace temperature applied to a rod-shaped specimen. Investigating the thermal transition (DSC, thermal and thermo-oxidative decomposition, as well as the viscosity of the polymer and collected drops completes the investigation. Different mechanisms of the flame retardants are associated with their influence on the dripping behaviour in the UL 94 test. Reduction in decomposition temperature and changed viscosity play a major role. A flow limit in flame-retarded PBT, enhanced decomposition of flame-retarded PP and PP-EP and the promotion of dripping in PA 6 are the salient features discussed.

Rheology of multiphase polymer systems using novel "melt rigidity" evaluation approach

Science.gov (United States)

Kracalik, Milan

2015-04-01

Multiphase polymer systems like blends, composites and nanocomposites exhibit complex rheological behaviour due to physical and also possibly chemical interactions between individual phases. Up to now, rheology of heterogeneous polymer systems has been usually described by evaluation of viscosity curve (shear thinning phenomenon), storage modulus curve (formation of secondary plateau) or plotting information about damping behaviour (e.g. Van Gurp-Palmen-plot). On the contrary to evaluation of damping behaviour, "melt rigidity" approach has been introduced for description of physical network of rigid particles in polymer matrix as relation of ∫G'/∫G" over specific frequency range. This approach has been experimentally proved for polymer nanocomposites in order to compare shear flow characteristics with elongational flow field. In this contribution, LDPE-clay nanocomposites with different dispersion grades (physical networks) have been prepared and characterized by both conventional as well as novel "melt rigidity" approach.

Integral equation theory study on the phase separation in star polymer nanocomposite melts.

Science.gov (United States)

Zhao, Lei; Li, Yi-Gui; Zhong, Chongli

2007-10-21

The polymer reference interaction site model theory is used to investigate phase separation in star polymer nanocomposite melts. Two kinds of spinodal curves were obtained: classic fluid phase boundary for relatively low nanoparticle-monomer attraction strength and network phase boundary for relatively high nanoparticle-monomer attraction strength. The network phase boundaries are much more sensitive with nanoparticle-monomer attraction strength than the fluid phase boundaries. The interference among the arm number, arm length, and nanoparticle-monomer attraction strength was systematically investigated. When the arm lengths are short, the network phase boundary shows a marked shift toward less miscibility with increasing arm number. When the arm lengths are long enough, the network phase boundaries show opposite trends. There exists a crossover arm number value for star polymer nanocomposite melts, below which the network phase separation is consistent with that of chain polymer nanocomposite melts. However, the network phase separation shows qualitatively different behaviors when the arm number is larger than this value.

Production of micron-sized polymer particles for additive manufacturing by melt emulsification

Energy Technology Data Exchange (ETDEWEB)

Fanselow, Stephanie; Schmidt, Jochen; Wirth, Karl-Ernst; Peukert, Wolfgang, E-mail: Wolfgang.Peukert@fau.de [Institute of Particle Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg, Cauerstrasse 4, 91058 Erlangen (Germany)

2016-03-09

Melt emulsification is an advanced top-down approach that permits to produce spherical particles and thus widens the availability of polymer feed materials for additive manufacturing. In the process the polymer is molten in a continuous phase and droplet breakup is realized in a rotor-stator-device. The stabilization of the newly formed surfaces is quite challenging. Therefore, a new method to identify an appropriate emulsifier by measuring the interfacial tension between the polymer and continuous phase using a high pressure / high temperature cell is presented. The obtained powders are characterized by scanning electron microscopy (SEM) and by a Zimmermann tensile strength tester to determine the powder flowability. The processability of the polymer powders for additive manufacturing is investigated and demonstrated by building single layers by laser beam melting.

Phase separation of comb polymer nanocomposite melts.

Science.gov (United States)

Xu, Qinzhi; Feng, Yancong; Chen, Lan

2016-02-07

In this work, the spinodal phase demixing of branched comb polymer nanocomposite (PNC) melts is systematically investigated using the polymer reference interaction site model (PRISM) theory. To verify the reliability of the present method in characterizing the phase behavior of comb PNCs, the intermolecular correlation functions of the system for nonzero particle volume fractions are compared with our molecular dynamics simulation data. After verifying the model and discussing the structure of the comb PNCs in the dilute nanoparticle limit, the interference among the side chain number, side chain length, nanoparticle-monomer size ratio and attractive interactions between the comb polymer and nanoparticles in spinodal demixing curves is analyzed and discussed in detail. The results predict two kinds of distinct phase separation behaviors. One is called classic fluid phase boundary, which is mediated by the entropic depletion attraction and contact aggregation of nanoparticles at relatively low nanoparticle-monomer attraction strength. The second demixing transition occurs at relatively high attraction strength and involves the formation of an equilibrium physical network phase with local bridging of nanoparticles. The phase boundaries are found to be sensitive to the side chain number, side chain length, nanoparticle-monomer size ratio and attractive interactions. As the side chain length is fixed, the side chain number has a large effect on the phase behavior of comb PNCs; with increasing side chain number, the miscibility window first widens and then shrinks. When the side chain number is lower than a threshold value, the phase boundaries undergo a process from enlarging the miscibility window to narrowing as side chain length increases. Once the side chain number overtakes this threshold value, the phase boundary shifts towards less miscibility. With increasing nanoparticle-monomer size ratio, a crossover of particle size occurs, above which the phase separation

The Considere condition and rapid stretching of linear and branched polymer melts

DEFF Research Database (Denmark)

McKinley, Gareth H; Hassager, Ole

1999-01-01

to larger Hencky strains as the number of branches is increased. Numerical computations at finite Deborah numbers also show that there is an optimal range of deformation rates over which homogeneous extensions can be maintained to large strain. We also consider other rapid homogeneous stretching...... deformations, such as biaxial and planar stretching, and show that the degree of stabilization afforded by inclusion of material with long-chain branching is a sensitive function of the imposed mode of deformation....

Large Core Three Branch Polymer Power Splitters

Directory of Open Access Journals (Sweden)

V. Prajzler

2015-12-01

Full Text Available We report about three branch large core polymer power splitters optimized for connecting standard plastic optical fibers. A new point of the design is insertion of a rectangle-shaped spacing between the input and the central part of the splitter, which will ensure more even distribution of the output optical power. The splitters were designed by beam propagation method using BeamPROP software. Acrylic-based polymers were used as optical waveguides being poured into the Y-grooves realized by computer numerical controlled engraving on poly(methyl methacrylate substrate. Measurement of the optical insertion losses proved that the insertion optical loss could be lowered to 2.1 dB at 650 nm and optical power coupling ratio could reach 31.8% : 37.3% : 30.9%.

Molecular dynamics simulation study of nonconcatenated ring polymers in a melt. II. Dynamics

Science.gov (United States)

Halverson, Jonathan D.; Lee, Won Bo; Grest, Gary S.; Grosberg, Alexander Y.; Kremer, Kurt

2011-05-01

Molecular dynamics simulations were conducted to investigate the dynamic properties of melts of nonconcatenated ring polymers and compared to melts of linear polymers. The longest rings were composed of N = 1600 monomers per chain which corresponds to roughly 57 entanglement lengths for comparable linear polymers. The ring melts were found to diffuse faster than their linear counterparts, with both architectures approximately obeying a D ˜ N-2.4 scaling law for large N. The mean-square displacement of the center-of-mass of the rings follows a sub-diffusive behavior for times and distances beyond the ring extension , neither compatible with the Rouse nor the reptation model. The rings relax stress much faster than linear polymers, and the zero-shear viscosity was found to vary as η0 ˜ N1.4 ± 0.2 which is much weaker than the N3.4 behavior of linear chains, not matching any commonly known model for polymer dynamics when compared to the observed mean-square displacements. These findings are discussed in view of the conformational properties of the rings presented in the preceding paper [J. D. Halverson, W. Lee, G. S. Grest, A. Y. Grosberg, and K. Kremer, J. Chem. Phys. 134, 204904 (2011)], 10.1063/1.3587137.

Thermodynamics and local structure of vinyl polymer melts

International Nuclear Information System (INIS)

Yethiraj, A.; Curro, J.G.; Rajasekaran, J.J.

1995-01-01

Monte Carlo simulation results are reported for the site-site pair correlations and equation of state of model vinyl polymer melts. The molecules are freely jointed hard chains with a hard sphere side-group attached to every other backbone bead. The local structure and pressure are investigated as a function of the diameter of the side group for melt-like densities. The intramolecular correlation functions are well represented by a single chain model where excluded volume interactions are included for beads separated by four bonds or less and neglected otherwise. The intermolecular correlation functions show interesting packing effects. The side group shields the backbone beads from approaching each other, to a degree that increases with increasing diameter of the side group. The polymer reference interaction site model integral equation theory is in good agreement with the simulation results for the pair correlation functions. At fixed volume fraction, the pressure is found to be a non-monotonic function of the size of the side group. copyright 1995 American Institute of Physics

Ampicillin-Ester Bonded Branched Polymers: Characterization, Cyto-, Genotoxicity and Controlled Drug-Release Behaviour

Directory of Open Access Journals (Sweden)

Ewa Oledzka

2014-06-01

Full Text Available The development and characterization of novel macromolecular conjugates of ampicillin using branched biodegradable polymers has been described in this study. The conjugates have been prepared coupling the β-lactam antibiotic with branched polymer matrices based on the natural oligopeptide core. The cyto- and genotoxicity of the synthesized polymers were evaluated with a bacterial luminescence test, two protozoan assays and Salmonella typhimurium TA1535. The presence of a newly formed covalent bond between the drug and the polymer matrices was confirmed by 1H-NMR and FTIR studies. A drug content (15.6 and 10.2 mole % in the macromolecular conjugates has been determined. The obtained macromolecular products have been subjected to further in vitro release studies. The total percentage of ampicillin released after 21 days of incubation was nearly 60% and 14% and this resulted from the different physicochemical properties of the polymeric matrices. This is the first report on the application of branched biodegradable polymeric matrices for the covalent conjugation of ampicillin. The obtained results showed that the synthesized macromolecular drug-conjugates might slowly release the active drug molecule and improve the pharmacokinetics of ampicillin.

Melt dispersion of thermoplastic polystyrene in polymer polyols

NARCIS (Netherlands)

2009-01-01

Polystyrene is dispersed into a polyol via a mechanical dispersion process. A stabilizer is present to stabilize the dispersed polymer particles. The stabilizer includes a copolymer of (1) from 10 to 70% by weight of a branched polyol which has a molecular weight of from 4000 to 20,000, from 0.2 to

A control scheme for filament stretching rheometers with application to polymer melts

DEFF Research Database (Denmark)

Román Marín, José Manuel; Huusom, Jakob Kjøbsted; Javier Alvarez, Nicolas

2013-01-01

We propose a new control scheme to maintain a constant strain rate of the mid-filament diameter in a filament stretching rheometer for polymer melts. The scheme is cast as a velocity algorithm and consists of a feed-back and a feed-forward contribution. The performance of the controller is demons......We propose a new control scheme to maintain a constant strain rate of the mid-filament diameter in a filament stretching rheometer for polymer melts. The scheme is cast as a velocity algorithm and consists of a feed-back and a feed-forward contribution. The performance of the controller...

Modeling of the branching influence on liquid–liquid equilibrium of binary and ternary polymer solutions by lattice–cluster theory

International Nuclear Information System (INIS)

Browarzik, Dieter; Langenbach, Kai; Enders, Sabine; Browarzik, Christina

2013-01-01

Highlights: ► Liquid–liquid equilibrium (LLE) is calculated with the lattice–cluster theory (LCT). ► Equations of the LCT are reduced to only three geometrical parameters. ► Branching influence on the LLE is modeled for binary and ternary polymer solutions. ► Branched and linear solvents and polymers are compared in their influence on LLE. ► Solutions of branched polymers in branched solvents show the best miscibility. -- Abstract: The liquid–liquid equilibrium (LLE) of ternary model systems of the type solvent A + polymer B + solvent C is treated in the framework of lattice–cluster theory (LCT). There are a linear and a branched type of A-molecules as well as a linear and two types of strongly branched polymer molecules. The C-molecules are assumed to occupy only one lattice site. For nine binary and six ternary polymer solutions the branching influence on LLE is discussed. Currently, the LCT is the most useful model to take the architecture of the molecules into account. However, particularly for ternary systems the model is not comfortable because of the very numerous terms of the Gibbs energy. Using some relationships between the geometrical parameters of the model a considerable simplification is possible. In this paper the new and simpler equations of the LCT are presented. For comparison with experimental data critical temperatures of solutions of linear and branched polyethylene samples in diphenyl ether are calculated

Crossover to entangled dynamics in polymer solutions and melts

International Nuclear Information System (INIS)

Schweizer, K.S.; Szamel, G.

1995-01-01

A statistical dynamical theory of the crossover from unentangled Rouse dynamics to entangled behavior is constructed for chain polymer solutions and melts. Both time and spatial crossovers in long chain fluids, and the degree of polymerization crossover for short polymers, are treated. The analysis is based on a microscopic theory of the perturbative dynamical corrections to Rouse theory arising from chain connectivity and intermolecular excluded volume forces. The dependence of crossover properties such as the plateau shear modulus and entanglement time and length scale on solution density, solvent quality, and chain statistical segment length are derived by combining the dynamical theory with equilibrium liquid state integral equation methods. Scaling relations are obtained which appear to be in general accord with most experiments on both solutions and melts. The physical origin of the predicted scaling behaviors is the fractional power law temporal decay of the entanglement friction memory function on intermediate time scales, and power law reduced density dependence of the equilibrium force correlations. The theory is also applied to compute the dependence of the chain normal mode relaxation times on polymer density and chain length. Favorable qualitative comparisons with recent neutron spin echo experiments are made. copyright 1995 American Institute of Physics

Conditional Monte Carlo sampling to find branching architectures of polymers from radical polymerizations with transfer to polymer and recombination termination

NARCIS (Netherlands)

Iedema, P.D.; Wulkow, M.; Hoefsloot, H.C.J.

2007-01-01

A model is developed that predicts branching architectures of polymers from radical polymerization with transfer to polymer and termination by disproportionation and recombination, in a continuously stirred tank reactor (CSTR). It is a so-called conditional Monte Carlo (MC) method generating

Single-molecule study on polymer diffusion in a melt state: Effect of chain topology

KAUST Repository

Habuchi, Satoshi

2013-08-06

We report a new methodology for studying diffusion of individual polymer chains in a melt state, with special emphasis on the effect of chain topology. A perylene diimide fluorophore was incorporated into the linear and cyclic poly(THF)s, and real-time diffusion behavior of individual chains in a melt of linear poly(THF) was measured by means of a single-molecule fluorescence imaging technique. The combination of mean squared displacement (MSD) and cumulative distribution function (CDF) analysis demonstrated the broad distribution of diffusion coefficient of both the linear and cyclic polymer chains in the melt state. This indicates the presence of spatiotemporal heterogeneity of the polymer diffusion which occurs at much larger time and length scales than those expected from the current polymer physics theory. We further demonstrated that the cyclic chains showed marginally slower diffusion in comparison with the linear counterparts, to suggest the effective suppression of the translocation through the threading-entanglement with the linear matrix chains. This coincides with the higher activation energy for the diffusion of the cyclic chains than of the linear chains. These results suggest that the single-molecule imaging technique provides a powerful tool to analyze complicated polymer dynamics and contributes to the molecular level understanding of the chain interaction. © 2013 American Chemical Society.

Single-molecule study on polymer diffusion in a melt state: Effect of chain topology

KAUST Repository

Habuchi, Satoshi; Fujiwara, Susumu; Yamamoto, Takuya; Vá cha, Martin; Tezuka, Yasuyuki

2013-01-01

We report a new methodology for studying diffusion of individual polymer chains in a melt state, with special emphasis on the effect of chain topology. A perylene diimide fluorophore was incorporated into the linear and cyclic poly(THF)s, and real-time diffusion behavior of individual chains in a melt of linear poly(THF) was measured by means of a single-molecule fluorescence imaging technique. The combination of mean squared displacement (MSD) and cumulative distribution function (CDF) analysis demonstrated the broad distribution of diffusion coefficient of both the linear and cyclic polymer chains in the melt state. This indicates the presence of spatiotemporal heterogeneity of the polymer diffusion which occurs at much larger time and length scales than those expected from the current polymer physics theory. We further demonstrated that the cyclic chains showed marginally slower diffusion in comparison with the linear counterparts, to suggest the effective suppression of the translocation through the threading-entanglement with the linear matrix chains. This coincides with the higher activation energy for the diffusion of the cyclic chains than of the linear chains. These results suggest that the single-molecule imaging technique provides a powerful tool to analyze complicated polymer dynamics and contributes to the molecular level understanding of the chain interaction. © 2013 American Chemical Society.

Non-local viscosity of polymer melts approaching their glassy state

DEFF Research Database (Denmark)

Puscasu, Ruslan; Todd, Billy; Daivis, Peter

2010-01-01

The nonlocal viscosity kernels of polymer melts have been determined by means of equilibrium molecular dynamics upon cooling toward the glass transition. Previous results for the temperature dependence of the self-diffusion coefficient and the value of the glass transition temperature are confirmed...

On the genealogy of branching random walks and of directed polymers

Science.gov (United States)

Derrida, Bernard; Mottishaw, Peter

2016-08-01

It is well known that the mean-field theory of directed polymers in a random medium exhibits replica symmetry breaking with a distribution of overlaps which consists of two delta functions. Here we show that the leading finite-size correction to this distribution of overlaps has a universal character which can be computed explicitly. Our results can also be interpreted as genealogical properties of branching Brownian motion or of branching random walks.

Molecular dynamics simulation study of nonconcatenated ring polymers in a melt. I. Statics

Science.gov (United States)

Halverson, Jonathan D.; Lee, Won Bo; Grest, Gary S.; Grosberg, Alexander Y.; Kremer, Kurt

2011-05-01

Molecular dynamics simulations were conducted to investigate the structural properties of melts of nonconcatenated ring polymers and compared to melts of linear polymers. The longest rings were composed of N = 1600 monomers per chain which corresponds to roughly 57 entanglement lengths for comparable linear polymers. For the rings, the radius of gyration squared, , was found to scale as N4/5 for an intermediate regime and N2/3 for the larger rings indicating an overall conformation of a crumpled globule. However, almost all beads of the rings are "surface beads" interacting with beads of other rings, a result also in agreement with a primitive path analysis performed in the next paper [J. D. Halverson, W. Lee, G. S. Grest, A. Y. Grosberg, and K. Kremer, J. Chem. Phys. 134, 204905 (2011)], 10.1063/1.3587138. Details of the internal conformational properties of the ring and linear polymers as well as their packing are analyzed and compared to current theoretical models.

Alternative polymer separation technology by centrifugal force in a melted state

International Nuclear Information System (INIS)

Dobrovszky, Károly; Ronkay, Ferenc

2014-01-01

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

Alternative polymer separation technology by centrifugal force in a melted state

Energy Technology Data Exchange (ETDEWEB)

Dobrovszky, Károly; Ronkay, Ferenc, E-mail: ronkay@pt.bme.hu

2014-11-15

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

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

Entangled Polymer Melts in Extensional Flow: Synthesis, Rheology, Neutron Scattering

DEFF Research Database (Denmark)

Dorokhin, Andriy

This thesis contains 5 chapters and reprints in Appendices, combined of both published and unpublished materials. The first chapter is an introduction to the goals, methods and problem identification of the project of the entangled polymer melts in extensional flow, which is aimed to shed some li...

Branched-linear and agglomerate protein polymers as vaccine platforms.

Science.gov (United States)

Wang, Leyi; Xia, Ming; Huang, Pengwei; Fang, Hao; Cao, Dianjun; Meng, Xiang-Jin; McNeal, Monica; Jiang, Xi; Tan, Ming

2014-09-01

Many viral structural proteins and their truncated domains share a common feature of homotypic interaction forming dimers, trimers, and/or oligomers with various valences. We reported previously a simple strategy for construction of linear and network polymers through the dimerization feature of viral proteins for vaccine development. In this study, technologies were developed to produce more sophisticated polyvalent complexes through both the dimerization and oligomerization natures of viral antigens. As proof of concept, branched-linear and agglomerate polymers were made via fusions of the dimeric glutathione-s-transferase (GST) with either a tetrameric hepatitis E virus (HEV) protruding protein or a 24-meric norovirus (NoV) protruding protein. Furthermore, a monomeric antigen, either the M2e epitope of influenza A virus or the VP8* antigen of rotavirus, was inserted and displayed by the polymer platform. All resulting polymers were easily produced in Escherichia coli at high yields. Immunization of mice showed that the polymer vaccines induced significantly higher specific humoral and T cell responses than those induced by the dimeric antigens. Additional evidence in supporting use of polymer vaccines included the significantly higher neutralization activity and protective immunity of the polymer vaccines against the corresponding viruses than those of the dimer vaccines. Thus, our technology for production of polymers containing different viral antigens offers a strategy for vaccine development against infectious pathogens and their associated diseases. Copyright © 2014 Elsevier Ltd. All rights reserved.

Small angle neutron scattering form polymer melts: structural investigation and phase behaviour

International Nuclear Information System (INIS)

Ertugrul, O.

2004-01-01

The Small-Angle Neutron Scattering (SANS) techniques have been used to study the structural properties and phase behavior of polymer melts. A model based on Random Phase Approximation (RPA) is proposed to predict the experimental data. By fitting the model to data we could be able to obtain radius of gyration (a measure of size of a polymer) and phase transition for the sample. (author)

Disorder effects on the static scattering function of star branched polymers

Directory of Open Access Journals (Sweden)

V. Blavatska

2012-10-01

Full Text Available We present an analysis of the impact of structural disorder on the static scattering function of f-armed star branched polymers in d dimensions. To this end, we consider the model of a star polymer immersed in a good solvent in the presence of structural defects, correlated at large distances r according to a power law ~r-a. In particular, we are interested in the ratio g(f of the radii of gyration of star and linear polymers of the same molecular weight, which is a universal experimentally measurable quantity. We apply a direct polymer renormalization approach and evaluate the results within the double ϵ = 4 - d, δ = 4 - a-expansion. We find an increase of g(f with an increasing δ. Therefore, an increase of disorder correlations leads to an increase of the size measure of a star relative to linear polymers of the same molecular weight.

Bis(thienothiophenyl) diketopyrrolopyrrole-based conjugated polymers with various branched alkyl side chains and their applications in thin-film transistors and polymer solar cells.

Science.gov (United States)

Shin, Jicheol; Park, Gi Eun; Lee, Dae Hee; Um, Hyun Ah; Lee, Tae Wan; Cho, Min Ju; Choi, Dong Hoon

2015-02-11

New thienothiophene-flanked diketopyrrolopyrrole and thiophene-containing π-extended conjugated polymers with various branched alkyl side-chains were successfully synthesized. 2-Octyldodecyl, 2-decyltetradecyl, 2-tetradecylhexadecyl, 2-hexadecyloctadecyl, and 2-octadecyldocosyl groups were selected as the side-chain moieties and were anchored to the N-positions of the thienothiophene-flanked diketopyrrolopyrrole unit. All five polymers were found to be soluble owing to the bulkiness of the side chains. The thin-film transistor based on the 2-tetradecylhexadecyl-substituted polymer showed the highest hole mobility of 1.92 cm2 V(-1) s(-1) due to it having the smallest π-π stacking distance between the polymer chains, which was determined by grazing incidence X-ray diffraction. Bulk heterojunction polymer solar cells incorporating [6,6]-phenyl-C71-butyric acid methyl ester as the n-type molecule and the additive 1,8-diiodooctane (1 vol %) were also constructed from the synthesized polymers without thermal annealing; the device containing the 2-octyldodecyl-substituted polymer exhibited the highest power conversion efficiency of 5.8%. Although all the polymers showed similar physical properties, their device performance was clearly influenced by the sizes of the branched alkyl side-chain groups.

Viscoelastic characterization of polymer melts with a new membrane inflation rheometer

DEFF Research Database (Denmark)

Rasmussen, Henrik K.; Christensen, Jens Horslund; Gøttsche, Søren

1999-01-01

The constitutive equation of high impact polystyrene (HIPS) has been obtained from experimental measurements of membrane inflation in a cylinder using finite element simulations, based on the 3D Lagrangian Integral Method. The polymer melt rheology of HIPS is modelled as a single integral model...

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

The use of radiation for the production of high melt strength polypropylene

International Nuclear Information System (INIS)

Lugao, A.B.; Cardoso, E.C.L.; Hustzler, B.; Tokumoto, S.; Mendes, A.N.F.

2001-01-01

PP suffers from low melt strength, i.e., the melted PP does not exhibits an increase in resistance to stretching during elongation. It is well known that the melt-strength properties of a polymer increase with molecular weight and with long chain branching due to the increase in the entanglement level (high melt strength PP-HMSPP). In spite of been the most fast growing polymeric commodity nowadays those new grades of PP and its development have been barely studied and its general chemical characterization have been even less studied with few exceptions. HMSPP as proposed by Montell patents are produced by low temperature and low dose irradiation of high molecular weight isotatica PP in N 2 atmosphere. So the well-known reactions would be mostly degradation and crosslinking. Degradation however is supposed to be the first and more intense reaction a the initial steps as already shown. So, according to Montell patents, another reaction is likely to occur, branching or T links competing with crosslinkings or H links. Radical are likely to decay very fast in amorphous phase, but under annealing the radicals entrapped in the crystal phase is likely to move to the boundary and react. The group of professor Silverman has already hypothesized in T links formation and also studied the radical decay of PP. It is easy to understand the difficulties in differentiate Hs from Ts links and even these links if in very small amount from the bulk or from virgin polymer, as the Ts links and even these links if in very small amount from the bulk or from virgin polymer, as the chemical groups and links are chemically speaking essentially the same

Modelling of the isothermal replication of surface microstructures in polymer melts

DEFF Research Database (Denmark)

Rasmussen, Henrik Koblitz; Eriksson, Torbjörn Gerhard

2005-01-01

boundary condition. This allows an investigation of the effect of the rheological properties of the polymer melt on the ability of the material to fill small structures in a mould surface. Series of isothermal compression moulding experiments were performed with a polycarbonate (PC) and a polystyrene (PS...

Viscosity of ring polymer melts

KAUST Repository

Pasquino, Rossana

2013-10-15

We have measured the linear rheology of critically purified ring polyisoprenes, polystyrenes, and polyethyleneoxides of different molar masses. The ratio of the zero-shear viscosities of linear polymer melts η0,linear to their ring counterparts η0,ring at isofrictional conditions is discussed as a function of the number of entanglements Z. In the unentangled regime η0,linear/η 0,ring is virtually constant, consistent with the earlier data, atomistic simulations, and the theoretical expectation η0,linear/ η0,ring = 2. In the entanglement regime, the Z-dependence of ring viscosity is much weaker than that of linear polymers, in qualitative agreement with predictions from scaling theory and simulations. The power-law extracted from the available experimental data in the rather limited range 1 < Z < 20, η0,linear/η0,ring ∼ Z 1.2±0.3, is weaker than the scaling prediction (η0,linear/η0,ring ∼ Z 1.6±0.3) and the simulations (η0,linear/ η0,ring ∼ Z2.0±0.3). Nevertheless, the present collection of state-of-the-art experimental data unambiguously demonstrates that rings exhibit a universal trend clearly departing from that of their linear counterparts, and hence it represents a major step toward resolving a 30-year-old problem. © 2013 American Chemical Society.

Viscosity of ring polymer melts

KAUST Repository

Pasquino, Rossana; Vasilakopoulos, Thodoris C.; Jeong, Youncheol; Lee, Hyojoon; Rogers, Simon A.; Sakellariou, Georgios; Allgaier, Jü rgen B.; Takano, Atsushi; Brá s, Ana Rita E; Chang, Taihyun; Gooß en, Sebastian; Pyckhout-Hintzen, Wim; Wischnewski, Andreas; Hadjichristidis, Nikolaos; Richter, Dieter R.; Rubinstein, Michael H.; Vlassopoulos, Dimitris

2013-01-01

We have measured the linear rheology of critically purified ring polyisoprenes, polystyrenes, and polyethyleneoxides of different molar masses. The ratio of the zero-shear viscosities of linear polymer melts η0,linear to their ring counterparts η0,ring at isofrictional conditions is discussed as a function of the number of entanglements Z. In the unentangled regime η0,linear/η 0,ring is virtually constant, consistent with the earlier data, atomistic simulations, and the theoretical expectation η0,linear/ η0,ring = 2. In the entanglement regime, the Z-dependence of ring viscosity is much weaker than that of linear polymers, in qualitative agreement with predictions from scaling theory and simulations. The power-law extracted from the available experimental data in the rather limited range 1 < Z < 20, η0,linear/η0,ring ∼ Z 1.2±0.3, is weaker than the scaling prediction (η0,linear/η0,ring ∼ Z 1.6±0.3) and the simulations (η0,linear/ η0,ring ∼ Z2.0±0.3). Nevertheless, the present collection of state-of-the-art experimental data unambiguously demonstrates that rings exhibit a universal trend clearly departing from that of their linear counterparts, and hence it represents a major step toward resolving a 30-year-old problem. © 2013 American Chemical Society.

Crystallization in melts of short, semiflexible hard polymer chains: An interplay of entropies and dimensions

Science.gov (United States)

Shakirov, T.; Paul, W.

2018-04-01

What is the thermodynamic driving force for the crystallization of melts of semiflexible polymers? We try to answer this question by employing stochastic approximation Monte Carlo simulations to obtain the complete thermodynamic equilibrium information for a melt of short, semiflexible polymer chains with purely repulsive nonbonded interactions. The thermodynamics is obtained based on the density of states of our coarse-grained model, which varies by up to 5600 orders of magnitude. We show that our polymer melt undergoes a first-order crystallization transition upon increasing the chain stiffness at fixed density. This crystallization can be understood by the interplay of the maximization of different entropy contributions in different spatial dimensions. At sufficient stiffness and density, the three-dimensional orientational interactions drive the orientational ordering transition, which is accompanied by a two-dimensional translational ordering transition in the plane perpendicular to the chains resulting in a hexagonal crystal structure. While the three-dimensional ordering can be understood in terms of Onsager theory, the two-dimensional transition can be understood in terms of the liquid-hexatic transition of hard disks. Due to the domination of lateral two-dimensional translational entropy over the one-dimensional translational entropy connected with columnar displacements, the chains form a lamellar phase. Based on this physical understanding, orientational ordering and translational ordering should be separable for polymer melts. A phenomenological theory based on this understanding predicts a qualitative phase diagram as a function of volume fraction and stiffness in good agreement with results from the literature.

Fluorescently Labeled Branched Polymers and Thermal Responsive Nanoparticles for Live Cell Imaging

NARCIS (Netherlands)

Zhou, D.; Ma, Y.; Poot, Andreas A.; Dijkstra, Pieter J.; Feijen, Jan

2012-01-01

Branched poly(methoxy-PEG acrylate) and thermally responsive poly(methoxy-PEG acrylate)-block-poly(N-isopropylacrylamide) are synthesized by RAFT polymerization. After reduction, these polymers are fluorescently labeled by reacting the free thiol groups with N-(5-fluoresceinyl)maleimide. As shown by

The influence of flexible branches in flexible polymers

International Nuclear Information System (INIS)

Wescott, J.T.

1998-06-01

In this work the influence of branches in flexible polymer systems has been investigated by consideration of (1) the behaviour of isolated poly-α-olefin chains and (2) the p -T phase behaviour of poly(4-methylpentene-1)(P4MP1). Molecular dynamics simulations of isolated poly-α-olefins were performed in order to gauge directly the effect of molecular structure on chain dimensions, flexibility (via the persistence length) and shape. Under Θ-conditions the addition of short linear branches was shown to increase the flexibility of the backbone. In conditions of good solvent, however, the effect of longer and bulkier branches was to increase the persistence length and average size of the coil with the arrangement of side chain atoms making a small difference. The side branches themselves also affected the solvent conditions experienced by the backbone, behaving much like bound solvent. Consideration of ethylene-α-olefin copolymers, where the branch content was varied from 0-50%, showed that under good solvent conditions the branches increased the chain stiffness only when the gap between side branches was less than five backbone carbon atoms. The backbone torsions were also shown to play an important role in determining these trends. For comparison with the above simulations, persistence length values for polyethylene (= 7.3±0.2A) and P4MP1 (=7.6±0.3A) were measured experimentally by neutron scattering in dilute solution. A value of 6.7±0.5 for the characteristic ratio of PE was also calculated. To investigate the role of a bulky side group in crystalline phases, wide angle X-ray diffraction experiments using a Hikosaka pressure cell were performed on P4MP1. Computer modelling, utilising the experimental data obtained, determined the structure of a disordered phase produced at room temperature and a new high pressure/high temperature phase. The disordered phase was found to be due to a collapse of the backbone combined with some disordering of the side chains

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

Science.gov (United States)

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

2017-01-01

Co-amorphous drug-amino acid systems have gained growing interest as an alternative to common amorphous formulations which contain polymers as stabilizers. Several preparation methods have recently been investigated, including vibrational ball milling on a laboratory scale or spray drying in a larger scale. In this study, the feasibility of hot melt extrusion for continuous manufacturing of co-amorphous drug-amino acid formulations was examined, challenging the fact that amino acids melt with degradation at high temperatures. Furthermore, the need for an addition of a polymer in this process was evaluated. After a polymer screening via the solvent evaporation method, co-amorphous indomethacin-arginine was prepared by a melting-solvent extrusion process without and with copovidone. The obtained products were characterized with respect to their solid-state properties, non-sink dissolution behavior, and stability. Results were compared to those of spray-dried formulations with the same compositions and to spray-dried indomethacin-copovidone. Overall, stable co-amorphous systems could be prepared by extrusion without or with copovidone, which exhibited comparable molecular interaction properties to the respective spray-dried products, while phase separation was detected by differential scanning calorimetry in several cases. The formulations containing indomethacin in combination with arginine and copovidone showed enhanced dissolution behavior over the formulations with only copovidone or arginine. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

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

Scaling of mesoscale simulations of polymer melts with the bare friction coefficient

NARCIS (Netherlands)

Kindt, P.; Kindt, P.; Briels, Willem J.

2005-01-01

Both the Rouse and reptation model predict that the dynamics of a polymer melt scale inversely proportional with the Langevin friction coefficient (E). Mesoscale Brownian dynamics simulations of polyethylene validate these scaling predictions, providing the reptational friction (E)R=(E)+(E)C is

Polymers and Random graphs: Asymptotic equivalence to branching processes

International Nuclear Information System (INIS)

Spouge, J.L.

1985-01-01

In 1974, Falk and Thomas did a computer simulation of Flory's Equireactive RA/sub f/ Polymer model, rings forbidden and rings allowed. Asymptotically, the Rings Forbidden model tended to Stockmayer's RA/sub f/ distribution (in which the sol distribution ''sticks'' after gelation), while the Rings Allowed model tended to the Flory version of the RA/sub f/ distribution. In 1965, Whittle introduced the Tree and Pseudomultigraph models. We show that these random graphs generalize the Falk and Thomas models by incorporating first-shell substitution effects. Moreover, asymptotically the Tree model displays postgelation ''sticking.'' Hence this phenomenon results from the absence of rings and occurs independently of equireactivity. We also show that the Pseudomultigraph model is asymptotically identical to the Branching Process model introduced by Gordon in 1962. This provides a possible basis for the Branching Process model in standard statistical mechanics

Synthesis of branched polymers under continuous-flow microprocess: an improvement of the control of macromolecular architectures.

Science.gov (United States)

Bally, Florence; Serra, Christophe A; Brochon, Cyril; Hadziioannou, Georges

2011-11-15

Polymerization reactions can benefit from continuous-flow microprocess in terms of kinetics control, reactants mixing or simply efficiency when high-throughput screening experiments are carried out. In this work, we perform for the first time the synthesis of branched macromolecular architecture through a controlled/'living' polymerization technique, in tubular microreactor. Just by tuning process parameters, such as flow rates of the reactants, we manage to generate a library of polymers with various macromolecular characteristics. Compared to conventional batch process, polymerization kinetics shows a faster initiation step and more interestingly an improved branching efficiency. Due to reduced diffusion pathway, a characteristic of microsystems, it is thus possible to reach branched polymers exhibiting a denser architecture, and potentially a higher functionality for later applications. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Melt dispersion of thermoplastic polystyrene in polymer polyols

OpenAIRE

2009-01-01

Polystyrene is dispersed into a polyol via a mechanical dispersion process. A stabilizer is present to stabilize the dispersed polymer particles. The stabilizer includes a copolymer of (1) from 10 to 70% by weight of a branched polyol which has a molecular weight of from 4000 to 20,000, from 0.2 to about 1.2 polymerizable ethylenically unsaturated groups per molecule and from about 3 to about 8 hydroxyl groups per molecule with (2) from 30 to 90% by weight of styrene or a mixture of styrene a...

Flow-induced correlation effects within a linear chain in a polymer melt

NARCIS (Netherlands)

Stepanyan, R.; Slot, J.J.M.; Molenaar, J.; Tchesnokov, M.A.

2005-01-01

A framework for a consistent description of the flow-induced correlation effects within a linear polymer chain in a melt is proposed. The formalism shows how correlations between chain segments in the flow can be incorporated into a hierarchy of distribution functions for tangent vectors. The

Bridging the Gap between Polymer Melts and Solutions in Extensional Rheology

DEFF Research Database (Denmark)

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

2015-01-01

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

Branching structure and strain hardening of branched metallocene polyethylenes

International Nuclear Information System (INIS)

Torres, Enrique; Li, Si-Wan; Costeux, Stéphane; Dealy, John M.

2015-01-01

There have been a number of studies of a series of branched metallocene polyethylenes (BMPs) made in a solution, continuous stirred tank reactor (CSTR) polymerization. The materials studied vary in branching level in a systematic way, and the most highly branched members of the series exhibit mild strain hardening. An outstanding question is which types of branched molecules are responsible for strain hardening in extension. This question is explored here by use of polymerization and rheological models along with new data on the extensional flow behavior of the most highly branched members of the set. After reviewing all that is known about the effects of various branching structures in homogeneous polymers and comparing this with the structures predicted to be present in BMPs, it is concluded that in spite of their very low concentration, treelike molecules with branch-on-branch structure provide a large number of deeply buried inner segments that are essential for strain hardening in these polymers

Branching structure and strain hardening of branched metallocene polyethylenes

Energy Technology Data Exchange (ETDEWEB)

Torres, Enrique; Li, Si-Wan; Costeux, Stéphane; Dealy, John M., E-mail: john.dealy@mcgill.ca [Department of Chemical Engineering, McGill University, Montreal, Quebec H3A 0C4 (Canada)

2015-09-15

There have been a number of studies of a series of branched metallocene polyethylenes (BMPs) made in a solution, continuous stirred tank reactor (CSTR) polymerization. The materials studied vary in branching level in a systematic way, and the most highly branched members of the series exhibit mild strain hardening. An outstanding question is which types of branched molecules are responsible for strain hardening in extension. This question is explored here by use of polymerization and rheological models along with new data on the extensional flow behavior of the most highly branched members of the set. After reviewing all that is known about the effects of various branching structures in homogeneous polymers and comparing this with the structures predicted to be present in BMPs, it is concluded that in spite of their very low concentration, treelike molecules with branch-on-branch structure provide a large number of deeply buried inner segments that are essential for strain hardening in these polymers.

Communication: Proton NMR dipolar-correlation effect as a method for investigating segmental diffusion in polymer melts

International Nuclear Information System (INIS)

Lozovoi, A.; Mattea, C.; Stapf, S.; Herrmann, A.; Rössler, E. A.; Fatkullin, N.

2016-01-01

A simple and fast method for the investigation of segmental diffusion in high molar mass polymer melts is presented. The method is based on a special function, called proton dipolar-correlation build-up function, which is constructed from Hahn Echo signals measured at times t and t/2. The initial rise of this function contains additive contributions from both inter- and intramolecular magnetic dipole-dipole interactions. The intermolecular contribution depends on the relative mean squared displacements (MSDs) of polymer segments from different macromolecules, while the intramolecular part reflects segmental reorientations. Separation of both contributions via isotope dilution provides access to segmental displacements in polymer melts at millisecond range, which is hardly accessible by other methods. The feasibility of the method is illustrated by investigating protonated and deuterated polybutadiene melts with molecular mass 196 000 g/mol at different temperatures. The observed exponent of the power law of the segmental MSD is close to 0.32 ± 0.03 at times when the root MSD is in between 45 Å and 75 Å, and the intermolecular proton dipole-dipole contribution to the total proton Hahn Echo NMR signal is larger than 50% and increases with time.

Design and Modeling of Symmetric Three Branch Polymer Planar Optical Power Dividers

Directory of Open Access Journals (Sweden)

V. Prajzler

2013-04-01

Full Text Available Two types of polymer-based three-branch symmetric planar optical power dividers (splitters were designed, multimode interference (MMI splitter and triangular shape-spacing splitter. By means of modeling the real structures were simulated as made of Epoxy Novolak Resin on silicon substrate, with silica buffer layer and polymethylmethacrylate as protection cover layer. The design of polymer waveguide structure was done by Beam Propagation Method. After comparing properties of both types of the splitters we have demonstrated that our new polymer based triangular shaped splitter can work simultaneously in broader spectrum, the only condition would be that the waveguides are single-mode guiding. It practically means that, what concerns communication wavelengths, it can on principle simultaneously operate at two mainly used wavelengths, 1310 and 1550 nm.

Colloidal polymers with controlled sequence and branching constructed from magnetic field assembled nanoparticles.

Science.gov (United States)

Bannwarth, Markus B; Utech, Stefanie; Ebert, Sandro; Weitz, David A; Crespy, Daniel; Landfester, Katharina

2015-03-24

The assembly of nanoparticles into polymer-like architectures is challenging and usually requires highly defined colloidal building blocks. Here, we show that the broad size-distribution of a simple dispersion of magnetic nanocolloids can be exploited to obtain various polymer-like architectures. The particles are assembled under an external magnetic field and permanently linked by thermal sintering. The remarkable variety of polymer-analogue architectures that arises from this simple process ranges from statistical and block copolymer-like sequencing to branched chains and networks. This library of architectures can be realized by controlling the sequencing of the particles and the junction points via a size-dependent self-assembly of the single building blocks.

A Novel Approach to Population Balance Modeling of Reactive Polymer Modification Leading to Branching

NARCIS (Netherlands)

Kryven, I.; Iedema, P.D.

2013-01-01

The mathematical treatment of polymer modification systems, described by population balances containing convolution is discussed. The two-dimensional case (molecular weight vs. number of branch points) was considered by utilizing approximations of distributions, expanding them in terms of Gaussian

Development of Fabrication Methods of Filler/Polymer Nanocomposites: With Focus on Simple Melt-Compounding-Based Approach without Surface Modification of Nanofillers

Science.gov (United States)

Tanahashi, Mitsuru

2010-01-01

Many attempts have been made to fabricate various types of inorganic nanoparticle-filled polymers (filler/polymer nanocomposites) by a mechanical or chemical approach. However, these approaches require modification of the nanofiller surfaces and/or complicated polymerization reactions, making them unsuitable for industrial-scale production of the nanocomposites. The author and coworkers have proposed a simple melt-compounding method for the fabrication of silica/polymer nanocomposites, wherein silica nanoparticles without surface modification were dispersed through the breakdown of loose agglomerates of colloidal nano-silica spheres in a kneaded polymer melt. This review aims to discuss experimental techniques of the proposed method and its advantages over other developed methods.

Development of Fabrication Methods of Filler/Polymer Nanocomposites: With Focus on Simple Melt-Compounding-Based Approach without Surface Modification of Nanofillers

Directory of Open Access Journals (Sweden)

Mitsuru Tanahashi

2010-03-01

Full Text Available Many attempts have been made to fabricate various types of inorganic nanoparticle-filled polymers (filler/polymer nanocomposites by a mechanical or chemical approach. However, these approaches require modification of the nanofiller surfaces and/or complicated polymerization reactions, making them unsuitable for industrial-scale production of the nanocomposites. The author and coworkers have proposed a simple melt-compounding method for the fabrication of silica/polymer nanocomposites, wherein silica nanoparticles without surface modification were dispersed through the breakdown of loose agglomerates of colloidal nano-silica spheres in a kneaded polymer melt. This review aims to discuss experimental techniques of the proposed method and its advantages over other developed methods.

An empirical model for the melt viscosity of polymer blends

International Nuclear Information System (INIS)

Dobrescu, V.

1981-01-01

On the basis of experimental data for blends of polyethylene with different polymers an empirical equation is proposed to describe the dependence of melt viscosity of blends on component viscosities and composition. The model ensures the continuity of viscosity vs. composition curves throughout the whole composition range, the possibility of obtaining extremum values higher or lower than the viscosities of components, allows the calculation of flow curves of blends from the flow curves of components and their volume fractions. (orig.)

Using 2D NMR to determine the degree of branching of complicated hyperbranched polymers

Institute of Scientific and Technical Information of China (English)

2008-01-01

Degree of branching (DB) is a crucial structure parameter of hyperbranched polymers, which can be determined by 1H NMR, quantitative 13C NMR, degradative method, etc. However, for complicated hy-perbranched polymers, intricate structure and severe overlap of spectral signals hinder the determina-tion of DB using traditional methods. In this work, the architecture of complicated hyperbranched polymers has been elucidated with the help of 2D NMR techniques. Using such a method, overlapped NMR signals can be well separated into a two-dimensional space, and additional structural information is also available. Correspondingly, quantitative analysis for complicated systems can be realized. De-termination of DBs for three types of complicated hyperbranched polymers synthesized from step-polymerization, self-condensation vinyl polymerization and self-condensation ring-opening po-lymerization is shown as examples.

Equivalence of chain conformations in the surface region of a polymer melt and a single Gaussian chain under critical conditions.

Science.gov (United States)

Skvortsov, A M; Leermakers, F A M; Fleer, G J

2013-08-07

In the melt polymer conformations are nearly ideal according to Flory's ideality hypothesis. Silberberg generalized this statement for chains in the interfacial region. We check the Silberberg argument by analyzing the conformations of a probe chain end-grafted at a solid surface in a sea of floating free chains of concentration φ by the self-consistent field (SCF) method. Apart from the grafting, probe chain and floating chains are identical. Most of the results were obtained for a standard SCF model with freely jointed chains on a six-choice lattice, where immediate step reversals are allowed. A few data were generated for a five-choice lattice, where such step reversals are forbidden. These coarse-grained models describe the equilibrium properties of flexible atactic polymer chains at the scale of the segment length. The concentration was varied over the whole range from φ = 0 (single grafted chain) to φ = 1 (probe chain in the melt). The number of contacts with the surface, average height of the free end and its dispersion, average loop and train length, tail size distribution, end-point and overall segment distributions were calculated for a grafted probe chain as a function of φ, for several chain lengths and substrate∕polymer interactions, which were varied from strong repulsion to strong adsorption. The computations show that the conformations of the probe chain in the melt do not depend on substrate∕polymer interactions and are very similar to the conformations of a single end-grafted chain under critical conditions, and can thus be described analytically. When the substrate∕polymer interaction is fixed at the value corresponding to critical conditions, all equilibrium properties of a probe chain are independent of φ, over the whole range from a dilute solution to the melt. We believe that the conformations of all flexible chains in the surface region of the melt are close to those of an appropriate single chain in critical conditions, provided

Networks 90: Polymer Networks Group Meeting (10th) and IUPAC international Symposium on Polymer Networks (10th) Held in Jerusalem on 20-25 May 1990. Programme and Abstracts

Science.gov (United States)

1990-05-25

Ingenieria Quimica, 12 de octubre 1842, 8000 Bahia Blanca, Argentina. P-36 BRANCHING KINETICS OF EPOXY POLYMERIZATION OF 1,4-BUTANEDIOL DIGLYCIDYL ETHER...OF ENTANGLED POLYMERS IN MELTS L-6 J. des Cloizeaux (France) 14:45-15:05 THE CONCEPT OF INTRINSIC CHAIN STRESS IN L-7 POLYMER NETWORKS J.J. Weiner, J...RELATION TO DIFFUSIVE TRANSPORT A.M. Weiss, K. Adler, A.J. Grodzinsky, M.L. Yarmush (Israel, USA) 15:05-15:25 DIFFUSION BEHAVIOUR IN SOLUTIONS OF L-25

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

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

KAUST Repository

Habuchi, Satoshi

2016-09-26

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used for the synthesis of the cyclic poly(tetrahydrofuran) (poly(THF)). The diffusive motion of individual cyclic polymer chains in a melt state is visualized using single molecule fluorescence imaging by incorporating a fluorophore unit in the cyclic chains. The diffusive motion of the chains is quantitatively characterized by means of a combination of mean-squared displacement (MSD) analysis and a cumulative distribution function (CDF) analysis. The cyclic polymer exhibits multiple-mode diffusion which is distinct from its linear counterpart. The results demonstrate that the diffusional heterogeneity of polymers that is often hidden behind ensemble averaging can be revealed by the efficient synthesis of the cyclic polymers using the ESA-CF process and the quantitative analysis of the diffusive motion at the single molecule level using the MSD and CDF analyses.

