Properties of Shocked Polymers: Mbar experiments on Z and multi-scale simulations

NASA Astrophysics Data System (ADS)

Mattsson, Thomas R.

2010-03-01

Significant progress has been made over the last few years in understanding properties of matter subject to strong shocks and other extreme conditions. High-accuracy multi-Mbar experiments and first-principles theoretical studies together provide detailed insights into the physics and chemistry of high energy-density matter. While comprehensive advances have been made for pure elements like deuterium, helium, and carbon, progress has been slower for equally important, albeit more challenging, materials like molecular crystals, polymers, and foams. Hydrocarbon based polymer foams are common materials and in particular they are used in designing shock- and inertial confinement fusion experiments. Depending on their initial density, foams shock to relatively higher pressure and temperature compared to shocked dense polymers/plastics. As foams and polymers are shocked, they exhibit both structural and chemical transitions. We will present experimental and theoretical results for shocked polymers in the Mbar regime. By shock impact of magnetically launched flyer plates on poly(4-methyl-1-pentene) foams, we create multi-Mbar pressures in a dense plasma mixture of hydrogen, carbon, at temperatures of several eV. Concurrently with executing experiments, we analyze the system by multi-scale simulations, from density functional theory to continuum magneto-hydrodynamics simulations. In particular, density functional theory (DFT) molecular dynamics (MD) and classical MD simulations of the principal shock Hugoniot will be presented in detail for two hydrocarbon polymers: polyethylene (PE) and poly(4-methyl-1-pentene) (PMP).

Composite material and method of making

DOEpatents

Fryxell, Glen E.; Samuels, William D.; Simmons, Kevin L.

2004-04-20

The composite material and methods of making the present invention rely upon a fully dense monolayer of molecules attached to an oxygenated surface at one end, and an organic terminal group at the other end, which is in turn bonded to a polymer. Thus, the composite material is a second material chemically bonded to a polymer with fully dense monolayer there between.

Thermal Spray Formation of Polymer Coatings

NASA Technical Reports Server (NTRS)

Coquill, Scott; Galbraith, Stephen L.; Tuss. Darren L.; Ivosevic, Milan

2008-01-01

This innovation forms a sprayable polymer film using powdered precursor materials and an in-process heating method. This device directly applies a powdered polymer onto a substrate to form an adherent, mechanically-sound, and thickness-regulated film. The process can be used to lay down both fully dense and porous, e.g., foam, coatings. This system is field-deployable and includes power distribution, heater controls, polymer constituent material bins, flow controls, material transportation functions, and a thermal spray apparatus. The only thing required for operation in the field is a power source. Because this method does not require solvents, it does not release the toxic, volatile organic compounds of previous methods. Also, the sprayed polymer material is not degraded because this method does not use hot combustion gas or hot plasma gas. This keeps the polymer from becoming rough, porous, or poorly bonded.

A New Self-Consistent Field Model of Polymer/Nanoparticle Mixture

NASA Astrophysics Data System (ADS)

Chen, Kang; Li, Hui-Shu; Zhang, Bo-Kai; Li, Jian; Tian, Wen-De

2016-02-01

Field-theoretical method is efficient in predicting assembling structures of polymeric systems. However, it’s challenging to generalize this method to study the polymer/nanoparticle mixture due to its multi-scale nature. Here, we develop a new field-based model which unifies the nanoparticle description with the polymer field within the self-consistent field theory. Instead of being “ensemble-averaged” continuous distribution, the particle density in the final morphology can represent individual particles located at preferred positions. The discreteness of particle density allows our model to properly address the polymer-particle interface and the excluded-volume interaction. We use this model to study the simplest system of nanoparticles immersed in the dense homopolymer solution. The flexibility of tuning the interfacial details allows our model to capture the rich phenomena such as bridging aggregation and depletion attraction. Insights are obtained on the enthalpic and/or entropic origin of the structural variation due to the competition between depletion and interfacial interaction. This approach is readily extendable to the study of more complex polymer-based nanocomposites or biology-related systems, such as dendrimer/drug encapsulation and membrane/particle assembly.

Dense Vertically Aligned Copper Nanowire Composites as High Performance Thermal Interface Materials.

PubMed

Barako, Michael T; Isaacson, Scott G; Lian, Feifei; Pop, Eric; Dauskardt, Reinhold H; Goodson, Kenneth E; Tice, Jesse

2017-12-06

Thermal interface materials (TIMs) are essential for managing heat in modern electronics, and nanocomposite TIMs can offer critical improvements. Here, we demonstrate thermally conductive, mechanically compliant TIMs based on dense, vertically aligned copper nanowires (CuNWs) embedded into polymer matrices. We evaluate the thermal and mechanical characteristics of 20-25% dense CuNW arrays with and without polydimethylsiloxane infiltration. The thermal resistance achieved is below 5 mm 2 K W -1 , over an order of magnitude lower than commercial heat sink compounds. Nanoindentation reveals that the nonlinear deformation mechanics of this TIM are influenced by both the CuNW morphology and the polymer matrix. We also implement a flip-chip bonding protocol to directly attach CuNW composites to copper surfaces, as required in many thermal architectures. Thus, we demonstrate a rational design strategy for nanocomposite TIMs that simultaneously retain the high thermal conductivity of aligned CuNWs and the mechanical compliance of a polymer.

Polymer brushes infiltrated by nanoparticles and applications to the nuclear pore complex

NASA Astrophysics Data System (ADS)

Opferman, Michael G.

Systems of grafted polymers in the presence of additives are useful in a variety of contexts including industrial applications, solar cells, organic electronics, drug delivery, and nucleocytoplasmic transport. In this thesis, we will consider the morphologies that polymer brushes attain when exposed to a solution of additives (which we generically term "nanoparticles"), particularly when those nanparticles interact attractively with the polymers. We find that nanoparticles of this type can have a dramatic effect on the height of the polymer chains above the grafting surface, and they can induce highly non-uniform morphologies, including ones in which a dense layer of nanoparticles and monomers forms near the grafting surface. We consider especially the relevance of the system to several experiments performed on biopolymers in the nuclear pore complex when they interact attractively with transport factors that regulate nucleocytoplasmic transport. We find that, although these experiments appear to give inconsistent results, the inconsistencies can be reconciled through two simple models: the Alexander-de Gennes polymer brush, and the Milner-Witten-Cates polymer brush. Our findings should contribute to the understanding of the nuclear pore complex in that experiments can be better understood in the context of their relevant control parameters.

Stochastic entangled chain dynamics of dense polymer solutions.

PubMed

Kivotides, Demosthenes; Wilkin, S Louise; Theofanous, Theo G

2010-10-14

We propose an adjustable-parameter-free, entangled chain dynamics model of dense polymer solutions. The model includes the self-consistent dynamics of molecular chains and solvent by describing the former via coarse-grained polymer dynamics that incorporate hydrodynamic interaction effects, and the latter via the forced Stokes equation. Real chain elasticity is modeled via the inclusion of a Pincus regime in the polymer's force-extension curve. Excluded volume effects are taken into account via the combined action of coarse-grained intermolecular potentials and explicit geometric tracking of chain entanglements. We demonstrate that entanglements are responsible for a new (compared to phantom chain dynamics), slow relaxation mode whose characteristic time scale agrees very well with experiment. Similarly good agreement between theory and experiment is also obtained for the equilibrium chain size. We develop methods for the solution of the model in periodic flow domains and apply them to the computation of entangled polymer solutions in equilibrium. We show that the number of entanglements Π agrees well with the number of entanglements expected on the basis of tube theory, satisfactorily reproducing the latter's scaling of Π with the polymer volume fraction φ. Our model predicts diminishing chain size with concentration, thus vindicating Flory's suggestion of excluded volume effects screening in dense solutions. The predicted scaling of chain size with φ is consistent with the heuristic, Flory theory based value.

Effects of polymer-nanoparticle interactions on the viscosity of unentangled polymers under extreme nanoconfinement during capillary rise infiltration.

PubMed

Hor, Jyo Lyn; Wang, Haonan; Fakhraai, Zahra; Lee, Daeyeon

2018-03-28

We explore the effect of confinement and polymer-nanoparticle interactions on the viscosity of unentangled polymers undergoing capillary rise infiltration (CaRI) in dense packings of nanoparticles. In CaRI, a polymer is thermally induced to wick into the dense packings of nanoparticles, leading to the formation of polymer-infiltrated nanoparticle films, a new class of thin film nanocomposites with extremely high concentrations of nanoparticles. To understand the effect of this extreme nanoconfinement, as well as polymer-nanoparticle interactions on the polymer viscosity in CaRI films, we use two polymers that are known to have very different interactions with SiO2 nanoparticles. Using in situ spectroscopic ellipsometry, we monitor the polymer infiltration process, from which we infer the polymer viscosity based on the Lucas-Washburn model. Our results suggest that physical confinement increases the viscosity by approximately two orders of magnitude. Furthermore, confinement also increases the glass transition temperature of both polymers. Thus, under extreme nanoconfinement, the physical confinement has a more significant impact than the polymer-nanoparticle interactions on the viscosity of unentangled polymers, measured through infiltration dynamics, as well as the glass transition temperature. These findings will provide fundamental frameworks for designing processes to enable the fabrication of CaRI nanocomposite films with a wide range of nanoparticles and polymers.

Evolution of sequence-defined highly functionalized nucleic acid polymers

NASA Astrophysics Data System (ADS)

Chen, Zhen; Lichtor, Phillip A.; Berliner, Adrian P.; Chen, Jonathan C.; Liu, David R.

2018-03-01

The evolution of sequence-defined synthetic polymers made of building blocks beyond those compatible with polymerase enzymes or the ribosome has the potential to generate new classes of receptors, catalysts and materials. Here we describe a ligase-mediated DNA-templated polymerization and in vitro selection system to evolve highly functionalized nucleic acid polymers (HFNAPs) made from 32 building blocks that contain eight chemically diverse side chains on a DNA backbone. Through iterated cycles of polymer translation, selection and reverse translation, we discovered HFNAPs that bind proprotein convertase subtilisin/kexin type 9 (PCSK9) and interleukin-6, two protein targets implicated in human diseases. Mutation and reselection of an active PCSK9-binding polymer yielded evolved polymers with high affinity (KD = 3 nM). This evolved polymer potently inhibited the binding between PCSK9 and the low-density lipoprotein receptor. Structure-activity relationship studies revealed that specific side chains at defined positions in the polymers are required for binding to their respective targets. Our findings expand the chemical space of evolvable polymers to include densely functionalized nucleic acids with diverse, researcher-defined chemical repertoires.

Traveling salesman problem, conformal invariance, and dense polymers.

PubMed

Jacobsen, J L; Read, N; Saleur, H

2004-07-16

We propose that the statistics of the optimal tour in the planar random Euclidean traveling salesman problem is conformally invariant on large scales. This is exhibited in the power-law behavior of the probabilities for the tour to zigzag repeatedly between two regions, and in subleading corrections to the length of the tour. The universality class should be the same as for dense polymers and minimal spanning trees. The conjectures for the length of the tour on a cylinder are tested numerically.

Narrowband 1.5-{mu}m Bragg filter based on a polymer waveguide with a laser-written refractive-index grating

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

Sokolov, Viktor I; Panchenko, Vladislav Ya; Seminogov, V N

We report the fabrication of narrowband frequency-selective filters for the 1.5-{mu}m telecom window, which include a single-mode polymer waveguide with a submicron Bragg grating inscribed by a helium-cadmium laser. The filters have a reflectance R > 98 % and a nearly rectangular reflection band with a bandwidth {Delta}{lambda}{approx}0.4nm. They can be used as components of optical multiplexers/demultiplexers for combining and separating signals in high-speed dense wavelength-division multiplexed optical fibre communication systems. (laser components)

Mean-Field Models of Structure and Dispersion of Polymer-nanoparticle Mixtures

DTIC Science & Technology

2010-07-29

out of the seminal descriptions of the wetting and dewetting of polymer melts on polymer brushes advanced by Leibler and coworkers.118,119 Explicitly...using scaling ideas and strong segregation theory calculations they delineated the regions where the matrix polymer wets or dewets the brush. In the...Explicitly, when dewetting of the melt chains is expected ( dry brush). In other words, situations involving long matrix polymers and/or densely grafted

Pressure-induced amorphization of a dense coordination polymer and its impact on proton conductivity

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

Umeyama, Daiki; Hagi, Keisuke; Ogiwara, Naoki

2014-12-01

The proton conductivity of a dense coordination polymer (CP) was investigated under high-pressure conditions. Impedance measurements under high pressures revealed that the proton conductivity of the CP decreased more than 1000-fold at pressures of 3–7 GPa and that the activation energy for proton conduction almost doubled compared with that at ambient pressure. A synchrotron X-ray study under high pressure identified the amorphization process of the CP during compression, which rationally explains the decrease in conductivity and increase in activation energy. This phenomenon is categorized as reversible pressure-induced amorphization of a dense CP and is regarded as a demonstration of themore » coupling of the mechanical and electrical properties of a CP.« less

Electroless Deposition of Palladium on Macroscopic 3D-Printed Polymers with Dense Microlattice Architectures for Development of Multifunctional Composite Materials

DOE PAGES

Jones, Christopher G.; Mills, Bernice E.; Nishimoto, Ryan K.; ...

2017-10-25

A simple procedure has been developed to create palladium (Pd) films on the surface of several common polymers used in commercial fused deposition modeling (FDM) and stereolithography (SLA) based three-dimensional (3D) printing by an electroless deposition process. The procedure can be performed at room temperature, with equipment less expensive than many 3D printers, and occurs rapidly enough to achieve full coverage of the film within a few minutes. 3D substrates composed of dense logpile or cubic lattices with part sizes in the mm to cm range, and feature sizes as small as 150 μm were designed and printed using commerciallymore » available 3D printers. The deposition procedure was successfully adapted to show full coverage in the lattice substrates. As a result, the ability to design, print, and metallize highly ordered three-dimensional microscale structures could accelerate development of a range of optimized chemical and mechanical engineering systems.« less

Electroless Deposition of Palladium on Macroscopic 3D-Printed Polymers with Dense Microlattice Architectures for Development of Multifunctional Composite Materials

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

Jones, Christopher G.; Mills, Bernice E.; Nishimoto, Ryan K.

A simple procedure has been developed to create palladium (Pd) films on the surface of several common polymers used in commercial fused deposition modeling (FDM) and stereolithography (SLA) based three-dimensional (3D) printing by an electroless deposition process. The procedure can be performed at room temperature, with equipment less expensive than many 3D printers, and occurs rapidly enough to achieve full coverage of the film within a few minutes. 3D substrates composed of dense logpile or cubic lattices with part sizes in the mm to cm range, and feature sizes as small as 150 μm were designed and printed using commerciallymore » available 3D printers. The deposition procedure was successfully adapted to show full coverage in the lattice substrates. As a result, the ability to design, print, and metallize highly ordered three-dimensional microscale structures could accelerate development of a range of optimized chemical and mechanical engineering systems.« less

Entropic depletion in colloidal suspensions and polymer liquids: Role of nanoparticle surface topography

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

Banerjee, Debapriya; Yang, Jian; Schweizer, Kenneth S.

2015-01-01

Here, we employ a hybrid Monte Carlo plus integral equation theory approach to study how dense fluids of small nanoparticles or polymer chains mediate entropic depletion interactions between topographically rough particles where all interaction potentials are hard core repulsion. The corrugated particle surfaces are composed of densely packed beads which present variable degrees of controlled topographic roughness and free volume associated with their geometric crevices. This pure entropy problem is characterized by competing ideal translational and (favorable and unfavorable) excess entropic contributions. Surface roughness generically reduces particle depletion aggregation relative to the smooth hard sphere case. However, the competition betweenmore » ideal and excess packing entropy effects in the bulk, near the particle surface and in the crevices, results in a non-monotonic variation of the particle-monomer packing correlation function as a function of the two dimensionless length scale ratios that quantify the effective surface roughness. As a result, the inter-particle potential of mean force (PMF), second virial coefficient, and spinodal miscibility volume fraction vary non-monotonically with the surface bead to monomer diameter and particle core to surface bead diameter ratios. A miscibility window is predicted corresponding to an optimum degree of surface roughness that completely destroys depletion attraction resulting in a repulsive PMF. Variation of the (dense) matrix packing fraction can enhance or suppress particle miscibility depending upon the amount of surface roughness. Connecting the monomers into polymer chains destabilizes the system via enhanced contact depletion attraction, but the non-monotonic variations with surface roughness metrics persist.« less

Tailored nanoporous coatings fabricated on conformable polymer substrates.