Measurement of elongational viscosity of polymer melts using SER Universal Testing Platform

Czech Academy of Sciences Publication Activity Database

Filip, Petr; Švrčinová, Petra

2012-01-01

Roč. 22, č. 1 (2012), s. 14776 ISSN 1430-6395 R&D Projects: GA ČR GA103/08/1307; GA ČR GA103/09/2066 Institutional research plan: CEZ:AV0Z20600510 Keywords : elongational viscosity * SER Universal Testing Platform * polymer melts * LDPE Subject RIV: BK - Fluid Dynamics Impact factor: 1.226, year: 2012 http://www.ar.ethz.ch/TMPPDF/23074299892.48/ApplRheol_22_14776.pdf

Elongational flow of polymer melts at constant strain rate, constant stress and constant force

Science.gov (United States)

Wagner, Manfred H.; Rolón-Garrido, Víctor H.

2013-04-01

Characterization of polymer melts in elongational flow is typically performed at constant elongational rate or rarely at constant tensile stress conditions. One of the disadvantages of these deformation modes is that they are hampered by the onset of "necking" instabilities according to the Considère criterion. Experiments at constant tensile force have been performed even more rarely, in spite of the fact that this deformation mode is free from necking instabilities and is of considerable industrial relevance as it is the correct analogue of steady fiber spinning. It is the objective of the present contribution to present for the first time a full experimental characterization of a long-chain branched polyethylene melt in elongational flow. Experiments were performed at constant elongation rate, constant tensile stress and constant tensile force by use of a Sentmanat Extensional Rheometer (SER) in combination with an Anton Paar MCR301 rotational rheometer. The accessible experimental window and experimental limitations are discussed. The experimental data are modelled by using the Wagner I model. Predictions of the steady-start elongational viscosity in constant strain rate and creep experiments are found to be identical, albeit only by extrapolation of the experimental data to Hencky strains of the order of 6. For constant stress experiments, a minimum in the strain rate and a corresponding maximum in the elongational viscosity is found at a Hencky strain of the order of 3, which, although larger than the steady-state value, follows roughly the general trend of the steady-state elongational viscosity. The constitutive analysis also reveals that constant tensile force experiments indicate a larger strain hardening potential than seen in constant elongation rate or constant tensile stress experiments. This may be indicative of the effect of necking under constant elongation rate or constant tensile stress conditions according to the Considère criterion.

Effect of block composition on thermal properties and melt viscosity of poly[2-(dimethylaminoethyl methacrylate], poly(ethylene oxide and poly(propylene oxide block co-polymers

Directory of Open Access Journals (Sweden)

2011-09-01

Full Text Available To modify the rheological properties of certain commercial polymers, a set of block copolymers were synthesized through oxyanionic polymerization of 2-(dimethylaminoethyl methacrylate to the chain ends of commercial prepolymers, namely poly(ethylene oxide (PEO, poly(ethylene oxide-block-poly(propylene oxide-block-poly(ethylene oxide (PEO-PPO-PEO, and poly(propylene oxide (PPO. The formed block copolymers were analysed with size exclusion chromatography and nuclear magnetic resonance spectroscopy in order to confirm block formation. Thermal characterization of the resulting polymers was done with differential scanning calorimetry. Thermal transition points were also confirmed with rotational rheometry, which was primarily used to measure melt strength properties of the resulting block co-polymers. It was observed that the synthesised poly[2-(dimethylaminoethyl methacrylate]-block (PDM affected slightly the thermal transition points of crystalline PEO-block but the influence was stronger on amorphous PPO-blocks. Frequency sweeps measured above the melting temperatures for the materials confirmed that the pre-polymers (PEO and PEO-PPO-PEO behave as Newtonian fluids whereas polymers with a PDM block structure exhibit clear shear thinning behaviour. In addition, the PDM block increased the melt viscosity when compared with that one of the pre-polymer. As a final result, it became obvious that pre-polymers modified with PDM were in entangled form, in the melted state as well in the solidified form.

Melt electrospinning of biodegradable polyurethane scaffolds

Science.gov (United States)

Karchin, Ari; Simonovsky, Felix I.; Ratner, Buddy D.; Sanders, Joan E.

2014-01-01

Electrospinning from the melt, in contrast to from solution, is an attractive tissue engineering scaffold manufacturing process as it allows for the formation of small diameter fibers while eliminating potentially cytotoxic solvents. Despite this, there is a dearth of literature on scaffold formation via melt electrospinning. This is likely due to the technical challenges related to the need for a well-controlled high temperature setup and the difficulty in developing an appropriate polymer. In this paper, a biodegradable and thermally stable polyurethane (PU) is described specifically for use in melt electrospinning. Polymer formulations of aliphatic PUs based on (CH2)4-content diisocyanates, polycaprolactone (PCL), 1,4-butanediamine and 1,4-butanediol (BD) were evaluated for utility in the melt electrospinning process. The final polymer formulation, a catalyst-purified PU based on 1,4-butane diisocyanate, PCL and BD in a 4/1/3 molar ratio with a weight-average molecular weight of about 40 kDa, yielded a nontoxic polymer that could be readily electrospun from the melt. Scaffolds electrospun from this polymer contained point bonds between fibers and mechanical properties analogous to many in vivo soft tissues. PMID:21640853

Early structural development in melt-quenched polymer PTT from atomistic molecular dynamic simulations

Science.gov (United States)

Hsieh, Min-Kang; Lin, Shiang-Tai

2009-12-01

Molecular dynamics simulations are performed to study the initial structural development in poly(trimethylene terephthalate) (PTT) when quenched below its melting point. The development of local ordering has been observed in our simulations. The thermal properties, such as the glass transition temperature (Tg) and the melting temperature (Tm), determined from our simulations are in reasonable agreement with experimental values. It is found that, between these two temperatures, the number of local structures quickly increases during the thermal relaxation period soon after the system is quenched and starts to fluctuate afterwards. The formation and development of local structures is found to be driven mainly by the torsional and van der Waals forces and follows the classical nucleation-growth mechanism. The variation of local structures' fraction with temperature exhibits a maximum between Tg and Tm, resembling the temperature dependence of the crystallization rate for most polymers. In addition, the backbone torsion distribution for segments within the local structures preferentially reorganizes to the trans-gauche-gauche-trans (t-g-g-t) conformation, the same as that in the crystalline state. As a consequence, we believe that such local structural ordering could be the baby nuclei that have been suggested to form in the early stage of polymer crystallization.

Radiation processing of biodegradable polymer and hydrogel

International Nuclear Information System (INIS)

Yoshii, Fumio

2000-01-01

Poly(ε-caprolactone), PCL, (melting temperature 60degC) was gamma-irradiated in the solid state at 30 to 55degC, the molten state, and the supercooled state(irradiation at 45 to 55degC after melting, 80degC) under vacuum to improve its heat resistance. Irradiation of PCL in the supercooled state led to the highest gel content and this polymer has high heat resistance. On the other hand, relatively smaller doses such as 15 and 30 kGy were effective to improve processability of PCL by formation of branch structure during irradiation. It was found that carboxymethylcellulose with relatively high degree of substitution led crosslinking at high concentration in aqueous solution such as 10% by irradiation. (author)

Radiation processing of biodegradable polymer and hydrogel

Energy Technology Data Exchange (ETDEWEB)

Yoshii, Fumio [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment

2000-03-01

Poly({epsilon}-caprolactone), PCL, (melting temperature 60degC) was gamma-irradiated in the solid state at 30 to 55degC, the molten state, and the supercooled state(irradiation at 45 to 55degC after melting, 80degC) under vacuum to improve its heat resistance. Irradiation of PCL in the supercooled state led to the highest gel content and this polymer has high heat resistance. On the other hand, relatively smaller doses such as 15 and 30 kGy were effective to improve processability of PCL by formation of branch structure during irradiation. It was found that carboxymethylcellulose with relatively high degree of substitution led crosslinking at high concentration in aqueous solution such as 10% by irradiation. (author)

Nonequilibrium molecular dynamics study of ring polymer melts under shear and elongation flows: A comparison with their linear analogs

Energy Technology Data Exchange (ETDEWEB)

Yoon, Jeongha; Kim, Jinseong; Baig, Chunggi, E-mail: cbaig@unist.ac.kr [Department of Chemical Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 689-798 (Korea, Republic of)

2016-07-15

We present detailed results for the structural and rheological properties of unknotted and unconcatenated ring polyethylene (PE) melts under shear and elongation flows via direct atomistic nonequilibrium molecular dynamics simulations. Short (C{sub 78}H{sub 156}) and long (C{sub 400}H{sub 800}) ring PE melts were subjected to planar Couette flow (PCF) and planar elongational flow (PEF) across a wide range of strain rates from linear to highly nonlinear flow regimes. The results are analyzed in detail through a direct comparison with those of the corresponding linear polymers. We found that, in comparison to their linear analogs, ring melts possess rather compact chain structures at or near the equilibrium state and exhibit a considerably lesser degree of structural deformation with respect to the applied flow strength under both PCF and PEF. The large structural resistance of ring polymers against an external flow field is attributed to the intrinsic closed-loop configuration of the ring and the topological constraint of nonconcatenation between ring chains in the melt. As a result, there appears to be a substantial discrepancy between ring and linear systems in terms of their structural and rheological properties such as chain orientation, the distribution of chain dimensions, viscosity, flow birefringence, hydrostatic pressure, the pair correlation function, and potential interaction energies. The findings and conclusions drawn in this work would be a useful guide in future exploration of the characteristic dynamical and relaxation mechanisms of ring polymers in bulk or confined systems under flowing conditions.

Comblike poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers as anti-infection surface modifying agents.

Science.gov (United States)

Mai-ngam, Katanchalee

2006-05-01

A series of structurally well-defined poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers that undergo surface induced self assembly on hydrophobic biomaterial surfaces were synthesized and characterized. The surfactant polymers consist of low molecular weight (Mw) chitosan backbone with hydrophilic poly(ethylene oxide) (PEO) and hydrophobic hexyl pendant groups. Chitosan was depolymerized by nitrous acid deaminative cleavage. Hexanal and aldehyde-terminated PEO chains were simultaneously attached to low Mw chitosan hydrochloride via reductive amination. The surfactant polymers were prepared with various ratios of the two side chains. The molecular composition of the surfactant polymers was determined by FT-IR and 1H NMR. Surface active properties at the air-water interface were determined by Langmuir film balance measurements. The surfactant polymers with PEO/hexyl ratios of 1:3.0 and 1:14.4 were used as surface modifying agents to investigate their anti-infection properties. E. coli adhesion on Silastic surface was decreased significantly by the surfactant polymer with PEO/hexyl 1:3.0. Surface growth of adherent E. coli was effectively suppressed by both tested surfactant polymers.

Polymer nanocomposites: polymer and particle dynamics

KAUST Repository

Kim, Daniel; Srivastava, Samanvaya; Narayanan, Suresh; Archer, Lynden A.

2012-01-01

Polymer nanocomposites containing nanoparticles smaller than the random coil size of their host polymer chains are known to exhibit unique properties, such as lower viscosity and glass transition temperature relative to the neat polymer melt. It has

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

Science.gov (United States)

Rastogi, Sanjay

2013-03-01

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

Segregation of chain ends to polymer melt surfaces and interfaces

International Nuclear Information System (INIS)

Zhao, W.; Zhao, X.; Rafailovich, M.H.; Sokolov, J.; Composto, R.J.; Smith, S.D.; Satkowski, M.; Russell, T.P.; Dozier, W.D.; Mansfield, T.

1993-01-01

The conformation of polymer chains in the melt near an impenetrable boundary has recently been studied by molecular dynamics and off-lattice Monte Carlo simulations. Both types of calculations show an enhancement of the chain end density within a distance of approximately two polymer segment lengths of the interface relative to the bulk. In the absence of preferential interactions between monomers and the interface, the segregation arises from minimizing the loss of conformational entropy near an impenetrable boundary; i.e., by positioning an end near the surface, only one unit rather than two is reflected. In order to obtain an experimental measure of this effect, monodisperse polystyrene (PS) chains of molecular weight 63 000 with short blocks of deuterated polystyrene (dPS) at each end were prepared. The block length was kept as short as possible, while yet producing sufficient neutron scattering contrast in order to minimize any preferential surface segregation due to isotopic effects. The synthesis was carried out via living anionic polymerization of a purified styrene monomer in cyclohexane at 60 C, utilizing sec-butyllithium as the initiator. The process was terminated using degassed methanol

Measuring the Extensional Properties of linear and branched Polymer Melts using Membrane Inflation into a Cylinder

DEFF Research Database (Denmark)

Rasmussen, Henrik Koblitz; Eggen, Svein; Kjær, Erik Michael

2001-01-01

The bubble inflation technique has been used for some time as a rheological characterization method for polymeric materials. Recently, this technique has been modified to the inflation of a polymeric sheet into a circular cylinder. In this work, the experimental inflation of sheets (or membranes......) of polymeric melts into a circular cylinder is modelled numerically to obtain the general extensional properties of the material....

CO2 capture by polymeric membranes composed of hyper-branched polymers with dense poly(oxyethylene comb and poly(amidoamine

Directory of Open Access Journals (Sweden)

Taniguchi Ikuo

2017-11-01

Full Text Available Due to CO2-philic nature of polyoxyethylene (POE, a dense POE comb structure was tethered onto PMMA backbone to develop CO2 separation membranes over N2. The resulting hyper-branched polymers displayed preferential CO2 permeation. When the polymer thin layer was formed on a high gas permeable polydimethylsiloxane (PDMS support by a spray-coating manner, the resulting thin film composite (TFC membranes displayed very high CO2 permeability. However, the CO2 selectivity, which was the permeability ratio of CO2 over N2, was moderate and lower than 50. To enhance the selectivity, poly(amidoamine (PAMAM was introduced to the hyper-branched polymers in the CO2-selective layer of the TFC membranes. The CO2 selectivity increased from 47 to 90 with increasing PAMAM content to 40 wt%, and it was drastically enhanced to 350 with PAMAM content of 50 wt%. Differential scanning calorimetry (DSC and laser microscope revealed formation of PAMAM-rich domain at the higher amine content, where CO2 could readily migrate in comparison to the other polymeric fractions.

CO2 capture by polymeric membranes composed of hyper-branched polymers with dense poly(oxyethylene) comb and poly(amidoamine)

Science.gov (United States)

Taniguchi, Ikuo; Wada, Norihisa; Kinugasa, Kae; Higa, Mitsuru

2017-11-01

Due to CO2-philic nature of polyoxyethylene (POE), a dense POE comb structure was tethered onto PMMA backbone to develop CO2 separation membranes over N2. The resulting hyper-branched polymers displayed preferential CO2 permeation. When the polymer thin layer was formed on a high gas permeable polydimethylsiloxane (PDMS) support by a spray-coating manner, the resulting thin film composite (TFC) membranes displayed very high CO2 permeability. However, the CO2 selectivity, which was the permeability ratio of CO2 over N2, was moderate and lower than 50. To enhance the selectivity, poly(amidoamine) (PAMAM) was introduced to the hyper-branched polymers in the CO2-selective layer of the TFC membranes. The CO2 selectivity increased from 47 to 90 with increasing PAMAM content to 40 wt%, and it was drastically enhanced to 350 with PAMAM content of 50 wt%. Differential scanning calorimetry (DSC) and laser microscope revealed formation of PAMAM-rich domain at the higher amine content, where CO2 could readily migrate in comparison to the other polymeric fractions.

Computer simulations of supercooled polymer melts in the bulk and in confined geometry

International Nuclear Information System (INIS)

Baschnagel, J; Varnik, F

2005-01-01

We survey results of computer simulations for the structure and dynamics of supercooled polymer melts and films. Our survey is mainly concerned with features of a coarse grained polymer model-a bead-spring model-in the temperature regime above the critical glass temperature T c of the ideal mode-coupling theory (MCT). We divide our discussion into two parts: a part devoted to bulk properties and a part dealing with thin films. The discussion of the bulk properties focuses on two aspects: a comparison of the simulation results with MCT and an analysis of dynamic heterogeneities. We explain in detail how the analyses are performed and what results may be obtained, and we critically assess their strengths and weaknesses. In discussing the application of MCT we also present first results of a quantitative comparison which does not rely on fits, but exploits static input from the simulation to predict the relaxation dynamics. The second part of this review is devoted to extensions of the simulations from the bulk to thin films. We explore in detail the influence of the boundary condition, imposed by smooth or rough walls, on the structure and dynamics of the polymer melt. Geometric confinement is found to shift the glass transition temperature T g (or T c in our case) relative to the bulk. We compare our and other simulation results for the T g shift with experimental data, briefly survey some theoretical ideas for explaining these shifts and discuss related simulation work on the glass transition of confined liquids. Finally, we also present some technical details of how to perform fits to MCT and give a brief introduction to another approach to the glass transition based on the potential energy landscape of a liquid. (topical review)

Application to the radiation processing of polymer

Energy Technology Data Exchange (ETDEWEB)

Yoshii, Fumio [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment

2003-02-01

Polypropylene (PP) and biodegradable polymer (blend of poly ({epsilon}-caploracton) 30/polybutylenesuccynate 70), PHB02 were irradiated with an electron beam to improve processability for production of thin film and foam. The processability of the polymer was improved due to enhancement of melt strength with irradiation at the dose range between 10 and 100 kGy. Increase of melt strength is due to entanglement of branch structure formed by irradiation. Possibility of high-speed production of thin film and production of foam have been achieved by this process. The soil degradation test showed that biodegradable polymer film buried in the soil was almost entirely degraded (97%) after two months and completely degraded after two and a half months. In the case of foam samples, 65% degradation was achieved after four months. Radiation crosslinked water-soluble polymer form hydrogel, which absorb much water. The hydrogel prepared by irradiation of polymer in aqueous solution was applied as dressing for healing of wound. In order to evaluate the healing effect of the polyethylene oxide (PEO) hydrogel dressing, wounds formed on the back of marmots were covered by the hydrogel. The healing under the wet environment of the hydrogel dressing had three advantages, compared with that of gauze dressing, which gives a dry environment: (1) enhancement of healing rate, (2) facilitation for changing the dressing, i.e. the hydrogel can be peeled off without any damage to the regenerated skin surface, and (3) hydrogel dressing material does not remain stuck on the wound. (author)

Application to the radiation processing of polymer

International Nuclear Information System (INIS)

Yoshii, Fumio

2003-01-01

Polypropylene (PP) and biodegradable polymer (blend of poly (ε-caploracton) 30/polybutylenesuccynate 70), PHB02 were irradiated with an electron beam to improve processability for production of thin film and foam. The processability of the polymer was improved due to enhancement of melt strength with irradiation at the dose range between 10 and 100 kGy. Increase of melt strength is due to entanglement of branch structure formed by irradiation. Possibility of high-speed production of thin film and production of foam have been achieved by this process. The soil degradation test showed that biodegradable polymer film buried in the soil was almost entirely degraded (97%) after two months and completely degraded after two and a half months. In the case of foam samples, 65% degradation was achieved after four months. Radiation crosslinked water-soluble polymer form hydrogel, which absorb much water. The hydrogel prepared by irradiation of polymer in aqueous solution was applied as dressing for healing of wound. In order to evaluate the healing effect of the polyethylene oxide (PEO) hydrogel dressing, wounds formed on the back of marmots were covered by the hydrogel. The healing under the wet environment of the hydrogel dressing had three advantages, compared with that of gauze dressing, which gives a dry environment: (1) enhancement of healing rate, (2) facilitation for changing the dressing, i.e. the hydrogel can be peeled off without any damage to the regenerated skin surface, and (3) hydrogel dressing material does not remain stuck on the wound. (author)

High through-plane thermal conduction of graphene nanoflake filled polymer composites melt-processed in an L-shape kinked tube.

Science.gov (United States)

Jung, Haejong; Yu, Seunggun; Bae, Nam-Seok; Cho, Suk Man; Kim, Richard Hahnkee; Cho, Sung Hwan; Hwang, Ihn; Jeong, Beomjin; Ryu, Ji Su; Hwang, Junyeon; Hong, Soon Man; Koo, Chong Min; Park, Cheolmin

2015-07-22

Design of materials to be heat-conductive in a preferred direction is a crucial issue for efficient heat dissipation in systems using stacked devices. Here, we demonstrate a facile route to fabricate polymer composites with directional thermal conduction. Our method is based on control of the orientation of fillers with anisotropic heat conduction. Melt-compression of solution-cast poly(vinylidene fluoride) (PVDF) and graphene nanoflake (GNF) films in an L-shape kinked tube yielded a lightweight polymer composite with the surface normal of GNF preferentially aligned perpendicular to the melt-flow direction, giving rise to a directional thermal conductivity of approximately 10 W/mK at 25 vol % with an anisotropic thermal conduction ratio greater than six. The high directional thermal conduction was attributed to the two-dimensional planar shape of GNFs readily adaptable to the molten polymer flow, compared with highly entangled carbon nanotubes and three-dimensional graphite fillers. Furthermore, our composite with its density of approximately 1.5 g/cm(3) was mechanically stable, and its thermal performance was successfully preserved above 100 °C even after multiple heating and cooling cycles. The results indicate that the methodology using an L-shape kinked tube is a new way to achieve polymer composites with highly anisotropic thermal conduction.

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

KAUST Repository

Habuchi, Satoshi; Yamamoto, Takuya; Tezuka, Yasuyuki

2016-01-01

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used

Study of the weathering of high melt strength polypropylene (HMS-PP)

Energy Technology Data Exchange (ETDEWEB)

Oliani, Washington L.; Parra, Duclerc F.; Otaguro, Harumi; Lima, Luis F.C.P.; Lugao, Ademar B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)], E-mail: dfparra@ipen.br

2007-07-01

One of the reasons for the good acceptance of the commercial PP is the fact that market requires products with features of 'engineering plastics' with prices in the range of commodities. High melt strength polypropylene (HMSPP) grades are produced by radiation process and have improved rheology for melt blow processes. The melt strength (MS) properties of a polymer increase with molecular weight and with long chain branching due to the increase in the entanglement level. The main scope of this study was to evaluate the stability of HMS-PP prepared by gamma radiation with doses of 12.5, 20 kGy in comparison with virgin PP. Many variables influence the rate of degradation of polymers by photo-oxidation. The irradiance and permeability to oxygen are the most important factors but other factors such as temperature and moisture have also influenced the degradation rates. Polypropylenes are sensitive to oxidation due to the presence of the tertiary carbon atom. Therefore, effective stabilization against oxidation (thermo and photo oxidation) is required. The samples submitted to the natural aging for a period of six months were characterized by: tensile test, thermogravimetry analysis (TGA), optical microscopy, scanning electronic microscopy (SEM) and infrared spectroscopy (FTIR). SEM analysis showed particular aspects of cracks on the surface. The loss of tensile strength is associated to the presence of fractures. The results showed that pronounced oxidation followed by chain scission occur at the initial periods of weathering exposition of the HMS-PP. (author)

Study of the weathering of high melt strength polypropylene (HMS-PP)

International Nuclear Information System (INIS)

Oliani, Washington L.; Parra, Duclerc F.; Otaguro, Harumi; Lima, Luis F.C.P.; Lugao, Ademar B.

2007-01-01

One of the reasons for the good acceptance of the commercial PP is the fact that market requires products with features of 'engineering plastics' with prices in the range of commodities. High melt strength polypropylene (HMSPP) grades are produced by radiation process and have improved rheology for melt blow processes. The melt strength (MS) properties of a polymer increase with molecular weight and with long chain branching due to the increase in the entanglement level. The main scope of this study was to evaluate the stability of HMS-PP prepared by gamma radiation with doses of 12.5, 20 kGy in comparison with virgin PP. Many variables influence the rate of degradation of polymers by photo-oxidation. The irradiance and permeability to oxygen are the most important factors but other factors such as temperature and moisture have also influenced the degradation rates. Polypropylenes are sensitive to oxidation due to the presence of the tertiary carbon atom. Therefore, effective stabilization against oxidation (thermo and photo oxidation) is required. The samples submitted to the natural aging for a period of six months were characterized by: tensile test, thermogravimetry analysis (TGA), optical microscopy, scanning electronic microscopy (SEM) and infrared spectroscopy (FTIR). SEM analysis showed particular aspects of cracks on the surface. The loss of tensile strength is associated to the presence of fractures. The results showed that pronounced oxidation followed by chain scission occur at the initial periods of weathering exposition of the HMS-PP. (author)

Application of film-casting technique to investigate drug-polymer miscibility in solid dispersion and hot-melt extrudate.

Science.gov (United States)

Parikh, Tapan; Gupta, Simerdeep Singh; Meena, Anuprabha K; Vitez, Imre; Mahajan, Nidhi; Serajuddin, Abu T M

2015-07-01

Determination of drug-polymer miscibility is critical for successful development of solid dispersions. This report details a practical method to predict miscibility and physical stability of drug with various polymers in solid dispersion and, especially, in melt extrudates by applying a film-casting technique. Mixtures of itraconazole (ITZ) with hydroxypropylmethylcellulose phthalate (HPMCP), Kollidon(®) VA 64, Eudragit(®) E PO, and Soluplus(®) were film-casted, exposed to 40°C/75% RH for 1 month and then analyzed using differential scanning calorimetry (DSC), powder X-ray diffractometry, and polarized light microscopy (PLM). ITZ had the highest miscibility with HPMCP, being miscible at drug to polymer ratio of 6:4 (w/w). There was a downward trend of lower miscibility with Soluplus(®) (miscible at 3:7, w/w, and a few microcrystals present at 4:6, w/w), Kollidon(®) VA 64 (2:8, w/w) and Eudragit(®) E PO (casting and hot-melt extrusion (HME) using a twin screw extruder. For ITZ-Soluplus(®) mixtures, HME at 4:6 (w/w) resulted in a single phase, whereas drug crystallization was observed at higher drug load. HME of ITZ-Kollidon(®) VA 64 mixtures also correlated well with the miscibility predicted by film casting. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

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

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

KAUST Repository

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

2015-01-01

Star polymers provide model architectures to understand the dynamic and rheological effects of chain confinement for a range of complex topological structures like branched polymers, colloids, and micelles. It is important to describe the structure of such macromolecular topologies using small-angle neutron and x-ray scattering to facilitate understanding of their structure-property relationships. Modeling of scattering from linear, Gaussian polymers, such as in the melt, has applied the random phase approximation using the Debye polymer scattering function. The Flory-Huggins interaction parameter can be obtained using neutron scattering by this method. Gaussian scaling no longer applies for more complicated chain topologies or when chains are in good solvents. For symmetric star polymers, chain scaling can differ from ν=0.5(df=2) due to excluded volume, steric interaction between arms, and enhanced density due to branching. Further, correlation between arms in a symmetric star leads to an interference term in the scattering function first described by Benoit for Gaussian chains. In this work, a scattering function is derived which accounts for interarm correlations in symmetric star polymers as well as the polymer-solvent interaction parameter for chains of arbitrary scaling dimension using a hybrid Unified scattering function. The approach is demonstrated for linear, four-arm and eight-arm polyisoprene stars in deuterated p-xylene.

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

KAUST Repository

Rai, Durgesh K.

2015-07-15

Star polymers provide model architectures to understand the dynamic and rheological effects of chain confinement for a range of complex topological structures like branched polymers, colloids, and micelles. It is important to describe the structure of such macromolecular topologies using small-angle neutron and x-ray scattering to facilitate understanding of their structure-property relationships. Modeling of scattering from linear, Gaussian polymers, such as in the melt, has applied the random phase approximation using the Debye polymer scattering function. The Flory-Huggins interaction parameter can be obtained using neutron scattering by this method. Gaussian scaling no longer applies for more complicated chain topologies or when chains are in good solvents. For symmetric star polymers, chain scaling can differ from ν=0.5(df=2) due to excluded volume, steric interaction between arms, and enhanced density due to branching. Further, correlation between arms in a symmetric star leads to an interference term in the scattering function first described by Benoit for Gaussian chains. In this work, a scattering function is derived which accounts for interarm correlations in symmetric star polymers as well as the polymer-solvent interaction parameter for chains of arbitrary scaling dimension using a hybrid Unified scattering function. The approach is demonstrated for linear, four-arm and eight-arm polyisoprene stars in deuterated p-xylene.

Oscillatory Shear Rheology in Examining the Drug-Polymer Interactions Relevant in Hot Melt Extrusion

DEFF Research Database (Denmark)

Aho, Johanna; Edinger, Magnus; Botker, Johan

2016-01-01

The flow properties of drug-polymer mixtures have a significant influence on their processability when using techniques such as hot melt extrusion (HME). Suitable extrusion temperature and screw speed to be used in laboratory scale HME were evaluated for mixtures containing 30% of paracetamol (PRC...... of the drug substances. Consecutively, the mixtures were extruded, and the maximum plasticizing weight fraction of each drug was determined by means of rheological measurements. IBU was found to have an efficient plasticizing functionality, decreasing the viscosity of the mixtures even above its apparent...

Thinning Approximation for Two-Dimensional Scattering Patterns from Coarse-Grained Polymer Melts under Shear Flow

Science.gov (United States)

Hagita, Katsumi; Murashima, Takahiro; Takano, Hiroshi; Kawakatsu, Toshihiro

2017-12-01

We proposed a thinning approximation (TA) for estimation of the two-dimensional (2D) wide-angle scattering patterns from Kremer-Grest polymer melts under shear. In the TA, extra particles are inserted at the middle of bonds for fine-graining of the coarse-grained polymers. For the case without the TA, spots corresponding to the orientation of bonds at a high shear rate are difficult to observe because the bond length of successive particles is comparable to the distance between neighboring particles. With the insertion of the extra particles, a ring pattern originating from the neighboring particles can be moved to a wide-angle region. Thus, we can observe the spots at high shear rates. We also examined the relationship between 2D scattering patterns and the Weissenberg number, which is defined as the product of the shear rate and the longest relaxation time. It is confirmed that the relationship for coarse-grained polymers with the TA is consistent with that of the all-atomistic model of polyethylene.

Environmentally friendly and highly productive bi-component melt spinning of thermoregulated smart polymer fibres with high latent heat capacity

Directory of Open Access Journals (Sweden)

Ch. Cherif

2018-03-01

Full Text Available A stable and reproducible bi-component melt spinning process on an industrial scale incorporating Phase Change Material (PCM into textile fibres has been successfully developed and carried out using a melt spinning machine. The key factor for a successful bi-component melt spinning process is that a deep insight into the thermal and rheological behaviour of PCM using Difference Scanning Calorimetry (DSC, Thermogravimetric Analysis (TGA, and an oscillatory rheological investigation. PCM is very sensitive to the temperature and residence time of the melt spinning process. It is found that the optimal process temperature of PCM is 210 °C. The textile-physical properties and the morphology of the melt spun and further drawn bi-component core and sheath fibres (bico fibres were investigated and interpreted. The heat capacities of PCM incorporated in bico fibres were also determined by means of DSC. The melt spun bico fibres integrating PCM provide a high latent heat of up to 22 J/g, which is three times higher than that of state-of-the-art fibres, which were also obtained using the melt spinning process. Therefore, they have the potential to be used as smart polymer fibres for textile and other technical applications.

Method for bonding a thermoplastic polymer to a thermosetting polymer component

NARCIS (Netherlands)

Van Tooren, M.J.L.

2012-01-01

The invention relates to a method for bonding a thermoplastic polymer to a thermosetting polymer component, the thermoplastic polymer having a melting temperature that exceeds the curing temperature of the thermosetting polymer. The method comprises the steps of providing a cured thermosetting

INVERSION SYMMETRY, ARCHITECTURE AND DISPERSITY, AND THEIR EFFECTS ON THERMODYNAMICS IN BULK AND CONFINED REGIONS: FROM RANDOMLY BRANCHED POLYMERS TO LINEAR CHAINS, STARS AND DENDRIMERS

Directory of Open Access Journals (Sweden)

P.D.Gujrati

2002-01-01

Full Text Available Theoretical evidence is presented in this review that architectural aspects can play an important role, not only in the bulk but also in confined geometries by using our recursive lattice theory, which is equally applicable to fixed architectures (regularly branched polymers, stars, dendrimers, brushes, linear chains, etc. and variable architectures, i.e. randomly branched structures. Linear chains possess an inversion symmetry (IS of a magnetic system (see text, whose presence or absence determines the bulk phase diagram. Fixed architectures possess the IS and yield a standard bulk phase diagram in which there exists a theta point at which two critical lines C and C' meet and the second virial coefficient A2 vanishes. The critical line C appears only for infinitely large polymers, and an order parameter is identified for this criticality. The critical line C' exists for polymers of all sizes and represents phase separation criticality. Variable architectures, which do not possess the IS, give rise to a topologically different phase diagram with no theta point in general. In confined regions next to surfaces, it is not the IS but branching and monodispersity, which becomes important in the surface regions. We show that branching plays no important role for polydisperse systems, but become important for monodisperse systems. Stars and linear chains behave differently near a surface.

Direct observation of the transition from free to constrained single segment motion in entangled polymer melts

International Nuclear Information System (INIS)

Monkenbusch, M.; Wischnewski, A.; Willner, L.; Richter, D.

2004-01-01

Incoherent neutron-spin-echo spectroscopy (NSE) has been employed to directly determine the time-dependent mean-squared segment displacement 2 > of a polymer chain in the melt covering the transition from free to constraint Rouse relaxation along the virtual tube of the reptation model. The predicted transition of the time dependence of 2 > from 2 >∝t 1/2 to ∝t 1/4 is clearly corroborated by the incoherent NSE results

Molecular rheology of branched polymers: Decoding and exploring the role of architectural dispersity through a synergy of anionic synthesis, interaction chromatography, rheometry and modeling

KAUST Repository

Van Ruymbeke, Evelyne

2014-01-01

An emerging challenge in polymer physics is the quantitative understanding of the influence of a macromolecular architecture (i.e., branching) on the rheological response of entangled complex polymers. Recent investigations of the rheology of well-defined architecturally complex polymers have determined the composition in the molecular structure and identified the role of side-products in the measured samples. The combination of different characterization techniques, experimental and/or theoretical, represents the current state-of-the-art. Here we review this interdisciplinary approach to molecular rheology of complex polymers, and show the importance of confronting these different tools for ensuring an accurate characterization of a given polymeric sample. We use statistical tools in order to relate the information available from the synthesis protocols of a sample and its experimental molar mass distribution (typically obtained from size exclusion chromatography), and hence obtain precise information about its structural composition, i.e. enhance the existing sensitivity limit. We critically discuss the use of linear rheology as a reliable quantitative characterization tool, along with the recently developed temperature gradient interaction chromatography. The latter, which has emerged as an indispensable characterization tool for branched architectures, offers unprecedented sensitivity in detecting the presence of different molecular structures in a sample. Combining these techniques is imperative in order to quantify the molecular composition of a polymer and its consequences on the macroscopic properties. We validate this approach by means of a new model asymmetric comb polymer which was synthesized anionically. It was thoroughly characterized and its rheology was carefully analyzed. The main result is that the rheological signal reveals fine molecular details, which must be taken into account to fully elucidate the viscoelastic response of entangled branched

Molecular rheology of branched polymers: decoding and exploring the role of architectural dispersity through a synergy of anionic synthesis, interaction chromatography, rheometry and modeling.

Science.gov (United States)

van Ruymbeke, E; Lee, H; Chang, T; Nikopoulou, A; Hadjichristidis, N; Snijkers, F; Vlassopoulos, D

2014-07-21

An emerging challenge in polymer physics is the quantitative understanding of the influence of a macromolecular architecture (i.e., branching) on the rheological response of entangled complex polymers. Recent investigations of the rheology of well-defined architecturally complex polymers have determined the composition in the molecular structure and identified the role of side-products in the measured samples. The combination of different characterization techniques, experimental and/or theoretical, represents the current state-of-the-art. Here we review this interdisciplinary approach to molecular rheology of complex polymers, and show the importance of confronting these different tools for ensuring an accurate characterization of a given polymeric sample. We use statistical tools in order to relate the information available from the synthesis protocols of a sample and its experimental molar mass distribution (typically obtained from size exclusion chromatography), and hence obtain precise information about its structural composition, i.e. enhance the existing sensitivity limit. We critically discuss the use of linear rheology as a reliable quantitative characterization tool, along with the recently developed temperature gradient interaction chromatography. The latter, which has emerged as an indispensable characterization tool for branched architectures, offers unprecedented sensitivity in detecting the presence of different molecular structures in a sample. Combining these techniques is imperative in order to quantify the molecular composition of a polymer and its consequences on the macroscopic properties. We validate this approach by means of a new model asymmetric comb polymer which was synthesized anionically. It was thoroughly characterized and its rheology was carefully analyzed. The main result is that the rheological signal reveals fine molecular details, which must be taken into account to fully elucidate the viscoelastic response of entangled branched

Equivalence of chain conformations in the surface region of a polymer melt and a single Gaussian chain nder critical conditions

NARCIS (Netherlands)

Skvortsov, A.M.; Leermakers, F.A.M.; Fleer, G.J.

2013-01-01

In the melt polymer conformations are nearly ideal according to Flory's ideality hypothesis. Silberberg generalized this statement for chains in the interfacial region. We check the Silberberg argument by analyzing the conformations of a probe chain end-grafted at a solid surface in a sea of

Klucel™ EF and ELF polymers for immediate-release oral dosage forms prepared by melt extrusion technology.

Science.gov (United States)

Mohammed, Noorullah Naqvi; Majumdar, Soumyajit; Singh, Abhilasha; Deng, Weibin; Murthy, Narasimha S; Pinto, Elanor; Tewari, Divya; Durig, Thomas; Repka, Michael A

2012-12-01

The objective of this research work was to evaluate Klucel™ hydroxypropylcellulose (HPC) EF and ELF polymers, for solubility enhancement as well as to address some of the disadvantages associated with solid dispersions. Ketoprofen (KPR), a Biopharmaceutics Classification System class II drug with poor solubility, was utilized as a model compound. Preliminary thermal studies were performed to confirm formation of a solid solution/dispersion of KPR in HPC matrix and also to establish processing conditions for hot-melt extrusion. Extrudates pelletized and filled into capsules exhibited a carrier-dependent release with ELF polymer exhibiting a faster release. Tablets compressed from milled extrudates exhibited rapid release owing to the increased surface area of the milled extrudate. Addition of mannitol (MNT) further enhanced the release by forming micro-pores and increasing the porosity of the extrudates. An optimized tablet formulation constituting KPR, MNT, and ELF in a 1:1:1 ratio exhibited 90% release in 15 min similar to a commercial capsule formulation. HPC polymers are non-ionic hydrophilic polymers that undergo polymer-chain-length-dependent solubilization and can be used to enhance solubility or dissolution rate of poorly soluble drugs. Dissolution/release rate could be tailored for rapid-release applications by selecting a suitable HPC polymer and altering the final dosage form. The release obtained from pellets was carrier-dependent and not drug-dependent, and hence, such a system can be effectively utilized to address solubility or precipitation issues with poorly soluble drugs in the gastrointestinal environment.

Numerical studies of the polymer melt flow in the extruder screw channel and the forming tool

Science.gov (United States)

Ershov, S. V.; Trufanova, N. M.

2017-06-01

To date, polymer compositions based on polyethylene or PVC is widely used as insulating materials. These materials processing conjugate with a number of problems during selection of the rational extrusion regimes. To minimize the time and cost when determining the technological regime uses mathematical modeling techniques. The paper discusses heat and mass transfer processes in the extruder screw channel, output adapter and the cable head. During the study were determined coefficients for three rheological models based on obtained viscosity vs. shear rate experimental data. Also a comparative analysis of this viscosimetric laws application possibility for studying polymer melt flow during its processing on the extrusion equipment was held. As a result of numerical study the temperature, viscosity and shear rate fields in the extruder screw channel and forming tool were obtained.

Structure and dynamics of confined flexible and unentangled polymer melts in highly adsorbing cylindrical pores

International Nuclear Information System (INIS)

Carrillo, Jan-Michael Y.; Sumpter, Bobby G.

2014-01-01

Coarse-grained molecular dynamics simulations are used to probe the dynamic phenomena of polymer melts confined in nanopores. The simulation results show excellent agreement in the values obtained for the normalized coherent single chain dynamic structure factor, (S(Q,Δt))/(S(Q,0)) . In the bulk configuration, both simulations and experiments confirm that the polymer chains follow Rouse dynamics. However, under confinement, the Rouse modes are suppressed. The mean-square radius of gyration 〈R g 2 〉 and the average relative shape anisotropy 〈κ 2 〉 of the conformation of the polymer chains indicate a pancake-like conformation near the surface and a bulk-like conformation near the center of the confining cylinder. This was confirmed by direct visualization of the polymer chains. Despite the presence of these different conformations, the average form factor of the confined chains still follows the Debye function which describes linear ideal chains, which is in agreement with small angle neutron scattering experiments (SANS). The experimentally inaccessible mean-square displacement (MSD) of the confined monomers, calculated as a function of radial distance from the pore surface, was obtained in the simulations. The simulations show a gradual increase of the MSD from the adsorbed, but mobile layer, to that similar to the bulk far away from the surface

Numerical analysis of the heating phase and densification mechanism in polymers selective laser melting process

Science.gov (United States)

Mokrane, Aoulaiche; Boutaous, M'hamed; Xin, Shihe

2018-05-01

The aim of this work is to address a modeling of the SLS process at the scale of the part in PA12 polymer powder bed. The powder bed is considered as a continuous medium with homogenized properties, meanwhile understanding multiple physical phenomena occurring during the process and studying the influence of process parameters on the quality of final product. A thermal model, based on enthalpy approach, will be presented with details on the multiphysical couplings that allow the thermal history: laser absorption, melting, coalescence, densification, volume shrinkage and on numerical implementation using FV method. The simulations were carried out in 3D with an in-house developed FORTRAN code. After validation of the model with comparison to results from literature, a parametric analysis will be proposed. Some original results as densification process and the thermal history with the evolution of the material, from the granular solid state to homogeneous melted state will be discussed with regards to the involved physical phenomena.

Depolymerization of post-consumer PET with multifunctional alcohol through melt processing

International Nuclear Information System (INIS)

Lessa, Tathiane C.R.F.; Mendes, Luis C.; Dias, Marcos L.

2009-01-01

The purpose of this study was to prepare oligomers from post-consumer PET with multifunctional alcohol, through melt processing, aiming to develop a new material, able to play a role as filler or property modifier. Maintaining constants the process conditions, content and kind of catalyst, the influence of the solvolysis agent on the PET depolymerization was investigated. The products were evaluated by wide-angle X-ray diffraction (WAXD) and thermogravimetry (TG/DTG). The changes in the WAXD curves and the shift of the maximum degradation temperature suggested that the ester linkages were broken being the ethylene glycol moieties replaced with hydroxyl-terminal groups of the multifunctional alcohol, as result of a transesterification reaction. The chemical structure of the new ester was named 'star-branching polymer'. (author)

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

Energy Technology Data Exchange (ETDEWEB)

Rumbles, Garry [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Reid, Obadiah G [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pace, Natalie A [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2018-02-19

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

Theoretical study of the self-assembly of Janus Bottlebrush Polymers from A-Branch-B Diblock Macromonomers

Science.gov (United States)

Gadelrab, Karim; Alexander-Katz, Alfredo; LaboratoryTheoretical Soft Materials Team

The self-assembly of block copolymers BCP has provided an impressive control over the nanoscale structure of soft matter. While the main focus of the research in the field has been directed towards simple linear diblocks, the development of advanced polymer architecture provided improved performance and access to new structures. In particular, bottlebrush BCPs (BBCPs) have interesting characteristics due to their dense functionality, high molecular weight, low levels of entanglement, and tendency to efficiently undergo rapid bulk phase separation. In this work, we are interested in theoretically studying the self-assembly of Janus-type ``A-branch-B'' BBCPs where A and B blocks can phase separate with the bottlebrush polymer backbone serving as the interface between the two blocks. Hence, the polymer backbone adds an extra constraint on the equilibrium spacing between neighboring linear diblock chains. In this regard, the segment length of the backbone separating the AB junctions has a direct effect of the observed domain spacing and effective segregation strength of the AB blocks. We employ self-consistent field theoretic SCFT simulations to capture the effect of volume fraction of different constituents and construct a phase diagram of the accessible morphologies of these BBCPs.

Hot-melt extruded filaments based on pharmaceutical grade polymers for 3D printing by fused deposition modeling.

Science.gov (United States)

Melocchi, Alice; Parietti, Federico; Maroni, Alessandra; Foppoli, Anastasia; Gazzaniga, Andrea; Zema, Lucia

2016-07-25

Fused deposition modeling (FDM) is a 3D printing technique based on the deposition of successive layers of thermoplastic materials following their softening/melting. Such a technique holds huge potential for the manufacturing of pharmaceutical products and is currently under extensive investigation. Challenges in this field are mainly related to the paucity of adequate filaments composed of pharmaceutical grade materials, which are needed for feeding the FDM equipment. Accordingly, a number of polymers of common use in pharmaceutical formulation were evaluated as starting materials for fabrication via hot melt extrusion of filaments suitable for FDM processes. By using a twin-screw extruder, filaments based on insoluble (ethylcellulose, Eudragit(®) RL), promptly soluble (polyethylene oxide, Kollicoat(®) IR), enteric soluble (Eudragit(®) L, hydroxypropyl methylcellulose acetate succinate) and swellable/erodible (hydrophilic cellulose derivatives, polyvinyl alcohol, Soluplus(®)) polymers were successfully produced, and the possibility of employing them for printing 600μm thick disks was demonstrated. The behavior of disks as barriers when in contact with aqueous fluids was shown consistent with the functional application of the relevant polymeric components. The produced filaments were thus considered potentially suitable for printing capsules and coating layers for immediate or modified release, and, when loaded with active ingredients, any type of dosage forms. Copyright © 2016 Elsevier B.V. All rights reserved.

Self organized striping in ultra thin polymer films near melt: An investigation using Monte Carlo simulation

Science.gov (United States)

Singh, Satya Pal

2018-05-01

This paper work presents the results of Monte Carlo simulation performed for ultra thin short chained polymer films near melt, under strong confinement. Thin polymer films get ruptured when annealed above their glass transition temperatures. The pattern formations are generally explained on the basis of spinodal mechanism, if the thickness of the film is of the order of few tens of nanometers i.e. film seems to tear apart in strips. The free end segments of the chains are more dynamic and coalescence into one another. This process seems to dominate over the spinodal waves resulting into a different type of dynamics. Polymer chains with 30 monomers are taken. 160, 200 and 240 chains are taken for three different cases of the studies. The three cases correspond to three different thickness of the films with 8, 10 and 12 layers of chains along direction perpendicular to the confining substrates. The bottom surface has affinity to monomers, whereas the upper surface has hard wall interaction with the monomers. Different time micrographs of the films are plotted along with density distributions of the monomers to explore the process.

Modeling of branching density and branching distribution in low-density polyethylene polymerization

NARCIS (Netherlands)

Kim, D.M.; Iedema, P.D.

2008-01-01

Low-density polyethylene (ldPE) is a general purpose polymer with various applications. By this reason, many publications can be found on the ldPE polymerization modeling. However, scission reaction and branching distribution are only recently considered in the modeling studies due to difficulties

Simulated glass-forming polymer melts: dynamic scattering functions, chain length effects, and mode-coupling theory analysis.

Science.gov (United States)

Frey, S; Weysser, F; Meyer, H; Farago, J; Fuchs, M; Baschnagel, J

2015-02-01

We present molecular-dynamics simulations for a fully flexible model of polymer melts with different chain length N ranging from short oligomers (N = 4) to values near the entanglement length (N = 64). For these systems we explore the structural relaxation of the supercooled melt near the critical temperature T c of mode-coupling theory (MCT). Coherent and incoherent scattering functions are analyzed in terms of the idealized MCT. For temperatures T > T c we provide evidence for the space-time factorization property of the β relaxation and for the time-temperature superposition principle (TTSP) of the α relaxation, and we also discuss deviations from these predictions for T ≈ T c. For T larger than the smallest temperature where the TTSP holds we perform a quantitative analysis of the dynamics with the asymptotic MCT predictions for the late β regime. Within MCT a key quantity, in addition to T c, is the exponent parameter λ. For the fully flexible polymer models studied we find that λ is independent of N and has a value (λ = 0.735 ) typical of simple glass-forming liquids. On the other hand, the critical temperature increases with chain length toward an asymptotic value T c (∞) . This increase can be described by T c (∞) - T c(N) ∼ 1/N and may be interpreted in terms of the N dependence of the monomer density ρ, if we assume that the MCT glass transition is ruled by a soft-sphere-like constant coupling parameter Γ c = ρ c T c (-1/4), where ρ c is the monomer density at T c. In addition, we also estimate T c from a Hansen-Verlet-like criterion and MCT calculations based on structural input from the simulation. For our polymer model both the Hansen-Verlet criterion and the MCT calculations suggest T c to decrease with increasing chain length, in contrast to the direct analysis of the simulation data.

Arm retraction dynamics of entangled star polymers: A forward flux sampling method study

Science.gov (United States)

Zhu, Jian; Likhtman, Alexei E.; Wang, Zuowei

2017-07-01

The study of dynamics and rheology of well-entangled branched polymers remains a challenge for computer simulations due to the exponentially growing terminal relaxation times of these polymers with increasing molecular weights. We present an efficient simulation algorithm for studying the arm retraction dynamics of entangled star polymers by combining the coarse-grained slip-spring (SS) model with the forward flux sampling (FFS) method. This algorithm is first applied to simulate symmetric star polymers in the absence of constraint release (CR). The reaction coordinate for the FFS method is determined by finding good agreement of the simulation results on the terminal relaxation times of mildly entangled stars with those obtained from direct shooting SS model simulations with the relative difference between them less than 5%. The FFS simulations are then carried out for strongly entangled stars with arm lengths up to 16 entanglements that are far beyond the accessibility of brute force simulations in the non-CR condition. Apart from the terminal relaxation times, the same method can also be applied to generate the relaxation spectra of all entanglements along the arms which are desired for the development of quantitative theories of entangled branched polymers. Furthermore, we propose a numerical route to construct the experimentally measurable relaxation correlation functions by effectively linking the data stored at each interface during the FFS runs. The obtained star arm end-to-end vector relaxation functions Φ (t ) and the stress relaxation function G(t) are found to be in reasonably good agreement with standard SS simulation results in the terminal regime. Finally, we demonstrate that this simulation method can be conveniently extended to study the arm-retraction problem in entangled star polymer melts with CR by modifying the definition of the reaction coordinate, while the computational efficiency will depend on the particular slip-spring or slip

Anisotropy of the monomer random walk in a polymer melt: local-order and connectivity effects

International Nuclear Information System (INIS)

Bernini, S; Leporini, D

2016-01-01

The random walk of a bonded monomer in a polymer melt is anisotropic due to local order and bond connectivity. We investigate both effects by molecular-dynamics simulations on melts of fully-flexible linear chains ranging from dimers (M  =  2) up to entangled polymers (M  =  200). The corresponding atomic liquid is also considered a reference system. To disentangle the influence of the local geometry and the bond arrangements, and to reveal their interplay, we define suitable measures of the anisotropy emphasising either the former or the latter aspect. Connectivity anisotropy, as measured by the correlation between the initial bond orientation and the direction of the subsequent monomer displacement, shows a slight enhancement due to the local order at times shorter than the structural relaxation time. At intermediate times—when the monomer displacement is comparable to the bond length—a pronounced peak and then decays slowly as t −1/2 , becoming negligible when the displacement is as large as about five bond lengths, i.e. about four monomer diameters or three Kuhn lengths. Local-geometry anisotropy, as measured by the correlation between the initial orientation of a characteristic axis of the Voronoi cell and the subsequent monomer dynamics, is affected at shorter times than the structural relaxation time by the cage shape with antagonistic disturbance by the connectivity. Differently, at longer times, the connectivity favours the persistence of the local-geometry anisotropy, which vanishes when the monomer displacement exceeds the bond length. Our results strongly suggest that the sole consideration of the local order is not enough to understand the microscopic origin of the rattling amplitude of the trapped monomer in the cage of the neighbours. (paper)

Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds

Energy Technology Data Exchange (ETDEWEB)

Xu, Wen-Sheng, E-mail: wsxu@uchicago.edu [James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States); Freed, Karl F., E-mail: freed@uchicago.edu [James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States); Department of Chemistry, The University of Chicago, Chicago, Illinois 60637 (United States)

2016-06-07

Telechelic polymers are chain macromolecules that may self-assemble through the association of their two mono-functional end groups (called “stickers”). A deep understanding of the relation between microscopic molecular details and the macroscopic physical properties of telechelic polymers is important in guiding the rational design of telechelic polymer materials with desired properties. The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telechelic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. 143, 024901 (2015)], but the physically associative (or called “sticky”) bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with

Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds

International Nuclear Information System (INIS)

Xu, Wen-Sheng; Freed, Karl F.

2016-01-01

Telechelic polymers are chain macromolecules that may self-assemble through the association of their two mono-functional end groups (called “stickers”). A deep understanding of the relation between microscopic molecular details and the macroscopic physical properties of telechelic polymers is important in guiding the rational design of telechelic polymer materials with desired properties. The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telechelic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. 143, 024901 (2015)], but the physically associative (or called “sticky”) bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with

Viscosity and volume properties of the Al-Cu melts

Directory of Open Access Journals (Sweden)

Kurochkin A.

2011-05-01

Full Text Available Temperature dependences of the kinematic viscosity v and the density ρ of Al-Cu melts were investigated in the same regime taking into account that viscometric experiments with the melts enriched with cupper have not been repeated since 1960th and densimetric measurements did not perform before at all. The first measurements were fulfilled using the method of dumping oscillation of a crucible filled in by a melt investigated. Its precision was as high as 1.5%. Density was measured using the gamma-absorption method with the accuracy of 0.2 to 0.3%. Crucibles of BeO were used in both the cases. In the course of the measurements a distinct branching of the heating and cooling curves were fixed below some temperature characteristic of each composition for most of the investigated samples. The branching temperature systematically changes with growth of cupper content. The authors believe that the effect is caused by the irreversible transition of the melts from microheterogeneous state inherited from the initial rough materials into a true solution state.

Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles.

Science.gov (United States)

Nakamura, Issei

2014-05-29

We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

Sum-frequency spectroscopic studies: I. Surface melting of ice, II. Surface alignment of polymers

Energy Technology Data Exchange (ETDEWEB)

Wei, Xing [Univ. of California, Berkeley, CA (United States)

2000-01-01

Surface vibrational spectroscopy via infrared-visible sum-frequency generation (SFG) has been established as a useful tool to study the structures of different kinds of surfaces and interfaces. This technique was used to study the (0001) face of hexagonal ice (Ih). SFG spectra in the O-H stretch frequency range were obtained at various sample temperatures. For the vapor(air)/ice interface, the degree of orientational order of the dangling OH bonds at the surface was measured as a function of temperature. Disordering sets in around 200 K and increases dramatically with temperature, which is strong evidence of surface melting of ice. For the other ice interfaces (silica/OTS/ice and silica/ice), a similar temperature dependence of the hydrogen bonded OH stretch peak was observed; the free OH stretch mode, however, appears to be different from that of the vapor (air)/ice interface due to interactions at the interfaces. The technique was also used to measure the orientational distributions of the polymer chains on a rubbed polyvinyl alcohol surface. Results show that the polymer chains at the surface appear to be well aligned by rubbing, and the adsorbed liquid crystal molecules are aligned, in turn, by the surface polymer chains. A strong correlation exists between the orientational distributions of the polymer chains and the liquid crystal molecules, indicating that the surface-induced bulk alignment of a liquid crystal film by rubbed polymer surfaces is via an orientational epitaxy-like mechanism. This thesis also contains studies on some related issues that are crucial to the above applications. An experiment was designed to measure SFG spectra in both reflection and transmission. The result confirms that SFG in reflection is generally dominated by the surface contribution. Another issue is the motional effect due to fast orientational motion of molecules at a surface or interface. Calculations show that the effect is significant if the molecular orientation varies

Polymer nanocomposites: polymer and particle dynamics

KAUST Repository

Kim, Daniel

2012-01-01

Polymer nanocomposites containing nanoparticles smaller than the random coil size of their host polymer chains are known to exhibit unique properties, such as lower viscosity and glass transition temperature relative to the neat polymer melt. It has been hypothesized that these unusual properties result from fast diffusion of the nanostructures in the host polymer, which facilitates polymer chain relaxation by constraint release and other processes. In this study, the effects of addition of sterically stabilized inorganic nanoparticles to entangled cis-1,4-polyisoprene and polydimethylsiloxane on the overall rheology of nanocomposites are discussed. In addition, insights about the relaxation of the host polymer chains and transport properties of nanoparticles in entangled polymer nanocomposites are presented. The nanoparticles are found to act as effective plasticizers for their entangled linear hosts, and below a critical, chemistry and molecular-weight dependent particle volume fraction, lead to reduced viscosity, glass transition temperature, number of entanglements, and polymer relaxation time. We also find that the particle motions in the polymer host are hyperdiffusive and at the nanoparticle length scale, the polymer host acts like a simple, ideal fluid and the composites\\' viscosity rises with increasing particle concentration. © 2012 The Royal Society of Chemistry.

Impact of polymer type on bioperformance and physical stability of hot melt extruded formulations of a poorly water soluble drug.

Science.gov (United States)

Mitra, Amitava; Li, Li; Marsac, Patrick; Marks, Brian; Liu, Zhen; Brown, Chad

2016-05-30

Amorphous solid dispersion formulations have been widely used to enhance bioavailability of poorly soluble drugs. In these formulations, polymer is included to physically stabilize the amorphous drug by dispersing it in the polymeric carrier and thus forming a solid solution. The polymer can also maintain supersaturation and promote speciation during dissolution, thus enabling better absorption as compared to crystalline drug substance. In this paper, we report the use of hot melt extrusion (HME) to develop amorphous formulations of a poorly soluble compound (FaSSIF solubility=1μg/mL). The poor solubility of the compound and high dose (300mg) necessitated the use of amorphous formulation to achieve adequate bioperformance. The effect of using three different polymers (HPMCAS-HF, HPMCAS-LF and copovidone), on the dissolution, physical stability, and bioperformance of the formulations was demonstrated. In this particular case, HPMCAS-HF containing HME provided the highest bioavailability and also had better physical stability as compared to extrudates using HPMCAS-LF and copovidone. The data demonstrated that the polymer type can have significant impact on the formulation bioperformance and physical stability. Thus a thorough understanding of the polymer choice is imperative when designing an amorphous solid dispersion formulation, such that the formulation provides robust bioperformance and has adequate shelf life. Copyright © 2016 Elsevier B.V. All rights reserved.

Distribution of degrees of polymerization in statistically branched polymers with tetrafunctional branch points: model calculations

Czech Academy of Sciences Publication Activity Database

Netopilík, Miloš; Kratochvíl, Pavel

2006-01-01

Roč. 55, č. 2 (2006), s. 196-203 ISSN 0959-8103 R&D Projects: GA AV ČR IAA100500501; GA AV ČR IAA4050403; GA AV ČR IAA4050409; GA ČR GA203/03/0617 Institutional research plan: CEZ:AV0Z40500505 Keywords : statistical branching * tetrafunctional branch points * molecular-weight distribution Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.475, year: 2006

Branch Point Withdrawal in Elongational Startup Flow by Time-Resolved Small Angle Neutron Scattering

KAUST Repository

Ruocco, N.

2016-05-27

We present a small angle neutron scattering (SANS) investigation of a blend composed of a dendritic polymer and a linear matrix with comparable viscosity in start-up of an elongational flow at Tg + 50. The two-generation dendritic polymer is diluted to 10% by weight in a matrix of a long well-entangled linear chains. Both components consist of mainly 1,4-cis-polyisoprene but differ in isotopic composition. The resulting scattering contrast is sufficiently high to permit time-resolved measurements of the system structure factor during the start-up phase and to follow the retraction processes involving the inner sections of the branched polymer in the nonlinear deformation response. The outer branches and the linear matrix, on the contrary, are in the linear deformation regime. The linear matrix dominates the rheological signature of the blend and the influence of the branched component can barely be detected. However, the neutron scattering intensity is predominantly that of the (branched) minority component so that its dynamics is clearly evident. In the present paper, we use the neutron scattering data to validate the branch point withdrawal process, which could not be unambiguously discerned from rheological measurements in this blend. The maximal tube stretch that the inner branches experience, before the relaxed outer arm material is incorporated into the tube is determined. The in situ scattering experiments demonstrate for the first time the leveling-off of the strain as the result of branch point withdrawal and chain retraction directly on the molecular level. We conclude that branch point motion in the mixture of architecturally complex polymers occurs earlier than would be expected in a purely branched system, presumably due to the different topological environment that the linear matrix presents to the hierarchically deep-buried tube sections. © 2016 American Chemical Society.

Branch Point Withdrawal in Elongational Startup Flow by Time-Resolved Small Angle Neutron Scattering

KAUST Repository

Ruocco, N.; Auhl, D.; Bailly, C.; Lindner, P.; Pyckhout-Hintzen, W.; Wischnewski, A.; Leal, L. G.; Hadjichristidis, Nikolaos; Richter, D.

2016-01-01

We present a small angle neutron scattering (SANS) investigation of a blend composed of a dendritic polymer and a linear matrix with comparable viscosity in start-up of an elongational flow at Tg + 50. The two-generation dendritic polymer is diluted to 10% by weight in a matrix of a long well-entangled linear chains. Both components consist of mainly 1,4-cis-polyisoprene but differ in isotopic composition. The resulting scattering contrast is sufficiently high to permit time-resolved measurements of the system structure factor during the start-up phase and to follow the retraction processes involving the inner sections of the branched polymer in the nonlinear deformation response. The outer branches and the linear matrix, on the contrary, are in the linear deformation regime. The linear matrix dominates the rheological signature of the blend and the influence of the branched component can barely be detected. However, the neutron scattering intensity is predominantly that of the (branched) minority component so that its dynamics is clearly evident. In the present paper, we use the neutron scattering data to validate the branch point withdrawal process, which could not be unambiguously discerned from rheological measurements in this blend. The maximal tube stretch that the inner branches experience, before the relaxed outer arm material is incorporated into the tube is determined. The in situ scattering experiments demonstrate for the first time the leveling-off of the strain as the result of branch point withdrawal and chain retraction directly on the molecular level. We conclude that branch point motion in the mixture of architecturally complex polymers occurs earlier than would be expected in a purely branched system, presumably due to the different topological environment that the linear matrix presents to the hierarchically deep-buried tube sections. © 2016 American Chemical Society.

Melt rheology and its applications in the plastics industry

CERN Document Server

Dealy, John M

2013-01-01

This is the second edition of Melt Rheology and its Role in Plastics Processing, although the title has changed to reflect its broadened scope. Advances in the recent years in rheometer technology and polymer science have greatly enhanced the usefulness of rheology in the plastics industry. It is now possible to design polymers having specific molecular structures and to predict the flow properties of melts having those structures. In addition, rheological properties now provide more precise information about molecular structure. This book provides all the information that is needed for the intelligent application of rheology in the development of new polymers, the determination of molecular structure and the correlation of processability with laboratory test data. Theory and equations are limited to what is essential for the use of rheology in the characterization of polymers, the development of new plastics materials and the prediction of plastics processing behavior. The emphasis is on information that wil...

Reactive polymer fused deposition manufacturing

Science.gov (United States)

Kunc, Vlastimil; Rios, Orlando; Love, Lonnie J.; Duty, Chad E.; Johs, Alexander

2017-05-16

Methods and compositions for additive manufacturing that include reactive or thermosetting polymers, such as urethanes and epoxies. The polymers are melted, partially cross-linked prior to the depositing, deposited to form a component object, solidified, and fully cross-linked. These polymers form networks of chemical bonds that span the deposited layers. Application of a directional electromagnetic field can be applied to aromatic polymers after deposition to align the polymers for improved bonding between the deposited layers.

Systematic coarse-graining of the dynamics of entangled polymer melts: the road from chemistry to rheology

International Nuclear Information System (INIS)

Padding, J T; Briels, W J

2011-01-01

For optimal processing and design of entangled polymeric materials it is important to establish a rigorous link between the detailed molecular composition of the polymer and the viscoelastic properties of the macroscopic melt. We review current and past computer simulation techniques and critically assess their ability to provide such a link between chemistry and rheology. We distinguish between two classes of coarse-graining levels, which we term coarse-grained molecular dynamics (CGMD) and coarse-grained stochastic dynamics (CGSD). In CGMD the coarse-grained beads are still relatively hard, thus automatically preventing bond crossing. This also implies an upper limit on the number of atoms that can be lumped together (up to five backbone carbon atoms) and therefore on the longest chain lengths that can be studied. To reach a higher degree of coarse-graining, in CGSD many more atoms are lumped together (more than ten backbone carbon atoms), leading to relatively soft beads. In that case friction and stochastic forces dominate the interactions, and action must be undertaken to prevent bond crossing. We also review alternative methods that make use of the tube model of polymer dynamics, by obtaining the entanglement characteristics through a primitive path analysis and by simulation of a primitive chain network. We finally review super-coarse-grained methods in which an entire polymer is represented by a single particle, and comment on ways to include memory effects and transient forces. (topical review)

Quaternized triethanolamine-sebacoyl moieties in highly branched polymer architecture as a host for the entrapment of acid dyes in aqueous solutions

Directory of Open Access Journals (Sweden)

Meriem Bendjelloul

2017-03-01

Full Text Available This paper reports the synthesis of a hyperbranched polymer by a cost-effective one-step copolymerization of A3 and B2 monomers, namely, triethanolamine and sebacoyl chloride, respectively, followed by methylation of tertiary amine groups. The structure of the hyperbranched polymer QTEAS as an efficient material for the removal of acid dyes was demonstrated by Fourier transform infrared spectroscopy (FTIR, cross polarization magic angle spinning (CPMAS 13C NMR, thermogravimetric analysis (TGA, powder X-ray diffraction (DRX and scanning electron microscopy (SEM. The removal of indigo carmine (IC and Evans blue (EB was expected to be driven by the electrostatic attraction between positively charged quaternary ammonium groups within the hyperbranched polymer and the negatively charged dyes. The removal process was found to be closely connected to the total number of sulfonate groups on the surface of the dyes. Nonetheless, the ionic strength does not affect the dyes' removal efficiency by the hyperbranched polymer. The sorption capacities at saturation of the monolayer qmax were determined to be 213.22 mg g−1 and 214.13 mg g−1, for IC and EB, respectively, thus showing the greater affinity of QTEAS sorbent for both dyes. Despite its extended molecular structure, EB is removed with the same effectiveness as IC. Finally, the great efficiency of the highly branched polymer for dye removal from colored wastewater was clearly demonstrated.

Multiscale simulations of star polymer melts

NARCIS (Netherlands)

Liu, L.

2014-01-01

Depending on the architecture, polymers are observed to show different dynamical and rheological properties. The results obtained from this work will not only contribute to a fundamental understanding of the character of star polymeric systems, but also possibly help to design industrial

Topological analysis of long-chain branching patterns in polyolefins.

Science.gov (United States)

Bonchev, D; Markel, E; Dekmezian, A

2001-01-01

Patterns in molecular topology and complexity for long-chain branching are quantitatively described. The Wiener number, the topological complexity index, and a new index of 3-starness are used to quantify polymer structure. General formulas for these indices were derived for the cases of 3-arm star, H-shaped, and B-arm comb polymers. The factors affecting complexity in monodisperse polymer systems are ranked as follows: number of arms > arm length > arm central position approximately equal to arm clustering > total molecular weight approximately equal to backbone molecular weight. Topological indices change rapidly and then plateau as the molecular weight of branches on a polyolefin backbone increases from 0 to 5 kD. Complexity calculations relate 2-arm or 3-arm comb structures to the corresponding 3-arm stars of equivalent complexity but much higher molecular weight. In a subsequent paper, we report the application of topological analysis for developing structure/property relationships for monodisperse polymers. While the focus of the present work is on the description of monodisperse, well-defined architectures, the methods may be extended to the description of polydisperse systems.

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

Science.gov (United States)

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

2016-02-01

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

Acrylic and metal based Y-branch plastic optical fiber splitter with optical NOA63 polymer waveguide taper region

Science.gov (United States)

Ehsan, Abang Annuar; Shaari, Sahbudin; Rahman, Mohd Kamil Abd.

2011-01-01

We proposed a simple low-cost acrylic and metal-based Y-branch plastic optical fiber (POF) splitter which utilizes a low cost optical polymer glue NOA63 as the main waveguiding medium at the waveguide taper region. The device is composed of three sections: an input POF waveguide, a middle waveguide taper region and output POF waveguides. A desktop high speed CNC engraver is utilized to produce the mold inserts used for the optical devices. Short POF fibers are inserted into the engraved slots at the input and output ports. UV curable optical polymer glue NOA63 is injected into the waveguide taper region and cured. The assembling is completed when the top plate is positioned to enclose the device structure and connecting screws are secured. Both POF splitters have an average insertion loss of 7.8 dB, coupling ratio of 55: 45 and 57: 43 for the acrylic and metal-based splitters respectively. The devices have excess loss of 4.82 and 4.73 dB for the acrylic and metal-based splitters respectively.

Reversed Extension Flow of Polymer melts

DEFF Research Database (Denmark)

Rasmussen, Henrik K.; Nielsen, Jens Kromann

2007-01-01

The measurement of the startup of uni axial elongational flow (potentially until steady state) followed by reversed bi axial flow, both with a constant elongational rate was made possible using a Filament Stretching Rheometer (FSR). The filament stretching rheometer rheometer is surrounded...... by a thermostated environment and allows measurements on polymeric melts and liquids from room temperatures until 200 °C. In the experiments the Hencky strain at which the stress becomes zero (the recovery strain) of the reversed flow can be identified....

Modelling Polymer Deformation during 3D Printing

Science.gov (United States)

McIlroy, Claire; Olmsted, Peter

Three-dimensional printing has the potential to transform manufacturing processes, yet improving the strength of printed parts, to equal that of traditionally-manufactured parts, remains an underlying issue. The fused deposition modelling technique involves melting a thermoplastic, followed by layer-by-layer extrusion to fabricate an object. The key to ensuring strength at the weld between layers is successful inter-diffusion. However, prior to welding, both the extrusion process and the cooling temperature profile can significantly deform the polymer micro-structure and, consequently, how well the polymers are able to ``re-entangle'' across the weld. In particular, polymer alignment in the flow can cause de-bonding of the layers and create defects. We have developed a simple model of the non-isothermal extrusion process to explore the effects that typical printing conditions and material rheology have on the conformation of a polymer melt. In particular, we incorporate both stretch and orientation using the Rolie-Poly constitutive equation to examine the melt structure as it flows through the nozzle, the subsequent alignment with the build plate and the resulting deformation due to the fixed nozzle height, which is typically less than the nozzle radius.

UHMW Ziegler–Natta polyethylene: Synthesis, crystallization, and melt behavior

KAUST Repository

Atiqullah, Muhammad

2017-04-26

The fabrication of normal and UHMW PE end-products involves melting and crystallization of the polymer. Therefore, the melt behavior and crystallization of as-synthesized UHMW PE, and NMW PE and E-1-hexene copolymer have been studied using a new nonisothermal crystallization model, Flory\\'s equilibrium theory and ethylene sequence length distribution concept (SLD), Gibbs–Thompson equation, and DSC experiments. By using this approach, the effects of MW, 1-hexene incorporation, ethylene SLD, the level of undercooling θ, and crystal surface free energy D on crystallite stability, relative crystallinity α, instantaneous crystallinity χ, the crystallization kinetic triplet, crystallization entropy, and lamellar thickness distribution (LTD) have been evaluated. Consequently, this study reports insightful new results, interpretations, and explanations regarding the melting and crystallization of the aforementioned polymers. The UHMW PE results significantly differ from the NMW PE and E-1-hexene copolymer ones. Ethylene sequences shorter than the so called minimum crystallizable ethylene sequence length, irrespective of E-1-hexene copolymer MW, can also crystallize. Additionally, the polymer preparation shows that the catalyst coordination environment and symmetry, as well as achiral ethylene versus prochiral α-olefin steric encumbrance and competitive diffusion affect the synthesis of UHMW PE, particularly the corresponding UHMW copolymers.

Properties of Confined Star-Branched and Linear Chains. A Monte Carlo Simulation Study

International Nuclear Information System (INIS)

Romiszowski, P.; Sikorski, A.

2004-01-01

A model of linear and star-branched polymer chains confined between two parallel and impenetrable surfaces was built. The polymer chains were restricted to a simple cubic lattice. Two macromolecular architectures of the chain: linear and star branched (consisted of f = 3 branches of equal length) were studied. The excluded volume was the only potential introduced into the model (the athermal system). Monte Carlo simulations were carried out using a sampling algorithm based on chain's local changes of conformation. The simulations were carried out at different confinement conditions: from light to high chain's compression. The scaling of chain's size with the chain length was studied and discussed. The influence of the confinement and the macromolecular architecture on the shape of a chain was studied. The differences in the shape of linear and star-branched chains were pointed out. (author)

Precision moulding of polymer micro components

DEFF Research Database (Denmark)

Tosello, Guido

2008-01-01

The present research work contains a study concerning polymer micro components manufacturing by means of the micro injection moulding (µIM) process. The overall process chain was considered and investigated during the project, including part design and simulation, tooling, process analysis, part...... optimization, quality control, multi-material solutions. A series of experimental investigations were carried out on the influence of the main µIM process factors on the polymer melt flow within micro cavities. These investigations were conducted on a conventional injection moulding machine adapted...... to the production of micro polymer components, as well as on a micro injection moulding machine. A new approach based on coordinate optical measurement of flow markers was developed during the project for the characterization of the melt flow. In-line pressure measurements were also performed to characterize...

Transient extensional viscosity of polymer melts in the filament stretching rheometer

DEFF Research Database (Denmark)

Rasmussen, Henrik Koblitz; Bach, Anders; Bastian, Heike

2002-01-01

In many polymer processing operations, the polymer molecules becomes highly elongated and the extensional viscosity becomes an inportant parameter in estimating properties during and after the process.......In many polymer processing operations, the polymer molecules becomes highly elongated and the extensional viscosity becomes an inportant parameter in estimating properties during and after the process....

Study of PP/Polybutene Blends Modified by Gamma Irradiation and HMS-PP/Polybutene Blends

International Nuclear Information System (INIS)

Lugao, A. B.

2006-01-01

The polypropylene (PP) has been applied to a wide range of production due to its various excellent properties such as cheapness, high stiffness, chemical resistance, no environmental pollution when incinerated, low specific density and good mechanical properties. However, PP is a linear polymer which exhibits low melt strength. One of the effective approaches to achieve high melt strength (HMS) is to add chain branches onto backbone polymers. High melt strength polypropylene (HMS-PP) has been recently developed and introduced in the market by the major international polypropylene producers. As a consequence different methods have been applied to modify polypropylenes by chain branches. The technology obtained by IPEN together with EMBRARAD and BRASKEM comprises chain branches added onto backbone species using gamma radiation, which is generated from a Co 6 0 source. Such radiation is very convenient in order to improve polymer materials by grafting, crosslinking and degradation. Another important approach to the development of polymer materials is based on the combination of different polymers into a new product having some of the desired properties of each component. In this work, gamma irradiation technique was used to induce chemical changes in commercial polypropylene (HMS-PP) that was after blended with polybutene and in polypropylene/polybutene blends. The samples were irradiated with a 60 C o source at doses of 12,5 and 20kGy in the presence of acetylene. It was investigated how the two different routes of blends processing can modify their properties. Indeed the results from melt flow, gel fraction and rheology reveal the influence of the process route in the blends properties. Effects on the elongation at break and break strength were observed by the results of mechanical tests. The results from rheology demonstrated an increase in melt strength and drawability of the blends

Small angle scattering and polymers

International Nuclear Information System (INIS)

Cotton, J.P.

1996-01-01

The determination of polymer structure is a problem of interest for both statistical physics and industrial applications. The average polymer structure is defined. Then, it is shown why small angle scattering, associated with isotopic substitution, is very well suited to the measurement of the chain conformation. The corresponding example is the old, but pedagogic, measurement of the chain form factor in the polymer melt. The powerful contrast variation method is illustrated by a recent determination of the concentration profile of a polymer interface. (author) 12 figs., 48 refs

Melted flux liquids in high-Tc superconductors

International Nuclear Information System (INIS)

Nelson, D.R.

1989-01-01

A theory of the entangles flux liquids which arise in the new high-T c superconductors is reviewed. New physics appears because of the weak interplanar couplings and high critical temperatures in these materials. Flux line wandering melts the conventional Abrikosov flux lattice over large portions of the phase diagram and leads to a novel entangled vortex state. The authors suggest that a heavily entangled flux liquid could exhibit glassy behavior on experimental time scales, in analogy with viscoelastic behavior in dense polymer melts

Pengaruh Kecepatan Pendinginan Terhadap Perubahan Volume Leburan Polymer Crystalline dan Non-Crystalline

OpenAIRE

Fahrurrozi, Mohammad; Moristanto, Bagus Senowulung dan

2003-01-01

AbstractThe study was directed to develop a method to predict the influence of the rate of cooling to the degree of crystallittitv (DOC) and volume change of crystalline polymers. Crystalline polymer melts exhibit volume shrinkage on cooling below melting point due to crystallization. Crystallization and volunrc shrinkage will proceed with varies rate as long as the temperature is above the glass tansition temperatrre. DOC achieved by polymer is not only determined by the inherent crystallini...

Dysprosium-free melt-spun permanent magnets

International Nuclear Information System (INIS)

Brown, D N; Wu, Z; He, F; Miller, D J; Herchenroeder, J W

2014-01-01

Melt-spun NdFeB powders can be formed into a number of different types of permanent magnet for a variety of applications in electronics, automotive and clean technology industries. The melt-spinning process produces flake powder with a fine uniform array of nanoscale Nd 2 Fe 14 B grains. These powders can be net-shape formed into isotropic polymer-bonded magnets or hot formed into fully dense magnets. This paper discusses the influence of heavy rare earth elements and microstructure on the magnetic performance, thermal stability and material cost of NdFeB magnets. Evidence indicates that melt-spun nanocrystalline NdFeB magnets are less dependent on heavy rare earth elements for high-temperature performance than the alternative coarser-grained sintered NdFeB magnets. In particular, hot-pressed melt-spun magnets are an attractive low-cost solution for applications that require thermal stability up to 175–200 °C. (paper)

Dysprosium-free melt-spun permanent magnets.

Science.gov (United States)

Brown, D N; Wu, Z; He, F; Miller, D J; Herchenroeder, J W

2014-02-12

Melt-spun NdFeB powders can be formed into a number of different types of permanent magnet for a variety of applications in electronics, automotive and clean technology industries. The melt-spinning process produces flake powder with a fine uniform array of nanoscale Nd2Fe14B grains. These powders can be net-shape formed into isotropic polymer-bonded magnets or hot formed into fully dense magnets. This paper discusses the influence of heavy rare earth elements and microstructure on the magnetic performance, thermal stability and material cost of NdFeB magnets. Evidence indicates that melt-spun nanocrystalline NdFeB magnets are less dependent on heavy rare earth elements for high-temperature performance than the alternative coarser-grained sintered NdFeB magnets. In particular, hot-pressed melt-spun magnets are an attractive low-cost solution for applications that require thermal stability up to 175-200 °C.

PGE mineralization and melt composition of chromitites in Proterozoic ophiolite complexes of Eastern Sayan, Southern Siberia

Directory of Open Access Journals (Sweden)

O. Kiseleva

2017-07-01

Full Text Available The Ospino-Kitoi and Kharanur ultrabasic massifs represent the northern and southern ophiolite branches respectively of the Upper Onot ophiolitic nappe and they are located in the southeastern part of the Eastern Sayan (SEPES ophiolites. Podiform chromitites with PGE mineralization occur as lensoid pods within dunites and rarely in harzburgites or serpentinized peridotites. The chromitites are classified into type I and type II based on their Cr#. Type I (Cr# = 59–85 occurs in both northern and southern branches, whereas type II (Cr# = 76–90 occurs only in the northern branch. PGE contents range from ∑PGE 88–1189 ppb, Pt/Ir 0.04–0.42 to ∑PGE 250–1700 ppb, Pt/Ir 0.03–0.25 for type I chromitites of the northern and southern branches respectively. The type II chromitites of the northern branch have ∑PGE contents higher than that of type I (468–8617 ppb, Pt/Ir 0.1–0.33. Parental melt compositions, in equilibrium with podiform chromitites, are in the range of boninitic melts and vary in Al2O3, TiO2 and FeO/MgO contents from those of type I and type II chromitites. Calculated melt compositions for type I chromitites are (Al2O3melt = 10.6–13.5 wt.%, (TiO2melt = 0.01–0.44 wt.%, (Fe/Mgmelt = 0.42–1.81; those for type II chromitites are: (Al2O3melt = 7.8–10.5 wt.%, (TiO2melt = 0.01–0.25 wt.%, (Fe/Mgmelt = 0.5–2.4. Chromitites are further divided into Os-Ir-Ru (I and Pt-Pd (II based on their PGE patterns. The type I chromitites show only the Os-Ir-Ru pattern whereas type II shows both Os-Ir-Ru and Pt-Pd patterns. PGE mineralization in type I chromitites is represented by the Os-Ir-Ru system, whereas in type II it is represented by the Os-Ir-Ru-Rh-Pt system. These results indicate that chromitites and PGE mineralization in the northern branch formed in a suprasubduction setting from a fluid-rich boninitic melt during active subduction. However, the chromitites and PGE mineralization of the southern

Phenomenology of polymer solution dynamics

National Research Council Canada - National Science Library

Phillies, George D. J

2011-01-01

... solutions, not dilute solutions or polymer melts. From centrifugation and solvent dynamics to viscosity and diffusion, experimental measurements and their quantitative representations are the core of the discussion...

Morphology of blends of linear and long-chain-branched polyethylenes in the solid state: A study by SANS, SAXS, and DSC

International Nuclear Information System (INIS)

Wignall, G.D.; Londono, J.D.; Lin, J.S.; Alamo, R.G.; Galante, M.J.; Mandelkern, L.

1995-01-01

Differential scanning calorimetry (DSC), small-angle neutron scattering (SANS), and X-ray scattering (SAXS) have been used to investigate the solid-state morphology of blends of linear (high density) and long-chain-branched (low-density) polyethylenes (HDPE/LDPE). The blends are homogeneous in the melt, as previously demonstrated by SANS using the contrast obtained by deuterating the linear polymer. However, due to the structural and melting point differences (∼ 20 C) between HDPE and LDPE, the components may phase segregate on slow cooling (0.75 C/min). For high concentrations (φ ≥ 0.5) of HDPE, relatively high rates of crystallization of the linear component lead to the formation of separate stacks of HDPE and LDPE lamellae, as indicated by two-peak SAXS curves. For predominantly branched blends, the difference in crystallization rate of the components becomes smaller and only one SAXS peak is observed, indicating that the two species are in the same lamellar stack. Moreover, the phases no longer consist of the pure component and the HDPE lamellae contain up to 15--20% LDPE (and vice versa). Rapid quenching into dry ice/2-propanol (-78 C) produces only one SAXS peak (and hence one lamellar stack) over the whole concentration range. The blends show extensive cocrystallization, along with a tendency for the branched material to be preferentially located in the amorphous interlamellar regions. For high concentrations (φ > 0.5) of HDPE-D, the overall scattering length density (SLD) is high and the excess concentration of LDPE between the lamellae enhances the SLD contrast between the crystalline and amorphous phases. Thus, the interlamellar spacing (long period) is clearly visible in the SANS pattern. The blend morphology is a strong function of the quenching rate, and samples quenched less rapidly (e.g., into water at 23 C) are similar to slowly cooled blends

Effect of polymer melt wall slip on the flow balance of profile extrusion dies

Science.gov (United States)

Carneiro, Olga S.; Ferrás, Luís L.; Pinho, Fernando T.; Nóbrega, João M.

2013-04-01

This work describes the implementation of the wall slip boundary condition in an in-house developed 3D numerical code based on the Finite Volume Method. For this purpose, several phenomenological models relating the velocity and the shear stress at the wall were implemented. This new feature is verified using a simple case study, by comparing the numerical results with those obtained through the corresponding analytical solution. Then, the potentialities of the new code are illustrated performing flow simulations of a polymer melt in a complex flow channel. The results obtained show that the slip at the wall influences the flow distribution at the die flow channel outlet. Therefore, and to assess the relevance of slippage in the optimal die geometry, the automatic optimization of a die flow channel, required for the production of a specific thermoplastic profile, is performed using both the no-slip and slip boundary conditions, together with two alternative optimization strategies. It is shown that slip favors the flow balance of the dies and also other issues of its performance.

Comparison of the Photovoltaic Characteristics and Nanostructure of Fullerenes Blended with Conjugated Polymers with Siloxane-Terminated and Branched Aliphatic Side Chains

KAUST Repository

Kim, Do Hwan

2013-02-12

All-organic bulk heterojunction solar cells based on blends of conjugated polymers with fullerenes have recently surpassed the 8% efficiency mark and are well on their way to the industrially relevant ∼15% threshold. Using a low band-gap conjugated polymer, we have recently shown that polymer side chain engineering can lead to dramatic improvement in the in-plane charge carrier mobility. In this article, we investigate the effectiveness of siloxy side chain derivatization in controlling the photovoltaic performance of polymer:[6,6]-phenyl-C[71]-butyric acid methyl ester (PC71BM) blends and hence its influence on charge transport in the out-of-plane direction relevant for organic solar cells. We find that, in neat blends, the photocurrent of the polymer with siloxy side chains (PII2T-Si) is 4 times greater than that in blends using the polymer with branched aliphatic side chains (PII2T-ref). This difference is due to a larger out-of-plane hole mobility for PII2T-Si brought about by a largely face-on crystallite orientation as well as more optimal nanoscale polymer:PC71BM mixing. However, upon incorporating a common processing additive, 1,8-diiodooctane (DIO), into the spin-casting blend solution and following optimization, the PII2T-ref:PC71BM OPV device performance undergoes a large improvement and becomes the better-performing device, almost independent of DIO concentration (>1%). We find that the precise amount of DIO plays a larger role in determining the efficiency of PII2T-Si:PC71BM, and even at its maximum, the device performance lags behind optimized PII2T-ref:PC71BM blends. Using a combination of atomic force microscopy and small- and wide-angle X-ray scattering, we are able to elucidate the morphological modifications associated with the DIO-induced changes in both the nanoscale morphology and the molecular packing in blend films. © 2012 American Chemical Society.

Hot melt extrusion versus spray drying: hot melt extrusion degrades albendazole.

Science.gov (United States)

Hengsawas Surasarang, Soraya; Keen, Justin M; Huang, Siyuan; Zhang, Feng; McGinity, James W; Williams, Robert O

2017-05-01

The purpose of this study was to enhance the dissolution properties of albendazole (ABZ) by the use of amorphous solid dispersions. Phase diagrams of ABZ-polymer binary mixtures generated from Flory-Huggins theory were used to assess miscibility and processability. Forced degradation studies showed that ABZ degraded upon exposure to hydrogen peroxide and 1 N NaOH at 80 °C for 5 min, and the degradants were albendazole sulfoxide (ABZSX), and ABZ impurity A, respectively. ABZ was chemically stable following exposure to 1 N HCl at 80 °C for one hour. Thermal degradation profiles show that ABZ, with and without Kollidon ® VA 64, degraded at 180 °C and 140 °C, respectively, which indicated that ABZ could likely be processed by thermal processing. Following hot melt extrusion, ABZ degraded up to 97.4%, while the amorphous ABZ solid dispersion was successfully prepared by spray drying. Spray-dried ABZ formulations using various types of acids (methanesulfonic acid, sulfuric acid and hydrochloric acid) and polymers (Kollidon ® VA 64, Soluplus ® and Eudragit ® E PO) were studied. The spray-dried ABZ with methanesulfonic acid and Kollidon ® VA 64 substantially improved non-sink dissolution in acidic media as compared to bulk ABZ (8-fold), physical mixture of ABZ:Kollidon ® VA 64 (5.6-fold) and ABZ mesylate salt (1.6-fold). No degradation was observed in the spray-dried product for up to six months and less than 5% after one-year storage. In conclusion, amorphous ABZ solid dispersions in combination with an acid and polymer can be prepared by spray drying to enhance dissolution and shelf-stability, whereas those made by melt extrusion are degraded.

Transient extensional viscosity of polymers in the filament strecthing rheometer. A. Bach, H.K. Rasmussen, O. Hassager

DEFF Research Database (Denmark)

Rasmussen, Henrik Koblitz; Bach, Anders; Hassager, Ole

2002-01-01

We investigate the transient uni-axial eextensional viscosity of polymer melts by means of a filament strecthing rheometer.......We investigate the transient uni-axial eextensional viscosity of polymer melts by means of a filament strecthing rheometer....

Flow boundary conditions for chain-end adsorbing polymer blends.

Science.gov (United States)

Zhou, Xin; Andrienko, Denis; Delle Site, Luigi; Kremer, Kurt

2005-09-08

Using the phenol-terminated polycarbonate blend as an example, we demonstrate that the hydrodynamic boundary conditions for a flow of an adsorbing polymer melt are extremely sensitive to the structure of the epitaxial layer. Under shear, the adsorbed parts (chain ends) of the polymer melt move along the equipotential lines of the surface potential whereas the adsorbed additives serve as the surface defects. In response to the increase of the number of the adsorbed additives the surface layer becomes thinner and solidifies. This results in a gradual transition from the slip to the no-slip boundary condition for the melt flow, with a nonmonotonic dependence of the slip length on the surface concentration of the adsorbed ends.

Role of polymer matrix on photo-sensitivity of CdSe polymer nanocomposites

Science.gov (United States)

Kaur, Ramneek; Tripathi, S. K.

2018-04-01

This paper reports the effect of three different polymer matrices (PVP, PMMA and PVK) and Ag doping on the photo-sensitivity of CdSe polymer nanocomposites. The results reveal that the photoconductivity is high for linear chain polymer nanocomposites as compared to aromatic ones with decreasing trend as: CdSe-PMMA > CdSe-PVP > CdSe-PVK. The large substituents or branches along the polymer backbone hinder the stacking sequences in CdSe-PVK nanocomposites resulting in lowest photoconductivity. On contrary, CdSe-PVK nanocomposite exhibit highest photosensitivity. The reason behind it is the low value of dark conductivity in CdSe-PVK nanocomposite and photoconductive PVK matrix. With Ag doping, no considerable effect on the value of photosensitivity has been observed. The obtained results indicate that the photo-conducting properties of these polymer nanocomposites can be tuned by using different polymer matrices.

Nucleation in Polymers and Soft Matter

Science.gov (United States)

Xu, Xiaofei; Ting, Christina L.; Kusaka, Isamu; Wang, Zhen-Gang

2014-04-01

Nucleation is a ubiquitous phenomenon in many physical, chemical, and biological processes. In this review, we describe recent progress on the theoretical study of nucleation in polymeric fluids and soft matter, including binary mixtures (polymer blends, polymers in poor solvents, compressible polymer-small molecule mixtures), block copolymer melts, and lipid membranes. We discuss the methodological development for studying nucleation as well as novel insights and new physics obtained in the study of the nucleation behavior in these systems.

Laser Processing of Metals and Polymers

Energy Technology Data Exchange (ETDEWEB)

Singaravelu, Senthilraja [Old Dominion Univ., Norfolk, VA (United States)

2012-05-01

A laser offers a unique set of opportunities for precise delivery of high quality coherent energy. This energy can be tailored to alter the properties of material allowing a very flexible adjustment of the interaction that can lead to melting, vaporization, or just surface modification. Nowadays laser systems can be found in nearly all branches of research and industry for numerous applications. Sufficient evidence exists in the literature to suggest that further advancements in the field of laser material processing will rely significantly on the development of new process schemes. As a result they can be applied in various applications starting from fundamental research on systems, materials and processes performed on a scientific and technical basis for the industrial needs. The interaction of intense laser radiation with solid surfaces has extensively been studied for many years, in part, for development of possible applications. In this thesis, I present several applications of laser processing of metals and polymers including polishing niobium surface, producing a superconducting phase niobium nitride and depositing thin films of niobium nitride and organic material (cyclic olefin copolymer). The treated materials were examined by scanning electron microscopy (SEM), electron probe microanalysis (EPMA), atomic force microscopy (AFM), high resolution optical microscopy, surface profilometry, Fourier transform infrared spectroscopy (FTIR) and x-ray diffraction (XRD). Power spectral density (PSD) spectra computed from AFM data gives further insight into the effect of laser melting on the topography of the treated niobium.

Thermodynamic scaling of dynamics in polymer melts: predictions from the generalized entropy theory.

Science.gov (United States)

Xu, Wen-Sheng; Freed, Karl F

2013-06-21

Many glass-forming fluids exhibit a remarkable thermodynamic scaling in which dynamic properties, such as the viscosity, the relaxation time, and the diffusion constant, can be described under different thermodynamic conditions in terms of a unique scaling function of the ratio ρ(γ)∕T, where ρ is the density, T is the temperature, and γ is a material dependent constant. Interest in the scaling is also heightened because the exponent γ enters prominently into considerations of the relative contributions to the dynamics from pressure effects (e.g., activation barriers) vs. volume effects (e.g., free volume). Although this scaling is clearly of great practical use, a molecular understanding of the scaling remains elusive. Providing this molecular understanding would greatly enhance the utility of the empirically observed scaling in assisting the rational design of materials by describing how controllable molecular factors, such as monomer structures, interactions, flexibility, etc., influence the scaling exponent γ and, hence, the dynamics. Given the successes of the generalized entropy theory in elucidating the influence of molecular details on the universal properties of glass-forming polymers, this theory is extended here to investigate the thermodynamic scaling in polymer melts. The predictions of theory are in accord with the appearance of thermodynamic scaling for pressures not in excess of ~50 MPa. (The failure at higher pressures arises due to inherent limitations of a lattice model.) In line with arguments relating the magnitude of γ to the steepness of the repulsive part of the intermolecular potential, the abrupt, square-well nature of the lattice model interactions lead, as expected, to much larger values of the scaling exponent. Nevertheless, the theory is employed to study how individual molecular parameters affect the scaling exponent in order to extract a molecular understanding of the information content contained in the exponent. The chain

Self-Healing Composite of Thermoset Polymer and Programmed Super Contraction Fibers

Science.gov (United States)

Li, Guoqiang (Inventor); Meng, Harper (Inventor)

2016-01-01

A composition comprising thermoset polymer, shape memory polymer to facilitate macro scale damage closure, and a thermoplastic polymer for molecular scale healing is disclosed; the composition has the ability to resolve structural defects by a bio-mimetic close-then heal process. In use, the shape memory polymer serves to bring surfaces of a structural defect into approximation, whereafter use of the thermoplastic polymer for molecular scale healing allowed for movement of the thermoplastic polymer into the defect and thus obtain molecular scale healing. The thermoplastic can be fibers, particles or spheres which are used by heating to a level at or above the thermoplastic's melting point, then cooling of the composition below the melting temperature of the thermoplastic. Compositions of the invention have the ability to not only close macroscopic defects, but also to do so repeatedly even if another wound/damage occurs in a previously healed/repaired area.