PubMed

Poxson, David J; Mont, Frank W; Cho, Jaehee; Schubert, E Fred; Siegel, Richard W

2012-11-01

Nanoporous coatings have become the subject of intense investigation, in part because they have been shown to have unique and tailorable physical properties that can depart greatly from their dense or macroscopic counterparts. Nanoporous coatings are frequently fabricated utilizing oblique-angle or glancing-angle physical vapor-phase deposition techniques. However, a significant limitation for such coatings exists; they are almost always deposited on smooth and rigid planar substrates, such as silicon and glass. This limitation greatly constrains the applicability, tailorability, functionality and even the economic viability, of such nanoporous coatings. Here, we report our findings on nanoporous/polymer composite systems (NPCS) fabricated by utilizing oblique-angle electron-beam methodology. These unique composite systems exhibit several favorable characteristics, namely, (i) fine-tuned control over coating nanoporosity and thickness, (ii) excellent adhesion between the nanoporous coating and polymer substrate, (iii) the ability to withstand significant and repeated bending, and (iv) the ability to be molded conformably on two and three-dimensional surfaces while closely retaining the composite system's designed nanoporous film structure and, hence, properties.

Metal-polymer composites comprising nanostructures and applications thereof

DOEpatents

Wang, Hsing-Lin [Los Alamos, NM; Jeon, Sea Ho [Dracut, MA; Mack, Nathan H [Los Alamos, NM

2011-08-02

Metal-polymer composites, and methods of making and use thereof, said composites comprising a thermally-cured dense polyaniline substrate; an acid dopant; and, metal nanostructure deposits wherein the deposits have a morphology dependent upon the acid dopant.

Metal-polymer composites comprising nanostructures and applications thereof

DOEpatents

Wang, Hsing-Lin [Los Alamos, NM; Jeon, Sea Ho [Dracut, MA; Mack, Nathan H [Los Alamos, NM

2012-04-03

Metal-polymer composites, and methods of making and use thereof, said composites comprising a thermally-cured dense polyaniline substrate; an acid dopant; and, metal nanostructure deposits wherein the deposits have a morphology dependent upon the acid dopant.

Application of Bottlebrush Block Copolymers as Photonic Crystals.

PubMed

Liberman-Martin, Allegra L; Chu, Crystal K; Grubbs, Robert H

2017-07-01

Brush block copolymers are a class of comb polymers that feature polymeric side chains densely grafted to a linear backbone. These polymers display interesting properties due to their dense functionality, low entanglement, and ability to rapidly self-assemble to highly ordered nanostructures. The ability to prepare brush polymers with precise structures has been enabled by advancements in controlled polymerization techniques. This Feature Article highlights the development of brush block copolymers as photonic crystals that can reflect visible to near-infrared wavelengths of light. Fabrication of these materials relies on polymer self-assembly processes to achieve nanoscale ordering, which allows for the rapid preparation of photonic crystals from common organic chemical feedstocks. The characteristic physical properties of brush block copolymers are discussed, along with methods for their preparation. Strategies to induce self-assembly at ambient temperatures and the use of blending techniques to tune photonic properties are emphasized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shell-corona microgels from double interpenetrating networks.

PubMed

Rudyak, Vladimir Yu; Gavrilov, Alexey A; Kozhunova, Elena Yu; Chertovich, Alexander V

2018-04-18

Polymer microgels with a dense outer shell offer outstanding features as universal carriers for different guest molecules. In this paper, microgels formed by an interpenetrating network comprised of collapsed and swollen subnetworks are investigated using dissipative particle dynamics (DPD) computer simulations, and it is found that such systems can form classical core-corona structures, shell-corona structures, and core-shell-corona structures, depending on the subchain length and molecular mass of the system. The core-corona structures consisting of a dense core and soft corona are formed at small microgel sizes when the subnetworks are able to effectively separate in space. The most interesting shell-corona structures consist of a soft cavity in a dense shell surrounded with a loose corona, and are found at intermediate gel sizes; the area of their existence depends on the subchain length and the corresponding mesh size. At larger molecular masses the collapsing network forms additional cores inside the soft cavity, leading to the core-shell-corona structure.

Prototype of low thermal expansion materials: fabrication of mesoporous silica/polymer composites with densely filled polymer inside mesopore space.

PubMed

Kiba, Shosuke; Suzuki, Norihiro; Okawauchi, Yoshinori; Yamauchi, Yusuke

2010-09-03

A prototype of novel low thermal expansion materials using mesoporous silica particles is demonstrated. Mesoporous silica/polymer composites with densely filled polymer inside the mesopore space are fabricated by mechanically mixing both organically modified mesoporous silica and epoxy polymer. The mesopores are easily penetrated by polymers as a result of the capillary force during the mechanical composite processing. Furthermore, we propose a new model of polymer mobility restriction using mesoporous silica with a large pore space. The robust inorganic frameworks covering the polymer effectively restrict the polymer mobility against thermal energy. As a result, the degree of total thermal expansion of the composites is drastically decreased. From the mass-normalized thermal mechanical analysis (TMA) charts of various composites with different amounts of mesoporous silica particles, it is observed that the coefficient of thermal expansion (CTE) values gradually increase with an increase of the polymer amount outside the mesopores. It is proven that the CTE values in the range over the glass-transition temperatures (T(g)) are perfectly proportional to the outside polymer amounts. Importantly, the Y-intercept of the relation equation obtained by a least-square method is the CTE value and is almost zero. This means that thermal expansion does not occur if no polymers are outside the mesopores. Through such a quantative discussion, we clarify that only the outside polymer affects the thermal expansion of the composites, that is, the embedded polymers inside the mesopores do not expand at all during the thermal treatment.

Mesoscopic Simulations of Crosslinked Polymer Networks

NASA Astrophysics Data System (ADS)

Megariotis, Grigorios; Vogiatzis, Georgios G.; Schneider, Ludwig; Müller, Marcus; Theodorou, Doros N.

2016-08-01

A new methodology and the corresponding C++ code for mesoscopic simulations of elastomers are presented. The test system, crosslinked ds-1’4-polyisoprene’ is simulated with a Brownian Dynamics/kinetic Monte Carlo algorithm as a dense liquid of soft, coarse-grained beads, each representing 5-10 Kuhn segments. From the thermodynamic point of view, the system is described by a Helmholtz free-energy containing contributions from entropic springs between successive beads along a chain, slip-springs representing entanglements between beads on different chains, and non-bonded interactions. The methodology is employed for the calculation of the stress relaxation function from simulations of several microseconds at equilibrium, as well as for the prediction of stress-strain curves of crosslinked polymer networks under deformation.

Effect of Polymer Electrode Morphology on Performance of a Lithium/Polypyrrole Battery. M.S. Thesis

NASA Technical Reports Server (NTRS)

Nicholson, Marjorie Anne

1991-01-01

A variety of conducting polymer batteries were described in the recent literature. In this work, a Li/Polypyrrole secondary battery is described. The effect of controlling the morphology of the polymer on enhancement of counterion diffusion in the polymer phase is explored. A method of preparing conducting polymers was developed which yields high surface area per unit volume of electrode material. A porous membrane is used as a template in which to electrochemically polymerize pyrrole, then the membrane is dissolved, leaving the polymer in a fibrillar form. Conventionally, the polymer is electrochemically polymerized as a dense polymer film on a smooth Pt disk electrode. Previous work has shown that when the polymer is electrochemically polymerized in fribrillar form, charge transport rates are faster and charge capacities are greater than for dense, conventionally grown films containing the same amount of polymer. The purpose is to expand previous work by further investigating the possibilities of the optimization of transport rates in polypyrrole films by controlling the morphology of the films. The utility of fibrillar polypyrrole as a cathode material in a lithium/polymer secondary battery is then assessed. The performance of the fibrillar battery is compared to the performance of an analogous battery which employed a conventionally grown polypyrrole film. The study includes a comparison of cyclic voltammetry, shape of charge/discharge curves, discharge time and voltage, cycle life, coulombic efficiencies, charge capacities, energy densities, and energy efficiencies.

Mass production of polymer nano-wires filled with metal nano-particles.

PubMed

Lomadze, Nino; Kopyshev, Alexey; Bargheer, Matias; Wollgarten, Markus; Santer, Svetlana

2017-08-17

Despite the ongoing progress in nanotechnology and its applications, the development of strategies for connecting nano-scale systems to micro- or macroscale elements is hampered by the lack of structural components that have both, nano- and macroscale dimensions. The production of nano-scale wires with macroscale length is one of the most interesting challenges here. There are a lot of strategies to fabricate long nanoscopic stripes made of metals, polymers or ceramics but none is suitable for mass production of ordered and dense arrangements of wires at large numbers. In this paper, we report on a technique for producing arrays of ordered, flexible and free-standing polymer nano-wires filled with different types of nano-particles. The process utilizes the strong response of photosensitive polymer brushes to irradiation with UV-interference patterns, resulting in a substantial mass redistribution of the polymer material along with local rupturing of polymer chains. The chains can wind up in wires of nano-scale thickness and a length of up to several centimeters. When dispersing nano-particles within the film, the final arrangement is similar to a core-shell geometry with mainly nano-particles found in the core region and the polymer forming a dielectric jacket.

Polymer absorption in dense polymer brushes vs. polymer adsorption on the brush-solvent interface

NASA Astrophysics Data System (ADS)

Milchev, Andrey; Binder, Kurt

2014-06-01

Molecular-dynamics simulations of a coarse-grained model of a dense brush of flexible polymers (of type A) interacting with a long flexible macromolecule (of type B) are presented, considering the case of an attractive AB interaction, while effective interactions between AA and BB pairs of monomers are repulsive. Varying the strength \\varepsilon_{AB} of the attraction between unlike monomers, an adsorption transition at some critical value \\varepsilon^c_{AB} is found, where the B-chain is bound to the brush-solvent interface, similar to the adsorption on a planar solid substrate. However, when \\varepsilon_{AB} is much higher than \\varepsilon^c_{AB} , the long macromolecule is gradually “sucked in” the brush, developing many pieces that are locally stretched in the z-direction perpendicular to the substrate, in order to fit between the brush chains. The resulting hairpin-like structures of the absorbed chain shows up via oscillatory decay of the bond vector autocorrelation function. Chain relaxation is only possible via reptation.

Preparation of non-porous microspheres with high entrapment efficiency of proteins by a (water-in-oil)-in-oil emulsion technique.

PubMed

Viswanathan, N B; Thomas, P A; Pandit, J K; Kulkarni, M G; Mashelkar, R A

1999-03-08

Emulsification-solvent removal methods have been widely used for encapsulating bioactive macromolecules like proteins and polypeptides in biodegradable polymers. We report, a (water-in-oil)-in-oil emulsion technique wherein proteins and polypeptides differing in molecular weight and shape were encapsulated in polymers of current biomedical interest. When an oil was used as the processing medium in combination with a carefully selected mixed solvent system such that a stable (w/o1/o2 emulsion is formed and solvents are removed by a combination of extraction and evaporation, the entrapment efficiency was high and the product nonporous. The entrapment efficiency of globular proteins exceeded 90% while that of fibrous proteins was around 70%. Fracture studies revealed that the polymer matrix was dense. The mechanism of entrapment involved solvent-induced precipitation of the protein as the microspheres were being formed. The principle of the method will find use in preparation of non-porous polymer microparticles with reduced burst effect.

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

Ma, Xiang; Zhang, Shuai; Jiao, Fang

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

ECM-Based Biohybrid Materials for Engineering Compliant, Matrix-Dense Tissues

PubMed Central

Bracaglia, Laura G.; Fisher, John P.

2015-01-01

An ideal tissue engineering scaffold should not only promote, but take an active role in, constructive remodeling and formation of site appropriate tissue. ECM-derived proteins provide unmatched cellular recognition, and therefore influence cellular response towards predicted remodeling behaviors. Materials built with only these proteins, however, can degrade rapidly or begin too weak to substitute for compliant, matrix-dense tissues. The focus of this review is on biohybrid materials that incorporate polymer components with ECM-derived proteins, to produce a substrate with desired mechanical and degradation properties, as well as actively guide tissue remodeling. Materials are described through four fabrication methods: (1) polymer and ECM-protein fibers woven together, (2) polymer and ECM proteins combined in a bilayer, (3) cell-built ECM on polymer scaffold, and (4) ECM proteins and polymers combined in a single hydrogel. Scaffolds from each fabrication method can achieve characteristics suitable for different types of tissue. In vivo testing has shown progressive remodeling in injury models, and suggests ECM-based biohybrid materials promote a prohealing immune response over single component alternatives. The prohealing immune response is associated with lasting success and long term host maintenance of the implant. PMID:26227679

Star polymers as unit cells for coarse-graining cross-linked networks

NASA Astrophysics Data System (ADS)

Molotilin, Taras Y.; Maduar, Salim R.; Vinogradova, Olga I.

2018-03-01

Reducing the complexity of cross-linked polymer networks by preserving their main macroscale properties is key to understanding them, and a crucial issue is to relate individual properties of the polymer constituents to those of the reduced network. Here we study polymer networks in a good solvent, by considering star polymers as their unit elements, and first quantify the interaction between their centers of masses. We then reduce the complexity of a network by replacing sets of its bridged star polymers by equivalent effective soft particles with dense cores. Our coarse graining allows us to approximate complex polymer networks by much simpler ones, keeping their relevant mechanical properties, as illustrated in computer experiments.

Method for forming a uniformly dense polymer foam body

DOEpatents

Whinnery, Jr., Leroy

2002-01-01

A method for providing a uniformly dense polymer foam body having a density between about 0.013 .sup.g /.sub.cm.sup..sub.3 to about 0.5 .sup.g /.sub.cm.sup..sub.3 is disclosed. The method utilizes a thermally expandable polymer microballoon material wherein some of the microballoons are unexpanded and some are only partially expanded. It is shown that by mixing the two types of materials in appropriate ratios to achieve the desired bulk final density, filling a mold with this mixture so as to displace all or essentially all of the internal volume of the mold, heating the mold for a predetermined interval at a temperature above about 130.degree. C., and then cooling the mold to a temperature below 80.degree. C. the molded part achieves a bulk density which varies by less then about .+-.6% everywhere throughout the part volume.

Simulation of ring polymer melts with GPU acceleration

NASA Astrophysics Data System (ADS)

Schram, R. D.; Barkema, G. T.

2018-06-01

We implemented the elastic lattice polymer model on the GPU (Graphics Processing Unit), and show that the GPU is very efficient for polymer simulations of dense polymer melts. The implementation is able to perform up to 4.1 ṡ109 Monte Carlo moves per second. Compared to our standard CPU implementation, we find an effective speed-up of a factor 92. Using this GPU implementation we studied the equilibrium properties and the dynamics of non-concatenated ring polymers in a melt of such polymers, using Rouse modes. With increasing polymer length, we found a very slow transition to compactness with a growth exponent ν ≈ 1 / 3. Numerically we find that the longest internal time scale of the polymer scales as N3.1, with N the molecular weight of the ring polymer.

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

NASA Astrophysics Data System (ADS)

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.

Self-assembly in densely grafted macromolecules with amphiphilic monomer units: diagram of states.

PubMed

Lazutin, A A; Vasilevskaya, V V; Khokhlov, A R

2017-11-22

By means of computer modelling, the self-organization of dense planar brushes of macromolecules with amphiphilic monomer units was addressed and their state diagram was constructed. The diagram of states includes the following regions: disordered position of monomer units with respect to each other, strands composed of a few polymer chains and lamellae with different domain spacing. The transformation of lamellae structures with different domain spacing occurred within the intermediate region and could proceed through the formation of so-called parking garage structures. The parking garage structure joins the lamellae with large (on the top of the brushes) and small (close to the grafted surface) domain spacing, which appears like a system of inclined locally parallel layers connected with each other by bridges. The parking garage structures were observed for incompatible A and B groups in selective solvents, which result in aggregation of the side B groups and dense packing of amphiphilic macromolecules in the restricted volume of the planar brushes.

Zeolite-imidazolate framework (ZIF-8) membrane synthesis on a mixed-matrix substrate.