Effective transformation of PCDTBT nanorods into nanotubes by polymer melts wetting approach

Directory of Open Access Journals (Sweden)

Fakhra Aziz

2017-09-01

Full Text Available In the present study, p-type conducting polymer of poly [N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole] (PCDTBT has been explored for nanostructures. A novel approach has been adopted to transform nanorods into nanotubes by altering template-wetting methods. PCDTBT nanorods are fabricated by infiltrating porous alumina template with various solution concentrations of 5, 10 and 15 mg/ml. Upon thermal annealing PCDTBT beyond its melting point, the nanorods are transformed into nanotubes. The morphological and optical investigations reveal that the nanorods prepared with a concentration of 10 mg/ml are longer, denser, well-arranged and red shifted as compared to other nanorods. The PCDTBT nanotubes of the same concentration prepared at 300 °C are found the best among all other nanotubes with improved length, density and alignment as compared to their nanorod counterparts. Furthermore, the optical spectra of the nanotubes demonstrate broad spectral region, augmented absorption intensity and significant red-shift. The changes observed in Raman shift indicate improvement in molecular arrangement of the nanotubes. Optimization of the solution concentration and annealing temperature leads to improvement of PCDTBT nanostructures. PCDTBT nanotubes, with better molecular arrangement and broad optical spectrum, can be exploited in the state-of-the-art photovoltaic devices.

Polymer architecture and drug delivery.

Science.gov (United States)

Qiu, Li Yan; Bae, You Han

2006-01-01

Polymers occupy a major portion of materials used for controlled release formulations and drug-targeting systems because this class of materials presents seemingly endless diversity in topology and chemistry. This is a crucial advantage over other classes of materials to meet the ever-increasing requirements of new designs of drug delivery formulations. The polymer architecture (topology) describes the shape of a single polymer molecule. Every natural, seminatural, and synthetic polymer falls into one of categorized architectures: linear, graft, branched, cross-linked, block, star-shaped, and dendron/dendrimer topology. Although this topic spans a truly broad area in polymer science, this review introduces polymer architectures along with brief synthetic approaches for pharmaceutical scientists who are not familiar with polymer science, summarizes the characteristic properties of each architecture useful for drug delivery applications, and covers recent advances in drug delivery relevant to polymer architecture.

Synthesis of waterborne, branched, functional poly(urethane)s and theire applications

OpenAIRE

Ongun, Nihan

2014-01-01

Polyurethanes are an important class of polymers that have wide application in a number of different industrial sectors. Their versatile chemistry enables researchers to design novel materials ranging from liquid, soft and rubbery solids to rigid thermoplastic and thermoset polymer for elastomeric materials, coating and adhesive. The present study focuses on synthesizing waterborne, branched and chemically functional polyurethanes with unique architectures via novel methodologies for coating ...

Phase Behavior of Blends of Linear and Branched Polyethylenes on Micron-Length Scales via Ultra-Small-Angle Neutron Scattering (USANS)

International Nuclear Information System (INIS)

Agamalian, M.M.; Alamo, R.G.; Londono, J.D.; Mandelkern, L.; Wignall, G.D.

1999-01-01

SANS experiments on blends of linear, high density (HD) and long chain branched, low density (LD) polyethylenes indicate that these systems form a one-phase mixture in the melt. However, the maximum spatial resolution of pinhole cameras is approximately equal to 10 3 and it has therefore been suggested that data might also be interpreted as arising from a bi-phasic melt with large a particle size ( 1 m), because most of the scattering from the different phases would not be resolved. We have addressed this hypothesis by means of USANS experiments, which confirm that HDPEILDPE blends are homogenous in the melt on length scales up to 20 m. We have also studied blends of HDPE and short-chain branched linear low density polyethylenes (LLDPEs), which phase separate when the branch content is sufficiently high. LLDPEs prepared with Ziegler-Natta catalysts exhibit a wide distribution of compositions, and may therefore be thought of as a blend of different species. When the composition distribution is broad enough, a fraction of highly branched chains may phase separate on m-length scales, and USANS has also been used to quantify this phenomenon

String-like collective motion in the α- and β-relaxation of a coarse-grained polymer melt

Science.gov (United States)

Pazmiño Betancourt, Beatriz A.; Starr, Francis W.; Douglas, Jack F.

2018-03-01

Relaxation in glass-forming liquids occurs as a multi-stage hierarchical process involving cooperative molecular motion. First, there is a "fast" relaxation process dominated by the inertial motion of the molecules whose amplitude grows upon heating, followed by a longer time α-relaxation process involving both large-scale diffusive molecular motion and momentum diffusion. Our molecular dynamics simulations of a coarse-grained glass-forming polymer melt indicate that the fast, collective motion becomes progressively suppressed upon cooling, necessitating large-scale collective motion by molecular diffusion for the material to relax approaching the glass-transition. In each relaxation regime, the decay of the collective intermediate scattering function occurs through collective particle exchange motions having a similar geometrical form, and quantitative relationships are derived relating the fast "stringlet" collective motion to the larger scale string-like collective motion at longer times, which governs the temperature-dependent activation energies associated with both thermally activated molecular diffusion and momentum diffusion.

Strain hardening in startup shear of long-chain branched polymer solutions.

Science.gov (United States)

Liu, Gengxin; Cheng, Shiwang; Lee, Hyojoon; Ma, Hongwei; Xu, Hongde; Chang, Taihyun; Quirk, Roderic P; Wang, Shi-Qing

2013-08-09

We show for the first time that entangled polymeric liquids containing long-chain branching can exhibit strain hardening upon startup shear. As the significant long-chain branching impedes chain disentanglement, Gaussian coils between entanglements can deform to reach the finite extensibility limit where the intrachain retraction force exceeds the value expected from the usual conformational entropy loss evaluated based on Gaussian chain statistics. The phenomenon is expected to lead to further theoretical understanding.

Polymers and colloids

International Nuclear Information System (INIS)

Schurtenberger, P.

1996-01-01

A wealth of structural information from colloid and polymer solutions on a large range of length scales can be obtained using small angle neutron scattering (SANS) experiments. After a general introduction to the field of soft condensed matter, I shall give a few selected examples on how SANS combined with suitable contrast variation schemes can be used to extract information on the size and conformation of polymer coils in solution and in the melt, and on the local structure and flexibility of polymerlike micelles and microemulsions. (author) 8 figs., tabs., 44 refs

Polymers and colloids

Energy Technology Data Exchange (ETDEWEB)

Schurtenberger, P [ETH Zurich, Inst. fuer Polymere, Zurich (Switzerland)

1996-11-01

A wealth of structural information from colloid and polymer solutions on a large range of length scales can be obtained using small angle neutron scattering (SANS) experiments. After a general introduction to the field of soft condensed matter, I shall give a few selected examples on how SANS combined with suitable contrast variation schemes can be used to extract information on the size and conformation of polymer coils in solution and in the melt, and on the local structure and flexibility of polymerlike micelles and microemulsions. (author) 8 figs., tabs., 44 refs.

Inflation of polymer melts into elliptic and circular cylinders

DEFF Research Database (Denmark)

Rasmussen, Henrik Koblitz; Christensen, Jens Horslund; Gøttsche, Søren

2000-01-01

A thin sheet (membrane) of the polymeric material is clamped between a Teflon-coated thermostated plate and a thermostated aluminium cylinder. By applying thermostated air through the plate, the polymer membrane deforms into an elliptic or a circular cylinder. The position of the top of the infla......A thin sheet (membrane) of the polymeric material is clamped between a Teflon-coated thermostated plate and a thermostated aluminium cylinder. By applying thermostated air through the plate, the polymer membrane deforms into an elliptic or a circular cylinder. The position of the top...

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....

Relationship Between Melting Kinetics and Disentangled State of UHMWPE

NARCIS (Netherlands)

Romano, Dario; Liu, Kangsheng; Tops, Niek; Rastogi, Sanjay

2017-01-01

Ultra-high molecular weight polyethylene (UHMWPE) is a simple polymer used for many engineering applications such as ballistic, medical and applications where high mechanical properties are desired. However, its processing has always been challenging due to the high melt viscosity caused by the

Silica/Perfluoropolymer nanocomposites fabricated by direct melt-compounding: a novel method without surface modification on nano-silica.

Science.gov (United States)

Tanahashi, Mitsuru; Hirose, Masaki; Watanabe, Yusuke; Lee, Jeong-Chang; Takeda, Kunihiko

2007-07-01

A novel method for the fabrication of silica/perfluoropolymer nanocomposites was investigated, whereby nano-sized silica particles without surface modification were dispersed uniformly through mechanical breakdown of loosely packed agglomerates of silica nanoparticles with low fracture strength in a polymer melt during direct melt-compounding. The method consists of two stages. The first stage involves preparation of the loose silica agglomerate, and the second stage involves melt-compounding of a completely hydrophobic perfluoropolymer, poly(tetrafluoroethyleneco-perfluoropropylvinylether), with the loose silica agglomerates prepared in the first stage. In the first stage, the packing structure and the fracture strength of the silica agglomerate were controlled by destabilizing an aqueous colloidal silica solution with a mean primary diameter of 190 nm via pH control and salt addition. In the next stage, the silica/perfluoropolymer nanocomposite was fabricated by breaking down the prepared loose silica agglomerates with low fracture strength by means of a shear force inside the polymer melt during melt-compounding.

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.

The Effect of Filler-Polymer Interactions on Cold-Crystallization Kinetics in Crosslinked, Silica Filled PDMS/PDPS Copolymer Melts

International Nuclear Information System (INIS)

Chien, A; DeTeresa, S; Thompson, L; Cohenour, R; Balazs, B; Maxwell, R S

2006-01-01

Crystallization in a series of variable crosslink density poly(dimethyl-diphenyl) siloxanes random block copolymers reinforced through a mixture of precipitated and fumed silica fillers has been studied by Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), and X-ray Diffraction (XRD). The silicone composite studied was composed of 94.6 mol% Dimethoylsiloxane, 5.1 mol% diphenylsiloxane, and 0.3 mol% methyl-vinyl siloxane (which formed crosslinking after a peroxide cure). The polymer was filled with a mixture of 21.6 wt. % fumed silica and 4.0 wt. % precipitated silica previously treated with 6.8 wt. % ethoxy-endblocked siloxane processing aid. The base composite was characterized by a molecular weight between crosslinks in the polymer network of ∼24 kDa and an overall molecular weight (including the influence of the silica fillers) between crosslinks of ∼11 kDa. Molecular weight between crosslinks and filler-polymer interaction strength were then modified by exposure to γ-irradiation in either air or vacuum. The unirradiated material exhibited crystallization at -80 C as measured by DSC with a 16% crystallization as measured by XRD. Isothermal DMA experiments illustrated that crystallization at -85 C occurred over a 1.8 hour period in silica-filled systems and 2.2-2.6 hours in unfilled systems. The onset of crystallization typically occurred after a 30-minute incubation/nucleation period. The crystallization kinetics were dependent on crosslink density. Changes in molecular weight of a factor of two did not, however, change the amount of crystallization. Irradiation in vacuum resulted in faster overall crystallization rates compared to air irradiation for the same crosslink density, likely due to a reduction in the interaction between the polymer chains and the silica filler surface. Modulated differential scanning calorimetry contrasted the crystallization and melting behavior of pure PDMS versus the PDMS/PDPS base copolymer and helped

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.

High cation transport polymer electrolyte

Science.gov (United States)

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

2007-06-05

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

Record high hole mobility in polymer semiconductors via side-chain engineering.

Science.gov (United States)

Kang, Il; Yun, Hui-Jun; Chung, Dae Sung; Kwon, Soon-Ki; Kim, Yun-Hi

2013-10-09

Charge carrier mobility is still the most challenging issue that should be overcome to realize everyday organic electronics in the near future. In this Communication, we show that introducing smart side-chain engineering to polymer semiconductors can facilitate intermolecular electronic communication. Two new polymers, P-29-DPPDBTE and P-29-DPPDTSE, which consist of a highly conductive diketopyrrolopyrrole backbone and an extended branching-position-adjusted side chain, showed unprecedented record high hole mobility of 12 cm(2)/(V·s). From photophysical and structural studies, we found that moving the branching position of the side chain away from the backbone of these polymers resulted in increased intermolecular interactions with extremely short π-π stacking distances, without compromising solubility of the polymers. As a result, high hole mobility could be achieved even in devices fabricated using the polymers at room temperature.

Thieno[3,4-c]pyrrole-4,6-dione-3,4-difluorothiophene Polymer Acceptors for Efficient All-Polymer Bulk Heterojunction Solar Cells

KAUST Repository

Liu, Shengjian

2016-09-16

Branched-alkyl-substituted poly(thieno[3,4-c]pyrrole-4,6-dione-alt-3,4-difluorothiophene) (PTPD[2F]T) can be used as a polymer acceptor in bulk heterojunction (BHJ) solar cells with a low-band-gap polymer donor (PCE10) commonly used with fullerenes. The

Comparing the results of lattice and off-lattice simulations for the melt of nonconcatenated rings

International Nuclear Information System (INIS)

Halverson, Jonathan D; Kremer, Kurt; Grosberg, Alexander Y

2013-01-01

To study the conformational properties of unknotted and nonconcatenated ring polymers in the melt, we present a detailed qualitative and quantitative comparison of simulation data obtained by molecular dynamics simulation using an off-lattice bead-spring model and by Monte Carlo simulation using a lattice model. We observe excellent, and sometimes even unexpectedly good, agreement between the off-lattice and lattice results for many quantities measured including the gyration radii of the ring polymers, gyration radii of their subchains, contact probabilities, surface characteristics, number of contacts between subchains, and the static structure factors of the rings and their subchains. These results are, in part, put in contrast to Moore curves, and the open, linear polymer counterparts. While our analysis is extensive, our understanding of the ring melt conformations is still rather preliminary. (paper)

Ceramic silicon-boron-carbon fibers from organic silicon-boron-polymers

Science.gov (United States)

Riccitiello, Salvatore R. (Inventor); Hsu, Ming-Ta S. (Inventor); Chen, Timothy S. (Inventor)

1993-01-01

Novel high strength ceramic fibers derived from boron, silicon, and carbon organic precursor polymers are discussed. The ceramic fibers are thermally stable up to and beyond 1200 C in air. The method of preparation of the boron-silicon-carbon fibers from a low oxygen content organosilicon boron precursor polymer of the general formula Si(R2)BR(sup 1) includes melt-spinning, crosslinking, and pyrolysis. Specifically, the crosslinked (or cured) precursor organic polymer fibers do not melt or deform during pyrolysis to form the silicon-boron-carbon ceramic fiber. These novel silicon-boron-carbon ceramic fibers are useful in high temperature applications because they retain tensile and other properties up to 1200 C, from 1200 to 1300 C, and in some cases higher than 1300 C.

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

Directory of Open Access Journals (Sweden)

Ritesh Fule

2014-01-01

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

Effect of waste wax and chain structure on the mechanical and physical properties of polyethylene

Directory of Open Access Journals (Sweden)

M.A. AlMaadeed

2015-05-01

The wax dispersion in the matrix strongly depends on the percentage of wax added to the polymer and the molecular structure of the polymer. It was found that increasing the wax content enhances the phase separation. LDPE undergoes less phase separation due to its highly branched structure composed of a network of short and long chain branches. The wax has no pronounced plasticising effect on the polymer. This is clearly manifested in LDPE as no change in the melting temperature occurred. LLDPE and HDPE were slightly affected by a high concentration of wax (30% and 40%. This is due to the non-uniform distribution of short chain branching along the LLDPE and HDPE main chains, which can interact with the wax structure.

Branched poly(ethyleneimine): a versatile scaffold for patterning polymer brushes by means of remote photocatalytic lithography

Science.gov (United States)

Panzarasa, Guido; Dübner, Matthias; Soliveri, Guido; Edler, Matthias; Griesser, Thomas

2017-09-01

Patterning of functional surfaces is one of the cornerstones of nanotechnology as it allows the fabrication of sensors and lab-on-a-chip devices. Here, the patterning of self-assembled monolayers of branched poly(ethyleneimine) (bPEI) on silica was achieved by means of remote photocatalytic lithography. Moreover, when 2-bromoisobutyryl-modified bPEI was used, the resulting pattern could be amplified by grafting polymer brushes by means of surface-initiated atom transfer radical polymerization. In contrast to previous reports for the patterning of bPEI, the present approach can be conducted in minutes instead of hours, reducing the exposure time to UV radiation and enhancing the overall efficiency. Furthermore, our approach is much more user-friendly, allowing a facile fabrication of patterned initiator-modified surfaces and the use of inexpensive instrumentation such as a low-power UV source and a simple photomask. Considering the versatility of bPEI as a scaffold for the development of biosensors, patterning by means of remote photocatalytic lithography will open new opportunities in a broad field of applications.

Cylindrical polymer brushes with dendritic side chains by iterative anionic reactions

KAUST Repository

Zhang, Hefeng

2015-05-01

We report in this paper an easy method for the synthesis of cylindrical polymer brushes with dendritic side chains through anionic reaction. The synthesis is accomplished by iteratively grafting a living block copolymer, polyisoprene-. b-polystyrenyllithium (PI-. b-PSLi), to the main chain and subsequently to the branches in a divergent way. PI segment is short and serves as a precursor for multifunctional branching unit. The grafting reaction involves two successive steps: i) epoxidation of internal double bonds of PI segments, either in main chain or side chains; ii) ring-opening addition to the resulting epoxy group by the living PI-. b-PSLi. Repeating the two steps affords a series of cylindrical polymer brushes with up to 3rd generation and extremely high molecular weight. The branching multiplicity depends on the average number of oxirane groups per PI segment, usually ca. 8 in the present work. The high branching multiplicity leads to tremendous increase in molecular weights of the cylindrical products with generation growth. Several series of cylindrical polymer brushes with tunable aspect ratios are prepared using backbones and branches with controlled lengths. Shape anisotropy is investigated in dilute solution using light scattering technique. Worm-like single molecular morphology with large persistence length is observed on different substrates by atomic force microscopy.

Laser Beam Melting of Multi-Material Components

Science.gov (United States)

Laumer, Tobias; Karg, Michael; Schmidt, Michael

First results regarding the realisation of multi-material components manufactured by Laser Beam Melting of polymers and metals are published. For realising composite structures from polymer powders by additive manufacturing, at first relevant material properties regarding compatibility have to be analysed. The paper shows the main requirements for compatibility between different materials and offers first results in form of a compatibility matrix of possible combinations for composite structures. For achieving gradient properties of additively manufactured metal parts by using composite materials the composition of alloying components in the powder and adapted process strategies are varied. As an alternative to atomizing pre-alloyed materials, mixtures of different powders are investigated.

A novel process for production of spherical PBT powders and their processing behavior during laser beam melting

Energy Technology Data Exchange (ETDEWEB)

Schmidt, Jochen, E-mail: jochen.schmidt@fau.de; Sachs, Marius; Fanselow, Stephanie; Wirth, Karl-Ernst; Peukert, Wolfgang [Friedrich-Alexander-Universität Erlangen-Nürnberg, Institute of Particle Technology, Cauerstr. 4, D-91058 Erlangen (Germany); Zhao, Meng; Wudy, Katrin; Drexler, Maximilian; Drummer, Dietmar [Friedrich-Alexander-Universität Erlangen-Nürnberg, Institute of Polymer Technology, Am Weichselgarten 9, D-91058 Erlangen (Germany)

2016-03-09

Additive manufacturing processes like laser beam melting of polymers are established for production of prototypes and individualized parts. The transfer to other areas of application and to serial production is currently hindered by the limited availability of polymer powders with good processability. Within this contribution a novel process route for the production of spherical polymer micron-sized particles of good flowability has been established and applied to produce polybutylene terephthalate (PBT) powders. Moreover, the applicability of the PBT powders in selective laser beam melting and the dependencies of process parameters on device properties will be outlined. First, polymer micro particles are produced by a novel wet grinding method. To improve the flowability the produced particles the particle shape is optimized by rounding in a heated downer reactor. A further improvement of flowability of the cohesive spherical PBT particles is realized by dry coating. An improvement of flowability by a factor of about 5 is achieved by subsequent rounding of the comminution product and dry-coating as proven by tensile strength measurements of the powders. The produced PBT powders were characterized with respect to their processability. Therefore thermal, rheological, optical and bulk properties were analyzed. Based on these investigations a range of processing parameters was derived. Parameter studies on thin layers, produced in a selective laser melting system, were conducted. Hence appropriate parameters for processing the PBT powders by laser beam melting, like building chamber temperature, scan speed and laser power have been identified.

A novel process for production of spherical PBT powders and their processing behavior during laser beam melting

International Nuclear Information System (INIS)

Schmidt, Jochen; Sachs, Marius; Fanselow, Stephanie; Wirth, Karl-Ernst; Peukert, Wolfgang; Zhao, Meng; Wudy, Katrin; Drexler, Maximilian; Drummer, Dietmar

2016-01-01

Additive manufacturing processes like laser beam melting of polymers are established for production of prototypes and individualized parts. The transfer to other areas of application and to serial production is currently hindered by the limited availability of polymer powders with good processability. Within this contribution a novel process route for the production of spherical polymer micron-sized particles of good flowability has been established and applied to produce polybutylene terephthalate (PBT) powders. Moreover, the applicability of the PBT powders in selective laser beam melting and the dependencies of process parameters on device properties will be outlined. First, polymer micro particles are produced by a novel wet grinding method. To improve the flowability the produced particles the particle shape is optimized by rounding in a heated downer reactor. A further improvement of flowability of the cohesive spherical PBT particles is realized by dry coating. An improvement of flowability by a factor of about 5 is achieved by subsequent rounding of the comminution product and dry-coating as proven by tensile strength measurements of the powders. The produced PBT powders were characterized with respect to their processability. Therefore thermal, rheological, optical and bulk properties were analyzed. Based on these investigations a range of processing parameters was derived. Parameter studies on thin layers, produced in a selective laser melting system, were conducted. Hence appropriate parameters for processing the PBT powders by laser beam melting, like building chamber temperature, scan speed and laser power have been identified.

Polymer research by neutron scattering

International Nuclear Information System (INIS)

Richter, D.

1993-01-01

Polymer physics aims on an understanding of the macroscopic behavior of polymer systems on the basis of their molecular structure and dynamics. For this purpose neutrons serve as a unique probe, allowing a simultaneous investigation of polymer structure and dynamics on a molecular scale. Furthermore, hydrogen deuterium exchange facilitates molecular labeling and offers the possibility to observe selected chains or chain parts in dense systems. Neutron small angle scattering reveals information on the conformation and possible aggregation of polymer chains. Data on linear and star like molecules are shown as examples. High resolution neutron spin-echospectroscopy observes the molecular dynamics of long chain molecules. Results on the large scale motion of chins in polymer melts are presented. finally, experiments on chain relaxation close to the glass transition are displayed. Three distinctly different relaxation processes are revealed. (author)

Challenges in Laser Sintering of Melt-Processable Thermoset Imide Resin

Science.gov (United States)

Chuang, Kathy C.; Gornet, Timothy; Koerner, Hilmar

2016-01-01

Polymer Laser Sintering (LS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the CAD model. LS generally uses thermoplastic polymeric powders, such as polyamides (i.e. Nylon), and the resultant 3D objects are often weaker in their strength compared to traditionally processed materials, due to the lack of polymer inter-chain connection in the z-direction. The objective of this project is to investigate the possibility of printing a melt-processable RTM370 imide resin powder terminated with reactive phenylethynyl groups by LS, followed by a postcure in order to promote additional crosslinking to achieve higher temperature (250-300 C) capability. A preliminary study to build tensile specimens by LS and the corresponding DSC and rheology study of RTM370 during LS process is presented.

Thermal spraying of polyethylene-based polymers: Processing and characterization

Science.gov (United States)

Otterson, David Mark

This research explores the development of a flame-spray process map as it relates to polymers. This work provides a more complete understanding of the thermal history of the coating material from injection, to deposition and finally to cooling. This was accomplished through precise control of the processing conditions during deposition. Mass flow meters were used to monitor air and fuel flows as they were systematically changed, while temperatures were simultaneously monitored along the length of the flame. A process model was then implemented that incorporated this information along with measured particle velocities, particle size distribution, the polymer's melting temperature and its enthalpy of melting. This computational model was then used to develop a process map that described particle softening, melting and decomposition phenomena as a function of particle size and standoff distance. It demonstrated that changes in particle size caused significant variations in particle states achieved in-flight. A series of experiments were used to determine the range of spray parameters within which a cohesive coating without visible signs of degradation could be sprayed. These results provided additional information that complimented the computational processing map. The boundaries established by these results were the basis for a Statistical Design of Experiments that tested the effects that subtle processing changes had on coating properties. A series of processing maps were developed that combined the computational and the experimental results to describe the manner in which processing parameters interact to determine the degree of melting, polymer degradation and coating porosity. Strong interactions between standoff distance and traverse rate can cause the polymer to degrade and form pores in the coating. A clear picture of the manner in which particle size and standoff distance interact to determine particle melting was provided by combining the computational

Hazardous Waste Cleanup: El Paso Energy Corporation Polymers Incorporated in Flemington, New Jersey

Science.gov (United States)

The El Paso Energy Corporation Polymers, Inc. (EPEC Polymers, Inc.), formerly known as Tenneco Polymers, Inc., is located at 45 River Road, at the juncture of the South Branch of the Raritan River and Bushkill Brook in Flemington/Raritan Townships,

Depolymerization of post-consumer PET with multifunctional alcohol through melt processing; Despolimerizacao de PET pos-consumo com alcool multifuncional atraves de processamento por fusao

Energy Technology Data Exchange (ETDEWEB)

Lessa, Tathiane C.R.F.; Mendes, Luis C.; Dias, Marcos L., E-mail: tathianecr@ima.ufrj.b [Universidade Federal do Rio de Janeiro (IMA/UFRJ), RJ (Brazil). Inst. de Macromoleculas Professora Eloisa Mano. Centro de Tecnologia

2009-07-01

The purpose of this study was to prepare oligomers from post-consumer PET with multifunctional alcohol, through melt processing, aiming to develop a new material, able to play a role as filler or property modifier. Maintaining constants the process conditions, content and kind of catalyst, the influence of the solvolysis agent on the PET depolymerization was investigated. The products were evaluated by wide-angle X-ray diffraction (WAXD) and thermogravimetry (TG/DTG). The changes in the WAXD curves and the shift of the maximum degradation temperature suggested that the ester linkages were broken being the ethylene glycol moieties replaced with hydroxyl-terminal groups of the multifunctional alcohol, as result of a transesterification reaction. The chemical structure of the new ester was named 'star-branching polymer'. (author)

Focused ion beam structuring of low melting polymeric materials

International Nuclear Information System (INIS)

Schmied, R.

2014-01-01

This thesis focuses on heating effects during focused ion beam (FIB) processing of low melting polymers. The combined approach using experiments and simulations identifies the in part massive local temperatures as a convolution between intrinsic ion-matter effects and a considerable, technically-induced heating component. While the former is invariable, the latter has been minimized by an alternative process strategy which massively improves the morphological stability and minimizes chemical damage during FIB processing, thus opening new possibilities for application on sensitive, low melting materials. The study starts with systematic experimental investigations which strongly suggested the existence of a technically-induced heating component as a consequence of classically-used serpentine or raster-like patterning strategies. Based on these results, a combined simulation approach of ion trajectories and thermal spike model calculations have been employed to get a deeper insight into spatial and temporal temperature evolution. The results were then combined with the thermodynamic behavior of polymers by means of melting and volatizing temperatures. The comparison of these simulationbased predictions with real FIB experiments revealed very good agreement, proving the applicability of the approach used to describe the temperature evolution from a fundamental point of view. As a next step, these simulations were then applied to the dierent scanning strategies which further con rmed the existence of a technically-induced heating component via classically-used patterning approaches. Due to the deep insight gained via simulations, an alternative patterning strategy was developed, which was expected to minimize these avoidable influences. This new strategy was then evaluated using a multi-technique approach, which revealed strongly reduced chemical damage together with increasing morphological stabilities even for temperature-sensitive polymers. Finally, this alternative

Designing Polymer Blends Through Modeling and Simulation

National Research Council Canada - National Science Library

Balazs, Anna

2001-01-01

...) of clay sheets in polymer melts. In addition, we determined how the coupling between phase separation and wetting interactions in polymeric composites effects the structural evolution and phase behavior of the material...

Using Flory-Huggins phase diagrams as a pre-formulation tool for the production of amorphous solid dispersions: a comparison between hot-melt extrusion and spray drying.

Science.gov (United States)

Tian, Yiwei; Caron, Vincent; Jones, David S; Healy, Anne-Marie; Andrews, Gavin P

2014-02-01

Amorphous drug forms provide a useful method of enhancing the dissolution performance of poorly water-soluble drugs; however, they are inherently unstable. In this article, we have used Flory-Huggins theory to predict drug solubility and miscibility in polymer candidates, and used this information to compare spray drying and melt extrusion as processes to manufacture solid dispersions. Solid dispersions were prepared using two different techniques (hot-melt extrusion and spray drying), and characterised using a combination of thermal (thermogravimetric analysis and differential scanning calorimetry), spectroscopic (Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction methods. Spray drying permitted generation of amorphous solid dispersions across a wider drug concentration than melt extrusion. Melt extrusion provided sufficient energy for more intimate mixing to be achieved between drug and polymer, which may improve physical stability. It was also confirmed that stronger drug-polymer interactions might be generated through melt extrusion. Remixing and dissolution of recrystallised felodipine into the polymeric matrices did occur during the modulated differential scanning calorimetry analysis, but the complementary information provided from FTIR confirms that all freshly prepared spray-dried samples were amorphous with the existence of amorphous drug domains within high drug-loaded samples. Using temperature-composition phase diagrams to probe the relevance of temperature and drug composition in specific polymer candidates facilitates polymer screening for the purpose of formulating solid dispersions. © 2013 Royal Pharmaceutical Society.

Hyperbranched Polymers - Engineering Materials and Degradation Behavior

National Research Council Canada - National Science Library

Wooley, Karen

2000-01-01

.... In the studies supported under this grant, hyperbranched polycarbonates were designed as analogs to common engineering polymers to investigate the effects of branching upon the chain-chain packing...

Liver glycogen in type 2 diabetic mice is randomly branched as enlarged aggregates with blunted glucose release.

Science.gov (United States)

Besford, Quinn Alexander; Zeng, Xiao-Yi; Ye, Ji-Ming; Gray-Weale, Angus

2016-02-01

Glycogen is a vital highly branched polymer of glucose that is essential for blood glucose homeostasis. In this article, the structure of liver glycogen from mice is investigated with respect to size distributions, degradation kinetics, and branching structure, complemented by a comparison of normal and diabetic liver glycogen. This is done to screen for differences that may result from disease. Glycogen α-particle (diameter ∼ 150 nm) and β-particle (diameter ∼ 25 nm) size distributions are reported, along with in vitro γ-amylase degradation experiments, and a small angle X-ray scattering analysis of mouse β-particles. Type 2 diabetic liver glycogen upon extraction was found to be present as large loosely bound, aggregates, not present in normal livers. Liver glycogen was found to aggregate in vitro over a period of 20 h, and particle size is shown to be related to rate of glucose release, allowing a structure-function relationship to be inferred for the tissue specific distribution of particle types. Application of branching theories to small angle X-ray scattering data for mouse β-particles revealed these particles to be randomly branched polymers, not fractal polymers. Together, this article shows that type 2 diabetic liver glycogen is present as large aggregates in mice, which may contribute to the inflexibility of interconversion between glucose and glycogen in type 2 diabetes, and further that glycogen particles are randomly branched with a size that is related to the rate of glucose release.

Stress and neutron scattering measurements on linear polymer melts undergoing steady elongational flow

DEFF Research Database (Denmark)

Hassager, Ole; Mortensen, Kell; Bach, Anders

2012-01-01

We use small-angle neutron scattering to measure the molecular stretching in polystyrene melts undergoing steady elongational flow at large stretch rates. The radius of gyration of the central segment of a partly deuterated polystyrene molecule is, in the stretching direction, increasing...... exhibited by the linear polystyrene melt....

1H-NMR/13C-NMR studies of branched structures in PVC obtained at atmospheric pressure

International Nuclear Information System (INIS)

Braun, D.; Holzer, G.; Hjertberg, T.

1981-01-01

The 1 H-NMR-spectra of raw poly (vinyl cloride) obtained at atmospheric pressure (U-PVC) have revealed the presence of high concentrations of branches. The content of labile chlorine was determined by reaction with phenole in order to estimate the branch points with tertiary chlorine. The branch length of reductively dehalogenated U-PVC by 13 C-NMR analysis have provided evidence for both short chain branches including chloromethyl groups and 2.4-dichloro-n-butyl groups and long chain branching. For a number of U-polymers the total amount of branching ranges from 7.5 to 13.5/1000 C. The 13 C-NMR measurements point to a ratio of methyl/butyl branches of 1:1 and short chains/long chains of 6:1. (orig.)

Solvent free low-melt viscosity imide oligomers and thermosetting polymide composites

Science.gov (United States)

Chuang, Chun-Hua (Inventor)

2012-01-01

.[.This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280.degree. C. When the imide oligomer melt is cured at about 371.degree. C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T.sub.g) equal to and above 310.degree. C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280.degree. C. (450-535.degree. F.) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343.degree. C. (550-650.degree. F.) high temperature performance capability..]. .Iadd.This invention relates to compositions and a solvent-free reaction process for preparing imide oligomers and polymers specifically derived from effective amounts of dianhydrides such as 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), at least one aromatic polyamine and an end-cap such as 4-phenylethynyphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260.degree. C.-280.degree. C..Iaddend.

Probing polymer crystallization at processing-relevant cooling rates with synchrotron radiation

Energy Technology Data Exchange (ETDEWEB)

Cavallo, Dario, E-mail: Dario.cavallo@unige.it [University of Genoa, Dept. of Chemistry and Industrial Chemistry, Via Dodecaneso 31, 16146 Genoa (Italy); Portale, Giuseppe [ESRF, Dubble CRG, Netherlands Organization of Scientific Research (NWO), 38043 Grenoble (France); Androsch, René [Martin-Luther-University Halle-Wittenberg, Center of Engineering Sciences, D-06099 Halle/S. (Germany)

2015-12-17

Processing of polymeric materials to produce any kind of goods, from films to complex objects, involves application of flow fields on the polymer melt, accompanied or followed by its rapid cooling. Typically, polymers solidify at cooling rates which span over a wide range, from a few to hundreds of °C/s. A novel method to probe polymer crystallization at processing-relevant cooling rates is proposed. Using a custom-built quenching device, thin polymer films are ballistically cooled from the melt at rates between approximately 10 and 200 °C/s. Thanks to highly brilliant synchrotron radiation and to state-of-the-art X-ray detectors, the crystallization process is followed in real-time, recording about 20 wide angle X-ray diffraction patterns per second while monitoring the instantaneous sample temperature. The method is applied to a series of industrially relevant polymers, such as isotactic polypropylene, its copolymers and virgin and nucleated polyamide-6. Their crystallization behaviour during rapid cooling is discussed, with particular attention to the occurrence of polymorphism, which deeply impact material’s properties.

Downstream processing from melt granulation towards tablets: In-depth analysis of a continuous twin-screw melt granulation process using polymeric binders.

Science.gov (United States)

Grymonpré, W; Verstraete, G; Vanhoorne, V; Remon, J P; De Beer, T; Vervaet, C

2018-03-01

The concept of twin-screw melt granulation (TSMG) has steadily (re)-gained interest in pharmaceutical formulation development as an intermediate step during tablet manufacturing. However, to be considered as a viable processing option for solid oral dosage forms there is a need to understand all critical sources of variability which could affect this granulation technique. The purpose of this study was to provide an in-depth analysis of the continuous TSMG process in order to expose the critical process parameters (CPP) and elucidate the impact of process and formulation parameters on the critical quality attributes (CQA) of granules and tablets during continuous TSMG. A first part of the study dealt with the screening of various amorphous polymers as binder for producing high-dosed melt granules of two model drug (i.e. acetaminophen and hydrochlorothiazide). The second part of this study described a quality-by-design (QbD) approach for melt granulation of hydrochlorothiazide in order to thoroughly evaluate TSMG, milling and tableting stage of the continuous TSMG line. Using amorphous polymeric binders resulted in melt granules with high milling efficiency due to their brittle behaviour without producing excessive amounts of fines, providing high granule yields with low friability. Therefore, it makes them extremely suitable for further downstream processing. One of the most important CPP during TSMG with polymeric binders was the granulation-torque, which - in case of polymers with high T g - increased during longer granulation runs to critical levels endangering the continuous process flow. However, by optimizing both screw speed and throughput or changing to polymeric binders with lower T g it was possible to significantly reduce this risk. This research paper highlighted that TSMG must be considered as a viable option during formulation development of solid oral dosage forms based on the robustness of the CQA of both melt granules and tablets. Copyright © 2017

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.

All-Polymer Microfluidic Systems with integrated Nanostructures for Cell Handling

DEFF Research Database (Denmark)

Matschuk, Maria

There is an increasing need for mass-production of nanostructures with high precision at polymer surfaces, for example to reduce the reflection of light, to reduce the adhesion of smudge, for optical data storage (e.g. Blu-ray discs), and for biological applications. In this project the effects...... of the polymer melt, interfacial effects like wetting and friction play a major role in injection molding of high aspect ratio nanostructures. The interfacial energy between mold and polymer needs to allow filling as well as demolding which are opposing properties: On the one hand, insufficient wetting...... cavity during demolding leading to nanostructural failure. It was found that the mold temperature has a major influence on the replication depth for tested mold coatings while other parameters (melt temperature, injection velocity and pressure, holding pressure and ejection temperature) do not have any...

Dimension of ring polymers in bulk studied by Monte-Carlo simulation and self-consistent theory.

Science.gov (United States)

Suzuki, Jiro; Takano, Atsushi; Deguchi, Tetsuo; Matsushita, Yushu

2009-10-14

We studied equilibrium conformations of ring polymers in melt over the wide range of segment number N of up to 4096 with Monte-Carlo simulation and obtained N dependence of radius of gyration of chains R(g). The simulation model used is bond fluctuation model (BFM), where polymer segments bear excluded volume; however, the excluded volume effect vanishes at N-->infinity, and linear polymer can be regarded as an ideal chain. Simulation for ring polymers in melt was performed, and the nu value in the relationship R(g) proportional to N(nu) is decreased gradually with increasing N, and finally it reaches the limiting value, 1/3, in the range of N>or=1536, i.e., R(g) proportional to N(1/3). We confirmed that the simulation result is consistent with that of the self-consistent theory including the topological effect and the osmotic pressure of ring polymers. Moreover, the averaged chain conformation of ring polymers in equilibrium state was given in the BFM. In small N region, the segment density of each molecule near the center of mass of the molecule is decreased with increasing N. In large N region the decrease is suppressed, and the density is found to be kept constant without showing N dependence. This means that ring polymer molecules do not segregate from the other molecules even if ring polymers in melt have the relationship nu=1/3. Considerably smaller dimensions of ring polymers at high molecular weight are due to their inherent nature of having no chain ends, and hence they have less-entangled conformations.

Molecular scale modeling of polymer imprint nanolithography.

Science.gov (United States)

Chandross, Michael; Grest, Gary S

2012-01-10

We present the results of large-scale molecular dynamics simulations of two different nanolithographic processes, step-flash imprint lithography (SFIL), and hot embossing. We insert rigid stamps into an entangled bead-spring polymer melt above the glass transition temperature. After equilibration, the polymer is then hardened in one of two ways, depending on the specific process to be modeled. For SFIL, we cross-link the polymer chains by introducing bonds between neighboring beads. To model hot embossing, we instead cool the melt to below the glass transition temperature. We then study the ability of these methods to retain features by removing the stamps, both with a zero-stress removal process in which stamp atoms are instantaneously deleted from the system as well as a more physical process in which the stamp is pulled from the hardened polymer at fixed velocity. We find that it is necessary to coat the stamp with an antifriction coating to achieve clean removal of the stamp. We further find that a high density of cross-links is necessary for good feature retention in the SFIL process. The hot embossing process results in good feature retention at all length scales studied as long as coated, low surface energy stamps are used.

Protein and Bacterial Antifouling Behavior of Melt-Coextruded Nanofiber Mats.

Science.gov (United States)

Kim, Si-Eun; Zhang, Cong; Advincula, Abigail A; Baer, Eric; Pokorski, Jonathan K

2016-04-13

Antifouling surfaces are important for biomedical devices to prevent secondary infections and mitigate the effects of the foreign body response. Herein, we describe melt-coextruded poly(ε-caprolactone) (PCL) nanofiber mats grafted with antifouling polymers. Nonwoven PCL fiber mats are produced using a multilayered melt coextrusion process followed by high-pressure hydroentanglement to yield porous patches. The resulting fiber mats show submicrometer cross-sectional fiber dimensions and yield pore sizes that were nearly uniform, with a mean pore size of 1.6 ± 0.9 μm. Several antifouling polymers, including hydrophilic, zwitterionic, and amphipathic molecules, are grafted to the surface of the mats using a two-step procedure that includes photochemistry followed by the copper-catalyzed azide-alkyne cycloaddition reaction. Fiber mats are evaluated using separate adsorption tests for serum proteins and E. coli. The results indicate that poly(oligo(ethylene glycol) methyl ether methacrylate)-co-(trifluoroethyl methacrylate) (poly(OEGMEMA-co-TFEMA)) grafted mats exhibit approximately 85% less protein adhesion and 97% less E. coli adsorption when compared to unmodified PCL fibermats. In dynamic antifouling testing, the amphiphilic fluorous polymer surface shows the highest flux and highest rejection value of foulants. The work presented within has implications on the high-throughput production of antifouling microporous patches for medical applications.

Resolving Properties of Polymers and Nanoparticle Assembly through Coarse-Grained Computational Studies.

Energy Technology Data Exchange (ETDEWEB)

Grest, Gary S. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2017-09-01

Coupled length and time scales determine the dynamic behavior of polymers and polymer nanocomposites and underlie their unique properties. To resolve the properties over large time and length scales it is imperative to develop coarse grained models which retain the atomistic specificity. Here we probe the degree of coarse graining required to simultaneously retain significant atomistic details a nd access large length and time scales. The degree of coarse graining in turn sets the minimum length scale instrumental in defining polymer properties and dynamics. Using polyethylene as a model system, we probe how the coarse - graining scale affects the measured dynamics with different number methylene group s per coarse - grained beads. Using these models we simulate polyethylene melts for times over 500 ms to study the viscoelastic properties of well - entangled polymer melts and large nanoparticle assembly as the nanoparticles are driven close enough to form nanostructures.

Transient Cooperative Processes in Dewetting Polymer Melts.

Science.gov (United States)

Chandran, Sivasurender; Reiter, Günter

2016-02-26

We compare the high velocity dewetting behavior, at elevated temperatures, of atactic polystyrene (aPS) and isotactic polystyrene (iPS) films, with the zero shear bulk viscosity (η_{bulk}) of aPS being approximately ten times larger than iPS. As expected, for aPS the apparent viscosity of the films (η_{f}) derived from high-shear dewetting is less than η_{bulk}, displaying a shear thinning behavior. Surprisingly, for iPS films, η_{f} is always larger than η_{bulk}, even at about 50 °C above the melting point, with η_{f}/η_{bulk} following an Arrhenius behavior. The corresponding activation energy of ∼160±10  kJ/mol for iPS films suggests a cooperative motion of segments which are aligned and agglomerated by fast dewetting.

High-Temperature Shape Memory Polymers

Science.gov (United States)

Yoonessi, Mitra; Weiss, Robert A.

2012-01-01

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing

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.

Blends of poly(hydroxybutyrate and poly (epsilon-caprolactone obtained from melting mixture

Directory of Open Access Journals (Sweden)

Maria Cecília M. Antunes

2005-06-01

Full Text Available Poly(3-hydroxybutyrate (PHB is a thermoplastic polyester with a great potential owing to its biodegradability, bioreabsorbation and biological synthesis from a renewable source. Despite these characteristics, the applications of this polymer are very restricted due to its poor mechanical properties and thermal instability at temperatures above its melting point (around 175°C. Among the possibilities of improvement of these materials, the development of blends is a relatively fast and inexpensive option. Poly(epsilon-caprolactone (PCL is a semi-crystalline polymer that may be used as a biomaterial. It presents good mechanical properties, a low melting point (around 55 °C, and could be a good option to develop PHB blends, maintaining the biodegradability and bioreabsorption properties. The objective of the present work was to obtain blends of PHB and PCL by melting mixture in an internal mixer. The compositions varied from 0 to 30 wt% of PCL. DSC, DMA, and SEM were used to characterize the blends. The blends were found to be imiscible with no indication of interaction either the amorphous or crystalline state. The morphology shows PHB as the matrix and PCL as the dispersed phase.

Constitutional Isomers of Dendrimer-like Star Polymers: Design, Synthesis and Conformational and Structural Properties; TOPICAL

International Nuclear Information System (INIS)

Pople, John A.

2001-01-01

The design, synthesis and solution properties of six constitutional isomers of dendrimer-like star polymers is described. Each of the polymers have comparable molecular weights ((approx) 80,000 g/mol), narrow polydispersities ( and lt; 1.19) and an identical number of branching junctures (45) and surface hydroxyl functionalities (48). The only difference in the six isomers is the placement of the branching junctures. The polymers are constructed from high molecular weight poly(e-caprolactone) with branching junctures derived from 2,2'-bis(hydroxylmethyl) propionic acid (bis-MPA) emanating from a central core. The use of various generations of dendritic initiators and dendrons coupled with the ring opening polymerization of e-caprolactones allowed a modular approach to the dendrimer-like star polymer isomers. The most pronounced effects on the physical properties/morphology and hydrodynamic volume was for those polymers in which the branching was distributed throughout the sample in a dendrimer-like fashion. The versatility of this approach has provided the possibility of understanding the relationship between architecture and physical properties. Dynamic light scattering and small angle X-ray scattering techniques were used to determine the hydrodynamic radius Rh and radius of gyration Rg respectively. The relationship between Rg and molecular weight was indicative of a compact star-like structure, and did not show advanced bias towards either the dense core or dense shell models. The radial density distribution of the isomers was therefore modeled according to a many arm star polymer, and good agreement was found with experimental measures of Rh/Rg

Methods of enhancing conductivity of a polymer-ceramic composite electrolyte

Science.gov (United States)

Kumar, Binod

2003-12-02

Methods for enhancing conductivity of polymer-ceramic composite electrolytes are provided which include forming a polymer-ceramic composite electrolyte film by a melt casting technique and uniaxially stretching the film from about 5 to 15% in length. The polymer-ceramic composite electrolyte is also preferably annealed after stretching such that it has a room temperature conductivity of from 10.sup.-4 S cm.sup.-1 to 10.sup.-3 S cm.sup.-1. The polymer-ceramic composite electrolyte formed by the methods of the present invention may be used in lithium rechargeable batteries.

Partial melting of UHP calc-gneiss from the Dabie Mountains

Science.gov (United States)

Liu, Penglei; Wu, Yao; Liu, Qiang; Zhang, Junfeng; Zhang, Li; Jin, Zhenmin

2014-04-01

Exhumation melting has been proposed for the ultra-high pressure (UHP) metamorphic rocks in the Dabie Mountains based on melting experiments. We document here the first petrological and mineralogical evidence demonstrating that the UHP calc-gneisses from the Ganjialing area in the Dabie Mountains experienced partial melting during early exhumation. The assemblage of garnet, phengite (Si = 3.65 pfu), coesite, rutile and carbonate preserved in the calc-gneisses indicates a peak metamorphic condition of 692-757 °C and 4.0-4.8 GPa. Partial melting is indicated by several lines of evidence: the melting textures of phengite, the feldspar-dominated films, bands, branches, blebs and veins, the euhedral K-feldspars, the intergrowth film of plagioclase and K-feldspar, the plagioclase + biotite intergrowth after garnet and the epidote poikiloblasts. Polyphase inclusions in garnet are characterized with wedge-like offshoots and serrate outlines whereas those in epidote display negative crystal shapes, which can be best interpreted by entrapment of former melts. We propose a wet melting reaction of Phn + Q ± Na-Cpx + H2O = Bt + Pl + Grt + felsic melts, which likely took place at ca.650-800 °C and ca.1.0-2.0 GPa, to interpret the melting event in the calc-gneisses. Chemical exchanges between garnet and melts produced new garnet domains with higher almandine, spessartine, MREE, HREE and Y but lower grossular, pyrope, P, Sc, Ti, V and Zr contents. Zr-in-rutile thermometer reveals a low temperature of 620-643 °C at 5 GPa, indicating a later reset for Zr in rutile. Healed fractures are suggested to be responsible for the formation of some polyphase inclusions in garnet.