PubMed

Barankova, Eva; Pradeep, Neelakanda; Peinemann, Klaus-Viktor

2013-10-21

A thin, dense, compact and hydrogen selective ZIF-8 membrane was synthesized on a polymer/metal oxide mixed-matrix support by a secondary seeding method. The new concept of incorporating ZnO particles into the support and PDMS coating of the ZIF-8 layer is introduced to improve the preparation of ZIF-polymer composite membranes.

Materials Design for Block Copolymer Lithography

NASA Astrophysics Data System (ADS)

Sweat, Daniel Patrick

Block copolymers (BCPs) have attracted a great deal of scientific and technological interest due to their ability to spontaneously self-assemble into dense periodic nanostructures with a typical length scale of 5 to 50 nm. The use of self-assembled BCP thin-films as templates to form nanopatterns over large-area is referred to as BCP lithography. Directed self-assembly of BCPs is now viewed as a viable candidate for sub-20 nm lithography by the semiconductor industry. However, there are multiple aspects of assembly and materials design that need to be addressed in order for BCP lithography to be successful. These include substrate modification with polymer brushes or mats, tailoring of the block copolymer chemistry, understanding thin-film assembly and developing epitaxial like methods to control long range alignment. The rational design, synthesis and self-assembly of block copolymers with large interaction parameters (chi) is described in the first part of this dissertation. Two main blocks were chosen for introducing polarity into the BCP system, namely poly(4-hydroxystyrene) and poly(2-vinylpyridine). Each of these blocks are capable of ligating Lewis acids which can increase the etch contrast between the blocks allowing for facile pattern transfer to the underlying substrate. These BCPs were synthesized by living anionic polymerization and showed excellent control over molecular weight and dispersity, providing access to sub 5-nm domain sizes. Polymer brushes consist of a polymer chain with one end tethered to the surface and have wide applicability in tuning surface energy, forming responsive surfaces and increasing biocompatibility. In the second part of the dissertation, we present a universal method to grow dense polymer brushes on a wide range of substrates and combine this chemistry with BCP assembly to fabricate nanopatterned polymer brushes. This is the first demonstration of introducing additional functionality into a BCP directing layer and opens up a wide slew of applications from directed self-assembly to biomaterial engineering.

Inelastic deformation of plasma polymerised thin films facilitated by transient dense plasma focus irradiation

NASA Astrophysics Data System (ADS)

Grant, Daniel S.; Rawat, Rajdeep S.; Bazaka, Kateryna; Jacob, Mohan V.

2017-09-01

The high degree of crosslinking present in plasma polymerised thin films, coupled with their high molecular weight, imbues these films with properties similar to those of thermosetting polymers. For instance, such films tend to be relatively hard, insoluble, and to date have not exhibited plasticity when subjected to elevated temperatures. In this paper it is demonstrated that plasma polymers can, in fact, undergo plastic deformation in response to the application of extremely short-lived thermal treatment delivered by a dense plasma focus device, as evidenced by the evolution of bubble-like structures from the thin film. This finding suggests new avenues for texturing plasma thin films, and synthesising cavities that may find utility as thermal insulators or domains for material encapsulation.

Compatibility of Medical-Grade Polymers with Dense CO2

PubMed Central

Jiménez, A; Thompson, G L; Matthews, M A; Davis, T A; Crocker, K; Lyons, J S; Trapotsis, A

2009-01-01

This study reports the effect of exposure to liquid carbon dioxide on the mechanical properties of selected medical polymers. The tensile strengths and moduli of fourteen polymers are reported. Materials were exposed to liquid CO2, or CO2 + trace amounts of aqueous H2O2, at 6.5 MPa and ambient temperature. Carbon dioxide uptake, swelling, and distortion were observed for the more amorphous polymers while polymers with higher crystallinity showed little effect from CO2 exposure. Changes in tensile strength were not statistically significant for most plastics, and most indicated good tolerance to liquid CO2. These results are relevant to evaluating the potential of liquid CO2-based sterilization technology. PMID:19756235

Toroidal-spiral particles for codelivery of anti-VEGFR-2 antibody and irinotecan: a potential implant to hinder recurrence of glioblastoma multiforme.

PubMed

Sharma, Vishal; Köllmer, Melanie; Szymusiak, Magdalena; Nitsche, Ludwig C; Gemeinhart, Richard A; Liu, Ying

2014-03-10

Heterogeneous toroidal-spiral particles (TSPs) were generated by polymer droplet sedimentation, interaction, and cross-linking. TSPs provide a platform for encapsulation and release of multiple compounds of different sizes and physicochemical properties. As a model system, we demonstrate the encapsulation and independently controlled release of an anti-VEGFR-2 antibody and irinotecan for the treatment of glioblastoma multiforme. The anti-VEGFR-2 antibody was released from the TS channels and its binding to HUVECs was confirmed by confocal microscopy and flow cytometry, suggesting active antibody encapsulation and release. Irinotecan, a small molecule drug, was released from the dense polymer matrix of poly(ethylene glycol) diacrylate (MW ~ 700 g/mol; PEGDA 700). Released irinotecan inhibited the proliferation of U251 malignant glioma cells. Since the therapeutic compounds are released through different pathways, specifically diffusion through the polymer matrix versus TS channels, the release rate can be controlled independently through the design of the structure and material of particle components.

Fabrication and Characterization of Dense Zirconia and Zirconia-Silica Ceramic Nanofibers

PubMed Central

Guo, Guangqing; Fan, Yuwei

2011-01-01

The objective of this study was to prepare dense zirconia-yttria (ZY), zirconia-silica (ZS) and zirconia-yttria-silica (ZYS) nanofibers as reinforcing elements for dental composites. Zirconium (IV) propoxide, yttrium nitrate hexahydrate, and tetraethyl orthosilicate (TEOS) were used as precursors for the preparation of zirconia, yttria, and silica sols. A small amount (1–1.5 wt%) of polyethylene oxide (PEO) was used as a carry polymer. The sols were preheated at 70 °C before electrospinning and their viscosity was measured with a viscometer at different heating time. The gel point was determined by viscosity–time (η–t) curve. The ZY, ZS and ZYS gel nanofibers were prepared using a special reactive electrospinning device under the conditions near the gel point. The as-prepared gel nanofibers had diameters between 200 and 400 nm. Dense (nonporous) ceramic nanofibers of zirconia-yttria (96/4), zirconia-silica (80/20) and zirconia-yttria-silica (76.8/3.2/20) with diameter of 100–300 nm were obtained by subsequent calcinations at different temperatures. The gel and ceramic nanofibers obtained were characterized by scanning electron microscope (SEM), high-resolution field-emission scanning electron microscope (FE-SEM), thermogravimetric analyzer (TGA), differential scanning calorimeter (DSC), Fourier transform infrared spectrometer (FT-IR), and X-ray diffraction (XRD). SEM micrograph revealed that ceramic ZY nanofibers had grained structure, while ceramic ZS and ZYS nanofibers had smooth surfaces, both showing no visible porosity under FE-SEM. Complete removal of the polymer PEO was confirmed by TGA/DSC and FT-IR. The formation of tetragonal phase of zirconia and amorphous silica was proved by XRD. In conclusion, dense zirconia-based ceramic nanofibers can be fabricated using the new reactive sol–gel electrospinning technology with minimum organic polymer additives. PMID:21133090

Innovative Processing of Composites for Ultra-High Temperature Applications. Book 3

DTIC Science & Technology

1993-11-01

SiC Samples Prepared with Four Preceramic Polymer Infiltration / Pyrolysis (at 15750C) Cycles Figure 21 Scanning Electron...Micrograph of Large Pores near the Surface of Siliconized SIC Sample with Four Preceramic Polymer Infiltration / Pyrolysis (at 1575*C) Cycles II...In order to achieve dense, bulk composites with maximum SiC /Si ratio, two infiltration / pyrolysis cycles were used. S (4) After siliconization,

Redox-Active Supramolecular Polymer Binders for Lithium–Sulfur Batteries That Adapt Their Transport Properties in Operando

DOE PAGES

Frischmann, Peter D.; Hwa, Yoon; Cairns, Elton J.; ...