Synthesis and characterization of an exact comb polyisoprene with three branches having the middle branch twice the molecular weight of the other two identical external branches

KAUST Repository

Ratkanthwar, Kedar

2013-01-01

An exact comb polyisoprene (PI) with three branches, with the middle branch having twice the molecular weight of the two other identical external branches, was synthesized by using anionic polymerization high vacuum techniques and appropriate chlorosilane chemistry. The synthetic approach involves (a) the selective replacement of the two chlorines of 4-(dichloromethylsilyl) diphenylethylene (DCMSDPE, key molecule) with identical PI chains by titration with PILi, (b) the addition of sec-BuLi to the double bond of DPE followed by the polymerization of isoprene from the newly created anionic site to form a 3-arm living star PI, (c) the selective replacement of the two chlorines of trichloromethylsilane with 3-arm star PI to form an H-shape intermediate, and (d) the replacement of the remaining chlorine of trichloromethylsilane by linear PI chains with double the molecular weight. All intermediate and final products were characterized via size exclusion chromatography, temperature gradient interaction chromatography and 1H-NMR spectroscopy. As expected, due to the inability to control the exact stoichiometry of the linking reactants, the main product (exact comb PI) is contaminated by a few by-products, despite the fact that anionic polymerization is the most efficient way to produce well-defined polymers. © 2013 The Royal Society of Chemistry.

A comparative study of the effect of spray drying and hot-melt extrusion on the properties of amorphous solid dispersions containing felodipine.

Science.gov (United States)

Mahmah, Osama; Tabbakh, Rami; Kelly, Adrian; Paradkar, Anant

2014-02-01

To compare the properties of solid dispersions of felodipine for oral bioavailability enhancement using two different polymers, polyvinylpyrrolidone (PVP) and hydroxypropyl methylcellulose acetate succinate (HPMCAS), by hot-melt extrusion (HME) and spray drying. Felodipine solid dispersions were prepared by HME and spray drying techniques. PVP and HPMCAS were used as polymer matrices at different drug : polymer ratios (1 : 1, 1 : 2 and 1 : 3). Detailed characterization was performed using differential scanning calorimetry, powder X-ray diffractometry, scanning electron microscopy and in-vitro dissolution testing. Dissolution profiles were evaluated in the presence of sodium dodecyl sulphate. Stability of different solid dispersions was studied under accelerated conditions (40°C/75% RH) over 8 weeks. Spray-dried formulations were found to release felodipine faster than melt extruded formulations for both polymer matrices. Solid dispersions containing HMPCAS exhibited higher drug release rates and better wettability than those produced with a PVP matrix. No significant differences in stability were observed except with HPMCAS at a 1 : 1 ratio, where crystallization was detected in spray-dried formulations. Solid dispersions of felodipine produced by spray drying exhibited more rapid drug release than corresponding melt extruded formulations, although in some cases improved stability was observed for melt extruded formulations. © 2013 Royal Pharmaceutical Society.

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.

On-chip magnetic bead-based DNA melting curve analysis using a magnetoresistive sensor

DEFF Research Database (Denmark)

Rizzi, Giovanni; Østerberg, Frederik Westergaard; Henriksen, Anders Dahl

2014-01-01

We present real-time measurements of DNA melting curves in a chip-based system that detects the amount of surface-bound magnetic beads using magnetoresistive magnetic field sensors. The sensors detect the difference between the amount of beads bound to the top and bottom sensor branches....... The beads are magnetized by the field arising from the bias current passed through the sensors. We demonstrate the first on-chip measurements of the melting of DNA hybrids upon a ramping of the temperature. This overcomes the limitation of using a single washing condition at constant temperature. Moreover...

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

Science.gov (United States)

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

2016-10-03

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

Utilization of poly(methyl methacrylate) – carbon nanotube and polystyrene – carbon nanotube in situ polymerized composites as masterbatches for melt mixing

OpenAIRE

M. Lahelin; M. Annala; J. Seppala

2012-01-01

Carbon nanotubes (CNTs) were melt mixed directly or by using an in situ polymerized masterbatch into a matrix polymer, polystyrene (PS) or poly(methyl methacrylate) (PMMA). The mechanical properties of the composites were mostly determined by the amount of CNTs, and not by the use of directly melt mixed CNTs or the use of the masterbatch. In contrast, the electrical resistivity of the composites was dependent on the manner in which the CNTs were added to the matrix polymer. When there was inc...

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.

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

Influence of additives on melt viscosity, surface tension, and film formation of dry powder coatings.

Science.gov (United States)

Sauer, Dorothea; McGinity, James W

2009-06-01

Limited information on thermally cured dry-powder coatings used for solid dosage forms has been available in the literature. The aim of this study was to characterize the film formation process of Eudragit L 100-55 dry-powder coatings and to investigate the influence of film additives on melt viscosity and surface tension. The coating process employed no liquids and the plasticizer was combined with the polymer using hot melt extrusion. Thermoanalytical methods including differential scanning calorimetry and thermogravimetric analysis (TGA) were used to investigate the thermal properties of the dry-coating formulations. The rheological behavior of the coating formulations were characterized with the extrusion torque, and the surface energy parameters were determined from contact angle measurements. The influence of the level of triethyl citrate (TEC) as plasticizer and polyethylene glycol (PEG) 3350 in the polymer film on film formation was investigated using a digital force tester. TGA confirmed thermal stability of all coating excipients at the investigated curing conditions. Increasing TEC levels and the addition of PEG 3350 as a low melting excipient in the coating reduced the viscosity of the polymer. Plasticization of the polymer with TEC increased the surface free energy, whereas the admixture of 10% PEG 3350 did not affect the surface free energy of Eudragit L 100-55. The spreading coefficient of the polymers over two sample tablet formulations was reduced with increasing surface free energy. During the curing process, puncture strength, and elongation of powder-cast films increased. The effect of curing time on the mechanical properties was dependent on the plasticizer content. The incorporation of TEC and PEG 3350 into the Eudragit L 100-55 powder coating formulation improved film formation. Mechanical testing of powder-cast films showed an increase of both elongation and puncture strength over the curing process as criterion for polymer particle fusion

The effects of temperature on the radiation chemistry of polymers

International Nuclear Information System (INIS)

Hill, D.J.T.

1995-01-01

The effects of high energy radiation on polymers is dependent on a number of factors. One of the most important factors is the radiolysis temperature. This paper discusses the effects of the α-transition and the other secondary transitions, as well as the ceiling and melting temperatures, on the nature of the radiolysis reactions which occur for a number of polymers. Some implications of changes in the radiation chemistry of polymers with a change in the temperature are also considered. (author)

Physically persistent stabilizers by functionalization of polymers

Czech Academy of Sciences Publication Activity Database

Pospíšil, Jan; Habicher, W. D.; Nešpůrek, Stanislav

2001-01-01

Roč. 164, - (2001), s. 389-399 ISSN 1022-1360. [Reactive Polymers in Inhomogeneous Systems, in Melts and at Interfaces. Dresden, 16.07.2000-19.07.2000] R&D Projects: GA MŠk ME 184; GA MŠk ME 372; GA AV ČR IAA1050901; GA ČR GA106/98/0700; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : nonvolatile antioxidants * photostabilizers * polymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.634, year: 2001

Gamma irradiation of melt processed biomedical PDLLA/HAP nanocomposites

International Nuclear Information System (INIS)

Dadbin, Susan; Kheirkhah, Yahya

2014-01-01

Poly(D-L lactide) PDLLA/hydroxyapatite (HAP) nanocomposites at various compositions were prepared by melt-compounding process and then subjected to gamma irradiation at a dose of 30 kGy. The morphology of the nanocomposites, characterized by transmission electron microscopy (TEM), displayed HAP nanoparticles at various sizes ranging from 10 to 100 nm distributed almost evenly within the polymer matrix. Differential scanning calorimetric (DSC) analysis of the irradiated nanocomposites showed an increase in the degree of crystallinity along with a melting peak split. The double melting peak suggested formation of different crystalline structures in the radiation exposed nanocomposites. Also the cold crystallization peak shifted to lower temperatures and became much sharper upon irradiation, indicating higher crystallization rate. The irradiated nanocomposites showed lower tensile strength and elongation at break, suggesting occurrence of some chain scission reactions in the PLA. - Highlights: • Biomedical polylactic acid/hydroxyapatite nanocomposites prepared by melt-compounding were gamma irradiated. • Transmission electron microscopy showed hydroxyapatite nanoparticles evenly distributed within polylactic acid ranging from 10 to 100 nm. • A halo appeared around hydroxyapatite particles showing interfacial interactions between polylactic acid and the particles. • Double melting peak appeared for polylactic acid in DSC thermograms upon gamma irradiation of the nanocomposites

Predictive modeling, simulation, and optimization of laser processing techniques: UV nanosecond-pulsed laser micromachining of polymers and selective laser melting of powder metals

Science.gov (United States)

Criales Escobar, Luis Ernesto

One of the most frequently evolving areas of research is the utilization of lasers for micro-manufacturing and additive manufacturing purposes. The use of laser beam as a tool for manufacturing arises from the need for flexible and rapid manufacturing at a low-to-mid cost. Laser micro-machining provides an advantage over mechanical micro-machining due to the faster production times of large batch sizes and the high costs associated with specific tools. Laser based additive manufacturing enables processing of powder metals for direct and rapid fabrication of products. Therefore, laser processing can be viewed as a fast, flexible, and cost-effective approach compared to traditional manufacturing processes. Two types of laser processing techniques are studied: laser ablation of polymers for micro-channel fabrication and selective laser melting of metal powders. Initially, a feasibility study for laser-based micro-channel fabrication of poly(dimethylsiloxane) (PDMS) via experimentation is presented. In particular, the effectiveness of utilizing a nanosecond-pulsed laser as the energy source for laser ablation is studied. The results are analyzed statistically and a relationship between process parameters and micro-channel dimensions is established. Additionally, a process model is introduced for predicting channel depth. Model outputs are compared and analyzed to experimental results. The second part of this research focuses on a physics-based FEM approach for predicting the temperature profile and melt pool geometry in selective laser melting (SLM) of metal powders. Temperature profiles are calculated for a moving laser heat source to understand the temperature rise due to heating during SLM. Based on the predicted temperature distributions, melt pool geometry, i.e. the locations at which melting of the powder material occurs, is determined. Simulation results are compared against data obtained from experimental Inconel 625 test coupons fabricated at the National

Inorganic polymers and materials. Final report

Energy Technology Data Exchange (ETDEWEB)

Sneddon, Larry G.

2001-01-01

This DOE-sponsored project was focused on the design, synthesis, characterization, and applications of new types of boron and silicon polymers with a goal of attaining processable precursors to advanced ceramic materials of technological importance. This work demonstrated a viable design strategy for the systematic formation of polymeric precursors to ceramics based on the controlled functionalization of preformed polymers with pendant groups of suitable compositions and crosslinking properties. Both the new dipentylamine-polyborazylene and pinacolborane-hydridopolysilazane polymers, unlike the parent polyborazylene and other polyborosilazanes, are stable as melts and can be easily spun into polymer fibers. Subsequent pyrolyses of these polymer fibers then provide excellent routes to BN and SiNCB ceramic fibers. The ease of synthesis of both polymer systems suggests new hybrid polymers with a range of substituents appended to polyborazylene or polysilazane backbones, as well as other types of preceramic polymers, should now be readily achieved, thereby allowing even greater control over polymer and ceramic properties. This control should now enable the systematic tailoring of the polymers and derived ceramics for use in different technological applications. Other major recent achievements include the development of new types of metal-catalyzed methods needed for the polymerization and modification of inorganic monomers and polymers, and the modification studies of polyvinylsiloxane and related polymers with substituents that enable the formation of single source precursors to high-strength, sintered SiC ceramics.

Structure, entanglements and dynamics of polymer nanocomposites containing spherical nanoparticles

International Nuclear Information System (INIS)

Karatrantos, A; Clarke, N; Composto, R J; Winey, K I

2014-01-01

We investigate the effect of nanoparticles on polymer structure, nanoparticle dynamics and topological constraints (entanglements) in polymer melts for nanoparticle loading above percolation threshold as high as 40.9% using stochastic molecular dynamics (MD) simulations. An increase in the number of entanglements (decrease of N e with 40.9% volume fraction of nanoparticles dispersed in the polymer matrix) in the nanocomposites is observed as evidenced by larger contour lengths of the primitive paths. Attraction between polymers and nanoparticles affects the entanglements in the nanocomposites and alters the primitive path. The diffusivity of small sized nanoparticles deviates significantly from the Stokes- Einstein relation

Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications.

Science.gov (United States)

Robinson, Joshua W; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J Timothy; Cosimbescu, Lelia

2016-01-05

We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach.

Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

Science.gov (United States)

Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J. Timothy; Cosimbescu, Lelia

2016-01-01

We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach.

Molecular self assembly of mixed comb-like dextran surfactant polymers for SPR virus detection.

Science.gov (United States)

Mai-Ngam, Katanchalee; Kiatpathomchai, Wansika; Arunrut, Narong; Sansatsadeekul, Jitlada

2014-11-04

The synthesis of two comb-like dextran surfactant polymers, that are different in their dextran molecular weight (MW) distribution and the presence of carboxylic groups, and their characterization are reported. A bimodal carboxylic dextran surfactant polymer consists of poly(vinyl amine) (PVAm) backbone with carboxyl higher MW dextran, non-functionalized lower MW dextran and hydrophobic hexyl branches; while a monomodal dextran surfactant polymer is PVAm grafted with non-functionalized lower MW dextran and hexyl branches. Layer formation of non-covalently attached dextran chains with bimodal MW distributions on a surface plasmon resonance (SPR) chip was investigated from the perspective of mixed physisorption of the bimodal and monomodal surfactant polymers. Separation distances between the carboxylic longer dextran side chains within the bimodal surfactant polymer and between the whole bimodal surfactant molecules on the chip surface could be well-controlled. SPR analysis of shrimp yellow head virus using our mixed surfactant chips showed dependence on synergetic adjustment of these separation distances. Copyright © 2014 Elsevier Ltd. All rights reserved.

Hyperbranched polymers from polymerization in solid state

International Nuclear Information System (INIS)

Tomaz, Vivian A.; Silva, Rafael; Muniz, Edvani C.; Rubira, Adley F.

2009-01-01

The macroscopic properties of polymers are directly related to the chemical characteristics of the monomeric units and also with the geometric arrangement of polymer chains. Thus, polymers were synthesized from two well-known chelators EDTA and EDA. We evaluated the conditions for the polymerization of the precursors in the solid state. The polymerization was carried out varying the proportions of reagents, aiming the polymers with different degrees of chain branching and the materials were characterized by FTIR. The materials obtained from the best condition for synthesis were purified by size-exclusion chromatography of and were subjected to characterization by FTIR and NMR of 1 H and 13 C. The content of end groups in these samples was determined by back titration. (author)

Rheology as a tool for evaluation of melt processability of innovative dosage forms

DEFF Research Database (Denmark)

Aho, Johanna Maaria; Boetker, Johan P; Baldursdottir, Stefania

2015-01-01

) printing, will have an increasingly important role when designing products for flexible dosing, since dosage forms based on compacting of a given powder mixture do not enable manufacturing of optimal pharmaceutical products for personalized treatments. The melt processability of polymers and API...

Renormalization of the one-loop theory of fluctuations in polymer blends and diblock copolymer melts.

Science.gov (United States)

Grzywacz, Piotr; Qin, Jian; Morse, David C

2007-12-01

Attempts to use coarse-grained molecular theories to calculate corrections to the random-phase approximation (RPA) for correlations in polymer mixtures have been plagued by an unwanted sensitivity to the value of an arbitrary cutoff length, i.e., by an ultraviolet (UV) divergence. We analyze the UV divergence of the inverse structure factor S(-1)(k) predicted by a "one-loop" approximation similar to that used in several previous studies. We consider both miscible homopolymer blends and disordered diblock copolymer melts. We show, in both cases, that all UV divergent contributions can be absorbed into a renormalization of the values of the phenomenological parameters of a generalized self-consistent field theory (SCFT). This observation allows the construction of an UV convergent theory of corrections to SCFT phenomenology. The UV-divergent one-loop contribution to S(-1)(k) is shown to be the sum of (i) a k -independent contribution that arises from a renormalization of the effective chi parameter, (ii) a k-dependent contribution that arises from a renormalization of monomer statistical segment lengths, (iii) a contribution proportional to k(2) that arises from a square-gradient contribution to the one-loop fluctuation free energy, and (iv) a k-dependent contribution that is inversely proportional to the degree of polymerization, which arises from local perturbations in fluid structure near chain ends and near junctions between blocks in block copolymers.

Biomimetic Fluorocarbon Surfactant Polymers Reduce Platelet Adhesion on PTFE/ePTFE Surfaces

Science.gov (United States)

Wang, Shuwu; Gupta, Anirban Sen; Sagnella, Sharon; Barendt, Pamela M.; Kottke-Marchant, Kandice; Marchant, Roger E.

2010-01-01

We describe a series of fluorocarbon surfactant polymers designed as surface-modifying agents for improving the thrombogenicity of ePTFE vascular graft materials by the reduction of platelet adhesion. The surfactant polymers consist of a poly(vinyl amine) backbone with pendent dextran and perfluoroundecanoyl branches. Surface modification is accomplished by a simple dip-coating process in which surfactant polymers undergo spontaneous surface-induced adsorption and assembly on PTFE/ePTFE surface. The adhesion stability of the surfactant polymer on PTFE was examined under dynamic shear conditions in PBS and human whole blood with a rotating disk system. Fluorocarbon surfactant polymer coatings with three different dextran to perfluorocarbon ratios (1:0.5, 1:1 and 1:2) were compared in the context of platelet adhesion on PTFE/ePTFE surface under dynamic flow conditions. Suppression of platelet adhesion was achieved for all three coated surfaces over the shear-stress range of 0–75 dyn/cm2 in platelet-rich plasma (PRP) or human whole blood. The effectiveness depended on the surfactant polymer composition such that platelet adhesion on coated surfaces decreased significantly with increasing fluorocarbon branch density at 0 dyn/cm2. Our results suggest that fluorocarbon surfactant polymers can effectively suppress platelet adhesion and demonstrate the potential application of the fluorocarbon surfactant polymers as non-thrombogenic coatings for ePTFE vascular grafts. PMID:19323880

Thermally conductive, electrically insulating and melt-processable polystyrene/boron nitride nanocomposites prepared by in situ reversible addition fragmentation chain transfer polymerization

International Nuclear Information System (INIS)

Huang, Xingyi; Wang, Shen; Zhu, Ming; Yang, Ke; Jiang, Pingkai; Bando, Yoshio; Golberg, Dmitri; Zhi, Chunyi

2015-01-01

Thermally conductive and electrically insulating polymer/boron nitride (BN) nanocomposites are highly attractive for various applications in many thermal management fields. However, so far most of the preparation methods for polymer/BN nanocomposites have usually caused difficulties in the material post processing. Here, an in situ grafting approach is designed to fabricate thermally conductive, electrically insulating and post-melt processable polystyrene (PS)/BN nanosphere (BNNS) nanocomposites by initiating styrene (St) on the surface functionalized BNNSs via reversible addition fragmentation chain transfer polymerization. The nanocomposites exhibit significantly enhanced thermal conductivity. For example, at a St/BN feeding ratio of 5:1, an enhancement ratio of 1375% is achieved in comparison with pure PS. Moreover, the dielectric properties of the nanocomposites show a desirable weak dependence on frequency, and the dielectric loss tangent of the nanocomposites remains at a very low level. More importantly, the nanocomposites can be subjected to multiple melt processing to form different shapes. Our method can become a universal approach to prepare thermally conductive, electrically insulating and melt-processable polymer nanocomposites with diverse monomers and nanofillers. (paper)

Performance limitations of polymer electrolytes based on ethylene oxide polymers

International Nuclear Information System (INIS)

Buriez, Olivier; Han, Yong Bong; Hou, Jun; Kerr, John B.; Qiao, Jun; Sloop, Steven E.; Tian, Minmin; Wang, Shanger

1999-01-01

Studies of polymer electrolyte solutions for lithium-polymer batteries are described. Two different salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium trifluoromethanesulfonate (LiTf), were dissolved in a variety of polymers. The structures were all based upon the ethylene oxide unit for lithium ion solvation and both linear and comb-branch polymer architectures have been examined. Conductivity, salt diffusion coefficient and transference number measurements demonstrate the superior transport properties of the LiTFSI salt over LiTf. Data obtained on all of these polymers combined with LiTFSI salts suggest that there is a limit to the conductivity achievable at room temperature, at least for hosts containing ethylene oxide units. The apparent conductivity limit is 5 x 10-5 S/cm at 25 C. Providing that the polymer chain segment containing the ethylene oxide units is at least 5-6 units long there appears to be little influence of the polymer framework to which the solvating groups are attached. To provide adequate separator function, the mechanical properties may be disconnected from the transport properties by selection of an appropriate architecture combined with an adequately long ethylene oxide chain. For both bulk and interfacial transport of the lithium ions, conductivity data alone is insufficient to understand the processes that occur. Lithium ion transference numbers and salt diffusion coefficients also play a major role in the observed behavior and the transport properties of these polymer electrolyte solutions appear to be quite inadequate for ambient temperature performance. At present, this restricts the use of such systems to high temperature applications. Several suggestions are given to overcome these obstacles

Study of Catalyst, Aging Time and Surfactant Effects on Silica Inorganic Polymer Characteristics

Directory of Open Access Journals (Sweden)

M. Pakizeh

2007-06-01

Full Text Available In the present study the sol-gel method is used for synthesis of amorphous nanostructure silica polymer using tetraethoxysilane (TEOS as silicon source. This polymer can be used in manufacturing of nanoporous asymmetricmembranes. The effect of catalyst on silica particle size has been studied under acidic and basic conditions.زAcid-catalyzed reaction leads to the formation of fine particles while the base-catalyzed reaction produceslarger particles. The presence of cationic template surfactant namely cetyl pyridinium bromide (CPBزdirects the structural formation of the polymer by preventing the highly branched polymeric clusters. This will increase the effective area of the produced silica membrane. Nitrogen physisorption tests by Brunaver- Emmett-Teller (BET and Barrett-Joyner-Halenda (BJH methods revealed that the surface area of the membrane increases significantly around 5-folds when acid-catalyzed reaction is used. 29Si-NMR test is also used to study the aging time effect on the level of silica polymer branching. The results show that in acidic condition, aging time up to three weeks can still affect branching. The calcinations process in which the organic materials and CPB (surfactant are burned and released from the silica particles, is studied on template free silica materials as well as templated silica materials using TGA and DTA techniques.

Rational Design of Branched Nanoporous Gold Nanoshells with Enhanced Physico-Optical Properties for Optical Imaging and Cancer Therapy.

Science.gov (United States)

Song, Jibin; Yang, Xiangyu; Yang, Zhen; Lin, Lisen; Liu, Yijing; Zhou, Zijian; Shen, Zheyu; Yu, Guocan; Dai, Yunlu; Jacobson, Orit; Munasinghe, Jeeva; Yung, Bryant; Teng, Gao-Jun; Chen, Xiaoyuan

2017-06-27

Reported procedures on the synthesis of gold nanoshells with smooth surfaces have merely demonstrated efficient control of shell thickness and particle size, yet no branch and nanoporous features on the nanoshell have been implemented to date. Herein, we demonstrate the ability to control the roughness and nanoscale porosity of gold nanoshells by using redox-active polymer poly(vinylphenol)-b-(styrene) nanoparticles as reducing agent and template. The porosity and size of the branches on this branched nanoporous gold nanoshell (BAuNSP) material can be facilely adjusted by control of the reaction speed or the reaction time between the redox-active polymer nanoparticles and gold ions (Au 3+ ). Due to the strong reduction ability of the redox-active polymer, the yield of BAuNSP was virtually 100%. By taking advantage of the sharp branches and nanoporous features, BAuNSP exhibited greatly enhanced physico-optical properties, including photothermal effect, surface-enhanced Raman scattering (SERS), and photoacoustic (PA) signals. The photothermal conversion efficiency can reach as high as 75.5%, which is greater than most gold nanocrystals. Furthermore, the nanoporous nature of the shells allows for effective drug loading and controlled drug release. The thermoresponsive polymer coated on the BAuNSP surface serves as a gate keeper, governing the drug release behavior through photothermal heating. Positron emission tomography imaging demonstrated a high passive tumor accumulation of 64 Cu-labeled BAuNSP. The strong SERS signal generated by the SERS-active BAuNSP in vivo, accompanied by enhanced PA signals in the tumor region, provide significant tumor information, including size, morphology, position, and boundaries between tumor and healthy tissues. In vivo tumor therapy experiments demonstrated a highly synergistic chemo-photothermal therapy effect of drug-loaded BAuNSPs, guided by three modes of optical imaging.

Rouse mode analysis of chain relaxation in polymer nanocomposites.

Science.gov (United States)

Kalathi, Jagannathan T; Kumar, Sanat K; Rubinstein, Michael; Grest, Gary S

2015-05-28

Large-scale molecular dynamics simulations are used to study the internal relaxations of chains in nanoparticle (NP)/polymer composites. We examine the Rouse modes of the chains, a quantity that is closest in spirit to the self-intermediate scattering function, typically determined in an (incoherent) inelastic neutron scattering experiment. Our simulations show that for weakly interacting mixtures of NPs and polymers, the effective monomeric relaxation rates are faster than in a neat melt when the NPs are smaller than the entanglement mesh size. In this case, the NPs serve to reduce both the monomeric friction and the entanglements in the polymer melt, as in the case of a polymer-solvent system. However, for NPs larger than half the entanglement mesh size, the effective monomer relaxation is essentially unaffected for low NP concentrations. Even in this case, we observe a strong reduction in chain entanglements for larger NP loadings. Thus, the role of NPs is to always reduce the number of entanglements, with this effect only becoming pronounced for small NPs or for high concentrations of large NPs. Our studies of the relaxation of single chains resonate with recent neutron spin echo (NSE) experiments, which deduce a similar entanglement dilution effect.

Modular Assembly of Hierarchically Structured Polymers

Science.gov (United States)

Leophairatana, Porakrit

The synthesis of macromolecules with complex yet highly controlled molecular architectures has attracted significant attention in the past few decades due to the growing demand for specialty polymers that possess novel properties. Despite recent efforts, current synthetic routes lack the ability to control several important architectural variables while maintaining low polydispersity index. This dissertation explores a new synthetic scheme for the modular assembly of hierarchically structured polymers (MAHP) that allows virtually any complex polymer to be assembled from a few basic molecular building blocks using a single common coupling chemistry. Complex polymer structures can be assembled from a molecular toolkit consisting of (1) copper-catalyzed azide-alkyne cycloaddition (CuAAC), (2) linear heterobifunctional macromonomers, (3) a branching heterotrifunctional molecule, (4) a protection/deprotection strategy, (5) "click" functional solid substrates, and (6) functional and responsive polymers. This work addresses the different challenges that emerged during the development of this synthetic scheme, and presents strategies to overcome those challenges. Chapter 3 investigates the alkyne-alkyne (i.e. Glaser) coupling side reactions associated with the atom transfer radical polymerization (ATRP) synthesis of alkyne-functional macromonomers, as well as with the CuAAC reaction of alkyne functional building blocks. In typical ATRP synthesis of unprotected alkyne functional polymers, Glaser coupling reactions can significantly compromise the polymer functionality and undermine the success of subsequent click reactions in which the polymers are used. Two strategies are reported that effectively eliminate these coupling reactions: (1) maintaining low temperature post-ATRP upon exposure to air, followed by immediate removal of copper catalyst; and (2) adding excess reducing agents post-ATRP, which prevents the oxidation of Cu(I) catalyst required by the Glaser coupling

A review on melt-state viscoelastic properties of polymer nanocomposites

CSIR Research Space (South Africa)

Hyoung, JC

2011-10-01

Full Text Available The mixing of polymer matrices with nanoparticles to form composite materials has been an area of great research interest. The mechanical and rheological properties of such composite materials are directly related to the properties of the matrix...

Equilibrium polymerization of cyclic carbonate oligomers. III. Chain branching and the gel transition

Science.gov (United States)

Ballone, P.; Jones, R. O.

2002-10-01

Ring-opening polymerization of cyclic polycarbonate oligomers, where monofunctional active sites act on difunctional monomers to produce an equilibrium distribution of rings and chains, leads to a "living polymer." Monte Carlo simulations [two-dimensional (2D) and three-dimensional (3D)] of the effects of single [J. Chem. Phys. 115, 3895 (2001)] and multiple active sites [J. Chem. Phys. 116, 7724 (2002)] are extended here to trifunctional active sites that lead to branching. Low concentrations of trifunctional particles c3 reduce the degree of polymerization significantly in 2D, and higher concentrations (up to 32%) lead to further large changes in the phase diagram. Gel formation is observed at high total density and sizable c3 as a continuous transition similar to percolation. Polymer and gel are much more stable in 3D than in 2D, and both the total density and the value of c3 required to produce high molecular weight aggregates are reduced significantly. The degree of polymerization in high-density 3D systems is increased by the addition of trifunctional monomers and reduced slightly at low densities and low c3. The presence of branching makes equilibrium states more sensitive (in 2D and 3D) to changes in temperature T. The stabilities of polymer and gel are enhanced by increasing T, and—for sufficiently high values of c3—there is a reversible polymer-gel transformation at a density-dependent floor temperature.

Suspensions of polymer-grafted nanoparticles with added polymers-Structure and effective pair-interactions.

Science.gov (United States)

Chandran, Sivasurender; Saw, Shibu; Kandar, A K; Dasgupta, C; Sprung, M; Basu, J K

2015-08-28

We present the results of combined experimental and theoretical (molecular dynamics simulations and integral equation theory) studies of the structure and effective interactions of suspensions of polymer grafted nanoparticles (PGNPs) in the presence of linear polymers. Due to the absence of systematic experimental and theoretical studies of PGNPs, it is widely believed that the structure and effective interactions in such binary mixtures would be very similar to those of an analogous soft colloidal material-star polymers. In our study, polystyrene-grafted gold nanoparticles with functionality f = 70 were mixed with linear polystyrene (PS) of two different molecular weights for obtaining two PGNP:PS size ratios, ξ = 0.14 and 2.76 (where, ξ = Mg/Mm, Mg and Mm being the molecular weights of grafting and matrix polymers, respectively). The experimental structure factor of PGNPs could be modeled with an effective potential (Model-X), which has been found to be widely applicable for star polymers. Similarly, the structure factor of the blends with ξ = 0.14 could be modeled reasonably well, while the structure of blends with ξ = 2.76 could not be captured, especially for high density of added polymers. A model (Model-Y) for effective interactions between PGNPs in a melt of matrix polymers also failed to provide good agreement with the experimental data for samples with ξ = 2.76 and high density of added polymers. We tentatively attribute this anomaly in modeling the structure factor of blends with ξ = 2.76 to the questionable assumption of Model-X in describing the added polymers as star polymers with functionality 2, which gets manifested in both polymer-polymer and polymer-PGNP interactions especially at higher fractions of added polymers. The failure of Model-Y may be due to the neglect of possible many-body interactions among PGNPs mediated by matrix polymers when the fraction of added polymers is high. These observations point to the need for a new framework to

New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

Science.gov (United States)

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

2005-01-01

A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

NASA Glenn Research Center Electrochemistry Branch Overview

Science.gov (United States)

Manzo, Michelle A.; Hoberecht, Mark; Reid, Concha

2010-01-01

This presentation covers an overview of NASA Glenn's history and heritage in the development of electrochemical systems for aerospace applications. Current programs related to batteries and fuel cells are addressed. Specific areas of focus are Li-ion batteries and Polymer Electrolyte Membrane Fuel cells systems and their development for future Exploration missions. The presentation covers details of current component development efforts for high energy and ultra high energy Li-ion batteries and non-flow-through fuel cell stack and balance of plant development. Electrochemistry Branch capabilities and facilities are also addressed.

Unsolved problems of crystallization and melting of flexible macromolecules

International Nuclear Information System (INIS)

Wunderlich, B.

1992-01-01

The thermodynamics, kinetics, and computer simulations of crystallization and melting is discussed. The thermodynamics is shown to be well understood, although for many specific crystals not enough details for full description are available. Experiments on the crystallization kinetics of poly(ethylene) and poly(oxyethylene) in the presence of crystal nuclei as a function of molecular mass revealed that with increasing mass, the crystallization behavior deviates increasingly from that of small, rigid molecules. Instead of showing a continuously changing, linear crystallization rate with temperature through the equilibrium melting temperature, T m 0 , these flexible macromolecules show a region of practically zero crystallization rate between T m 0 and about (T m 0 - 15) K, creating a temperature region of metastability in the melt that cannot be broken by nucleation with pregrown crystals. Molecular Nucleation was proposed as a cooperative process to be of overriding importance for the description of polymer crystallization, and to be at the center of segregation of molecules of lower molecular mass by growing crystal fronts. Initial efforts to model sufficiently large crystals using Monte Carlo and molecular dynamics methods are presented. Some of the short-time intermediates in the melting, crystallization, and annealing processes seem to have little similarity to commonly assumed models of crystallization and melting and are presented as discussion topics

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

Ion beam irradiation effects on aromatic polymers

International Nuclear Information System (INIS)

Shukushima, Satoshi; Ueno, Keiji

1995-01-01

We studied the optical and thermal properties of aromatic polymer films which had been irradiated with 1 MeV H + , H 2 + and He + ions. The examined aromatic polymers were polyetherether ketone(PEEK), polyetherimide(PEI), polyether sulfon(PES), polysulfon(PSF), and polyphenylene sulfide(PPS). The optical densities at 300nm of PES and PSF greatly increased after the irradiation. The optical densities at 400nm of all the examined polymer lineally increased with the irradiation dose. The PEEK film which had been irradiated with 1 MeV H + was not deformed above melting point. This demonstrates that cross-linking occurs in PEEK films by ion beam irradiation. As for the effects, depending on the mass of the irradiated ions, it was found that the ions with a high mass induced larger effects on the aromatic polymers for the same absorption energy. (author)

Core-shell polymer nanorods by a two-step template wetting process

International Nuclear Information System (INIS)

Dougherty, S; Liang, J

2009-01-01

One-dimensional core-shell polymer nanowires offer many advantages and great potential for many different applications. In this paper we introduce a highly versatile two-step template wetting process to fabricate two-component core-shell polymer nanowires with controllable shell thickness. PLLA and PMMA were chosen as model polymers to demonstrate the feasibility of this process. Solution wetting with different concentrations of polymer solutions was used to fabricate the shell layer and melt wetting was used to fill the shell with the core polymer. The shell thickness was analyzed as a function of the polymer solution concentration and viscosity, and the core-shell morphology was observed with TEM. This paper demonstrates the feasibility of fabricating polymer core-shell nanostructures using our two-step template wetting process and opens the arena for optimization and future experiments with polymers that are desirable for specific applications.

Power ultrasound effects for in situ compatibilization of polymer-clay nanocomposites

International Nuclear Information System (INIS)

Ryu, Joung Gul; Park, Sang Wan; Kim, Hyungsu; Lee, Jae Wook

2004-01-01

Polymer-clay nanocomposites of various concentrations were prepared by ultrasonically assisted polymerization and melt mixing processes. The sonication process using power ultrasonic wave was employed to enhance nano-scale dispersion during melt mixing of monomer, polymer and organically modified clay. According to the unique mode of power ultrasound wave, we expected enhanced breakup of layered silicate bundle and further reduction in the size of dispersed phase with better homogeneity compared to the in situ polymerization. The optimum conditions to perform stable exfoliated nanocomposites were studied by various compositions and conditions. Dispersion characteristics and morphology of the nanocomposites were verified by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Rheological behaviors were measured under dynamic frequency sweep mode using Rheometric science ARES

Additive manufacturing of polymer-derived ceramics

Science.gov (United States)

Eckel, Zak C.; Zhou, Chaoyin; Martin, John H.; Jacobsen, Alan J.; Carter, William B.; Schaedler, Tobias A.

2016-01-01

The extremely high melting point of many ceramics adds challenges to additive manufacturing as compared with metals and polymers. Because ceramics cannot be cast or machined easily, three-dimensional (3D) printing enables a big leap in geometrical flexibility. We report preceramic monomers that are cured with ultraviolet light in a stereolithography 3D printer or through a patterned mask, forming 3D polymer structures that can have complex shape and cellular architecture. These polymer structures can be pyrolyzed to a ceramic with uniform shrinkage and virtually no porosity. Silicon oxycarbide microlattice and honeycomb cellular materials fabricated with this approach exhibit higher strength than ceramic foams of similar density. Additive manufacturing of such materials is of interest for propulsion components, thermal protection systems, porous burners, microelectromechanical systems, and electronic device packaging.

An investigation on the effect of surface characteristics on adhesion between polymer melts and replication tools

DEFF Research Database (Denmark)

Delaney, Kevin D.; Kennedy, Jonathan David; Bissacco, Giuliano

2012-01-01

Understanding interfacial characteristics between a polymer and its associated tool surface is critical to successful optimization of processes such as injection moulding, embossing and extrusion used to produce polymer parts. One of the factors characterizing the strength of the polymer-tool int......Understanding interfacial characteristics between a polymer and its associated tool surface is critical to successful optimization of processes such as injection moulding, embossing and extrusion used to produce polymer parts. One of the factors characterizing the strength of the polymer...... the results of an experimental study aimed at determining the effect of selected tool surface characteristics on the work of adhesion, by measuring contact angles of polymer droplets on the surfaces. The experimental set-up, selection of test parameters and main challenges faced to date are described...

Pressure-induced melting of micellar crystal

DEFF Research Database (Denmark)

Mortensen, K.; Schwahn, D.; Janssen, S.

1993-01-01

that pressure improves the solvent quality of water, thus resulting in decomposition of the micelles and consequent melting of the micellar crystal. The combined pressure and temperature dependence reveals that in spite of the apparent increase of order on the 100 angstrom length scale upon increasing......Aqueous solutions of triblock copolymers of poly(ethylene oxide) and poly(propylene oxide) aggregate at elevated temperatures into micelles which for polymer concentrations greater-than-or-equal-to 20% make a hard sphere crystallization to a cubic micellar crystal. Structural studies show...... temperature (decreasing pressure) the overall entropy increases through the inverted micellar crystallization characteristic....

Effect of pH grade on polymer-gel dosimeter and its brachytherapy application

International Nuclear Information System (INIS)

Spevacek, V.; Hrbacek, J.; Dvorak, P.; Cechak, T.; Novotny, J.

2003-01-01

To evaluate impact of pH grade on characteristics of polymer-gel dosimeter and its application in dose distribution verification in brachytherapy. A polymer-gel dosimeter based on radiation induced polymerization and crosslinking of acrylic monomers (acrylic acid, N,N' methylen-bis-acrylamide) was investigated with respect to its pH grade. pH grade of a dosimeter was varied by concentration of natrium hydroxide. Afterwards, dosimeter was split into several samples which were uniformly irradiated with Co-60 gamma rays. The range of doses applied was usually from 0 to 50 Gy with the main interest in region up to 20 Gy. Evaluation of dosimeter dose response was performed using MRI (T2). Dose response curves obtained were evaluated with respect to pH grade as a parameter. In parallel, there was studied temperature resistance (melting temperature) of gels with various pH grade. pH grade modified polymer-gel dosimeter was then used to compare dose distribution calculated with brachytherapy treatment planning system for simple irradiation geometry with Ir-192 HDR source. Additionaly, Monte Carlo calculated data were also included in the brachytherapy study. There was observed effect of pH grade on dose-response curve parameters (slope of linear fit, background response, linear range and maximum measurable dose). In general, the lower pH grade the higher sensitivity. Another positive effect of decreased pH grade is significantly higher maximum measurable dose. Maximum melting temperature of a gel was observed with pH grade between 3.5 and 4. For both higher and lower pH grades the melting temperature was lower. Using pH modified polymer-gel dosimeter simple brachytherapy dose distribution was measured and compared with calculated and Monte Carlo simulated data. There was observed strong dependence of dose-response relationship on pH grade of polymer-gel dosimeter resulting in significant improvement of dosimeter characteristics, namely sensitivity, applicable range of

Modelling Polymer Deformation and Welding Behaviour during 3D Printing

Science.gov (United States)

McIlroy, Claire; Olmsted, Peter

2016-11-01

3D printing has the potential to transform manufacturing processes, yet improving the strength of printed parts, to equal that of traditionally-manufactured parts, remains an underlying issue. The most common method, fused deposition modelling, involves melting a thermoplastic, followed by layer-by-layer extrusion of the material to fabricate a three-dimensional object. The key to the ensuring strength at the weld between these layers is successful inter-diffusion. However, as the printed layer cools towards the glass transition temperature, the time available for diffusion is limited. In addition, the extrusion process significantly deforms the polymer micro-structure prior to welding and consequently affects how the polymers "re-entangle" across the weld. We have developed a simple model of the non-isothermal printing process to explore the effects that typical printing conditions and amorphous polymer rheology have on the ultimate weld structure. In particular, we incorporate both the stretch and orientation of the polymer using the Rolie-Poly constitutive equation to examine how the melt flows through the nozzle and is deposited onto the build plate. We then address how this deformation relaxes and contributes to the thickness and structure of the weld. National Institute for Standards and Technology (NIST) and Georgetown University.

The role of oleate-functionalized layered double hydroxide in the melt compounding of polypropylene nanocomposites

Czech Academy of Sciences Publication Activity Database

Donato, R. K.; Luza, L.; da Silva, R. F.; Moro, C. C.; Guzatto, R.; Samios, D.; Matějka, Libor; Dimzoski, Bojan; Amico, S. C.; Schrekker, H. S.

2012-01-01

Roč. 32, č. 8 (2012), s. 2396-2403 ISSN 0928-4931 Institutional research plan: CEZ:AV0Z40500505 Keywords : renewable feedstock functionalized nanofiller * polymer-matrix nanocomposite * melt compounding Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.404, year: 2012

Improving proton conduction pathways in di- and triblock copolymer membranes: Branched versus linear side chains

Science.gov (United States)

Dorenbos, G.

2017-06-01

Phase separation within a series of polymer membranes in the presence of water is studied by dissipative particle dynamics. Each polymer contains hydrophobic A beads and hydrophilic C beads. Three parent architectures are constructed from a backbone composed of connected hydrophobic A beads to which short ([C]), long ([A3C]), or symmetrically branched A5[AC][AC] side chains spring off. Three di-block copolymer derivatives are constructed by covalently bonding an A30 block to each parent architecture. Also three tri-blocks with A15 blocks attached to both ends of each parent architecture are modeled. Monte Carlo tracer diffusion calculations through the water containing pores for 1226 morphologies reveal that water diffusion for parent architectures is slowest and diffusion through the di-blocks is fastest. Furthermore, diffusion increases with side chain length and is highest for branched side chains. This is explained by the increase of water pore size with , which is the average number of bonds that A beads are separated from a nearest C bead. Optimization of within the amphiphilic parent architecture is expected to be essential in improving proton conduction in polymer electrolyte membranes.

Origin of glass transition temperature behavior in polymer nanocomposites

Science.gov (United States)

Kropka, Jamie; Ganesan, Venkat; Green, Peter

2008-03-01

Local composition variations inherent in multi-component materials, even when the material constituents are miscible, generally lead to heterogeneous behavior in the properties of mixtures relative to their single component counterparts. In contrast, experiments have suggested that some polymer nanocomposite materials exhibit changes in their bulk Tg without displaying excess heterogeneity in their dynamics, as measured mechanically, relative to the neat polymer. Incoherent neutron scattering measurements on materials that fit this description, C60-PMMA mixtures, suggest that modifications of the polymer melt dynamics are limited to the vicinity of the particles. A model by which the localized modifications of polymer dynamics can account for the apparent homogeneous change in Tg is proposed to explain the experimental findings. Computations based on percolation theory support the model.

Synthesis by irradiation and mechanism and structural characterization study of high melt strength polypropylene

International Nuclear Information System (INIS)

Lugao, Ademar Benevolo

2004-01-01

Polypropylene molecular structure is made only by linear molecules interacting by weak forces. The resulting PP has very low melt strength (MS). MS is important to make feasible to process PP by all the transformation technologies based on the free expansion of the melt. The aim of this work was to develop a new process to synthesize PP with crosslinks and/or long chain branches, known as High Melt Strength Polypropylene (HMSPP) and to characterize its structure and synthesis mechanism. HMSPP was obtained by the irradiation of PP under a crosslinking (acetylene) atmosphere or inert or oxidative one, followed by thermal treatment for radical recombination and thermal treatment for annihilation of the remaining radicals under reactive or inert atmosphere. The results from rheological characterization showed that the highest levels of MS were obtained by conducting irradiation and thermal treatments under crosslinking atmospheres. The results for the elucidation of reaction mechanism by electron spin resonance (ESR) showed that acetylene irradiation is effective in promoting the creation of double bonds, based on the formation of polyenil radicals. The results of structural unraveling showed that radiation promotes predominantly the degradation of atactic molecules or molecules with atactic defects. These results support the hypothesis of formation of branched PP molecules based on the reaction of those fragments with the double bonds created in the PP molecules. (author)

Unique morphology of dispersed clay particles in a polymer nanocomposite

CSIR Research Space (South Africa)

Malwela, T

2011-02-01

Full Text Available This communication reports a unique morphology of dispersed clay particles in a polymer nanocomposite. A nanocomposite of poly[butylene succinate)-co-adipate] (PBSA) with 3 wt% of organically modified montmorillonite was prepared by melt...

Influence of melt mixer on injection molding of thermoset elastomers

Science.gov (United States)

Rochman, Arif; Zahra, Keith

2016-10-01

One of the drawbacks in injection molding is that the plasticizing screw is short such that polymers having high concentrations of additives, such as thermoset elastomers, might not mix homogeneously within the short period of time during the plasticizing stage. In this study, various melt mixers inside the nozzle chamber, together forming a mixing nozzle, were developed. Three different materials were investigated, namely nitrile butadiene rubber (NBR), ethylene propylene-diene monomer (EPDM) and fluorocarbon (FKM). The use of these melt mixers resulted in better homogeneity and properties of the molded parts despite a curing time reduction of 10 s. This was due to the increase in mixing and shearing introduced a higher rate of crosslinking formation in the molded parts.

On the chain length dependence of local correlations in polymer melts and a perturbation theory of symmetric polymer blends.

Science.gov (United States)

Morse, David C; Chung, Jun Kyung

2009-06-14

The self-consistent field (SCF) approach to the thermodynamics of dense polymer liquids is based on the idea that short-range correlations in a polymer liquid are almost independent of how monomers are connected into polymers over larger scales. Some limits of this idea are explored in the context of a perturbation theory for symmetric polymer blends. We consider mixtures of two structurally identical polymers, A and B, in which the AB monomer pair interaction differs slightly from the AA and BB interactions by an amount proportional to a parameter alpha. An expansion of the free energy to first order in alpha yields an excess free energy of mixing per monomer of the form alphaz(N)phi(A)phi(B) in both lattice and continuum models, where z(N) is a measure of the number of intermolecular near neighbors per monomer in a one-component (alpha=0) reference liquid with chains of length N. The quantity z(N) decreases slightly with increasing N because the concentration of intramolecular near neighbors is slightly higher for longer chains, creating a slightly deeper intermolecular correlation hole. We predict that z(N)=z(infinity)[1+betaN(-1/2)], where N is an invariant degree of polymerization and beta=(6/pi)(3/2) is a universal coefficient. This and related predictions about the slight N dependence of local correlations are confirmed by comparison to simulations of a continuum bead-spring model and to published lattice Monte Carlo simulations. We show that a renormalized one-loop theory for blends correctly describes this N dependence of local liquid structure. We also propose a way to estimate the effective interaction parameter appropriate for comparisons of simulation data to SCF theory and to coarse-grained theories of corrections to SCF theory, which is based on an extrapolation of perturbation theory to the limit N-->infinity.

Influence of Polymer-Clay Interfacial Interactions on the Ignition Time of Polymer/Clay Nanocomposites.

Science.gov (United States)

Zope, Indraneel S; Dasari, Aravind; Yu, Zhong-Zhen

2017-08-11

Metal ions present on smectite clay (montmorillonite) platelets have preferential reactivity towards peroxy/alkoxy groups during polyamide 6 (PA6) thermal decomposition. This changes the decomposition pathway and negatively affects the ignition response of PA6. To restrict these interfacial interactions, high-temperature-resistant polymers such as polyetherimide (PEI) and polyimide (PI) were used to coat clay layers. PEI was deposited on clay by solution-precipitation, whereas PI was deposited through a solution-imidization-precipitation technique before melt blending with PA6. The absence of polymer-clay interfacial interactions has resulted in a similar time-to-ignition of PA6/PEI-clay (133 s) and PA6/PI-clay (139 s) composites as neat PA6 (140 s). On the contrary, PA6 with conventional ammonium-based surfactant modified clay has showed a huge drop in time-to-ignition (81 s), as expected. The experimental evidences provided herein reveal the role of the catalytic activity of clay during the early stages of polymer decomposition.

Melt electrospinning of poly(lactic acid) and polycaprolactone microfibers by using a hand-operated Wimshurst generator

Science.gov (United States)

Qin, Chong-Chong; Duan, Xiao-Peng; Wang, Le; Zhang, Li-Hua; Yu, Miao; Dong, Rui-Hua; Yan, Xu; He, Hong-Wei; Long, Yun-Ze

2015-10-01

A conventional melt electrospinning setup usually needs a large, heavy high-voltage power supply and cannot work without a plug (electricity supply). In this article, we report a new melt electrospinning setup based on a small hand-operated Wimshurst generator, which can avoid electrical interference between the high-voltage spinning system and the heating system, and make the setup very portable and safe. Poly(lactic acid) (PLA) and polycaprolactone (PCL) fibers with diameters of 15-45 μm were fabricated successfully by using this apparatus. Experimental parameters such as the rotational speed of the generator handle (a half turn to two turns per second) and the spinning distance (2-14 cm) were investigated. In addition, PLA and PCL fibers were directly melt-electrospun onto a pork liver, and the temperature and adhesiveness of the deposited fibers were studied. The results indicate that the apparatus and melt-electrospun polymer microfibers may be used in dressing for wound healing.A conventional melt electrospinning setup usually needs a large, heavy high-voltage power supply and cannot work without a plug (electricity supply). In this article, we report a new melt electrospinning setup based on a small hand-operated Wimshurst generator, which can avoid electrical interference between the high-voltage spinning system and the heating system, and make the setup very portable and safe. Poly(lactic acid) (PLA) and polycaprolactone (PCL) fibers with diameters of 15-45 μm were fabricated successfully by using this apparatus. Experimental parameters such as the rotational speed of the generator handle (a half turn to two turns per second) and the spinning distance (2-14 cm) were investigated. In addition, PLA and PCL fibers were directly melt-electrospun onto a pork liver, and the temperature and adhesiveness of the deposited fibers were studied. The results indicate that the apparatus and melt-electrospun polymer microfibers may be used in dressing for wound healing

Petrological Geodynamics of Mantle Melting II. AlphaMELTS + Multiphase Flow: Dynamic Fractional Melting

Science.gov (United States)

Tirone, Massimiliano

2018-03-01

In this second installment of a series that aims to investigate the dynamic interaction between the composition and abundance of the solid mantle and its melt products, the classic interpretation of fractional melting is extended to account for the dynamic nature of the process. A multiphase numerical flow model is coupled with the program AlphaMELTS, which provides at the moment possibly the most accurate petrological description of melting based on thermodynamic principles. The conceptual idea of this study is based on a description of the melting process taking place along a 1-D vertical ideal column where chemical equilibrium is assumed to apply in two local sub-systems separately on some spatial and temporal scale. The solid mantle belongs to a local sub-system (ss1) that does not interact chemically with the melt reservoir which forms a second sub-system (ss2). The local melt products are transferred in the melt sub-system ss2 where the melt phase eventually can also crystallize into a different solid assemblage and will evolve dynamically. The main difference with the usual interpretation of fractional melting is that melt is not arbitrarily and instantaneously extracted from the mantle, but instead remains a dynamic component of the model, hence the process is named dynamic fractional melting (DFM). Some of the conditions that may affect the DFM model are investigated in this study, in particular the effect of temperature, mantle velocity at the boundary of the mantle column. A comparison is made with the dynamic equilibrium melting (DEM) model discussed in the first installment. The implications of assuming passive flow or active flow are also considered to some extent. Complete data files of most of the DFM simulations, four animations and two new DEM simulations (passive/active flow) are available following the instructions in the supplementary material.

Solvent Free Low-Melt Viscosity Imide Oligomers And Thermosetting Polyimide Composites

Science.gov (United States)

Chuang, CHun-Hua (Inventor)

2006-01-01

This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine' and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280" C. When the imide oligomer melt is cured at about 371 C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T(sub g)) equal to and above 310 C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280 C. (450-535 F) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343C (550-650 F) high temperature performance capability.

Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

Directory of Open Access Journals (Sweden)

Syed Shahabuddin

2015-01-01

Full Text Available Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydroxyphenylethane, a trifunctional core molecule, to give well-defined triple-arm star-branched polystyrene.

Concentrated Polymer Solutions are Different from Melts: Role of Entanglement Molecular Weight

DEFF Research Database (Denmark)

Huang, Qian; Mednova, Olga; Rasmussen, Henrik K.

2013-01-01

We compare viscoelastic properties of several polystyrene solutions and melts with the same number of entanglements. It is demonstrated that the modulus and time can be shifted such that the linear viscoelastic properties are identical provided the number of entanglements are identical. However...

Multi-scale entropic depletion phenomena in polymer liquids

Energy Technology Data Exchange (ETDEWEB)

Banerjee, Debapriya [Department of Materials Science, University of Illinois, Urbana, Illinois 61801 (United States); Schweizer, Kenneth S., E-mail: kschweiz@illinois.edu [Department of Materials Science, University of Illinois, Urbana, Illinois 61801 (United States); Department of Chemistry, University of Illinois, Urbana, Illinois 61801 (United States); Frederick Seitz Materials Research Laboratory, University of Illinois, Urbana, Illinois 61801 (United States)

2015-06-07

We apply numerical polymer integral equation theory to study the entropic depletion problem for hard spheres dissolved in flexible chain polymer melts and concentrated solutions over an exceptionally wide range of polymer radius of gyration to particle diameter ratios (R{sub g}/D), particle-monomer diameter ratios (D/d), and chain lengths (N) including the monomer and oligomer regimes. Calculations are performed based on a calibration of the effective melt packing fraction that reproduces the isobaric dimensionless isothermal compressibility of real polymer liquids. Three regimes of the polymer-mediated interparticle potential of mean force (PMF) are identified and analyzed in depth. (i) The magnitude of the contact attraction that dominates thermodynamic stability scales linearly with D/d and exhibits a monotonic and nonperturbative logarithmic increase with N ultimately saturating in the long chain limit. (ii) A close to contact repulsive barrier emerges that grows linearly with D/d and can attain values far in excess of thermal energy for experimentally relevant particle sizes and chain lengths. This raises the possibility of kinetic stabilization of particles in nanocomposites. The barrier grows initially logarithmically with N, attains a maximum when 2R{sub g} ∼ D/2, and then decreases towards its asymptotic long chain limit as 2R{sub g} ≫ D. (iii) A long range (of order R{sub g}) repulsive, exponentially decaying component of the depletion potential emerges when polymer coils are smaller than, or of order, the nanoparticle diameter. Its amplitude is effectively constant for 2R{sub g} ≤ D. As the polymer becomes larger than the particle, the amplitude of this feature decreases extremely rapidly and becomes negligible. A weak long range and N-dependent component of the monomer-particle pair correlation function is found which is suggested to be the origin of the long range repulsive PMF. Implications of our results for thermodynamics and miscibility are

The influence of polymer topology on pharmacokinetics: differences between cyclic and linear PEGylated poly(acrylic acid) comb polymers.

Science.gov (United States)

Chen, Bo; Jerger, Katherine; Fréchet, Jean M J; Szoka, Francis C

2009-12-16

Water-soluble polymers for the delivery of chemotherapeutic drugs passively target solid tumors as a consequence of reduced renal clearance and the enhanced permeation and retention (EPR) effect. Elimination of the polymers in the kidney occurs due to filtration through biological nanopores with a hydrodynamic diameter comparable to the polymer. Therefore we have investigated chemical features that may broadly be grouped as "molecular architecture" such as: molecular weight, chain flexibility, number of chain ends and branching, to learn how they impact polymer elimination. In this report we describe the synthesis of four pairs of similar molecular weight cyclic and linear polyacrylic acid polymers grafted with polyethylene glycol (23, 32, 65, 114 kDa) with low polydispersities using ATRP and "click" chemistry. The polymers were radiolabeled with (125)I and their pharmacokinetics and tissue distribution after intravenous injection were determined in normal and C26 adenocarcinoma tumored BALB/c mice. Cyclic polymers above the renal threshold of 30 kDa had a significantly longer elimination time (between 10 and 33% longer) than did the comparable linear polymer (for the 66 kDa cyclic polymer, t(1/2,beta)=35+/-2 h) and a greater area under the serum concentration versus time curve. This resulted in a greater tumor accumulation of the cyclic polymer than the linear polymer counterpart. Thus water-soluble cyclic comb polymers join a growing list of polymer topologies that show greatly extended circulation times compared to their linear counterparts and provide alternative polymer architecture for use as drug carriers.

Application of support vector regression for optimization of vibration flow field of high-density polyethylene melts characterized by small angle light scattering

Science.gov (United States)

Xian, Guangming

2018-03-01

In this paper, the vibration flow field parameters of polymer melts in a visual slit die are optimized by using intelligent algorithm. Experimental small angle light scattering (SALS) patterns are shown to characterize the processing process. In order to capture the scattered light, a polarizer and an analyzer are placed before and after the polymer melts. The results reported in this study are obtained using high-density polyethylene (HDPE) with rotation speed at 28 rpm. In addition, support vector regression (SVR) analytical method is introduced for optimization the parameters of vibration flow field. This work establishes the general applicability of SVR for predicting the optimal parameters of vibration flow field.

Characterization of the melting process of PTFE using positron annihilation spectroscopy

International Nuclear Information System (INIS)

Honda, Y; Nishijima, S

2015-01-01

Poly(tetrafluoroethylene) (PTFE) is a semi-crystalline polymer and the lifetime of ortho-positronium(o-Ps) is known to be able to be separated into two components due to annihilation in the crystal region and in the amorphous region. The melting process of PTFE was investigated using positron annihilation spectroscopy and X-ray diffraction. The results indicated that volume expansion with an increase of temperature is dominantly due to the expansion of the amorphous region and a Ps bubble is formed at melting in both regions. The o-Ps relating to the crystal region definitely remains on the surface of crystal at the time of annihilation. The production of lower energy electrons at melting was deduced by the analysis of the Doppler broadened annihilation photopeak, and the increase in the number of such electrons was found to have great influence on the formation of the o-Ps and annihilation processes of positron and o-Ps. (paper)

Nanocomposites Based on Biodegradable Polymers

Directory of Open Access Journals (Sweden)

Ilaria Armentano

2018-05-01

Full Text Available In the present review paper, our main results on nanocomposites based on biodegradable polymers (on a time scale from 2010 to 2018 are reported. We mainly focused our attention on commercial biodegradable polymers, which we mixed with different nanofillers and/or additives with the final aim of developing new materials with tunable specific properties. A wide list of nanofillers have been considered according to their shape, properties, and functionalization routes, and the results have been discussed looking at their roles on the basis of different adopted processing routes (solvent-based or melt-mixing processes. Two main application fields of nanocomposite based on biodegradable polymers have been considered: the specific interaction with stem cells in the regenerative medicine applications or as antimicrobial materials and the active role of selected nanofillers in food packaging applications have been critically revised, with the main aim of providing an overview of the authors’ contribution to the state of the art in the field of biodegradable polymeric nanocomposites.

Mechanical response of melt-spun amorphous filaments

International Nuclear Information System (INIS)

Leal, A A; Reifler, F A; Hufenus, R; Mohanty, G; Michler, J

2014-01-01

High-speed melt spinning of a cyclo-olefin polymer (COP) and a copolyamide (CoPA) have been performed. Differential scanning calorimetry curves of the resulting monofilaments show that they remain in an amorphous state even after hot drawing. Wide angle x-ray diffraction patterns of undrawn and drawn COP filaments show that although the material remains in an amorphous state, a degree of orientation is induced in the polymer after drawing. The amorphous filaments show an enhanced bending recovery with respect to different semi-crystalline monofilaments commercially available. However, single fiber axial compressive testing indicates that the amorphous filaments exhibit a compressive modulus value which is 50% lower than what is observed for a reference semi-crystalline PET filament. Analysis of the compressive strains applied by the bending recovery test indicates that while the maximum applied strains remain well within the region of elastic deformation of the amorphous materials, the threshold between elastic and plastic deformation is reached for the semi-crystalline materials. (paper)

Abnormal viscoelastic behavior of side-chain liquid-crystal polymers

Science.gov (United States)

Gallani, J. L.; Hilliou, L.; Martinoty, P.; Keller, P.

1994-03-01

We show that, contrary to what is commonly believed, the isotropic phase of side-chain liquid-crystal polymers has viscoelastic properties which are totally different from those of ordinary flexible melt polymers. The results can be explained by the existence of a transient network created by the dynamic association of mesogenic groups belonging to different chains. The extremely high sensitivity of the compound to the state of the surfaces with which it is in contact offers us an unexpected method of studying surface states.

Computer simulations of polymers in a confined environment

International Nuclear Information System (INIS)

Sikorski, Andrzej; Romiszowski, Piotr

2007-01-01

A coarse-grained model of star-branched polymers confined in a slit formed by two parallel impenetrable surfaces, which were attractive for polymer segments, was developed and studied. The model chains were regular stars consisting of f = 3 branches of equal length. The flexible chains were constructed of united atoms (segments) and were restricted to vertices of a simple cubic lattice. Good solvent conditions were modelled and, thus, the macromolecules interacted only with the excluded volume. The properties of the model chains were determined by means of Monte Carlo simulations with a sampling algorithm based on the local changes of conformation of the chains. It appeared that the strongly adsorbed chains located in slits of appropriate width could swap between both confining surfaces. The influence of the chain length, width of the slit and the temperature on the frequency of such jumps was studied. The mechanism of the chain motion is also discussed

GLASS MELTING PHENOMENA, THEIR ORDERING AND MELTING SPACE UTILISATION

Directory of Open Access Journals (Sweden)

Němec L.

2013-12-01

Full Text Available Four aspects of effective glass melting have been defined – namely the fast kinetics of partial melting phenomena, a consideration of the melting phenomena ordering, high utilisation of the melting space, and effective utilisation of the supplied energy. The relations were defined for the specific melting performance and specific energy consumption of the glass melting process which involve the four mentioned aspects of the process and indicate the potentials of effective melting. The quantity “space utilisation” has been treated in more detail as an aspect not considered in practice till this time. The space utilisation was quantitatively defined and its values have been determined for the industrial melting facility by mathematical modelling. The definitions of the specific melting performance and specific energy consumption have been used for assessment of the potential impact of a controlled melt flow and high space utilisation on the melting process efficiency on the industrial scale. The results have shown that even the partial control of the melt flow, leading to the partial increase of the space utilisation, may considerably increase the melting performance, whereas a decrease of the specific energy consumption was determined to be between 10 - 15 %.

Fabrication of polymer-alloy based on polytetrafluoroethylene by radiation-crosslinking

International Nuclear Information System (INIS)

Oshima, A.; Asano, S.; Hyunga, T.; Ichizuri, S.; Washio, M.

2003-01-01

Perfluoropolymer such as polytetrafluoroethylene (PTFE), tetrafluoroethylene co-perfluoroalkylvinylether (PFA) and tetrafluoroethylene-co-hexafluoropropylene (FFP) have been classified to be a typical polymer of radiation-induced degradation. However, we confirmed that the crosslinking of PTFE, PFA and FEP proceed by irradiation under selective condition where oxygen-free and high temperature above the melting temperature of them. In this study, fabrication of polymer-alloy based on PTFE has been demonstrated by radiation-crosslinking techniques. The polymer alloy, which was PTFE fine powder contained with other polymeric materials, was obtained by electron beams irradiation under oxygen-free atmosphere. Characterization of polymer-alloy based on PTFE has been studied by various measurements such as solid state 19F- and 13C-NMR spectroscopy, thermal analysis (DSC, TGA)

Infrared thermography of welding zones produced by polymer extrusion additive manufacturing✩

OpenAIRE

Seppala, Jonathan E.; Migler, Kalman D.

2016-01-01

In common thermoplastic additive manufacturing (AM) processes, a solid polymer filament is melted, extruded though a rastering nozzle, welded onto neighboring layers and solidified. The temperature of the polymer at each of these stages is the key parameter governing these non-equilibrium processes, but due to its strong spatial and temporal variations, it is difficult to measure accurately. Here we utilize infrared (IR) imaging - in conjunction with necessary reflection corrections and calib...

Synthesis and phase behavior of end-functionalized associating polymers

Science.gov (United States)

Wrue, Michelle H.

We have explored polymer blend phase behavior in the presence of multiple hydrogen bonding end-groups. This work details the synthesis of functionalized polymers and their subsequent use in miscibility studies. The synthesis of end-functionalized hydrogen bonding polymers and the investigation of their physical properties and miscibility is presented. Mono-functional and telechelic ureidopyrimidinone (UPy) functionalized polymers were prepared by two main routes: post-polymerization functionalization (of commercially available or synthesized polymers); and polymerization of monomers using a functionalized initiator. UPy-functionalized polymers were prepared with a variety of polymer backbones including poly(ethylene oxide)s; poly(butadiene)s, poly(dimethyl siloxanxe)s; poly(styrene)s and poly(methyl methacrylate)s. The most successful route to polymers with UPy end-groups was atom transfer radical polymerization (ATRP) using a UPy-functionalized initiator, followed by atom transfer radical coupling (ATRC). The incorporation of ureidopyrimidinone end-groups was shown to affect the physical properties of the polymer backbone. Parent polymers that were liquids became viscous liquids or waxy solids upon UPy-functionalization of chain end. UPy-functionalization of a hydroxyl-terminated polybutadiene (HO-PB-OH) resulted in a waxy solid while the HO-PB-OH precursor was a viscous liquid. The thermal properties of functionalized polymers also differed from those of the unfunctionalized parent polymers. Hot-stage optical microscopy revealed that UPy-functionalized PEO displayed a depressed melting point relative to the analogous unfunctionalized precursor. Differential scanning calorimetry was also used to investigate the synthesized UPy-polymers. UPy-functionalized polystyrenes and poly(methyl methacrylate)s showed an increased T g compared to the equivalent homopolymer standards. This increased Tg was determined to be dependent upon the fraction of UPy groups present and

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.

Morphological Development of Melt Crystallized Poly(propylene oxide) by In Situ AFM: Formation of Banded Spherulites

NARCIS (Netherlands)

Beekmans, L.G.M.; Hempenius, Mark A.; Vancso, Gyula J.

2004-01-01

The morphology of poly(propylene oxide) (PPO) crystals grown from the melt was investigated. The spherulites of the optically pure S polymers displayed a regular pattern of concentric rings as observed by polarizing optical microscopy, while the stereocopolymer developed irregularly banded, or

Antimicrobial polymer films for food packaging

Science.gov (United States)

Concilio, S.; Piotto, S.; Sessa, L.; Iannelli, P.; Porta, A.; Calabrese, E. C.; Galdi, M. R.; Incarnato, L.

2012-07-01

New antimicrobial polymeric systems were realized introducing new antimicrobial azo compounds in PP and LDPE matrices. The polymeric materials containing different percentage of azo compounds were mold-casted and the obtained film were tested in vitro against Gram+ and Gram- bacteria and fungi. These results hold promise for the fabrication of bacteria-resistant polymer films by means of simple melt processing with antimicrobial azo-dyes.

ASSOCIATION OF BRANCHED POLYETHYLENE IMINE WITH SURFACTANTS IN AQUEOUS SOLUTION

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Ismael C. Bellettini

2015-07-01

Full Text Available Three polymer-surfactant systems comprised of branched polyethylene imine (PEI with an anionic surfactant (sodium dodecylsulfate; SDS, a cationic surfactant (tetradecyltrimethylammonium bromide; TTAB, and a zwitterionic surfactant (N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate; SB3-14 were studied based on the properties of surface tension, pyrene fluorescence emission, dynamic light scattering, pH, and zeta potential measurements. The critical aggregation concentration (cac and polymer saturation point (psp were determined for all three systems. The effect of these surfactants on the physico-chemical characteristics (diameter and surface charge of the complexes formed was determined. Polymer-surfactant interactions occurred in all of the systems studied, with the strongest interactions, electrostatic in nature, occurring in the SDS-PEI system. After the neutralization of the polymer charges with the addition of the surfactant, the hydrophobic effect started to control the interlacing of the polymer chains. For the PEI-TTAB system, a very dense film was formed at surfactant concentrations above 2.0 mmol L-1. In this case, the bromide counter-ion interacted with both the positively-charged PEI and the head of the surfactant, which is responsible for the formation of double layer coordination complexes. For the system composed of PEI and the zwitterionic surfactant, less cooperative associations occurred in comparison with the other systems.

CO partial pressure dependence of the kinetics of melting of HbS aggregates studied in high concentration phosphate buffer

Science.gov (United States)

Aroutiounian, Svetlana

2002-10-01

Deoxygenated sickle cell hemoglobin (HbS) monomers enter the polymer phase either by incorporation into a critical nucleus, through heterogeneous nucleation and or through linear growth of the polymers when the concentration of monomers exceeds the solubility. CO-bound, R-state HbS monomers do not polymerize. Thus, polymer melting is enhanced by binding of carbon monoxide (CO) to HbS polymerized monomers. In our study, the melting of HbS aggregates mediated by dilution and CO binding to polymerized monomers is observed with time-resolved extinction spectroscopy. The CO partial pressure (pCO) dependence of the kinetics of melting is studied for pCO = 0, 0.25, 0.5, 0.75, 1 atm with difference progress curves. A phenomenological description with slow and fast relaxation modes reveals a variable relaxation time near the pCO=0.5 due to competition of kinetic mechanisms. The slow component increases with increasing pCO. It has a positive intercept due to the combined action of dilution of the sample and CO-ligation. The pCO dependence is near linear due to non-cooperative CO binding. Significant slowing down of aged samples, most likely due to gelation, is observed. As possible mechanism for variable relaxation time near pCO=0.5atm the fractional percolation threshold is discussed. This work was supported by NIH grant HL58091 (awarded to Daniel. B. Kim-Shapiro).

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.

Petrological Geodynamics of Mantle Melting I. AlphaMELTS + Multiphase Flow: Dynamic Equilibrium Melting, Method and Results

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Massimiliano Tirone

2017-10-01

Full Text Available The complex process of melting in the Earth's interior is studied by combining a multiphase numerical flow model with the program AlphaMELTS which provides a petrological description based on thermodynamic principles. The objective is to address the fundamental question of the effect of the mantle and melt dynamics on the composition and abundance of the melt and the residual solid. The conceptual idea is based on a 1-D description of the melting process that develops along an ideal vertical column where local chemical equilibrium is assumed to apply at some level in space and time. By coupling together the transport model and the chemical thermodynamic model, the evolution of the melting process can be described in terms of melt distribution, temperature, pressure and solid and melt velocities but also variation of melt and residual solid composition and mineralogical abundance at any depth over time. In this first installment of a series of three contributions, a two-phase flow model (melt and solid assemblage is developed under the assumption of complete local equilibrium between melt and a peridotitic mantle (dynamic equilibrium melting, DEM. The solid mantle is also assumed to be completely dry. The present study addresses some but not all the potential factors affecting the melting process. The influence of permeability and viscosity of the solid matrix are considered in some detail. The essential features of the dynamic model and how it is interfaced with AlphaMELTS are clearly outlined. A detailed and explicit description of the numerical procedure should make this type of numerical models less obscure. The general observation that can be made from the outcome of several simulations carried out for this work is that the melt composition varies with depth, however the melt abundance not necessarily always increases moving upwards. When a quasi-steady state condition is achieved, that is when melt abundance does not varies significantly

Chip bonding of low-melting eutectic alloys by transmitted laser radiation

Science.gov (United States)

Hoff, Christian; Venkatesh, Arjun; Schneider, Friedrich; Hermsdorf, Jörg; Bengsch, Sebastian; Wurz, Marc C.; Kaierle, Stefan; Overmeyer, Ludger

2017-06-01

Present-day thermode bond systems for the assembly of radio-frequency identification (RFID) chips are mechanically inflexible, difficult to control, and will not meet future manufacturing challenges sufficiently. Chip bonding, one of the key processes in the production of integrated circuits (ICs), has a high potential for optimization with respect to process duration and process flexibility. For this purpose, the technologies used, so far, are supposed to be replaced by a transmission laser-bonding process using low-melting eutectic alloys. In this study, successful bonding investigations of mock silicon chips and of RFID chips on flexible polymer substrates are presented using the low-melting eutectic alloy, 52In48Sn, and a laser with a wavelength of 2 μm.

Tethered Nanoparticle–Polymer Composites: Phase Stability and Curvature

KAUST Repository

Srivastava, Samanvaya

2012-04-17

Phase behavior of poly(ethylene glycol) (PEG) tethered silica nanoparticles dispersed in PEG hosts is investigated using small-angle X-ray scattering. Phase separation in dispersions of densely grafted nanoparticles is found to display strikingly different small-angle X-ray scattering signatures in comparison to phase-separated composites comprised of bare or sparsely grafted nanoparticles. A general diagram for the dispersion state and phase stability of polymer tethered nanoparticle-polymer composites incorporating results from this as well as various other contemporary studies is presented. We show that in the range of moderate to high grafting densities the dispersion state of nanoparticles in composites is largely insensitive to the grafting density of the tethered chains and chemistry of the polymer host. Instead, the ratio of the particle diameter to the size of the tethered chain and the ratio of the molecular weights of the host and tethered polymer chains (P/N) are shown to play a dominant role. Additionally, we find that well-functionalized nanoparticles form stable dispersions in their polymer host beyond the P/N limit that demarcates the wetting/dewetting transition in polymer brushes on flat substrates interacting with polymer melts. A general strategy for achieving uniform nanoparticle dispersion in polymers is proposed. © 2012 American Chemical Society.

Polyhydroxyester films obtained by non-catalyzed melt-polycondensation of natural occurring fatty polyhydroxyacids.

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Jose Jesus Benitez

2015-08-01

Full Text Available Free-standing polyesters films from mono and polyhydroxylated fatty acids (C16 and C18 have been obtained by non-catalyzed melt-condensation polymerization in air at 150°C. Chemical characterization by Fourier Transform Infrared Spectroscopy (FTIR and 13C Magic Angle Spinning Nuclear Magnetic Resonance (13C MAS-NMR has confirmed the formation of the corresponding esters and the occurrence of hydroxyl partial oxidation which extent depends on the type of hydroxylation of the monomer (primary or secondary. Generally, polyester films obtained are hydrophobic, insoluble in common solvents, amorphous and infusible as revealed by X-ray Diffraction (XRD and Differential Scanning Calorimetry (DSC. In -polyhydroxy acids, esterification reaction with primary hydroxyls is preferential and, therefore, the structure can be defined as linear with variable branching depending on the amount of esterified secondary hydroxyls. The occurrence side oxidative reactions like the diol cleavage are responsible for chain cross-linking. Films are thermally stable up to 200-250°C though this limit can be extended up to 300°C in the absence of ester bonds involving secondary hydroxyls. By analogy with natural occurring fatty polyesters (i.e. cutin in higher plants these polymers are proposed as biodegradable and non-toxic barrier films or coatings to be used, for instance, in food packing

Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

OpenAIRE

Shahabuddin, Syed; Hamime Ismail, Fatem; Mohamad, Sharifah; Muhamad Sarih, Norazilawati

2015-01-01

Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydro...

Multiscale simulations of PS-SiO2 nanocomposites: from melt to glassy state.

Science.gov (United States)

Mathioudakis, I G; Vogiatzis, G G; Tzoumanekas, C; Theodorou, D N

2016-09-28

The interaction energetics, molecular packing, entanglement network properties, segmental dynamics, and elastic constants of atactic polystyrene-amorphous silica nanocomposites in the molten and the glassy state are studied via molecular simulations using two interconnected levels of representation: (a) a coarse-grained one, wherein each polystyrene repeat unit is mapped onto a single "superatom" and the silica nanoparticle is viewed as a solid sphere. Equilibration at all length scales at this level is achieved via connectivity-altering Monte Carlo simulations. (b) A united-atom (UA) level, wherein the polymer chains are represented in terms of a united-atom forcefield and the silica nanoparticle is represented in terms of a simplified, fully atomistic model. Initial configurations for UA molecular dynamics (MD) simulations are obtained by reverse mapping well-equilibrated coarse-grained configurations. By analysing microcanonical UA MD trajectories, the polymer density profile is studied and the polymer is found to exhibit layering in the vicinity of the nanoparticle surface. An estimate of the enthalpy of mixing between polymer and nanoparticles, derived from the UA simulations, compares favourably against available experimental values. The dynamical behaviour of polystyrene (in neat and filled melt systems) is characterized in terms of bond orientation and dihedral angle time autocorrelation functions. At low concentration in the molten polymer matrix, silica nanoparticles are found to cause a slight deceleration of the segmental dynamics close to their surface compared to the bulk polymer. Well-equilibrated coarse-grained long-chain configurations are reduced to entanglement networks via topological analysis with the CReTA algorithm, yielding a slightly lower density of entanglements in the filled than in the neat systems. UA melt configurations are glassified by MD cooling. The elastic moduli of the resulting glassy nanocomposites are computed through an

Statistical properties of multi-theta polymer chains

Science.gov (United States)

Uehara, Erica; Deguchi, Tetsuo

2018-04-01

We study statistical properties of polymer chains with complex structures whose chemical connectivities are expressed by graphs. The multi-theta curve of m subchains with two branch points connected by them is one of the simplest graphs among those graphs having closed paths, i.e. loops. We denoted it by θm , and for m  =  2 it is given by a ring. We derive analytically the pair distribution function and the scattering function for the θm -shaped polymer chains consisting of m Gaussian random walks of n steps. Surprisingly, it is shown rigorously that the mean-square radius of gyration for the Gaussian θm -shaped polymer chain does not depend on the number m of subchains if each subchain has the same fixed number of steps. For m  =  3 we show the Kratky plot for the theta-shaped polymer chain consisting of hard cylindrical segments by the Monte-Carlo method including reflection at trivalent vertices.

Radiation processing of polymers and semiconductors at the Institute of Nuclear Chemistry and Technology

International Nuclear Information System (INIS)

Zimek, Z.; Przybytniak, G.; Kaluska, I.

2006-01-01

R(and)D studies in the field of radiation technology in Poland are mostly concentrated at the Institute of Nuclear Chemistry and Technology (INCT). The results of the INCT works on polymer and semiconductor modification have been implemented in various branches of national economy, particularly in industry and medicine. Radiation technology for polymer modification was implemented in the middle of the 1970-ties. Among others, the processes of irradiation and heat shrinkable products expansion have been developed. The transfer of this technology to Polish industry was performed in the middle of the 1980-ties. The present study aims at the formulation of new PE composites better suited to new generation of heat shrinkable products, for example, a new generation of hot-melt adhesives has been developed to meet specific requirements of customers. Modified polypropylene was used for the production of medical devices sterilized by radiation, especially disposable syringes, to overcome the low radiation resistance of the basic material. Modified polypropylene (PP-M) has been formulated at the INCT to provide material suitable for medical application and radiation sterilization process. Modification of semiconductor devices by EB was applied on an industrial scale since 1978 when the INCT and the LAMINA semiconductor factory successfully adopted that technology to improve specific semiconductor devices. This activity is continued on commercial basis where the INCT facilities served to contract irradiation of certain semiconductor devices according to the manufacturing program of the Polish factory and customers from abroad. (author)

Melt flow and mechanical properties of silica/perfluoropolymer nanocomposites Fabricated by direct melt-compounding without surface modification on nano-silica.

Science.gov (United States)

Tanahashi, Mitsuru; Watanabe, Yusuke; Lee, Jeong-Chang; Takeda, Kunihiko; Fujisawa, Toshiharu

2009-01-01

The authors have previously developed a novel method for the fabrication of silica/perfluoropolymer nanocomposites, wherein nano-sized silica particles without surface modification were dispersed uniformly through breakdown of loosely packed agglomerates of silica nanoparticles with low fracture strength in a polymer melt during direct melt-compounding. The method consists of two stages; the first stage involves preparation of the loose silica agglomerate, and the second stage involves melt-compounding of a completely hydrophobic perfluoropolymer, PFA (poly(tetrafluoroethylene-co-perfluoropropylvinylether)), with the loose silica agglomerates. By using this simple method without any lipophilic treatment of the silica surfaces, silica nanoparticles with a primary diameter of 190 nm could be dispersed uniformly into the PFA matrix. The main purpose of the present study is to evaluate the melt flow and tensile properties of silica/PFA nanocomposites fabricated by the above method. In order to elucidate the effects of the size of the dispersed silica in the PFA matrix on the properties of the composites, silica/PFA composite samples exhibiting the dispersion of larger-sized silica particle-clusters were fabricated as negative controls of the silica dispersion state. The results obtained under the present experimental conditions showed that the size of the dispersed silica in the PFA matrix exerts a strong influence on the ultimate tensile properties, such as tensile strength and elongation at break, and the melt flow rate (MFR) of the composite materials. The MFR of the silica/PFA nanocomposite became higher than that of the pure PFA without silica addition, although the MFR of the PFA composites containing larger silica particle-clusters became much lower than that of the pure PFA. Furthermore, uniform dispersion of isolated silica nanoparticles was found to improve not only the Young's modulus but also the ultimate tensile properties of the composite.

Structure and dynamics of amorphous polymers: computer simulations compared to experiment and theory

International Nuclear Information System (INIS)

Paul, Wolfgang; Smith, Grant D

2004-01-01

This contribution considers recent developments in the computer modelling of amorphous polymeric materials. Progress in our capabilities to build models for the computer simulation of polymers from the detailed atomistic scale up to coarse-grained mesoscopic models, together with the ever-improving performance of computers, have led to important insights from computer simulations into the structural and dynamic properties of amorphous polymers. Structurally, chain connectivity introduces a range of length scales from that of the chemical bond to the radius of gyration of the polymer chain covering 2-4 orders of magnitude. Dynamically, this range of length scales translates into an even larger range of time scales observable in relaxation processes in amorphous polymers ranging from about 10 -13 to 10 -3 s or even to 10 3 s when glass dynamics is concerned. There is currently no single simulation technique that is able to describe all these length and time scales efficiently. On large length and time scales basic topology and entropy become the governing properties and this fact can be exploited using computer simulations of coarse-grained polymer models to study universal aspects of the structure and dynamics of amorphous polymers. On the largest length and time scales chain connectivity is the dominating factor leading to the strong increase in longest relaxation times described within the reptation theory of polymer melt dynamics. Recently, many of the universal aspects of this behaviour have been further elucidated by computer simulations of coarse-grained polymer models. On short length scales the detailed chemistry and energetics of the polymer are important, and one has to be able to capture them correctly using chemically realistic modelling of specific polymers, even when the aim is to extract generic physical behaviour exhibited by the specific chemistry. Detailed studies of chemically realistic models highlight the central importance of torsional dynamics

Melting and thermal history of poly(hydroxybutyrate-co-hydroxyvalerate) using step-scan DSC

International Nuclear Information System (INIS)

Gunaratne, L.M.W.K.; Shanks, R.A.

2005-01-01

Melting behaviour and crystal morphology of poly(3-hydroxybutyrate) (PHB) and its copolymer of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with various hydroxyvalerate (HV) contents [5 wt.% (PHB5HV), 8 wt.% (PHB8HV) and 12 wt.% (PHB12HV)] have been investigated by conventional DSC, step-scan differential scanning calorimetry (SDSC) and hot-stage polarised optical microscopy (HSPOM). Crystallisation behaviour of PHB and its copolymers were investigated by SDSC. Thermal properties were investigated after different crystallisation treatments, fast, medium and slow cooling. Multiple melting peak behaviour was observed for all polymers. SDSC data revealed that PHB and its copolymers undergo melting-recrystallisation-remelting during heating, as evidenced by exothermic peaks in the IsoK baseline (non-reversing signal). An increase in degree of crystallinity due to significant melt-recrystallisation was observed for slow-cooled copolymers. PHB5HV showed different crystal morphologies for various crystallisation conditions. SDSC proved a convenient and precise method for measurement of the apparent thermodynamic specific heat (reversing signal) HSPOM results showed that the crystallisation rates and sizes of spherulites were significantly reduced as crystallisation rate increased

Melt Electrospinning Writing of Three-dimensional Poly(ε-caprolactone) Scaffolds with Controllable Morphologies for Tissue Engineering Applications.

Science.gov (United States)

Wunner, Felix M; Bas, Onur; Saidy, Navid T; Dalton, Paul D; Pardo, Elena M De-Juan; Hutmacher, Dietmar W

2017-12-23

This tutorial reflects on the fundamental principles and guidelines for electrospinning writing with polymer melts, an additive manufacturing technology with great potential for biomedical applications. The technique facilitates the direct deposition of biocompatible polymer fibers to fabricate well-ordered scaffolds in the sub-micron to micro scale range. The establishment of a stable, viscoelastic, polymer jet between a spinneret and a collector is achieved using an applied voltage and can be direct-written. A significant benefit of a typical porous scaffold is a high surface-to-volume ratio which provides increased effective adhesion sites for cell attachment and growth. Controlling the printing process by fine-tuning the system parameters enables high reproducibility in the quality of the printed scaffolds. It also provides a flexible manufacturing platform for users to tailor the morphological structures of the scaffolds to their specific requirements. For this purpose, we present a protocol to obtain different fiber diameters using melt electrospinning writing (MEW) with a guided amendment of the parameters, including flow rate, voltage and collection speed. Furthermore, we demonstrate how to optimize the jet, discuss often experienced technical challenges, explain troubleshooting techniques and showcase a wide range of printable scaffold architectures.

Quantification of interaction and topological parameters of polyisoprene star polymers under good solvent conditions

KAUST Repository

Rai, Durgesh K.

2016-05-05

Mass fractal scaling, reflected in the mass fractal dimension df, is independently impacted by topology, reflected in the connectivity dimension c, and by tortuosity, reflected in the minimum dimension dmin. The mass fractal dimension is related to these other dimensions by df=cdmin. Branched fractal structures have a higher mass fractal dimension compared to linear structures due to a higher c, and extended structures have a lower dimension compared to convoluted self-avoiding and Gaussian walks due to a lower dmin. It is found, in this work, that macromolecules in thermodynamic equilibrium display a fixed mass fractal dimension df under good solvent conditions, regardless of chain topology. These equilibrium structures accommodate changes in chain topology such as branching c by a decrease in chain tortuosity dmin. Symmetric star polymers are used to understand the structure of complex macromolecular topologies. A recently published hybrid Unified scattering function accounts for interarm correlations in symmetric star polymers along with polymer-solvent interaction for chains of arbitrary scaling dimension. Dilute solutions of linear, three-arm and six-arm polyisoprene stars are studied under good solvent conditions in deuterated p-xylene. Reduced chain tortuosity can be viewed as steric straightening of the arms. Steric effects for star topologies are quantified, and it is found that steric straightening of arms is more significant for lower-molecular-weight arms. The observation of constant df is explained through a modification of Flory-Krigbaum theory for branched polymers.

PEG encapsulated by porous triamide-linked polymers as support for solid-liquid phase change materials for energy storage

Science.gov (United States)

Andriamitantsoa, Radoelizo S.; Dong, Wenjun; Gao, Hongyi; Wang, Ge

2017-03-01

A series of porous triamide-linked polymers labeled as PTP were prepared by condensation of 1,3,5-benzenetricarbonyl trichloride with benzene-1,4-diamine (A), 4,4‧-methylenediamine (B) and 1,3,5-triazine-2,4,6-triamine (C) respectively. The as-synthesized polymers exhibit permanent porosity and high surface areas which guarantee to hold polyethylene glycol (PEG) molecules in their network for shape-stabilized phase change materials. They possess different effects on the phase change properties of the composite due to their different porosities. PTP-A have intrinsic well-ordered morphology, microstructure and good enough pores to keep the PCMs compared to PTP-B and PTP-C. PEG 2000 used as PCMs could be retained up to 85 wt% in PTP-A polymer materials and these composites were defined as form-stable composite PCMs without the leakage of melted PCM. The thermal study revealed a good storage effect of encapsulated polymer and the enthalpy of melting increases in the order PTP-C PCMs.

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.

Performance Modification of Asphalt Binders using Thermoplastic Polymers

Directory of Open Access Journals (Sweden)

H. I. Al-Abdul Wahhab

2004-12-01

Full Text Available There is a need to improve the performance of asphalt binders to minimize stress cracking that occurs at low temperatures and plastic deformation at high temperatures. Importation of used asphalt-polymers from abroad, leads to an increase in the total construction cost as compared to the cost if the used polymers were of local origin. The main objective of this research was to modify locally produced asphalt. Ten polymers were identified as potential asphalt modifiers based on their physical properties and chemical composition. After preliminary laboratory evaluation for the melting point of these polymers, five polymers were selected for local asphalt modification. In the initial stage, required mixing time was decided based on the relation between shear loss modulus and mixing time .The optimum polymer content was selected based on Superpave binder performance grade specifications.The suitability of improvement was verified through the evaluation of permanent deformation and fatigue behavior of laboratory prepared asphalt concrete mixes. The results indicated that the rheological properties of the modified binders improved significantly with sufficient polymer content (3%. The aging properties of the modified binders were found to be dependent on the type of polymer.The fatigue life and resistance to permanent deformation were significantly improved due to enhanced binder rheological properties.  Thus, local asphalts can be modified using thermoplastic polymers.

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

Compositions of volatile organic compounds emitted from melted virgin and waste plastic pellets.

Science.gov (United States)

Yamashita, Kyoko; Yamamoto, Naomichi; Mizukoshi, Atsushi; Noguchi, Miyuki; Ni, Yueyong; Yanagisawa, Yukio

2009-03-01

To characterize potential air pollution issues related to recycling facilities of waste plastics, volatile organic compounds (VOCs) emitted from melted virgin and waste plastics pellets were analyzed. In this study, laboratory experiments were performed to melt virgin and waste plastic pellets under various temperatures (150, 200, and 250 degrees C) and atmospheres (air and nitrogen [N2]). In the study presented here, low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS) and the recycled waste plastic pellets were used. The VOCs generated from each plastic pellets were collected by Tenax/Carboxen adsorbent tubes and analyzed by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). The result showed the higher temperatures generated larger amounts of total VOCs (TVOCs). The VOCs emitted from the virgin plastic pellets likely originated from polymer degradation. Smaller TVOC emissions were observed in N2 atmosphere than in air atmosphere. In particular, larger amounts of the oxygenated compounds, which are generally hazardous and malodorous, were detected in air than in N2. In addition to the compounds originating from polymer degradation, the compounds originating from the plastic additives were also detected from LDPE and PS. Furthermore, various species of VOCs likely originating from contaminant inseparate polyvinyl chloride (PVC), food residues, cleaning agents, degreasers, and so on were detected from the waste plastic. Thus, melting waste plastics, as is conducted in recycling facilities, might generate larger amounts of potentially toxic compounds than producing virgin plastics.

Nonequilibrium thermodynamics of dilute polymer solutions in flow.

Science.gov (United States)

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

2014-11-07

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

Compatibilizing Bulk Polymer Blends by Using Organoclays

Science.gov (United States)

Si, Mayu; Gersappe, Dilip; Zhang, Wenhua; Ade, Harald; Rafailovich, Miriam; Sokolov, Jonathan; Rudomen, Gregory; Schwartz, Bradley; Fisher, Robert

2004-03-01

We investigated the compatiblizing performance of organoclays on melt mixed binary and tertiary polymer blends, such as, PS/PMMA, PC/SAN, PS/PMMA/PVC and PS/PMMA/PE. These polymer blends were characterized by TEM, STXM, DSC and DMA. TEM and STXM photographs show that the addition of organoclays into polymer blends drastically reduces the average domain size of the component phases. And the organoclay goes to the interfacial region between the different polymers and effectively slows down the domain size increasing during high temperature annealing. DMA and DSC results show the effect of organoclays on the mechanical properties and glass transitions temperature, which indicates the compatibilization on the molecular level. The generalized compatibilization induced by the nanoscale fillers for blends can be explained in terms of mean field models where the reduction of interfacial tension induced by in-situ grafting is counterbalanced by the increased bending energy due to the rigidity of the filler. This in turn can be shown to be a function of the degree of exfoliation, aspect ratio, and polymer filler interactions. Supported by NSF funded MRSEC at Stony Brook

Emerging melt quality control solution technologies for aluminium melt

Directory of Open Access Journals (Sweden)

Arturo Pascual, Jr

2009-11-01

Full Text Available The newly developed “MTS 1500” Melt Treatment System is performing the specifi cally required melt treatment operations like degassing, cleaning, modification and/or grain refinement by an automated process in one step and at the same location. This linked process is saving time, energy and metal losses allowing - by automated dosage of the melt treatment agents - the production of a consistent melt quality batch after batch. By linking the MTS Metal Treatment System with sensors operating on-line in the melt, i.e., with a hydrogen sensor “Alspek H”, a fully automated control of parts of the process chain like degassing is possible. This technology does guarantee a pre-specifi ed and documented melt quality in each melt treatment batch. Furthermore, to ensure that castings are consistent and predictable there is a growing realization that critical parameters such as metal cleanliness must be measured prior to casting. There exists accepted methods for measuring the cleanliness of an aluminum melt but these can be both slow and costly. A simple, rapid and meaningful method of measuring and bench marking the cleanliness of an aluminum melt has been developed to offer the foundry a practical method of measuring melt cleanliness. This paper shows the structure and performance of the integrated MTS melt treatment process and documents achieved melt quality standards after degassing, cleaning, modifi cation and grain refi nement operations under real foundry conditions. It also provides an insight on a melt cleanliness measuring device “Alspek MQ” to provide foundry men better tools in meeting the increasing quality and tighter specifi cation demand from the industry.

Computing the non-Markovian coarse-grained interactions derived from the Mori-Zwanzig formalism in molecular systems: Application to polymer melts

Science.gov (United States)

Li, Zhen; Lee, Hee Sun; Darve, Eric; Karniadakis, George Em

2017-01-01

Memory effects are often introduced during coarse-graining of a complex dynamical system. In particular, a generalized Langevin equation (GLE) for the coarse-grained (CG) system arises in the context of Mori-Zwanzig formalism. Upon a pairwise decomposition, GLE can be reformulated into its pairwise version, i.e., non-Markovian dissipative particle dynamics (DPD). GLE models the dynamics of a single coarse particle, while DPD considers the dynamics of many interacting CG particles, with both CG systems governed by non-Markovian interactions. We compare two different methods for the practical implementation of the non-Markovian interactions in GLE and DPD systems. More specifically, a direct evaluation of the non-Markovian (NM) terms is performed in LE-NM and DPD-NM models, which requires the storage of historical information that significantly increases computational complexity. Alternatively, we use a few auxiliary variables in LE-AUX and DPD-AUX models to replace the non-Markovian dynamics with a Markovian dynamics in a higher dimensional space, leading to a much reduced memory footprint and computational cost. In our numerical benchmarks, the GLE and non-Markovian DPD models are constructed from molecular dynamics (MD) simulations of star-polymer melts. Results show that a Markovian dynamics with auxiliary variables successfully generates equivalent non-Markovian dynamics consistent with the reference MD system, while maintaining a tractable computational cost. Also, transient subdiffusion of the star-polymers observed in the MD system can be reproduced by the coarse-grained models. The non-interacting particle models, LE-NM/AUX, are computationally much cheaper than the interacting particle models, DPD-NM/AUX. However, the pairwise models with momentum conservation are more appropriate for correctly reproducing the long-time hydrodynamics characterised by an algebraic decay in the velocity autocorrelation function.