2016-10-25

π-Stacked perylene bisimide (PBI) molecules are implemented here as highly networked, redox-active supramolecular polymer binders in sulfur cathodes for lightweight and energy-dense Li-S batteries. We show that the in operando reduction and lithiation of these PBI binders sustainably reduces Li-S cell impedance relative to nonredox active conventional polymer binders. This lower impedance enables high-rate cycling in Li-S cells with excellent durability, a critical step toward unlocking the full potential of Li-S batteries for electric vehicles and aviation.

Molecular simulation of simple fluids and polymers in nanoconfinement

NASA Astrophysics Data System (ADS)

Rasmussen, Christopher John

Prediction of phase behavior and transport properties of simple fluids and polymers confined to nanoscale pores is important to a wide range of chemical and biochemical engineering processes. A practical approach to investigate nanoscale systems is molecular simulation, specifically Monte Carlo (MC) methods. One of the most challenging problems is the need to calculate chemical potentials in simulated phases. Through the seminal work of Widom, practitioners have a powerful method for calculating chemical potentials. Yet, this method fails for dense and inhomogeneous systems, as well as for complex molecules such as polymers. In this dissertation, the gauge cell MC method, which had previously been successfully applied to confined simple fluids, was employed and extended to investigate nanoscale fluids in several key areas. Firstly, the process of cavitation (the formation and growth of bubbles) during desorption of fluids from nanopores was investigated. The dependence of cavitation pressure on pore size was determined with gauge cell MC calculations of the nucleation barriers correlated with experimental data. Additional computational studies elucidated the role of surface defects and pore connectivity in the formation of cavitation bubbles. Secondly, the gauge cell method was extended to polymers. The method was verified against the literature results and found significantly more efficient. It was used to examine adsorption of polymers in nanopores. These results were applied to model the dynamics of translocation, the act of a polymer threading through a small opening, which is implicated in drug packaging and delivery, and DNA sequencing. Translocation dynamics was studied as diffusion along the free energy landscape. Thirdly, we show how computer simulation of polymer adsorption could shed light on the specifics of polymer chromatography, which is a key tool for the analysis and purification of polymers. The quality of separation depends on the physico-chemical mechanisms of polymer/pore interaction. We considered liquid chromatography at critical conditions, and calculated the dependence of the partition coefficient on chain length. Finally, solvent-gradient chromatography was modeled using a statistical model of polymer adsorption. A model for predicting separation of complex polymers (with functional groups or copolymers) was developed for practical use in chromatographic separations.

Refractory Ceramic Foams for Novel Applications

NASA Technical Reports Server (NTRS)

Stackpoole, M.

2008-01-01

Workers at NASA Ames Research center are endeavoring to develop durable, oxidation-resistant, foam thermal protection systems (TPSs) that would be suitable for covering large exterior spacecraft surfaces, would have low to moderate densities, and would have temperature capabilities comparable to those of carbon-based TPSs [reusable at 3,000 F (.1,650 C)] with application of suitable coatings. These foams may also be useful for repairing TPSs while in orbit. Moreover, on Earth as well as in outer space, these foams might be useful as catalyst supports and filters. Preceramic polymers are obvious candidates for use in making the foams in question. The use of these polymers offers advantages over processing routes followed in making conventional ceramics. Among the advantages are the ability to plastically form parts, the ability to form pyrolized ceramic materials at lower temperatures, and the ability to form high-purity microstructures having properties that can be tailored to satisfy requirements. Heretofore, preceramic polymers have been used mostly in the production of such low-dimensional products as fibers because the loss of volatiles during pyrolysis of the polymers leads to porosity and large shrinkage (in excess of 30 percent). In addition, efforts to form bulk structures from preceramic polymers have resulted in severe cracking during pyrolysis. However, because the foams in question would consist of networks of thin struts (in contradistinction to nonporous dense solids), these foams are ideal candidates for processing along a preceramic-polymer route.

Surface modification of starch based blends using potassium permanganate-nitric acid system and its effect on the adhesion and proliferation of osteoblast-like cells.

PubMed

Pashkuleva, I; Marques, A P; Vaz, F; Reis, R L

2005-01-01

The surface modification of three starch based polymeric biomaterials, using a KMnO4/HNO3 oxidizing system, and the effect of that modification on the osteoblastic cell adhesion has been investigated. The rationale of this work is as follows--starch based polymers have been proposed for use as tissue engineering scaffolds in several publications. It is known that in biodegradable systems it is quite difficult to have both cell adhesion and proliferation. Starch based polymers have shown to perform better than poly-lactic acid based materials but there is still room for improvement. This particular work is aimed at enhancing cell adhesion and proliferation on the surface of several starch based polymer blends that are being proposed as tissue engineering scaffolds. The surface of the polymeric biomaterials was chemically modified using a KMnO4/HNO3 system. This treatment resulted in more hydrophilic surfaces, which was confirmed by contact angle measurements. The effect of the treatment on the bioactivity of the surface modified biomaterials was also studied. The bioactivity tests, performed in simulated body fluid after biomimetic coating, showed that a dense film of calcium phosphate was formed after 30 days. Finally, human osteoblast-like cells were cultured on unmodified (control) and modified materials in order to observe the effect of the presence of higher numbers of polar groups on the adhesion and proliferation of those cells. Two of the modified polymers presented changes in the adhesion behavior and a significant increase in the proliferation rate kinetics when compared to the unmodified controls.

Hot Melt Extrudates Formulated Using Design Space: One Simple Process for Both Palatability and Dissolution Rate Improvement.

PubMed

Malaquias, Lorena F B; Schulte, Heidi L; Chaker, Juliano A; Karan, Kapish; Durig, Thomas; Marreto, Ricardo N; Gratieri, Tais; Gelfuso, Guilherme M; Cunha-Filho, Marcilio

2018-01-01

This work aimed at obtaining an optimized itraconazole (ITZ) solid oral formulation in terms of palatability and dissolution rate by combining different polymers using hot melt extrusion (HME), according to a simplex centroid mixture design. For this, the polymers Plasdone ® (poly(1-vinylpyrrolidone-co-vinyl acetate) [PVP/VA]), Klucel ® ELF (2-hydroxypropyl ether cellulose [HPC]), and Soluplus ® (SOL, polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol) were processed using a laboratory HME equipment operating without recirculation at constant temperature. Samples were characterized by physicochemical assays, as well as dissolution rate and palatability using an e-tongue. All materials became homogeneous and dense after HME processing. Thermal and structural analyses demonstrated drug amorphization, whereas IR spectroscopy evidenced drug stability and drug-excipient interactions in HME systems. Extrudates presented a significant increase in dissolution rate compared to ITZ raw material, mainly with formulations containing PVP/VA and HPC. A pronounced improvement in taste masking was also identified for HME systems, especially in those containing higher amounts of SOL and HPC. Data showed polymers act synergistically favoring formulation functional properties. Predicted best formulation should contain ITZ 25.0%, SOL 33.2%, HPC 28.9%, and PVP/VA 12.9% (w/w). Optimized response considering dissolution rate and palatability reinforces the benefit of polymer combinations. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Uniformly dense polymeric foam body

DOEpatents

Whinnery, Jr., Leroy

2003-07-15

A method for providing a uniformly dense polymer foam body having a density between about 0.013 g/cm.sup.3 to about 0.5 g/cm.sup.3 is disclosed. The method utilizes a thermally expandable polymer microsphere material wherein some of the microspheres are unexpanded and some are only partially expanded. It is shown that by mixing the two types of materials in appropriate ratios to achieve the desired bulk final density, filling a mold with this mixture so as to displace all or essentially all of the internal volume of the mold, heating the mold for a predetermined interval at a temperature above about 130.degree. C., and then cooling the mold to a temperature below 80.degree. C. the molded part achieves a bulk density which varies by less then about .+-.6% everywhere throughout the part volume.

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

PubMed

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

2018-06-13

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

Effects of Molecular Weight upon Irradiation-Cross-Linked Poly(vinyl alcohol)/Clay Aerogel Properties.