Small angle neutron scattering by polymer solutions

International Nuclear Information System (INIS)

Farnoux, B.; Jannink, G.

1980-08-01

Small angle neutron scattering is an experimental technique introduced since about 10 years for the observation of the polymer conformation in all the concentration range from dilute solution to the melt. After a brief recall of the elementary relations between scattering amplitude, index of refraction and scattered intensity, two concepts related to this last quantity (the contrast and the pair correlation function) are discussed in details

Inclusion and Functionalization of Polymers with Cyclodextrins: Current Applications and Future Prospects

Directory of Open Access Journals (Sweden)

Christian Folch-Cano

2014-09-01

Full Text Available The numerous hydroxyl groups available in cyclodextrins are active sites that can form different types of linkages. They can be crosslinked with one another, or they can be derivatized to produce monomers that can form linear or branched networks. Moreover, they can form inclusion complexes with polymers and different substrates, modifying their physicochemical properties. This review shows the different applications using polymers with cyclodextrins, either by forming inclusion complexes, ternary complexes, networks, or molecularly imprinted polymers (MIPs. On one hand, the use of cyclodextrins enhances the properties of each polymer, and on the other the use of polymers decreases the amount of cyclodextrins required in different formulations. Both cyclodextrins and polymers contribute synergistically in several applications such as pharmacological, nutritional, environmental, and other industrial fields. The use of polymers based on cyclodextrins is a low cost easy to use potential tool with great future prospects.

Decoration of multi-walled carbon nanotubes by polymer wrapping and its application in MWCNT/polyethylene composites.

Science.gov (United States)

Hsiao, An-En; Tsai, Shu-Ya; Hsu, Mei-Wen; Chang, Shinn-Jen

2012-05-06

We dispersed the non-covalent functionalization of multi-walled carbon nanotubes (CNTs) with a polymer dispersant and obtained a powder of polymer-wrapped CNTs. The UV-vis absorption spectrum was used to investigate the optimal weight ratio of the CNTs and polymer dispersant. The powder of polymer-wrapped CNTs had improved the drawbacks of CNTs of being lightweight and difficult to process, and it can re-disperse in a solvent. Then, we blended the polymer-wrapped CNTs and polyethylene (PE) by melt-mixing and produced a conductive masterbatch and CNT/PE composites. The polymer-wrapped CNTs showed lower surface resistivity in composites than the raw CNTs. The scanning electron microscopy images also showed that the polymer-wrapped CNTs can disperse well in composites than the raw CNTs.

Flow of Polymer Melts in Plane- and Axi-symmetric Converging Dies

DEFF Research Database (Denmark)

Lauridsen, Carsten Linding; Kjær, Erik Michael; Haudrum, Jan

1997-01-01

The extensional flow has considerable influence on the pressure loss in converging flows, which are present in both extrusion and injection moulding. Both plane- and axi-symmetric converging flows have been studied with LDPE, HDPE and PS. The transient extensional viscosities are determined in al...... for the LDPE and the PS melts. Further more, the pressure losses are characterised with the Deborah number in which the characteristic time of the material is shear rate dependent and the characteristic rime of the now is Hencky strain rate dependent....

Single-molecule imaging reveals topological isomer-dependent diffusion by 4-armed star and dicyclic 8-shaped polymers

KAUST Repository

Habuchi, Satoshi

2015-04-21

Diffusion dynamics of topological isomers of polymer molecules was investigated at the single-molecule level in a melt state by employing the fluorophore-incorporated 4-armed star and the corresponding doubly-cyclized, 8-shaped poly(THF) chains. While the single-molecule fluorescence imaging experiment revealed that the diffusion of the 4-armed star polymer was described by a single Gaussian distribution, the diffusion of the 8-shaped polymer exhibited a double Gaussian distribution behaviour. We reasoned that the two 8-shaped polymeric isomers have distinct diffusion modes in the melt state, although ensemble-averaged experimental methods cannot detect differences in overall conformational state of the isomers. The single-molecule experiments suggested that one of the 8-shaped polymeric isomer, having the horizontally oriented form, causes an efficient threading with the linear matrix chains which leads to the slower diffusion compared with the corresponding 4-armed star polymer, while the other 8-shaped polymeric isomer, having the vertically oriented form, displayed faster diffusion by the suppression of effective threading with the linear matrix chains due to its contracted chain conformation.

Gel Formation in Polymers Undergoing Radiation-Induced Crosslinking and Scission

DEFF Research Database (Denmark)

Handlos, V. N.; Singer, Klaus Albert Julius

1976-01-01

A study was made of the solubility of irradiated polyethylene. The experimental data were treated according to the Saito-Inokuti theory for gel formation in polymers exposed to ionizing radiation. Among other things, this theory is based upon the molecular weight distribution of the unirradiated...... polymer; in the present work, the actual distributions were determined by high-temperature gel permeation chromatography and corrected for long-chain branching. Under these circumstances, good agreement between theory and experimental data was obtained, which allowed the determination of the radiation...

Binding of sodium dodecyl sulfate with linear and branched polyethyleneimines in aqueous solution at different pH values.

Science.gov (United States)

Wang, Hao; Wang, Yilin; Yan, Haike; Zhang, Jin; Thomas, Robert K

2006-02-14

Isothermal titration microcalorimetry (ITC), conductivity, and turbidity measurements have been carried out to study the interaction of sodium dodecyl sulfate (SDS) with polyethyleneimines (PEI) including linear PEI and branched PEI at different pH values of 3, 7, and 10. In all cases, the polymers show a remarkable affinity toward SDS. At pH 3, the polymer PEI is a strong polycation, and the binding is dominated by electrostatic 1:1 charge neutralization with the anionic surfactant. At pH 7, the electrostatic attraction between SDS and PEI is weak, and the hydrophobic interaction becomes stronger. At the natural pH of 10, PEI is essentially nonionic and binds SDS in the form of polymer-bound surfactant aggregates. The charge neutralization concentration (C1) of SDS for the PEI-SDS complex can be derived from the curves of variation of the enthalpy, conductivity, and turbidity with SDS concentration. There is good agreement between the results from the three methods and all show a decrease with increasing pH. The total interaction enthalpies (deltaH(total)) of PEI with SDS are obtained from the observed enthalpy curves and the difference enthalpy (deltaH*) between the total enthalpy of branched PEI with SDS, and the total enthalpy of linear PEI with SDS can be derived from the obtained deltaH(total). The difference deltaH* increases dramatically as pH increases, which indicates that the interactions are different for linear PEI and branched PEI at high pH values. A schematic map of the different states of aggregation is presented.

What is the Entanglement Length in a Polymer Melt?

International Nuclear Information System (INIS)

Grest, Gary S.; Kremer, Kurt; Putz, Mathias

1999-01-01

We present the results of molecular dynamics simulations of very long model polymer chains analyzed by various experimentally relevant techniques. The segment motion of the chains is found to be in very good agreement with the reptation model. We also calculated the plateau modulus G 0 N . The predictions of the entanglement length N e from G 0 N and from the mean square displacement of the chain segments disagree by a factor of about 2.2(2), indicating an error in the prefactor in the standard formula for G 0 N . We show that recent neutron spin echo measurements were carried out for chain lengths which are too small to allow for a correct determination of N e

Modulatory effect of polymer type and composition on drug release ...

African Journals Online (AJOL)

The purpose of this study was to investigate the effects of polymer type and composition on drug release from the matrix of diclofenac sodium sustained release tablets formulated using three different granulation methods. Ten (10) batches of diclofenac sodium tablets (F01 - F10) were prepared by melt granulation, ...

Development of Composite Made of HDPE and Fiber Reinforced Polymer Dust

International Nuclear Information System (INIS)

Muhamad Noor Izwan Ishak; Ismail Mustapha; Mohd Reusmazran Yusof; Yusof Abdullah; Nor Pai'za Mohamad Hasan; Mohamad Ridzuan Ahamad; Md Fakarudin Ab Rahman; Hafizal Yazid; Ainul Mardhiah Terry; Airwan Affandi Mahmood; Nurliyana Abdullah

2016-01-01

Full text: Composite of High Density Polyethylene and Fiber Reinforced Polymer Dust (HDPE/ FRPD) were prepared by melt mixing technique. The blend was mixed and compression molded by hydraulic press at 150 degree Celsius. Effect of blend ratio on mechanical properties of the developed composite was determined. Tensile properties of the blends found to show decreasing trend with addition of FRPD. While impact strength and hardness properties showed promising result. Reuse of ' Fiber Reinforced Polymer ' dust can be improved by the present invention. (author)

Linear side chains in benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c] pyrrole-4,6-dione polymers direct self-assembly and solar cell performance

KAUST Repository

Cabanetos, Clement

2013-03-27

While varying the size and branching of solubilizing side chains in π-conjugated polymers impacts their self-assembling properties in thin-film devices, these structural changes remain difficult to anticipate. This report emphasizes the determining role that linear side-chain substituents play in poly(benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers for bulk heterojunction (BHJ) solar cell applications. We show that replacing branched side chains by linear ones in the BDT motifs induces a critical change in polymer self-assembly and backbone orientation in thin films that correlates with a dramatic drop in solar cell efficiency. In contrast, we show that for polymers with branched alkyl-substituted BDT motifs, controlling the number of aliphatic carbons in the linear N-alkyl-substituted TPD motifs is a major contributor to improved material performance. With this approach, PBDTTPD polymers were found to reach power conversion efficiencies of 8.5% and open-circuit voltages of 0.97 V in BHJ devices with PC71BM, making PBDTTPD one of the best polymer donors for use in the high-band-gap cell of tandem solar cells. © 2013 American Chemical Society.

Coherent states field theory in supramolecular polymer physics

Science.gov (United States)

Fredrickson, Glenn H.; Delaney, Kris T.

2018-05-01

In 1970, Edwards and Freed presented an elegant representation of interacting branched polymers that resembles the coherent states (CS) formulation of second-quantized field theory. This CS polymer field theory has been largely overlooked during the intervening period in favor of more conventional "auxiliary field" (AF) interacting polymer representations that form the basis of modern self-consistent field theory (SCFT) and field-theoretic simulation approaches. Here we argue that the CS representation provides a simpler and computationally more efficient framework than the AF approach for broad classes of reversibly bonding polymers encountered in supramolecular polymer science. The CS formalism is reviewed, initially for a simple homopolymer solution, and then extended to supramolecular polymers capable of forming reversible linkages and networks. In the context of the Edwards model of a non-reacting homopolymer solution and one and two-component models of telechelic reacting polymers, we discuss the structure of CS mean-field theory, including the equivalence to SCFT, and show how weak-amplitude expansions (random phase approximations) can be readily developed without explicit enumeration of all reaction products in a mixture. We further illustrate how to analyze CS field theories beyond SCFT at the level of Gaussian field fluctuations and provide a perspective on direct numerical simulations using a recently developed complex Langevin technique.

Volatile diffusion in silicate melts and its effects on melt inclusions

Directory of Open Access Journals (Sweden)

P. Scarlato

2005-06-01

Full Text Available A compendium of diffusion measurements and their Arrhenius equations for water, carbon dioxide, sulfur, fluorine, and chlorine in silicate melts similar in composition to natural igneous rocks is presented. Water diffusion in silicic melts is well studied and understood, however little data exists for melts of intermediate to basic compositions. The data demonstrate that both the water concentration and the anhydrous melt composition affect the diffusion coefficient of water. Carbon dioxide diffusion appears only weakly dependent, at most, on the volatilefree melt composition and no effect of carbon dioxide concentration has been observed, although few experiments have been performed. Based upon one study, the addition of water to rhyolitic melts increases carbon dioxide diffusion by orders of magnitude to values similar to that of 6 wt% water. Sulfur diffusion in intermediate to silicic melts depends upon the anhydrous melt composition and the water concentration. In water-bearing silicic melts sulfur diffuses 2 to 3 orders of magnitude slower than water. Chlorine diffusion is affected by both water concentration and anhydrous melt composition; its values are typically between those of water and sulfur. Information on fluorine diffusion is rare, but the volatile-free melt composition exerts a strong control on its diffusion. At the present time the diffusion of water, carbon dioxide, sulfur and chlorine can be estimated in silicic melts at magmatic temperatures. The diffusion of water and carbon dioxide in basic to intermediate melts is only known at a limited set of temperatures and compositions. The diffusion data for rhyolitic melts at 800°C together with a standard model for the enrichment of incompatible elements in front of growing crystals demonstrate that rapid crystal growth, greater than 10-10 ms-1, can significantly increase the volatile concentrations at the crystal-melt interface and that any of that melt trapped

Flow of Polymer Melts in Plane- and Axi-Symmetric Converging Dies

DEFF Research Database (Denmark)

Lauridsen, Carsten Linding; Kjær, Erik Michael; Haudrum, Jan

1998-01-01

The extensional flow has considerable influence on the pressure loss in converging flows, which are present in both extrusion and injection moulding. Both plane- and axi-symmetric converging flows have been studied with LDPE, HDPE and PS. The transient extensional viscosities are determined in al...... are comparable for the LDPE and the PS melts. Furthermore, the pressure losses are characterized with the Deborah number in which the characteristic time of the material is shear rate dependent and the characteristic time of the flow is Hencky strain rate dependent....

Asymmetric Alkyl Side-Chain Engineering of Naphthalene Diimide-Based n-Type Polymers for Efficient All-Polymer Solar Cells.

Science.gov (United States)

Jia, Tao; Li, Zhenye; Ying, Lei; Jia, Jianchao; Fan, Baobing; Zhong, Wenkai; Pan, Feilong; He, Penghui; Chen, Junwu; Huang, Fei; Cao, Yong

2018-02-13

The design and synthesis of three n-type conjugated polymers based on a naphthalene diimide-thiophene skeleton are presented. The control polymer, PNDI-2HD, has two identical 2-hexyldecyl side chains, and the other polymers have different alkyl side chains; PNDI-EHDT has a 2-ethylhexyl and a 2-decyltetradecyl side chain, and PNDI-BOOD has a 2-butyloctyl and a 2-octyldodecyl side chain. These copolymers with different alkyl side chains exhibit higher melting and crystallization temperatures, and stronger aggregation in solution, than the control copolymer PNDI-2HD that has the same side chain. Polymer solar cells based on the electron-donating copolymer PTB7-Th and these novel copolymers exhibit nearly the same open-circuit voltage of 0.77 V. Devices based on the copolymer PNDI-BOOD with different side chains have a power-conversion efficiency of up to 6.89%, which is much higher than the 4.30% obtained with the symmetric PNDI-2HD. This improvement can be attributed to the improved charge-carrier mobility and the formation of favorable film morphology. These observations suggest that the molecular design strategy of incorporating different side chains can provide a new and promising approach to developing n-type conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extensional Strain Hardening Induced by π -π Interactions in Barely Entangled Polymer Chains: The Curious Case of Poly(4-vinylbiphenyl)

Science.gov (United States)

López-Barrón, Carlos R.; Zhou, Huaxing

2017-12-01

Aromatic π -π interactions between phenyl groups of adjacent chains in poly(4-vinylbiphenyl) (PVBP) have profound effects on the dynamics of this polymer. We report two unexpected nonlinear viscoelastic responses of PVBP when subjected to uniaxial flow. One is the unprecedented observation of extensional strain hardening (SH) in a barely entangled polymer melt. An even more intriguing finding is that SH of lightly (or even barely) entangled melts occurs at strain rates one order of magnitude below the coil-stretch transition predicted by Rouse theory (ɛ˙ H=0.5 /τR ).We postulate that this behavior is due to a molecular rearrangement mechanism (supported by x-ray diffraction measurements) that involves flow-induced π -π stacking of the phenyl groups, which results in an enhancement of the friction coefficient between polymer chains.

Relaxation of entangled model H-shaped polymers a SANS investigation

CERN Document Server

Heinrich, M; Richter, D; Straube, E; Wiedenmann, A

2002-01-01

This study is related to the understanding of rheology of long-chain branched polymers. A model compound for long-chain branching (H-shaped architecture) was investigated in elongational flow as a function of time after a step strain to lambda=2. The experiments were performed in a strain rig with temperature and strain-rate control. The structure factor was measured after specific relaxation times intimately connected to the microscopic hierarchy of the polymer structure. The correlation hole effect and the quenched disorder in the scattering were described in a random phase approximation approach. This approach, already used for permanent rubber-elastic networks, has been modified to permit the observation of strain locally along the faster-relaxing arms. The data roughly follow the time scale of linear-shear rheology from which shift factors were derived. They confirm that bridge and arm relaxations can be treated in a decoupled, hierarchical way in time, although details of the analysis remain unsolved. (...

Non-uniformity of phase structure in immiscible polymer blends

Czech Academy of Sciences Publication Activity Database

Fortelný, Ivan; Lapčíková, Monika; Lednický, František; Starý, Zdeněk; Kruliš, Zdeněk

2008-01-01

Roč. 48, č. 3 (2008), s. 564-571 ISSN 0032-3888 R&D Projects: GA ČR GA106/06/0729; GA ČR GA106/06/0761 Institutional research plan: CEZ:AV0Z40500505 Keywords : polymer blends * melt mixing * non-uniform morphology Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.245, year: 2008

A NOVEL INTERPRETATION OF CONCENTRATION DEPENDENCE OF VISCOSITY OF DILUTE POLYMER SOLUTION

Institute of Scientific and Technical Information of China (English)

Yan Pan; Rong-shi Cheng

2000-01-01

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

Synthesis, Morphology, and Optical Properties of Au/CdS Hybrid Nanocomposites Stabilized by Branched Polymer Matrices

Directory of Open Access Journals (Sweden)

V. A. Chumachenko

2016-01-01

Full Text Available Metal/semiconductor (Au/CdS nanocomposites were synthesized in the solution of branched D-g-PAA polymer. TEM and DLS of Au/CdS/D-g-PAA nanocomposites revealed complicated nanocomposite structure consisting of the Au nanoparticles (NPs of 6 nm in size surrounded by small CdS NPs with size of 3 nm. These nanocomposites formed the aggregates-clusters with average size of 50–800 nm. Absorption spectra of Au/CdS nanocomposites consist of the bands of excitons in CdS NPs and surface plasmons in Au ones. The surface plasmon band of gold NPs is red shifted and broadened in Au/CdS/D-g-PAA nanocomposites comparing to the one of Au NPs in Au/D-g-PAA proving the fact of close location of CdS and Au NPs in the synthesized Au/CdS/D-g-PAA nanocomposites. The PL spectra of Au/CdS nanocomposites originate from the radiative transitions in excitons in CdS NPs. The 4-fold increase of intensity of free exciton PL is observed for CdS NPs in Au/CdS/D-g-PAA comparing to CdS ones in CdS/D-g-PAA that is due to PL enhancement by local field of surface plasmons of Au NPs. Also, the 12-fold decrease of intensity of localized exciton PL is observed for CdS NPs in Au/CdS/D-g-PAA comparing to CdS ones in CdS/D-g-PAA. Most probably, it is due to passivation of the surface of CdS NPs carried out by the Au ones.

Double melting in polytetrafluoroethylene γ-irradiated above its melting point

International Nuclear Information System (INIS)

Serov, S.A.; Khatipov, S.A.; Sadovskaya, N.V.; Tereshenkov, A.V.; Chukov, N.A.

2012-01-01

Highlights: ► PTFE irradiation leads to formation of double melting peaks in DSC curves. ► This is connected to dual crystalline morphology typical for PTFE. ► Two crystalline types exist in the PTFE irradiated in the melt. - Abstract: PTFE irradiation above its melting point leads to formation of double melting and crystallization peaks in DSC curves. Splitting of melting peaks is connected to dual crystalline morphology typical for PTFE irradiated in the melt. According to electron microscopy, two crystalline types with different size and packing density exist in the irradiated PTFE.

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

Molecular Rheology of Complex Fluids

DEFF Research Database (Denmark)

Huang, Qian; Rasmussen, Henrik Koblitz

following a stress maximum were reported for two LDPE melts. However the rheological significance of the stress maximum as well as the existence of steady flow conditions following the maximum is still a matter of some debate. This thesis focuses on the experimental study of extensional rheology of linear...... and branched polymer melts. We report the stress–strain measurements in extensional flows using a unique Filament Stretching Rheometer (FSR) in controlled strain rate mode and controlled stress mode. Extensional flow is difficult to measure reliably in Laboratory circumstances. In this thesis we first present...

Development of polymer packaging for power cable

Directory of Open Access Journals (Sweden)

S. Sremac

2014-10-01

Full Text Available This paper discusses the issues of product design and the procedure of developing polymer packaging as one of the most important engineering tasks. For the purpose of packing power cables a polymer packaging has been designed in the form of drum. Packaging and many other consumer products are largely produced using polymeric materials due to many positive features. High Density Polyethylene is the type of polyethylene proposed for packaging purposes due to its low degree of branching and strong intermolecular forces. Transport and storage processes were automated based on the radio-frequency identification technology. The proposed system is flexible in terms of its possibility of accepting and processing different types of cables and other products.

Polymer-Derived In- Situ Metal Matrix Composites Created by Direct Injection of a Liquid Polymer into Molten Magnesium

Science.gov (United States)

Sudarshan; Terauds, Kalvis; Anilchandra, A. R.; Raj, Rishi

2014-02-01

We show that a liquid organic precursor can be injected directly into molten magnesium to produce nanoscale ceramic dispersions within the melt. The castings made in this way possess good resistance to tensile deformation at 673 K (400 °C), confirming the non-coarsening nature of these dispersions. Direct liquid injection into molten metals is a significant step toward inserting different chemistries of liquid precursors to generate a variety of polymer-derived metal matrix composites.

Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

International Nuclear Information System (INIS)

Tewatia, Arya; Hendrix, Justin; Dong, Zhizhong; Taghon, Meredith; Tse, Stephen; Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas; Lynch, Jennifer

2017-01-01

Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

Energy Technology Data Exchange (ETDEWEB)

Tewatia, Arya; Hendrix, Justin [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Dong, Zhizhong [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Taghon, Meredith [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Tse, Stephen [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Lynch, Jennifer, E-mail: jklynch@rci.rutgers.edu [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States)

2017-02-15

Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

On the microscopic approach to the nonlinear dynamics of entangled polymer melts

NARCIS (Netherlands)

Stepanyan, R.; Slot, J.J.M.; Molenaar, J.

2004-01-01

A framework for a consistent description of the correlation effects along polymer chains subject to flow is proposed. The formalism shows how correlations between chain segments in the flow can be incorporated into a hierarchy of distribution functions for tangent vectors. The present description

Inline UV/Vis spectroscopy as PAT tool for hot-melt extrusion.

Science.gov (United States)

Wesholowski, Jens; Prill, Sebastian; Berghaus, Andreas; Thommes, Markus

2018-01-11

Hot-melt extrusion on co-rotating twin screw extruders is a focused technology for the production of pharmaceuticals in the context of Quality by Design. Since it is a continuous process, the potential for minimizing product quality fluctuation is enhanced. A typical application of hot-melt extrusion is the production of solid dispersions, where an active pharmaceutical ingredient (API) is distributed within a polymer matrix carrier. For this dosage form, the product quality is related amongst others to the drug content. This can be monitored on- or inline as critical quality attribute by a process analytical technology (PAT) in order to meet the specific requirements of Quality by Design. In this study, an inline UV/Vis spectrometer from ColVisTec was implemented in an early development twin screw extruder and the performance tested in accordance to the ICH Q2 guideline. Therefore, two API (carbamazepine and theophylline) and one polymer matrix (copovidone) were considered with the main focus on the quantification of the drug load. The obtained results revealed the suitability of the implemented PAT tool to quantify the drug load in a typical range for pharmaceutical applications. The effort for data evaluation was minimal due to univariate data analysis, and in combination with a measurement frequency of 1 Hz, the system is sufficient for real-time data acquisition.

Utilization of poly(methyl methacrylate – carbon nanotube and polystyrene – carbon nanotube in situ polymerized composites as masterbatches for melt mixing

Directory of Open Access Journals (Sweden)

M. Lahelin

2012-10-01

Full Text Available Carbon nanotubes (CNTs were melt mixed directly or by using an in situ polymerized masterbatch into a matrix polymer, polystyrene (PS or poly(methyl methacrylate (PMMA. The mechanical properties of the composites were mostly determined by the amount of CNTs, and not by the use of directly melt mixed CNTs or the use of the masterbatch. In contrast, the electrical resistivity of the composites was dependent on the manner in which the CNTs were added to the matrix polymer. When there was increased interfacial adhesion between the components, as for PS and the CNTs, the use of directly melt mixed CNTs gave better resistivity results. Without strong interactions between the CNTs and the matrix, as with PMMA and CNTs, the use of a tailored masterbatch had a significant effect on properties of the final composites. The molecular weight and viscosity of masterbatches can be varied and when the PMMA-masterbatch had optimized viscosity with respect to the PMMA matrix, electrical resistivity of the final composites decreased noticeably.

Radiation-induced branching and crosslinking of poly(tetrafluoroethylene) (PTFE)

International Nuclear Information System (INIS)

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

2001-01-01

The effect of electron beams on poly(tetrafluoroethylene) (PTFE) at elevated temperatures above the melting point on oxygen-free conditions has been studied using differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS), Fourier-transform infrared (FTIR) spectroscopy, thermo-gravimetric analysis (TGA) and tensile test. The investigations have shown that the chemical structure and several properties of PTFE are greatly altered by the irradiation. DSC and WAXS indicate that the crystallinity of the PTFE irradiated with high doses is reduced. CF 3 side groups and branched structures are assumed to hinder the crystallization. TGA has shown that the thermal stability of the radiation-modified PTFE is considerably lower than that of unirradiated PTFE

Melting method for miscellaneous radioactive solid waste and melting furnace

International Nuclear Information System (INIS)

Osaki, Toru; Furukawa, Hirofumi; Uda, Nobuyoshi; Katsurai, Kiyomichi

1998-01-01

A vessel containing miscellaneous solid wastes is inserted in a crucible having a releasable material on the inner surface, they are induction-heated from the outside of the crucible by way of low temperature heating coils to melt low melting point materials in the miscellaneous wastes within a temperature range at which the vessel does not melt. Then, they are induction-heated by way of high temperature heating coils to melt the vessel and not yet melted materials, those molten materials are cooled, solidified molten material and the releasable material are taken out, and then the crucible is used again. Then, the crucible can be used again, so that it can be applied to a large scaled melting furnace which treats wastes by a unit of drum. In addition, since the cleaning of the used crucible and the application of the releasable material can be conducted without interrupting the operation of the melting furnace, the operation cycle of the melting furnace can be shortened. (N.H.)

Interplay Between Side Chain Pattern, Polymer Aggregation, and Charge Carrier Dynamics in PBDTTPD:PCBM Bulk-Heterojunction Solar Cells

KAUST Repository

Dyer-Smith, Clare

2015-05-01

Poly(benzo[1,2-b:4,5-b′]dithiophene–alt–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymer donors with linear side-chains yield bulk-heterojunction (BHJ) solar cell power conversion efficiencies (PCEs) of about 4% with phenyl-C71-butyric acid methyl ester (PC71BM) as the acceptor, while a PBDTTPD polymer with a combination of branched and linear substituents yields a doubling of the PCE to 8%. Using transient optical spectroscopy it is shown that while the exciton dissociation and ultrafast charge generation steps are not strongly affected by the side chain modifications, the polymer with branched side chains exhibits a decreased rate of nongeminate recombination and a lower fraction of sub-nanosecond geminate recombination. In turn the yield of long-lived charge carriers increases, resulting in a 33% increase in short circuit current (J sc). In parallel, the two polymers show distinct grazing incidence X-ray scattering spectra indicative of the presence of stacks with different orientation patterns in optimized thin-film BHJ devices. Independent of the packing pattern the spectroscopic data also reveals the existence of polymer aggregates in the pristine polymer films as well as in both blends which trap excitons and hinder their dissociation.

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.

Three-dimensional bioprinting of cell-laden constructs with polycaprolactone protective layers for using various thermoplastic polymers.

Science.gov (United States)

Kim, Byoung Soo; Jang, Jinah; Chae, Suhun; Gao, Ge; Kong, Jeong-Sik; Ahn, Minjun; Cho, Dong-Woo

2016-08-22

Three-dimensional (3D) cell-printed constructs have been recognized as promising biological substitutes for tissue/organ regeneration. They provide tailored physical properties and biological cues via multi-material printing process. In particular, hybrid bioprinting, enabling to use biodegradable synthetic polymers as framework, has been an attractive method to support weak hydrogels. The constructs with controlled architecture and high shape fidelity were fabricated through this method, depositing spatial arrangement of multi-cell types into microscale constructs. Among biodegradable synthetic polymers, polycaprolactone (PCL) has been commonly chosen in fabrication of cell-printed constructs because of its low melting temperature of 60 °C to be dispensed with extrusion-based bioprinting system. However, in addition to PCL, various synthetic polymers have been widely applied for tissue regeneration. These polymers have distinctive characteristics essential for tissue/organ regeneration. Nevertheless, it is difficult to use some polymers, such as poly (lactic-co-glycolic acid) (PLGA) and polylactic acid (PLA) with 3D bioprinting technology because of their high melting temperature to be dispensed, which can result in thermal damage to the cells in the printed constructs during the fabrication process. We present a novel bioprinting method to use various synthetic polymers in fabrication of cell-printed constructs. PCL was introduced as a protective layer to prevent thermal damage caused by high temperature of polymers during fabrication. Remarkable improvement in cellular activities in the printed constructs with PCL layers was observed compared with the construct without PCL. This bioprinting method can be applied to fabricate more tissue-like constructs through the use of various biomaterials.

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.

Estimation of a melting probe's penetration velocity range to reach icy moons' subsurface ocean

Science.gov (United States)

Erokhina, Olga; Chumachenko, Eugene

2014-05-01

In modern space science one of the actual branches is icy satellites explorations. The main interest is concentrated around Jovian's moons Europa and Ganymede, Saturn's moons Titan and Enceladus that are covered by thick icy layer according to "Voyager1", "Voyager2", "Galileo" and "Cassini" missions. There is a big possibility that under icy shell could be a deep ocean. Also conditions on these satellites allow speculating about possible habitability, and considering these moons from an astrobiological point of view. One of the possible tasks of planned missions is a subsurface study. For this goal it is necessary to design special equipment that could be suitable for planetary application. One of the possible means is to use a melting probe which operates by melting and moves by gravitational force. Such a probe should be relatively small, should not weight too much and should require not too much energy. In terrestrial case such kind of probe has been successfully used for glaciers study. And it is possible to extrapolate the usage of such probe to extraterrestrial application. One of the tasks is to estimate melting probe's penetration velocity. Although there are other unsolved problems such as analyzing how the probe will move in low gravity and low atmospheric pressure; knowing whether hole will be closed or not when probe penetrate thick enough; and considering what order could be a penetration velocity. This study explores two techniques of melting probe's movement. One of them based on elasto-plastic theory and so-called "solid water" theory, and other one takes phase changing into account. These two techniques allow estimating melting probe's velocity range and study whole process. Based on these technique several cases of melting probe movement were considered, melting probe's velocity range estimated, influence of different factors studied and discussed and an easy way to optimize parameters of the melting probe proposed.

Effect of Chain Conformation on the Single-Molecule Melting Force in Polymer Single Crystals: Steered Molecular Dynamics Simulations Study.

Science.gov (United States)

Feng, Wei; Wang, Zhigang; Zhang, Wenke

2017-02-28

Understanding the relationship between polymer chain conformation as well as the chain composition within the single crystal and the mechanical properties of the corresponding single polymer chain will facilitate the rational design of high performance polymer materials. Here three model systems of polymer single crystals, namely poly(ethylene oxide) (PEO), polyethylene (PE), and nylon-66 (PA66) have been chosen to study the effects of chain conformation, helical (PEO) versus planar zigzag conformation (PE, PA66), and chain composition (PE versus PA66) on the mechanical properties of a single polymer chain. To do that, steered molecular dynamics simulations were performed on those polymer single crystals by pulling individual polymer chains out of the crystals. Our results show that the patterns of force-extension curve as well as the chain moving mode are closely related to the conformation of the polymer chain in the single crystal. In addition, hydrogen bonds can enhance greatly the force required to stretch the polymer chain out of the single crystal. The dynamic breaking and reformation of multivalent hydrogen bonds have been observed for the first time in PA66 at the single molecule level.

Development of foams from linear polypropylene (PP) and high melt strength polypropylene (HMSPP) polymeric blends

International Nuclear Information System (INIS)

Cardoso, Elisabeth Carvalho Leite

2009-01-01

Foamed polymers are future materials, with a comprehensive application field. They can be used in order to improve appearance of insulation structures, for example, or to reduce costs involving materials. This work address to Isotactic Polypropylene / High Melt Strength Polypropylene blends, for foams production. Rheological behavior of polymer melt, especially referring to viscosity in processing temperature, plays a decisive role in applications where dominates extensional flow, as in case of foaming. If the viscosity is very low, it will correspond to a low melt strength, as in case of linear homopolymer (Isotact PP), and the foam will be prejudiced, due to the impossibility of expansion. Otherwise, if the viscosity is very high, with a high melt strength, the foam will collapse immediately after its formation. In order to get foams with an homogeneous and defined cellular structure, there were accomplished blends, 50% in weight, between linear homopolymer (isotactic PP) and HMSPP, from PP modified as per gamma radiation, in acetylene environment and at a 12.5 kGy doses. Extrusion process used a soluble foaming methodology, according to a processing/dissolution principle, which involves the dissolution of a Physical Blowing Agent (PBA), under 30 bar pressure, homogeneously mixed with polymeric melt. Extrusion conditions, that generally involve temperature, pressure and viscoelastic material flow control were experimentally investigated to define prevalent characteristics for producing foams. Nitrogen was the used PBA and process extrusion parameters were adapted to PP, HMSPP and their 50% in weight mixtures thereof. Major PP and HMSPP characteristics were obtained via melt Index and melt strength and thermal analyses (DSC/TGA), in order to make viable and to reproduce foaming as per extrusion process. Foams cellular morphology of PP, HMSPP and their 50% in weight mixtures thereof was investigated, with and without talc addition, as nucleating agent, by using

A multi-species exchange model for fully fluctuating polymer field theory simulations.

Science.gov (United States)

Düchs, Dominik; Delaney, Kris T; Fredrickson, Glenn H

2014-11-07

Field-theoretic models have been used extensively to study the phase behavior of inhomogeneous polymer melts and solutions, both in self-consistent mean-field calculations and in numerical simulations of the full theory capturing composition fluctuations. The models commonly used can be grouped into two categories, namely, species models and exchange models. Species models involve integrations of functionals that explicitly depend on fields originating both from species density operators and their conjugate chemical potential fields. In contrast, exchange models retain only linear combinations of the chemical potential fields. In the two-component case, development of exchange models has been instrumental in enabling stable complex Langevin (CL) simulations of the full complex-valued theory. No comparable stable CL approach has yet been established for field theories of the species type. Here, we introduce an extension of the exchange model to an arbitrary number of components, namely, the multi-species exchange (MSE) model, which greatly expands the classes of soft material systems that can be accessed by the complex Langevin simulation technique. We demonstrate the stability and accuracy of the MSE-CL sampling approach using numerical simulations of triblock and tetrablock terpolymer melts, and tetrablock quaterpolymer melts. This method should enable studies of a wide range of fluctuation phenomena in multiblock/multi-species polymer blends and composites.

The melting and crystallization behavior of irradiated poly(1-butene)

International Nuclear Information System (INIS)

Markovic, V.; Silverman, J.

1982-01-01

Isotactic poly(1-butene) samples were melted and crystallized. This treatment leaves the polymer in the unstable crystalline form, known as Modification II. The transformation to stable Modification I normally has a half life of 1 day. Samples were irradiated within 30 min after crystallization with high doses of electrons delivered in intervals up to a few minutes. This permitted measurements of radiation effects on Modification II under circumstances where the II-I crystal transformation was negligibly small. Similar measurements were performed on stable Modification I, which was obtained by waiting for the completion of the II-I transformation; for this stable crystalline form, relatively low dose rate γ-exposures serve as well as high dose rate electron beams in measuring radiation effects. DSC and IR absorption measurements were performed. The effect of radiation on the fusion endotherms, melting points, IR spectra, and some aspects of the kinetics of crystalline transformation are presented. (author)

Tin in granitic melts: The role of melting temperature and protolith composition

Science.gov (United States)

Wolf, Mathias; Romer, Rolf L.; Franz, Leander; López-Moro, Francisco Javier

2018-06-01

Granite bound tin mineralization typically is seen as the result of extreme magmatic fractionation and late exsolution of magmatic fluids. Mineralization, however, also could be obtained at considerably less fractionation if initial melts already had enhanced Sn contents. We present chemical data and results from phase diagram modeling that illustrate the dominant roles of protolith composition, melting conditions, and melt extraction/evolution for the distribution of Sn between melt and restite and, thus, the Sn content of melts. We compare the element partitioning between leucosome and restite of low-temperature and high-temperature migmatites. During low-temperature melting, trace elements partition preferentially into the restite with the possible exception of Sr, Cd, Bi, and Pb, that may be enriched in the melt. In high-temperature melts, Ga, Y, Cd, Sn, REE, Pb, Bi, and U partition preferentially into the melt whereas Sc, V, Cr, Co, Ni, Mo, and Ba stay in the restite. This contrasting behavior is attributed to the stability of trace element sequestering minerals during melt generation. In particular muscovite, biotite, titanite, and rutile act as host phases for Sn and, therefore prevent Sn enrichment in the melt as long as they are stable phases in the restite. As protolith composition controls both the mineral assemblage and modal contents of the various minerals, protolith composition eventually also controls the fertility of a rock during anatexis, restite mineralogy, and partitioning behavior of trace metals. If a particular trace element is sequestered in a phase that is stable during partial melting, the resulting melt is depleted in this element whereas the restite becomes enriched. Melt generation at high temperature may release Sn when Sn-hosts become unstable. If melt has not been lost before the breakdown of Sn-hosts, Sn contents in the melt will increase but never will be high. In contrast, if melt has been lost before the decomposition of Sn

Study of optical properties of Erbium doped Tellurite glass-polymer composite

Science.gov (United States)

Sushama, D.

2014-10-01

Chalcogenide glasses have wide applications in optical device technology. But it has some disadvantages like thermal instability. Among them Tellurite glasses exhibits high thermal Stability. Doping of rare earth elements into the Tellurite glasses improve its optical properties. To improve its mechanical properties composites of this Tellurite glasses with polymer are prepared. Bulk samples of Er2O3 doped TeO2-WO3-La2O3 Tellurite glasses are prepared from high purity oxide mixtures, melting in an alumina crucible in air atmosphere. Composites of this Tellurite glasses with polymer are prepared by powder mixing method and the thin films of these composites are prepared using polymer press. Variations in band gap of these composites are studied from the UV/Vis/NIR absorption.

Synthesis, Characterization and Biological Studies of New Linear Thermally Stable Schiff Base Polymers with Flexible Spacers.

Science.gov (United States)

Qureshi, Farah; Khuhawar, Muhammad Yar; Jahangir, Taj Muhammad; Channar, Abdul Hamid

2016-01-01

Five new linear Schiff base polymers having azomethine structures, ether linkages and extended aliphatic chain lengths with flexible spacers were synthesized by polycondensation of dialdehyde (monomer) with aliphatic and aromatic diamines. The formation yields of monomer and polymers were obtained within 75-92%. The polymers with flexible spacers of n-hexane were somewhat soluble in acetone, chloroform, THF, DMF and DMSO on heating. The monomer and polymers were characterized by melting point, elemental microanalysis, FT-IR, (1)HNMR, UV-Vis spectroscopy, thermogravimetry (TG), differential thermal analysis (DTA), fluorescence emission, scanning electron microscopy (SEM) and viscosities and thermodynamic parameters measurements of their dilute solutions. The studies supported formation of the monomer and polymers and on the basis of these studies their structures have been assigned. The synthesized polymers were tested for their antibacterial and antifungal activities.

Comparative Study on Two Melting Simulation Methods: Melting Curve of Gold

International Nuclear Information System (INIS)

Liu Zhong-Li; Li Rui; Sun Jun-Sheng; Zhang Xiu-Lu; Cai Ling-Cang

2016-01-01

Melting simulation methods are of crucial importance to determining melting temperature of materials efficiently. A high-efficiency melting simulation method saves much simulation time and computational resources. To compare the efficiency of our newly developed shock melting (SM) method with that of the well-established two-phase (TP) method, we calculate the high-pressure melting curve of Au using the two methods based on the optimally selected interatomic potentials. Although we only use 640 atoms to determine the melting temperature of Au in the SM method, the resulting melting curve accords very well with the results from the TP method using much more atoms. Thus, this shows that a much smaller system size in SM method can still achieve a fully converged melting curve compared with the TP method, implying the robustness and efficiency of the SM method. (paper)

Operating features of decorative polymer-impregnated concretes under severe operating conditions

International Nuclear Information System (INIS)

Kapustina, I.B.; Lobasenok, V.A.; Yakimtsiv, V.P.

1991-01-01

The study was carried out to investigate the possibility of a decorative polymer-impregnated concrete as a lining material in radiation-endangered rooms. Their extreme properties such as radiation resistance, decontamination ability, fire resistance and melting-freezing cycle resistance were studied. The material proposed shows substantially high resistance under severe operating conditions

Effect of organoclay on the orientation and thermal properties of liquid-crystalline polymers

CSIR Research Space (South Africa)

Bandyopadhyay, J

2007-08-01

Full Text Available in the pure LCP; in the nanocomposites, the polymer chains tended to orient in the direction of the dispersed clay layers. According to the DSC results, during first heating, the first melting peak represents the crystalline to nematic transition and, after...

General approach to polymer chains confined by interacting boundaries.

Science.gov (United States)

Freed, Karl F; Dudowicz, Jacek; Stukalin, Evgeny B; Douglas, Jack F

2010-09-07

Polymer chains, confined to cavities or polymer layers with dimensions less than the chain radius of gyration, appear in many phenomena, such as gel chromatography, rubber elasticity, viscolelasticity of high molar mass polymer melts, the translocation of polymers through nanopores and nanotubes, polymer adsorption, etc. Thus, the description of how the constraints alter polymer thermodynamic properties is a recurrent theoretical problem. A realistic treatment requires the incorporation of impenetrable interacting (attractive or repulsive) boundaries, a process that introduces significant mathematical complications. The standard approach involves developing the generalized diffusion equation description of the interaction of flexible polymers with impenetrable confining surfaces into a discrete eigenfunction expansion, where the solutions are normally truncated at the first mode (the "ground state dominance" approximation). This approximation is mathematically well justified under conditions of strong confinement, i.e., a confinement length scale much smaller than the chain radius of gyration, but becomes unreliable when the polymers are confined to dimensions comparable to their typically nanoscale size. We extend a general approach to describe polymers under conditions of weak to moderate confinement and apply this semianalytic method specifically to determine the thermodynamics and static structure factor for a flexible polymer confined between impenetrable interacting parallel plate boundaries. The method is first illustrated by analyzing chain partitioning between a pore and a large external reservoir, a model system with application to chromatography. Improved agreement is found for the partition coefficients of a polymer chain in the pore geometry. An expression is derived for the structure factor S(k) in a slit geometry to assist in more accurately estimating chain dimensions from scattering measurements for thin polymer films.

Synthesis and Characterization of Branched Ionomers for Performance in Ionic Liquid â Swollen Ionic Polymer Transducers

OpenAIRE

Duncan, Andrew Jay

2009-01-01

Ionic polymer transducers (IPT) are a class of electroactive polymer devices that exhibit electromechanical coupling through charge transport in ionomeric membranes that contain a charge mobilizing diluent and are interfaced with conducting electrodes. Applications of these active materials have been broadly developed in the field of actuators and sensors. Advances in fundamental understanding of IPT performance mechanisms and tuning of the device components has primarily focused on transduce...

Comparative Study of Different Methods for the Prediction of Drug-Polymer Solubility

DEFF Research Database (Denmark)

Knopp, Matthias Manne; Tajber, Lidia; Tian, Yiwei

2015-01-01

monomer weight ratios. The drug–polymer solubility at 25 °C was predicted using the Flory–Huggins model, from data obtained at elevated temperature using thermal analysis methods based on the recrystallization of a supersaturated amorphous solid dispersion and two variations of the melting point......, which suggests that this method can be used as an initial screening tool if a liquid analogue is available. The learnings of this important comparative study provided general guidance for the selection of the most suitable method(s) for the screening of drug–polymer solubility....

Universal size properties of a star-ring polymer structure in disordered environments

Science.gov (United States)

Haydukivska, K.; Blavatska, V.

2018-03-01

We consider the complex polymer system, consisting of a ring polymer connected to the f1-branched starlike structure, in a good solvent in the presence of structural inhomogeneities. In particular cases f1=1 and f1=2 , such a system restores the synthesized tadpole-shaped polystyrenes [Doi et al., Macromolecules 46, 1075 (2013), 10.1021/ma302511j]. We assume that structural defects are correlated at large distances x according to a power law x-a. Applying the direct polymer renormalization approach, we evaluate the universal size characteristics such as the ratio of the radii of gyration of star-ring and star topologies, and compare the effective sizes of single arms in complex structures and isolated polymers of the same total molecular weight. The nontrivial impact of disorder on these quantities is analyzed.

Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

Energy Technology Data Exchange (ETDEWEB)

Ylikantola, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Linnanto, J., E-mail: juha.m.linnanto@gmail.com [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); University of Tartu, Institute of Physics, Riia 142, EE-51014 Tartu (Estonia); Knuutinen, J.; Oravilahti, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Toivakka, M. [Åbo Akademi University, Laboratory of Paper Coating and Converting and Center for Functional Materials, FI-20500 Turku/Åbo (Finland)

2013-07-01

The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree–Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree–Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree–Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

Olivine/melt transition metal partitioning, melt composition, and melt structure—Melt polymerization and Qn-speciation in alkaline earth silicate systems

Science.gov (United States)

Mysen, Bjorn O.

2008-10-01

The two most abundant network-modifying cations in magmatic liquids are Ca 2+ and Mg 2+. To evaluate the influence of melt structure on exchange of Ca 2+ and Mg 2+ with other geochemically important divalent cations ( m-cations) between coexisting minerals and melts, high-temperature (1470-1650 °C), ambient-pressure (0.1 MPa) forsterite/melt partitioning experiments were carried out in the system Mg 2SiO 4-CaMgSi 2O 6-SiO 2 with ⩽1 wt% m-cations (Mn 2+, Co 2+, and Ni 2+) substituting for Ca 2+ and Mg 2+. The bulk melt NBO/Si-range ( NBO/Si: nonbridging oxygen per silicon) of melt in equilibrium with forsterite was between 1.89 and 2.74. In this NBO/Si-range, the NBO/Si(Ca) (fraction of nonbridging oxygens, NBO, that form bonds with Ca 2+, Ca 2+- NBO) is linearly related to NBO/Si, whereas fraction of Mg 2+- NBO bonds is essentially independent of NBO/Si. For individual m-cations, rate of change of KD( m-Mg) with NBO/Si(Ca) for the exchange equilibrium, mmelt + Mg olivine ⇌ molivine + Mg melt, is linear. KD( m-Mg) decreases as an exponential function of increasing ionic potential, Z/ r2 ( Z: formal electrical charge, r: ionic radius—here calculated with oxygen in sixfold coordination around the divalent cations) of the m-cation. The enthalpy change of the exchange equilibrium, Δ H, decreases linearly with increasing Z/ r2 [Δ H = 261(9)-81(3)· Z/ r2 (Å -2)]. From existing information on (Ca,Mg)O-SiO 2 melt structure at ambient pressure, these relationships are understood by considering the exchange of divalent cations that form bonds with nonbridging oxygen in individual Qn-species in the melts. The negative ∂ KD( m-Mg) /∂( Z/ r2) and ∂(Δ H)/∂( Z/ r2) is because increasing Z/ r2 is because the cations forming bonds with nonbridging oxygen in increasingly depolymerized Qn-species where steric hindrance is decreasingly important. In other words, principles of ionic size/site mismatch commonly observed for trace and minor elements in crystals, also

Sago Starch-Mixed Low-Density Polyethylene Biodegradable Polymer: Synthesis and Characterization

Directory of Open Access Journals (Sweden)

Md Enamul Hoque

2013-01-01

Full Text Available This research focuses on synthesis and characterization of sago starch-mixed LDPE biodegradable polymer. Firstly, the effect of variation of starch content on mechanical property (elongation at break and Young’s modulus and biodegradability of the polymer was studied. The LDPE was combined with 10%, 30%, 50%, and 70% of sago for this study. Then how the cross-linking with trimethylolpropane triacrylate (TMPTA and electron beam (EB irradiation influence the mechanical and thermal properties of the polymer was investigated. In the 2nd study, to avoid overwhelming of data LDPE polymer was incorporated with only 50% of starch. The starch content had direct influence on mechanical property and biodegradability of the polymer. The elongation at break decreased with increase of starch content, while Young’s modulus and mass loss (i.e., degradation were found to increase with increase of starch content. Increase of cross-linker (TMPTA and EB doses also resulted in increased Young’s modulus of the polymer. However, both cross-linking and EB irradiation processes rendered lowering of polymer’s melting temperature. In conclusion, starch content and modification processes play significant roles in controlling mechanical, thermal, and degradation properties of the starch-mixed LDPE synthetic polymer, thus providing the opportunity to modulate the polymer properties for tailored applications.

STUDY OF SURFACE MODIFIED POLYMERS IN THE MODIFICATION OF NANOMATERIALS

Directory of Open Access Journals (Sweden)

G. V. Popov

2014-01-01

Full Text Available The comparative study of change of surface tension of solutions of some commercial rubbers before and after thermal ageing technique du-Nui, analyzed the features of change of surface tension of solutions of various rubbers in the presence of a mixture of fullerenes. Calculations of the Gibbs energy and the analysis of the obtained data to predict the behavior of polymer systems when changes are made to mix of fullerenes in a wide concentration range. When comparing the results of changes in Gibbs energy and the surface tension in fluids rubbers shown that mentioned above in solutions of elastomers aged, than the control. This fact confirms the initial chapeau of physic-chemical interactions of molecules fullerenes by segments of the Kuna and end groups of the polymer chains, as it is known that when thermal-oxidative degradation of rubbers, respectively the number of segments of the Kuna and branched loose ends of macromolecules that are free to react with fullerenes in solution, free from spatial constraints. A comparative analysis of the interaction of rubbers with different chemical composition with double branches has shown that it is easier to just react and has minimum energy polibutadien interaction that has to do with lack of branching and no radicals in its structure and in the backbone chain. The maximum energy of interaction with Fullerenes have SBS rubber because it has large styrene blocks in the main polymer chain that causes the spatial constraints to direct contact with fullerene molecules, you can assume that the interaction is only low-molecular fraction of Fullerenes mixture, possessing the necessary dimensions. As a result of the study shows that the application of the method of separation ring (Du-Nui allows you to predict the properties of rubber with modified nanomaterial’s with minimal labor costs.

On-chip magnetic bead-based DNA melting curve analysis using a magnetoresistive sensor

International Nuclear Information System (INIS)

Rizzi, Giovanni; Østerberg, Frederik W.; Henriksen, Anders D.; Dufva, Martin; Hansen, Mikkel F.

2015-01-01

We present real-time measurements of DNA melting curves in a chip-based system that detects the amount of surface-bound magnetic beads using magnetoresistive magnetic field sensors. The sensors detect the difference between the amount of beads bound to the top and bottom sensor branches of the differential sensor geometry. The sensor surfaces are functionalized with wild type (WT) and mutant type (MT) capture probes, differing by a single base insertion (a single nucleotide polymorphism, SNP). Complementary biotinylated targets in suspension couple streptavidin magnetic beads to the sensor surface. The beads are magnetized by the field arising from the bias current passed through the sensors. We demonstrate the first on-chip measurements of the melting of DNA hybrids upon a ramping of the temperature. This overcomes the limitation of using a single washing condition at constant temperature. Moreover, we demonstrate that a single sensor bridge can be used to genotype a SNP. - Highlights: • We apply magnetoresistive sensors to study solid-surface hybridization kinetics of DNA. • We measure DNA melting profiles for perfectly matching DNA duplexes and for a single base mismatch. • We present a procedure to correct for temperature dependencies of the sensor output. • We reliably extract melting temperatures for the DNA hybrids. • We demonstrate direct measurement of differential binding signal for two probes on a single sensor

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

Science.gov (United States)

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

2017-01-30

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

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)

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

Permeability and 3-D melt geometry in shear-induced high melt fraction conduits

Science.gov (United States)

Zhu, W.; Cordonnier, B.; Qi, C.; Kohlstedt, D. L.

2017-12-01

Observations of dunite channels in ophiolites and uranium-series disequilibria in mid-ocean ridge basalt suggest that melt transport in the upper mantle beneath mid-ocean ridges is strongly channelized. Formation of high melt fraction conduits could result from mechanical shear, pyroxene dissolution, and lithological partitioning. Deformation experiments (e.g. Holtzman et al., 2003) demonstrate that shear stress causes initially homogeneously distributed melt to segregate into an array of melt-rich bands, flanked by melt-depleted regions. At the same average melt fraction, the permeability of high melt fraction conduits could be orders of magnitude higher than that of their homogenous counterparts. However, it is difficult to determine the permeability of melt-rich bands. Using X-ray synchrotron microtomography, we obtained high-resolution images of 3-dimensional (3-D) melt distribution in a partially molten rock containing shear-induced high melt fraction conduits. Sample CQ0705, an olivine-alkali basalt aggregate with a nominal melt fraction of 4%, was deformed in torsion at a temperature of 1473 K and a confining pressure of 300 MPa to a shear strain of 13.3. A sub-volume of CQ0705 encompassing 3-4 melt-rich bands was imaged. Microtomography data were reduced to binary form so that solid olivine is distinguishable from basalt glass. At a spatial resolution of 160 nm, the 3-D images reveal the shape and connectedness of melt pockets in the melt-rich bands. Thin melt channels formed at grain edges are connected at large melt nodes at grain corners. Initial data analysis shows a clear preferred orientation of melt pockets alignment subparallel to the melt-rich band. We use the experimentally determined geometrical parameters of melt topology to create a digital rock with identical 3-D microstructures. Stokes flow simulations are conducted on the digital rock to obtain the permeability tensor. Using this digital rock physics approach, we determine how deformation

Shaped articles of cross-linked fluorocarbon polymers

International Nuclear Information System (INIS)

Gotcher, A.J.; Germeraad, P.B.

1981-01-01

A process is described which comprises (1) contacting (a) a shaped article of a polymeric composition wherein the polymer is a fluorocarbon polymer having a melting point of at least 200 0 C, the article having a tensile strength of at least 3,000 psi, with (b) a fluid composition comprising a cross-linking agent, until the article contains at least 2.5% by weight of the cross-linking agent; and (2) irradiating the shaped article with ionising radiation to a dosage not exceeding 50 Mrads under conditions such that the composition is cross-linked sufficiently to impart thereto an M 100 value of at least 300 psi, while maintaining a tensile strength of at least 3000 psi, the shaped article containing a specified proportion of the cross-linking agent. (author)

A combined experimental and theoretical approach to establish the relationship between shear force and clay platelet delamination in melt-processed polypropylene nanocomposites

CSIR Research Space (South Africa)

Bandyopadhyay, J

2014-04-01

Full Text Available In this article, a combined experimental and theoretical approach has been proposed to establish a relationship between the required shear force and the degree of delamination of clay tactoids during the melt-processing of polymer nanocomposites...

Radiation application for synthesis of advanced materials and the related research on polymers

International Nuclear Information System (INIS)

Seguchi, T.

1996-01-01

The irradiation effects of polymers was studied in the wide temperature range from very low temperature to high temperature under vacuum or oxygen free atmosphere.The chemical reactions for polymers showed a rather large difference depending on irradiation temperature in quality and/or quantity. The dependence is though to be the difference in molecular motion of polymers during irradiation. The clear difference on irradiation temperature was observed for polytetrafluoroethylene(PTFE) and polystyrene(PS). For other polymers, the irradiation temperature effects are observed, which may be expanding to develop new products. The newly developed technology in radiation application is the curing of polymer fiber as ceramic fiber precursor. The silicon carbide(SiC) fiber is synthesized from silicon containing polymer of polycarbosilane(PCS) fiber by the pyrolysis at high temperature of 1200 deg or more. As the melting temperature of PCS is about 230 deg, the fiber must be cured to not melt down during the pyrolysis. The purpose of this work was the radiation crosslinking of PCS fiber without oxygen contamination. The basic research was carried out using gamma-rays irradiation under vacuum, where the fundamental data were obtained such as the yield of active sites and the reactivity with oxygen and the decomposed gases. The SiC fiber obtained from the radiation cured PCS fiber has a high tensile strength of 3GPa and high heat-resistance up to 1700 deg. The heat resistance of SiC fiber obtained from ordinary processing is about 1200 deg. This technology was transferred to a company and the product is supplied to the market. The silicon nitride(Si 3 N 4 ) fibre was also synthesized from radiation cured PCS fiber by the pyrolysis in ammonia gas atmosphere

Mechanical Properties of a Library of Low-Band-Gap Polymers

DEFF Research Database (Denmark)

Roth, Bérenger; Savagatrup, Suchol; de los Santos, Nathaniel V.

2016-01-01

The mechanical properties of low-band-gap polymers are important for the long-term survivability of roll to-roll processed organic electronic devices. Such devices, e.g., solar cells, displays, and thin-film transistors, must survive the rigors of roll-to-roll coating and also thermal...... of low-band-gap polymers to better understand the connection between molecular structures and mechanical properties in order to design conjugated polymers that permit mechanical robustness and even extreme deformability. While one of the principal conclusions of these experiments is that the structure...... of an isolated molecule only partially determines the mechanical properties another important codeterminant is the packing structure some general trends can be identified. (1) Fused rings tend to increase the modulus and decrease the ductility. (2) Branched side chains have the opposite effect. Despite...

From polymers to quantum gravity: Triple-scaling in rectangular random matrix models

International Nuclear Information System (INIS)

Myers, R.C.; Periwal, V.

1993-01-01

Rectangular NxM matrix models can be solved in several qualitatively distinct large-N limits, since two independent parameters govern the size of the matrix. Regarded as models of random surfaces, these matrix models interpolate between branched polymer behaviour and two-dimensional quantum gravity. We solve such models in a 'triple-scaling' regime in this paper, with N and M becoming large independently. A correspondence between phase transitions and singularities of mappings from R 2 to R 2 is indicated. At different critical points, the scaling behaviour is determined by (i) two decoupled ordinary differential equations; (ii) an ordinary differential equation and a finite-difference equation; or (iii) two coupled partial differential equations. The Painleve II equation arises (in conjunction with a difference equation) at a point associated with branched polymers. For critical points described by partial differential equations, there are dual weak-coupling/strong-coupling expansions. It is conjectured that the new physics is related to microscopic topology fluctuations. (orig.)

Entropy-induced separation of star polymers in porous media

International Nuclear Information System (INIS)

Blavats'ka, V.; Ferber, C. von; Holovatch, Yu.

2006-01-01

We present a quantitative picture of the separation of star polymers in a solution where part of the volume is influenced by a porous medium. To this end, we study the impact of long-range-correlated quenched disorder on the entropy and scaling properties of f-arm star polymers in a good solvent. We assume that the disorder is correlated on the polymer length scale with a power-law decay of the pair correlation function g(r)∼r -a . Applying the field-theoretical renormalization group approach we show in a double expansion in ε=4-d and δ=4-a that there is a range of correlation strengths δ for which the disorder changes the scaling behavior of star polymers. In a second approach we calculate for fixed space dimension d=3 and different values of the correlation parameter a the corresponding scaling exponents γ f that govern entropic effects. We find that γ f -1, the deviation of γ f from its mean field value is amplified by the disorder once we increase δ beyond a threshold. The consequences for a solution of diluted chain and star polymers of equal molecular weight inside a porous medium are that star polymers exert a higher osmotic pressure than chain polymers and in general higher branched star polymers are expelled more strongly from the correlated porous medium. Surprisingly, polymer chains will prefer a stronger correlated medium to a less or uncorrelated medium of the same density while the opposite is the case for star polymers

Effects of Melt Processing on Evolution of Structure in PEEK

Science.gov (United States)

Georgiev, Georgi; Dai, Patrick Shuanghua; Oyebode, Elizabeth; Cebe, Peggy; Capel, Malcolm

1999-01-01

We report on the effects of melt processing temperature on structure formation in Poly(ether-ether-ketone), PEEK. Real time Small Angle X-ray Scattering, SAXS, and thermal analysis are used to follow the melting behavior after various stages of processing. Assignment of peaks to structural entities within the material, the relative perfection of the crystals, and the possibility of their reorganization, are all influenced by the melt processing history. With the advent of high intensity synchrotron sources of X-radiation, polymer scientists gain a research tool which, when used along with thermal analysis, provides additional structural information about the crystals during growth and subsequent melting. PEEK is an engineering thermoplastic polymer with a very high glass transition temperature (145 C) and crystal melting point (337 C). PEEK has been the subject of recent studies by X-ray scattering in which melt and cold crystallization were followed in real-time. X-ray scattering and thermal studies have been used to address the formation of dual endothermic response which has been variously ascribed to lamellar insertion, dual crystal populations, or melting followed by re-crystallization. Another important issue is whether all of the amorphous phase is located in interlamellar regions, or alternatively whether some is located in "pockets" away from the crystalline lamellar stacks. The interpretation of scattering from lamellar stacks varies depending upon whether such amorphous pockets are formed. Some groups believe all of the amorphous phase is interlamellar. This leads to selection of a smaller thickness for the crystals. Other groups suggest that most amorphous phase is not interlamellar, and this leads to the suggestion that the crystal thickness is larger than the amorphous layer within the stacks. To investigate these ideas, we used SAXS and Differential Scanning Calorimetry to compare results of single and dual stage melt crystallization of PEEK using a

The Research on Polymer Microcapsulation for Cell Technology

Institute of Scientific and Technical Information of China (English)

ZHANG Zhi-bin; LI Min; SONG Hong; FANG Yi; HUA Hui; CHEN Li-guo; ZHOU Wei; WANG Zheng-rong

2004-01-01

Microcapsulation is a technology that enwrapped the solid or liquid or some gas matter with membrane materials to form microparticles(i.e.microcapsules). The materials of microcapsule is composed of naturnal polymers or modified naturnal polymers or synthesized polymers. The water-soluble core matter can only use oil-soluble wall materials, and vice versa.Synthesized methods of polymer microcapsulesSynthesized methods with monomers as raw materialsThis kind of methods include suspension polymerization, emulsion polymerization, dispersal polymerization, precipitation polymerization,suspension condensation polymerization, dispersal condensation polymerization, deposition condensation polymerization, interface condensation polymerization, and so on.Synthesized methods with polymers as raw materialsThese methods are suspension cross-linked polymerization, coacervation phase separation,extraction with solvent evaporation, polymer deposition, polymer chelation, polymer gel,solidification of melting polymer, tray-painted ways, fluidized bed ways, and so forth.Polymer materials to synthesize microcapsules2.1. Naturnal polymer materialsThe characteristics of this kind of materials are easy to form membrane, good stability and no toxicity. The polymer materials include lipids(liposome), amyloses, proteins, plant gels, waxes, etc.2.2. Modified polymer materialsThe characteristics of these materials are little toxicity, high viscidity(viscosity), soluble salt materials. But they cannot be used in water, acidic environment and high temperature environment for a long time. The materials include all kind of derivants of celluloses.2.3. Synthesized polymer materialsThe characteristics of the materials are easy to form membrane, good stability and adjustment of membrane properties. The synthesized polymer materials include degradable polymers(PLA, PGA,PLGA, PCL, PHB, PHV, PHA, PEG, PPG and the like) and indegradable polymers(PA, PMMA,PAM, PS, PVC, PB, PE, PU, PUA, PVA and otherwise

Engineering Polymer Blends for Impact Damage Mitigation

Science.gov (United States)

Gordon, Keith L.; Smith, Russell W.; Working, Dennis C.; Siochi, Emilie J.

2016-01-01

Structures containing polymers such as DuPont's Surlyn® 8940, demonstrate puncture healing when impacted by a 9 millimeter projectile traveling from speeds near 300 meters per second (1,100 feet per second) to hypervelocity impacts in the micrometeoroid velocity range of 5 kilometers per second (16,000 feet per second). Surlyn® 8940 puncture heals over a temperature range of minus 30 degrees Centigrade to plus 70 degrees Centigrade and shows potential for use in pressurized vessels subject to impact damage. However, such polymers are difficult to process and limited in applicability due to their low thermal stability, poor chemical resistance and overall poor mechanical properties. In this work, several puncture healing engineered melt formulations were developed. Moldings of melt blend formulations were impacted with a 5.56 millimeter projectile with a nominal velocity of 945 meters per second (3,100 feet per second) at about 25 degrees Centigrade, 50 degrees Centigrade and 100 degrees Centigrade, depending upon the specific blend being investigated. Self-healing tendencies were determined using surface vacuum pressure tests and tensile tests after penetration using tensile dog-bone specimens (ASTM D 638-10). For the characterization of tensile properties both pristine and impacted specimens were tested to obtain tensile modulus, yield stress and tensile strength, where possible. Experimental results demonstrate a range of new puncture healing blends which mitigate damage in the ballistic velocity regime.

Branches of the Facial Artery.

Science.gov (United States)

Hwang, Kun; Lee, Geun In; Park, Hye Jin

2015-06-01

The aim of this study is to review the name of the branches, to review the classification of the branching pattern, and to clarify a presence percentage of each branch of the facial artery, systematically. In a PubMed search, the search terms "facial," AND "artery," AND "classification OR variant OR pattern" were used. The IBM SPSS Statistics 20 system was used for statistical analysis. Among the 500 titles, 18 articles were selected and reviewed systematically. Most of the articles focused on "classification" according to the "terminal branch." Several authors classified the facial artery according to their terminal branches. Most of them, however, did not describe the definition of "terminal branch." There were confusions within the classifications. When the inferior labial artery was absent, 3 different types were used. The "alar branch" or "nasal branch" was used instead of the "lateral nasal branch." The angular branch was used to refer to several different branches. The presence as a percentage of each branch according to the branches in Gray's Anatomy (premasseteric, inferior labial, superior labial, lateral nasal, and angular) varied. No branch was used with 100% consistency. The superior labial branch was most frequently cited (95.7%, 382 arteries in 399 hemifaces). The angular branch (53.9%, 219 arteries in 406 hemifaces) and the premasseteric branch were least frequently cited (53.8%, 43 arteries in 80 hemifaces). There were significant differences among each of the 5 branches (P < 0.05) except between the angular branch and the premasseteric branch and between the superior labial branch and the inferior labial branch. The authors believe identifying the presence percentage of each branch will be helpful for surgical procedures.

Distortion of chain conformation and reduced entanglement in polymer-graphene oxide nanocomposites

Science.gov (United States)

Weir, Michael; Boothroyd, Stephen; Johnson, David; Thompson, Richard; Coleman, Karl; Clarke, Nigel

Graphene and related two-dimensional materials are excellent candidates as filler materials in polymer nanocomposites due to their extraordinary physical properties and high aspect ratio. To explore the mechanism by which the filler affects the bulk properties of these unique systems, and to build understanding from the macromolecular level upwards, we use a combination of small-angle neutron scattering (SANS) and oscillatory rheology. Where a good dispersion is achieved in poly(methyl methacrylate)-graphene oxide (PMMA-GO) nanocomposites, we observe a reduction in the polymer radius of gyration with increasing GO concentration that is consistent with the predicted behavior of polymer melt chains at a solid interface. We use concepts from thin-film polymer physics to formulate a scaling relation for the reduction in entanglements caused by the GO interfaces. Using these scaling arguments, we utilize SANS results to directly estimate the changes to the elastic plateau modulus of the network of entangled polymer chains, and find a correlation with the measured bulk rheology. We present a direct link between interfacial confinement effects and the bulk polymer nanocomposite properties, whilst demonstrating a model system for measuring thin film polymer physics in the bulk.

Study of optical properties of Erbium doped Tellurite glass-polymer composite

Energy Technology Data Exchange (ETDEWEB)

Sushama, D., E-mail: sushasukumar@gmail.com [Research Awardee, LAMP, Dept. of Physics, Nit, Calicut, India and Dept. of Physics, M.S.M. College, Kayamkulam, Kerala (India)

2014-10-15

Chalcogenide glasses have wide applications in optical device technology. But it has some disadvantages like thermal instability. Among them Tellurite glasses exhibits high thermal Stability. Doping of rare earth elements into the Tellurite glasses improve its optical properties. To improve its mechanical properties composites of this Tellurite glasses with polymer are prepared. Bulk samples of Er{sub 2}O{sub 3} doped TeO{sub 2}‐WO{sub 3}‐La{sub 2}O{sub 3} Tellurite glasses are prepared from high purity oxide mixtures, melting in an alumina crucible in air atmosphere. Composites of this Tellurite glasses with polymer are prepared by powder mixing method and the thin films of these composites are prepared using polymer press. Variations in band gap of these composites are studied from the UV/Vis/NIR absorption.

Study of optical properties of Erbium doped Tellurite glass-polymer composite

International Nuclear Information System (INIS)

Sushama, D.

2014-01-01

Chalcogenide glasses have wide applications in optical device technology. But it has some disadvantages like thermal instability. Among them Tellurite glasses exhibits high thermal Stability. Doping of rare earth elements into the Tellurite glasses improve its optical properties. To improve its mechanical properties composites of this Tellurite glasses with polymer are prepared. Bulk samples of Er 2 O 3 doped TeO 2 ‐WO 3 ‐La 2 O 3 Tellurite glasses are prepared from high purity oxide mixtures, melting in an alumina crucible in air atmosphere. Composites of this Tellurite glasses with polymer are prepared by powder mixing method and the thin films of these composites are prepared using polymer press. Variations in band gap of these composites are studied from the UV/Vis/NIR absorption

A novel approach in preparing polymer/nano-CaCO3 composites

Institute of Scientific and Technical Information of China (English)

Zhengying LIU; Runze YU; Mingbo YANG; Jianmin FENG; Wei YANG; Bo YIN

2008-01-01

An novel compounding process using nano-CaCO3 aqueous suspension for preparing polymer/ nano-CaCO3 composites with nanoparticles dispersed at the nanoscale is reported. The process is called the mild mixing method. In this method, the pre-dispersed nano-particle suspensions are blended with melting polymers in a weak shearing field using an extruder, followed by removing the water from the vent. The four typical poly-meric nanocomposites were prepared by mild mixing method. The dispersion of nano-CaCO3 in the matrix of the polymer at the nanoscale was confirmed by scanning electron microscopy (SEM). The molecular weights of polycarbonate (PC) and its nanocomposite showed that the degradation had not occurred during the mild mixing processing. The mechanical properties of the composite with 1.5 wt-% nano-CaCO3 improve slightly. It proved that this approach is suitable for the preparation of nano-composites based on both polar and non-polar polymers.

50th Anniversary Perspective: Polymers with Complex Architectures

KAUST Repository

Polymeropoulos, George

2017-02-09

The scope of this Perspective is to highlight innovative contributions in the synthesis of well-defined complex macromolecular architectures and to emphasize the importance of these materials to polymer physical chemistry, physics, theory, and applications. In addition, this Perspective tries to enlighten the past and show possible pathways for the future. Among the plethora of polymerization methods, we briefly report the impact of the truly living and controlled/living polymerization techniques focusing mainly on anionic polymerization, the mother of all living and controlled/living polymerizations. Through anionic polymerization well-defined model polymers with complex macromolecular architectures having the highest molecular weight, structural and compositional homogeneity can be achieved. The synthesized structures include star, comb/graft, cyclic, branched and hyberbranched, dendritic, and multiblock multicomponent polymers. In our opinion, in addition to the work needed on the synthesis, properties, and application of copolymers with more than three chemically different blocks and complex architecture, the polymer chemists in the future should follow closer the approaches Nature, the perfect chemist, uses to make functional complex macromolecular structures by noncovalent chemistry. Moreover, development of new analytical methods for the characterization/purification of polymers with complex macromolecular architectures is essential for the synthesis and properties study of this family of polymeric materials.

Modification of polymer blends by irradiation

International Nuclear Information System (INIS)

Zuchowska, D.; Zagorski, Z.P.

1999-01-01

Modification of polymers, especially of polyolefin-elastomer blends (e. g. ethylene/propylene/diene terpolymer, ethylene propylene copolymer, ethylene/vinyl acetate copolymer etc.), by irradiation with a beam of fast electrons is discussed. Irradiation of polymer blends usually results in enhanced interactions between the constituents, caused among other things, by grafting induced at the polymer interphase. As a result, mechanical properties are affected to an extent depending on the proportion and type of constituent polymers, stabilizer content and radiation dose. Breaking strength (σ) relative elongation at break (ε) and melt flow rate (MFR), were examined for a triblock styrene/butadiene/styrene (SBS) copolymer, polypropylene (PP), and a PP-SBS blend (50:50 by wt.). In PP, the content of the crystal phase was determined. Irradiation was found to make SBS crosslink, as a result, σ rose by 25% and ε remained unaffected. PP was found to become degraded upon irradiation (MFR rose as much as 16 times), thereby σ and ε decreased considerably. In pure PP, the content of the crystal phase was found to increase. The variations of σ and ε in the irradiated PP-SBS blend follow a tendency similar to that in the SBS copolymer examined. This fact suggests the SBS copolymer to have a decisive effect on the macroscopic properties of the PP-SBS blend. (author)

In-situ observation of structure formation in polymer processing

International Nuclear Information System (INIS)

Murase, Hiroki

2009-01-01

In-situ X-ray scattering in polymer processing is a crucial method to elucidate the mechanism of structure formation in the process. Fiber spinning is one such process primarily imposing extensional deformation on polymeric melt at the spin-line during rapid cooling. In-situ small-angle X-ray scattering using synchrotron radiation on the spinning process allows direct observation of the transient structure developing in the process. (author)

Radiation crosslinking of polymer materials

International Nuclear Information System (INIS)

Yoshii, Fumio

2004-01-01

It was found that some polyfunctional monomers (PFM) like triallyl isocyanurate (TAIC) and trimethallyl isocyanurate (TMAIC) when incorporated at low concentrations, are effective for promotion of crosslinking of biodegradable polymers such as polycaprolactone (PCL), poly(butylene succinate-co-adipate) (PBS) and poly(lactic acid) (PLA). PFM are kneaded with biodegradable polymers at molten condition before irradiation. Radiation crosslinking of PBS and PCL with 1% TAIC gave gel fractions of 80% at 20 kGy. This crosslinking is effective to improve deformation of biodegradable polymers at high temperature. The irradiated materials retained their biodegradability even after crosslinking when subjected to soil burial test. Irradiation at molten state (melting temperature, 340degC) led to crosslinking structures for polytetrafluoroethylene (PTFE). Crosslinked PTFE forms transparent films with high abrasion property and high radiation resistance. High-density polyethylene (HDPE) has a higher gel fraction in irradiation at molten state than irradiation at ordinary temperature. Crosslinked HDPE has been applied as knee joints in order to have high abrasion. Radiation crosslinked polycarbosilane (PCS) fiber gives high heat resistant silicon carbide (SiC) after firing. EB irradiation of PCS is effective to improve strength of product and to inhibit flow during carbonization. SiC, being resistant to high temperature will be applied in turbine and body of rockets. (author)

Thermal and dynamic mechanical characterization of thermoplastic polyurethane/organoclay nanocomposites prepared by melt compounding

International Nuclear Information System (INIS)

Barick, A.K.; Tripathy, D.K.

2010-01-01

Thermoplastic polyurethane (TPU) nanocomposites based on organically modified layered silicate (OMLS) were prepared by melt intercalation process followed by compression molding. Different percentage of organoclays was incorporated into the TPU matrix in order to examine the influence of the nanoscaled fillers on nanostructure morphology and material properties. The microscopic morphology of the nanocomposites was evaluated by wide angle X-ray diffraction (WAXD), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The observation revealed that both nanoclay-polymer interactions and shear stress developed during melt mixing are responsible for the effectively organoclay dispersion in TPU matrix resulting intercalated/exfoliated morphology. Thermal stability of the nanocomposites measured by thermogravimetric analysis (TGA) was improved significantly with the addition of nanoclay. The differential scanning calorimetry (DSC) analysis reveals that melting point of the nanocomposites increased with incorporation of nanoclay. The dynamic mechanical properties of the TPU nanocomposites were analyzed using a dynamic mechanical thermal analyzer (DMTA), which indicates that the storage modulus (E'), loss modulus (E''), and glass transition temperature (T g ) are significantly increased with increasing nanoclay content.

Disentanglement Effects on the Welding Behaviour of Polymer Melts during the Fused-Filament-Fabrication Method for Additive Manufacturing

OpenAIRE

McIlroy, Claire; Olmsted, Peter

2017-01-01

Although 3D printing has the potential to transform manufacturing processes, the strength of printed parts often does not rival that of traditionally-manufactured parts. The fused-filament fabrication method involves melting a thermoplastic, followed by layer-by-layer extrusion of the molten viscoelastic material to fabricate a three-dimensional object. The strength of the welds between layers is controlled by interdiffusion and entanglement of the melt across the interface. However, diffusio...

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)

Crosslinked polybenzimidazoles containing branching structure as membrane materials with excellent cell performance and durability for fuel cell applications

Science.gov (United States)

Hu, Meishao; Ni, Jiangpeng; Zhang, Boping; Neelakandan, Sivasubramaniyan; Wang, Lei

2018-06-01

Crosslinking is an effective method to improve the properties of high temperature proton exchange membranes based on polybenzimidazole. However, the compact structure of crosslinked polybenzimidazole hinders the phosphoric acid absorption of the membranes, resulting in a relatively poor fuel cell performance. Recently, we find that branched polymers can absorb more phosphoric acid with a larger free volume, but suffer from deteriorated mechanical strength. In this work, a new method is proposed to obtain excellent over-all properties of high temperature proton exchange membranes. A series of crosslinked polybenzimidazoles containing branching structure as membrane materials are successfully prepared for the first time. Compared with conventional crosslinked membranes, these crosslinked polybenzimidazole membranes containing branching structure exhibit a higher phosphoric acid doping level and proton conductivity, improved durability, lower swelling rate and comparable mechanical strength. In particular, the fuel cell base on the crosslinked and branched membrane with a 10% ratio of crosslinker in non-humidified hydrogen/air at 160 °C achieves a power density of 404 mW cm-2. The results indicate that the combination of crosslinking and branching is an effective approach to improve the properties of polybenzimidazole membrane materials.

Computational Design of Molecularly Imprinted Polymers

Science.gov (United States)

Subrahmanyam, Sreenath; Piletsky, Sergey A.

Artificial receptors have been in use for several decades as sensor elements, in affinity separation, and as models for investigation of molecular recognition. Although there have been numerous publications on the use of molecular modeling in characterization of their affinity and selectivity, very few attempts have been made on the application of molecular modeling in computational design of synthetic receptors. This chapter discusses recent successes in the use of computational design for the development of one particular branch of synthetic receptors - molecularly imprinted polymers.

Evaluation of Melt Behavior with initial Melt Velocity under SFR Severe Accidents

Energy Technology Data Exchange (ETDEWEB)

Heo, Hyo; Bang, In Cheol [UNIST, Ulsan (Korea, Republic of); Jerng, Dong Wook [Chung-Ang Univ, Seoul (Korea, Republic of)

2015-10-15

In the current Korean sodium-cooled fast reactor (SFR) program, early dispersion of the molten metallic fuel within a subchannel is suggested as one of the inherent safety strategies for the initiating phase of hypothetical core disruptive accident (HCDA). The safety strategy provides negative reactivity driven by the melt dispersal, so it could reduce the possibility of the recriticality event under a severe triple or more fault scenario for SFR. Since the behavior of the melt dispersion is unpredictable, it depends on the accident condition, particularly core region. While the voided coolant channel region is usually developed in the inner core, the unvoided coolant channel region is formed in the outer core. It is important to confirm the fuel dispersion with the core region, but there are not sufficient existing studies for them. From the existing studies, the coolant vapor pressure is considered as one of driving force to move the melt towards outside of the core. There is a complexity of the phenomena during intermixing of the melt with the coolant after the horizontal melt injections. It is too difficult to understand the several combined mechanisms related to the melt dispersion and the fragmentation. Thus, it could be worthwhile to study the horizontal melt injections at lower temperature as a preliminary study in order to identify the melt dispersion phenomena. For this reason, it is required to clarify whether the coolant vapor pressure is the driving force of the melt dispersion with the core region. The specific conditions to be well dispersed for the molten metallic fuel were discussed in the experiments with the simulant materials. The each melt behavior was compared to evaluate the melt dispersion under the coolant void condition and the boiling condition. As the results, the following results are remarked: 1. The upward melt dispersion did not occur for a given melt and coolant temperature in the nonboiling range. Over current range of conditions

Evaluation of Melt Behavior with initial Melt Velocity under SFR Severe Accidents

International Nuclear Information System (INIS)

Heo, Hyo; Bang, In Cheol; Jerng, Dong Wook

2015-01-01

In the current Korean sodium-cooled fast reactor (SFR) program, early dispersion of the molten metallic fuel within a subchannel is suggested as one of the inherent safety strategies for the initiating phase of hypothetical core disruptive accident (HCDA). The safety strategy provides negative reactivity driven by the melt dispersal, so it could reduce the possibility of the recriticality event under a severe triple or more fault scenario for SFR. Since the behavior of the melt dispersion is unpredictable, it depends on the accident condition, particularly core region. While the voided coolant channel region is usually developed in the inner core, the unvoided coolant channel region is formed in the outer core. It is important to confirm the fuel dispersion with the core region, but there are not sufficient existing studies for them. From the existing studies, the coolant vapor pressure is considered as one of driving force to move the melt towards outside of the core. There is a complexity of the phenomena during intermixing of the melt with the coolant after the horizontal melt injections. It is too difficult to understand the several combined mechanisms related to the melt dispersion and the fragmentation. Thus, it could be worthwhile to study the horizontal melt injections at lower temperature as a preliminary study in order to identify the melt dispersion phenomena. For this reason, it is required to clarify whether the coolant vapor pressure is the driving force of the melt dispersion with the core region. The specific conditions to be well dispersed for the molten metallic fuel were discussed in the experiments with the simulant materials. The each melt behavior was compared to evaluate the melt dispersion under the coolant void condition and the boiling condition. As the results, the following results are remarked: 1. The upward melt dispersion did not occur for a given melt and coolant temperature in the nonboiling range. Over current range of conditions

Branched polynomial covering maps

DEFF Research Database (Denmark)

Hansen, Vagn Lundsgaard

2002-01-01

A Weierstrass polynomial with multiple roots in certain points leads to a branched covering map. With this as the guiding example, we formally define and study the notion of a branched polynomial covering map. We shall prove that many finite covering maps are polynomial outside a discrete branch ...... set. Particular studies are made of branched polynomial covering maps arising from Riemann surfaces and from knots in the 3-sphere. (C) 2001 Elsevier Science B.V. All rights reserved.......A Weierstrass polynomial with multiple roots in certain points leads to a branched covering map. With this as the guiding example, we formally define and study the notion of a branched polynomial covering map. We shall prove that many finite covering maps are polynomial outside a discrete branch...

Single-molecule imaging reveals topological isomer-dependent diffusion by 4-armed star and dicyclic 8-shaped polymers

KAUST Repository

Habuchi, Satoshi; Fujiwara, Susumu; Yamamoto, Takuya; Tezuka, Yasuyuki

2015-01-01

Diffusion dynamics of topological isomers of polymer molecules was investigated at the single-molecule level in a melt state by employing the fluorophore-incorporated 4-armed star and the corresponding doubly-cyclized, 8-shaped poly(THF) chains

Determination of Quantum Chemistry Based Force Fields for Molecular Dynamics Simulations of Aromatic Polymers

Science.gov (United States)

Jaffe, Richard; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

Ab initio quantum chemistry calculations for model molecules can be used to parameterize force fields for molecular dynamics simulations of polymers. Emphasis in our research group is on using quantum chemistry-based force fields for molecular dynamics simulations of organic polymers in the melt and glassy states, but the methodology is applicable to simulations of small molecules, multicomponent systems and solutions. Special attention is paid to deriving reliable descriptions of the non-bonded and electrostatic interactions. Several procedures have been developed for deriving and calibrating these parameters. Our force fields for aromatic polyimide simulations will be described. In this application, the intermolecular interactions are the critical factor in determining many properties of the polymer (including its color).

Blended polymer materials extractable with supercritical carbon dioxide

Science.gov (United States)

Cai, Mei

, physical, thermal, and phase behavior of the blended polymers studied in this dissertation includes solubility in SCF CO2, the melt viscosity, the melting temperature depression, and phase equilibrium under SCF conditions. Several hypotheses are investigated to determine which mechanism plays the major role in the extraction. Finally a novel metal casting process is discussed with the materials developed in this study. This new method utilizes an adhesive or binder film composition for the purpose of building up a casting pattern of resin-bonded aggregate particles. The pattern is then encased in a conventional rigid shell mold that is not susceptible to degradation by SCF CO2. The pattern is then disintegrated within an unaffected mold by exposure to SCF CO 2. This is an efficient and low cost method of making patterns and molds, especially for the casting of a relatively low number of parts such as in prototype evaluations.

Microscopic theory for dynamics in entangled polymer nanocomposites

Science.gov (United States)

Yamamoto, Umi

New microscopic theories for describing dynamics in polymer nanocomposites are developed and applied. The problem is addressed from two distinct perspectives and using two different theoretical approaches. The first half of this dissertation studies the long-time and intermediate-time dynamics of nanoparticles in entangled and unentangled polymer melts for dilute particle concentrations. Using a combination of mode-coupling, Brownian motion, and polymer physics ideas, the nanoparticle long-time diffusion coefficients is formulated in terms of multiple length-scales, packing microstructures, and spatially-resolved polymer density fluctuation dynamics. The key motional mechanism is described via the parallel relaxation of the force exerted on the particle controlled by collective polymer constraint-release and the particle self-motion. A sharp but smooth crossover from the hydrodynamic to the non-hydrodynamic regime is predicted based on the Stokes-Einstein violation ratio as a function of all the system variables. Quantitative predictions are made for the recovery of the Stokes-Einstein law, and the diffusivity in the crossover regime agrees surprisingly well with large-scale molecular dynamics simulations for all particle sizes and chain lengths studied. The approach is also extended to address intermediate-time anomalous transport of a single nanoparticle and two-particle relative diffusion. The second half of this dissertation focuses on developing a novel dynamical theory for a liquid of infinitely-thin rods in the presence of hard spherical obstacles, aiming at a technical and conceptual extension of the existing paradigm for entangled polymer dynamics. As a fundamental theoretical development, the two-component generalization of a first-principles dynamic meanfield approach is presented. The theory enforces inter-needle topological uncrossability and needlesphere impenetrability in a unified manner, leading to a generalized theory of entanglements that

Exploring the applications of fractional calculus: Hierarchically built semiflexible polymers

International Nuclear Information System (INIS)

Fürstenberg, Florian; Dolgushev, Maxim; Blumen, Alexander

2015-01-01

In this article we study, through extensions of the generalized Gaussian scheme, the dynamics of semiflexible treelike polymers under the influence of external forces acting on particular (say, charged) monomers. Semiflexibility is introduced following our previous work (Dolgushev and Blumen, 2009 [15]), a procedure which allows one to study treelike structures with arbitrary stiffness and branching. Exemplarily, we illustrate the procedure using linear chains and hyperbranched polymers modeled through Vicsek fractals, and obtain in every case the monomer displacement averaged over the structure. Anomalous behavior manifests itself in the intermediate time region, where the different fractal architectures show distinct scaling behaviors. These behaviors are due to the power law behavior of the spectral density and lead, for arbitrary pulling forces, based on causality and the linear superposition principle, to fractional calculus expressions, in accordance to former phenomenological fractional laws in polymer physics.

Dynamical behavior of a single polymer chain under nanometric confinement

Science.gov (United States)

Lagrené, K.; Zanotti, J.-M.; Daoud, M.; Farago, B.; Judeinstein, P.

2010-10-01

We address the dynamical behavior of a single polymer chain under nanometric confinement. We consider a polymer melt made of a mixture of hydrogenated and deuterated high molecular mass Poly(Ethylene Oxide) (PEO). The confining material is a membrane of Anodic Aluminum Oxide (AAO), a macroscopically highly ordered confining system made of parallel cylindrical channels. We use Neutron Spin-Echo (NSE) under the Zero Average Contrast (ZAC) condition to, all at once, i) match the intense porous AAO detrimental elastic SANS (Small Angle Neutron Scattering) contribution to the total intermediate scattering function I(Q,t) and ii) measure the Q dependence of the dynamical modes of a single chain under confinement. The polymer dynamics is probed on an extremely broad spacial ([2.2 10-2 Å-1, 0.2 Å-1]) and temporal ([0.1 ns, 600 ns]) ranges. We do not detect any influence of confinement on the polymer dynamics. This result is discussed in the framework of the debate on the existence of a "corset effect" recently suggested by NMR relaxometry data.

Rapakivi texture formation via disequilibrium melting in a contact partial melt zone, Antarctica

Science.gov (United States)

Currier, R. M.

2017-12-01

In the McMurdo Dry Valleys of Antarctica, a Jurassic aged dolerite sill induced partial melting of granite in the shallow crust. The melt zone can be traced in full, from high degrees of melting (>60%) along the dolerite contact, to no apparent signs of melting, 10s of meters above the contact. Within this melt zone, the well-known rapakivi texture is found, arrested in various stages of development. High above the contact, and at low degrees of melting, K-feldspar crystals are slightly rounded and unmantled. In the lower half of the melt zone, mantles of cellular textured plagioclase appear on K-feldspar, and thicken towards the contact heat source. At the highest degrees of melting, cellular-textured plagioclase completely replaces restitic K-feldspar. Because of the complete exposure and intact context, the leading models of rapakivi texture formation can be tested against this system. The previously proposed mechanisms of subisothermal decompression, magma-mixing, and hydrothermal exsolution all fail to adequately describe rapakivi generation in this melt zone. Preferred here is a closed system model that invokes the production of a heterogeneous, disequilibrium melt through rapid heating, followed by calcium and sodium rich melt reacting in a peritectic fashion with restitic K-feldspar crystals. This peritectic reaction results in the production of plagioclase of andesine-oligoclase composition—which is consistent with not just mantles in the melt zone, but globally as well. The thickness of the mantle is diffusion limited, and thus a measure of the diffusive length scale of sodium and calcium over the time scale of melting. Thermal modeling provides a time scale of melting that is consistent with the thickness of observed mantles. Lastly, the distribution of mantled feldspars is highly ordered in this melt zone, but if it were mobilized and homogenized—mixing together cellular plagioclase, mantled feldspars, and unmantled feldspars—the result would be

Side-chain tunability of furan-containing low-band-gap polymers provides control of structural order in efficient solar cells

KAUST Repository

Yiu, Alan T.; Beaujuge, Pierre; Lee, Olivia P.; Woo, Claire; Toney, Michael F.; Frechet, Jean

2012-01-01

The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells. © 2011 American Chemical Society.

Side-chain tunability of furan-containing low-band-gap polymers provides control of structural order in efficient solar cells

KAUST Repository

Yiu, Alan T.

2012-02-01

The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells. © 2011 American Chemical Society.

Biopolymers form a gelatinous microlayer at the air-sea interface when Arctic sea ice melts.

Science.gov (United States)

Galgani, Luisa; Piontek, Judith; Engel, Anja

2016-07-20

The interface layer between ocean and atmosphere is only a couple of micrometers thick but plays a critical role in climate relevant processes, including the air-sea exchange of gas and heat and the emission of primary organic aerosols (POA). Recent findings suggest that low-level cloud formation above the Arctic Ocean may be linked to organic polymers produced by marine microorganisms. Sea ice harbors high amounts of polymeric substances that are produced by cells growing within the sea-ice brine. Here, we report from a research cruise to the central Arctic Ocean in 2012. Our study shows that microbial polymers accumulate at the air-sea interface when the sea ice melts. Proteinaceous compounds represented the major fraction of polymers supporting the formation of a gelatinous interface microlayer and providing a hitherto unrecognized potential source of marine POA. Our study indicates a novel link between sea ice-ocean and atmosphere that may be sensitive to climate change.

Effect of oligonucleic acid (ONA) backbone features on assembly of ONA-star polymer conjugates: a coarse-grained molecular simulation study.

Science.gov (United States)

Condon, Joshua E; Jayaraman, Arthi

2017-10-04

Understanding the impact of incorporating new physical and chemical features in oligomeric DNA mimics, termed generally as "oligonucleic acids" (ONAs), on their structure and thermodynamics will be beneficial in designing novel materials for a variety of applications. In this work, we conduct coarse-grained molecular simulations of ONA-star polymer conjugates with varying ONA backbone flexibility, ONA backbone charge, and number of arms in the star polymer at a constant ONA strand volume fraction to elucidate the effect of these design parameters on the thermodynamics and assembly of multi-arm ONA-star polymer conjugates. We quantify the thermo-reversible behavior of the ONA-star polymer conjugates by quantifying the hybridization of the ONA strands in the system as a function of temperature (i.e. melting curve). Additionally, we characterize the assembly of the ONA-star polymer conjugates by tracking cluster formation and percolation as a function of temperature, as well as cluster size distribution at temperatures near the assembly transition region. The key results are as follows. The melting temperature (T m ) of the ONA strands decreases upon going from a neutral to a charged ONA backbone and upon increasing flexibility of the ONA backbone. Similar behavior is seen for the assembly transition temperature (T a ) with varying ONA backbone charge and flexibility. While the number of arms in the ONA-star polymer conjugate has a negligible effect on the ONA T m in these systems, as the number of ONA-star polymer arms increase, the assembly temperature T a increases and local ordering in the assembled state improves. By understanding how factors like ONA backbone charge, backbone flexibility, and ONA-star polymer conjugate architecture impact the behavior of ONA-star polymer conjugate systems, we can better inform how the selection of ONA chemistry will influence resulting ONA-star polymer assembly.

Melt-Flow Behaviours of Thermoplastic Materials under Fire Conditions: Recent Experimental Studies and Some Theoretical Approaches

Directory of Open Access Journals (Sweden)

Paul Joseph

2015-12-01

Full Text Available Polymeric materials often exhibit complex combustion behaviours encompassing several stages and involving solid phase, gas phase and interphase. A wide range of qualitative, semi-quantitative and quantitative testing techniques are currently available, both at the laboratory scale and for commercial purposes, for evaluating the decomposition and combustion behaviours of polymeric materials. They include, but are not limited to, techniques such as: thermo-gravimetric analysis (TGA, oxygen bomb calorimetry, limiting oxygen index measurements (LOI, Underwriters Laboratory 94 (UL-94 tests, cone calorimetry, etc. However, none of the above mentioned techniques are capable of quantitatively deciphering the underpinning physiochemical processes leading to the melt flow behaviour of thermoplastics. Melt-flow of polymeric materials can constitute a serious secondary hazard in fire scenarios, for example, if they are present as component parts of a ceiling in an enclosure. In recent years, more quantitative attempts to measure the mass loss and melt-drip behaviour of some commercially important chain- and step-growth polymers have been accomplished. The present article focuses, primarily, on the experimental and some theoretical aspects of melt-flow behaviours of thermoplastics under heat/fire conditions.

Melt-Flow Behaviours of Thermoplastic Materials under Fire Conditions: Recent Experimental Studies and Some Theoretical Approaches.

Science.gov (United States)

Joseph, Paul; Tretsiakova-McNally, Svetlana

2015-12-15