PubMed

Chen, Hong-Bing; Zhao, Yan; Shen, Peng; Wang, Jun-Sheng; Huang, Wei; Schiraldi, David A

2015-09-16

Facile fabrication of mechanically strong poly(vinyl alcohol) (PVOH)/clay aerogel composites through a combination of increasing polymer molecular weights and gamma irradiation-cross-linking is reported herein. The aerogels produced from high polymer molecular weights exhibit significantly increased compressive moduli, similar to the effect of irradiation-induced cross-linking. The required irradiation dose for fabricating strong PVOH composite aerogels with dense microstructure decreased with increasing polymer molecular weight. Neither thermal stability nor flammability was significantly changed by altering the polymer molecular weight or by modest gamma irradiation, but they were highly dependent upon the polymer/clay ratio in the aerogel. Optimization of the mechanical, thermal, and flammability properties of these composite aerogels could therefore be obtained by using relatively low levels of polymer, with very high polymer molecular weight, or lower molecular weight coupled with moderate gamma irradiation. The facile preparation of strong, low flammability aerogels is an alternative to traditional polymer foams in applications where fire safety is important.

Polymer brush covalently attached to OH-functionalized mica surface via surface-initiated ATRP: control of grafting density and polymer chain length.

PubMed

Lego, Béatrice; François, Marion; Skene, W G; Giasson, Suzanne

2009-05-05

The controlled grafting density of poly(tert-butyl acrylate) was studied on OH-activated mica substrates via surface-initiated atom-transfer radical polymerization (ATRP). By properly adjusting parameters such as the immobilization reaction time and the concentration of an ATRP initiator, a wide range of initiator surface coverages and hence polymer densities on mica were possible. The covalently immobilized initiator successfully promoted the polymerization of tert-butyl acrylate on mica surfaces. The resulting polymer layer thickness was measured by AFM using a step-height method. Linear relationships of the polymer thickness with respect to the molecular weight of the free polymer and with respect to the monomer conversion were observed, suggesting that ATRP is well controlled and relatively densely end-grafted layers were obtained. The polymer grafting density controlled by adjusting the initiator surface coverage was confirmed by the polymer layer swelling capacity and film thickness measurements.

The Art and Science of Polymer Brushes: Recent Developments in Patterning and Characterization Approaches.

PubMed

Panzarasa, Guido

2017-06-28

Polymer brushes are dense arrays of macromolecular chains tethered by one end at a surface. They are at the cutting edge of polymer nanotechnology since the dawn of controlled surface-initiated polymerization techniques unlocked new prospects for the synthesis of polymer brushes with tailorable properties. More recently, thanks to the growing interest in the use of brushes for the generation of functional surfaces, the need for advanced patterning and characterization approaches rapidly increased. Meeting these needs requires the contribution of experts from different disciplines: polymer chemistry, surface science, electrochemistry and particle physics. The focus of this review is to highlight recent developments in the field of polymer brushes, specifically the application of photocatalytic lithography as a versatile patterning strategy, the study of grafted-from polymer brushes by electrochemical methods and, most importantly, the introduction of positron annihilation spectroscopy as a powerful technique for the investigation of the structure of polymer brushes and of their composites with nanoparticles.

Preparing high-density polymer brushes by mechanically assisted polymer assembly (MAPA)

NASA Astrophysics Data System (ADS)

Wu, Tao; Efimenko, Kirill; Genzer, Jan

2001-03-01

We introduce a novel method of modifying the surface properties of materials. This technique, called MAPA (="mechanically assisted polymer assembly"), is based on: 1) chemically attaching polymerization initiators to the surface of an elastomeric network that has been previously stretched by a certain length, Δx, and 2) growing end-anchored macromolecules using surface initiated ("grafting from") atom transfer living radical polymerization. After the polymerization, the strain is removed from the substrate, which returns to its original size causing the grafted macromolecules to stretch away from the substrate and form a dense polymer brush. We demonstrate the feasibility of the MAPA method by preparing high-density polymer brushes of poly(acryl amide), PAAm. We show that, as expected, the grafting density of the PAAm brushes can be increased by increasing Δx. We demonstrate that polymer brushes with extremely high grafting densities can be successfully prepared by MAPA.

Temperature-responsive chromatography for the separation of biomolecules.

PubMed

Kanazawa, Hideko; Okano, Teruo

2011-12-09

Temperature-responsive chromatography for the separation of biomolecules utilizing poly(N-isopropylacrylamide) (PNIPAAm) and its copolymer-modified stationary phase is performed with an aqueous mobile phase without using organic solvent. The surface properties and function of the stationary phase are controlled by external temperature changes without changing the mobile-phase composition. This analytical system is based on nonspecific adsorption by the reversible transition of a hydrophilic-hydrophobic PNIPAAm-grafted surface. The driving force for retention is hydrophobic interaction between the solute molecules and the hydrophobized polymer chains on the stationary phase surface. The separation of the biomolecules, such as nucleotides and proteins was achieved by a dual temperature- and pH-responsive chromatography system. The electrostatic and hydrophobic interactions could be modulated simultaneously with the temperature in an aqueous mobile phase, thus the separation system would have potential applications in the separation of biomolecules. Additionally, chromatographic matrices prepared by a surface-initiated atom transfer radical polymerization (ATRP) exhibit a strong interaction with analytes, because the polymerization procedure forms a densely packed polymer, called a polymer brush, on the surfaces. The copolymer brush grafted surfaces prepared by ATRP was an effective tool for separating basic biomolecules by modulating the electrostatic and hydrophobic interactions. Applications of thermally responsive columns for the separations of biomolecules are reviewed here. Copyright © 2011 Elsevier B.V. All rights reserved.

Active matter and Curvature

NASA Astrophysics Data System (ADS)

Sknepnek, Rastko

Coupling between active motion and curvature is an integral part of many fundamental biological processes such as gastrulation and intestinal crypt fission. However, to date very little is known about how curvature affects active motion. Here we use a particle-based model to study the interplay between activity and curvature in dense systems. Using detailed numerical simulations and simple physical arguments, we show that the presence of curvature results in a number of steady-state configurations that have no analogues in flat geometries. These states are particularly interesting if topological constraints require the presence of defects in the ground states in the passive limit. We focus on polar and nematic active systems confined to move on the surface of a sphere and show that activity can lead to the formation of moving band and multidefect states. We extend our model to self-propelled filaments confined to a plane or the surface of a sphere. We show that the activity leads to an effective softening of the polymer chain. As a result of this softening, with the increase in activity, the system transitions between a jammed polymer-melt state, an active turbulent state characterised by a proliferation of hair-pin defects, to a region dominated by phase segregation (MIPS), finally followed by the onset of a homogenous state characterised by spiral motion of individual polymers. UK EPSRC EP/M009599/1.

In situ ultra-small-angle X-ray scattering study under uniaxial stretching of colloidal crystals prepared by silica nanoparticles bearing hydrogen-bonding polymer grafts

DOE PAGES

Ishige, Ryohei; Williams, Gregory A.; Higaki, Yuji; ...

2016-04-19

A molded film of single-component polymer-grafted nanoparticles (SPNP), consisting of a spherical silica core and densely grafted polymer chains bearing hydrogen-bonding side groups capable of physical crosslinking, was investigated byin situultra-small-angle X-ray scattering (USAXS) measurement during a uniaxial stretching process. Static USAXS revealed that the molded SPNP formed a highly oriented twinned face-centered cubic (f.c.c.) lattice structure with the [11-1] plane aligned nearly parallel to the film surface in the initial state. Structural analysis ofin situUSAXS using a model of uniaxial deformation induced by rearrangement of the nanoparticles revealed that the f.c.c. lattice was distorted in the stretching direction inmore » proportion to the macroscopic strain until the strain reached 35%, and subsequently changed into other f.c.c. lattices with different orientations. The lattice distortion and structural transition behavior corresponded well to the elastic and plastic deformation regimes, respectively, observed in the stress–strain curve. The attractive interaction of the hydrogen bond is considered to form only at the top surface of the shell and then plays an effective role in cross-linking between nanoparticles. The rearrangement mechanism of the nanoparticles is well accounted for by a strong repulsive interaction between the densely grafted polymer shells of neighboring particles.« less

Depletion interaction between colloids mediated by an athermal polymer blend

NASA Astrophysics Data System (ADS)

Chervanyov, A. I.

2018-03-01

We calculate the immersion energy of a colloid and the potential of the depletion interaction (DI) acting between colloids immersed in an athermal polymer blend. The developed theory has no limitations with respect to the polymer-to-colloid size ratios and polymer densities, covering, in particular, dense polymer blends. We demonstrate that in addition to the standard compressibility-induced mechanism of the DI there exists the mechanism relying on the correlations between compositional fluctuations specific to polymer blends. We quantitatively investigate this "compositional" mechanism of the DI and demonstrate that it causes significant contributions to the effective force acting between colloids. Further we show that relative significance of the contributions to the colloid immersion energy and the depletion potential caused by the above compositional mechanism strongly depends on the mass fractions of the polymer species and their size ratio. We find out that these contributions strongly affect the range of the DI, thus causing a significant increase in the absolute value of the second virial coefficient of the effective potential acting between colloids.

Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states

NASA Astrophysics Data System (ADS)

Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W.; Edmondson, Steve; Malmström, Eva

2016-08-01

We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors. Electronic supplementary information (ESI) available: Figures of LCST, polymerization kinetics, melt-processed films, DLS, TGA, precipitated fiber and powder, TEM (of isotropic GO), birefringence, OP-data, DMTA-data and DSC. See DOI: 10.1039/c6nr01502f

Deciphering the relationship among phosphate dynamics, electron-dense body and lipid accumulation in the green alga Parachlorella kessleri

PubMed Central

Ota, Shuhei; Yoshihara, Mai; Yamazaki, Tomokazu; Takeshita, Tsuyoshi; Hirata, Aiko; Konomi, Mami; Oshima, Kenshiro; Hattori, Masahira; Bišová, Kateřina; Zachleder, Vilém; Kawano, Shigeyuki

2016-01-01

Phosphorus is an essential element for life on earth and is also important for modern agriculture, which is dependent on inorganic fertilizers from phosphate rock. Polyphosphate is a biological polymer of phosphate residues, which is accumulated in organisms during the biological wastewater treatment process to enhance biological phosphorus removal. Here, we investigated the relationship between polyphosphate accumulation and electron-dense bodies in the green alga Parachlorella kessleri. Under sulfur-depleted conditions, in which some symporter genes were upregulated, while others were downregulated, total phosphate accumulation increased in the early stage of culture compared to that under sulfur-replete conditions. The P signal was detected only in dense bodies by energy dispersive X-ray analysis. Transmission electron microscopy revealed marked ultrastructural variations in dense bodies with and without polyphosphate. Our findings suggest that the dense body is a site of polyphosphate accumulation, and P. kessleri has potential as a phosphate-accumulating organism. PMID:27180903

Ordering nanoparticles with polymer brushes

NASA Astrophysics Data System (ADS)

Cheng, Shengfeng; Stevens, Mark J.; Grest, Gary S.

2017-12-01

Ordering nanoparticles into a desired super-structure is often crucial for their technological applications. We use molecular dynamics simulations to study the assembly of nanoparticles in a polymer brush randomly grafted to a planar surface as the solvent evaporates. Initially, the nanoparticles are dispersed in a solvent that wets the polymer brush. After the solvent evaporates, the nanoparticles are either inside the brush or adsorbed at the surface of the brush, depending on the strength of the nanoparticle-polymer interaction. For strong nanoparticle-polymer interactions, a 2-dimensional ordered array is only formed when the brush density is finely tuned to accommodate a single layer of nanoparticles. When the brush density is higher or lower than this optimal value, the distribution of nanoparticles shows large fluctuations in space and the packing order diminishes. For weak nanoparticle-polymer interactions, the nanoparticles order into a hexagonal array on top of the polymer brush as long as the grafting density is high enough to yield a dense brush. An interesting healing effect is observed for a low-grafting-density polymer brush that can become more uniform in the presence of weakly adsorbed nanoparticles.

Materials with structural hierarchy

NASA Technical Reports Server (NTRS)

Lakes, Roderic

1993-01-01

The role of structural hierarchy in determining bulk material properties is examined. Dense hierarchical materials are discussed, including composites and polycrystals, polymers, and biological materials. Hierarchical cellular materials are considered, including cellular solids and the prediction of strength and stiffness in hierarchical cellular materials.

Confined Pattern-Directed Assembly of Polymer-Grafted Nanoparticles in a Phase Separating Blend with a Homopolymer Matrix.

PubMed

Zhang, Ren; Lee, Bongjoon; Bockstaller, Michael R; Douglas, Jack F; Stafford, Christopher M; Kumar, Sanat K; Raghavan, Dharmaraj; Karim, Alamgir

The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. We show that the phase separation of polymer-tethered nanoparticles immersed in a chemically different polymer matrix provides an effective and scalable method for fabricating defined submicron-sized amorphous NP domains in melt polymer thin films. We investigate this phenomenon with a view towards understanding and controlling the phase separation process through directed nanoparticle assembly. In particular, we consider isothermally annealed thin films of polystyrene-grafted gold nanoparticles (AuPS) dispersed in a poly(methyl methacrylate) (PMMA) matrix. Classic binary polymer blend phase separation related morphology transitions, from discrete AuPS domains to bicontinuous to inverse domain structure with increasing nanoparticle composition is observed, yet the kinetics of the AuPS/PMMA polymer blends system exhibit unique features compared to the parent PS/PMMA homopolymer blend. We further illustrate how to pattern-align the phase-separated AuPS nanoparticle domain shape, size and location through the imposition of a simple and novel external symmetry-breaking perturbation via soft-lithography. Specifically, submicron-sized topographically patterned elastomer confinement is introduced to direct the nanoparticles into kinetically controlled long-range ordered domains, having a dense yet well-dispersed distribution of non-crystallizing nanoparticles. The simplicity, versatility and roll-to-roll adaptability of this novel method for controlled nanoparticle assembly should make it useful in creating desirable patterned nanoparticle domains for a variety of functional materials and applications.

Polyelectrolyte scaling laws for microgel yielding near jamming.

PubMed

Bhattacharjee, Tapomoy; Kabb, Christopher P; O'Bryan, Christopher S; Urueña, Juan M; Sumerlin, Brent S; Sawyer, W Gregory; Angelini, Thomas E

2018-02-28

Micro-scale hydrogel particles, known as microgels, are used in industry to control the rheology of numerous different products, and are also used in experimental research to study the origins of jamming and glassy behavior in soft-sphere model systems. At the macro-scale, the rheological behaviour of densely packed microgels has been thoroughly characterized; at the particle-scale, careful investigations of jamming, yielding, and glassy-dynamics have been performed through experiment, theory, and simulation. However, at low packing fractions near jamming, the connection between microgel yielding phenomena and the physics of their constituent polymer chains has not been made. Here we investigate whether basic polymer physics scaling laws predict macroscopic yielding behaviours in packed microgels. We measure the yield stress and cross-over shear-rate in several different anionic microgel systems prepared at packing fractions just above the jamming transition, and show that our data can be predicted from classic polyelectrolyte physics scaling laws. We find that diffusive relaxations of microgel deformation during particle re-arrangements can predict the shear-rate at which microgels yield, and the elastic stress associated with these particle deformations predict the yield stress.

Fast dynamics in glass-forming polymers revisited

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

Colmenero, J.; Arbe, A.; Mijangos, C.

1997-12-31

The so called fast-dynamics of glass-forming systems as observed by time of flight (TOF) neutron scattering techniques is revisited. TOF-results corresponding to several glass-forming polymers with different chemical microstructure and glass-transition temperature are presented together with the theoretical framework proposed by the authors to interpret these results. The main conclusion is that the TOF-data can be explained in terms of quasiharmonic vibrations and the particular short time behavior of the segmental dynamics. The segmental dynamics display in the very short time range (t {approx} 2 ps) a crossover from a simple exponential behavior towards a non-exponential regime. The first exponentialmore » decay, which is controlled by C-C rotational barriers, can be understood as a trace of the behavior of the system in absence of the effects (correlations, cooperativity, memory effects {hor_ellipsis}) which characterize the dense supercooled liquid like state against the normal liquid state. The non-exponential regime at t > 2 ps corresponds to what is usually understood as {alpha} and {beta} relaxations. Some implications of these results are also discussed.« less

Towards a more versatile alpha-glucan biosynthesis in plants.

PubMed

Kok-Jacon, Géraldine A; Ji, Qin; Vincken, Jean-Paul; Visser, Richard G F

2003-07-01

Starch is an important storage polysaccharide in many plants. It is composed of densely packed alpha-glucans, consisting of 1,4- and 1,4,6-linked glucose residues. The starch polymers are used in many industrial applications. The biosynthetic machinery for assembling the granule has been manipulated in many different ways to gain insight into the process of starch biosynthesis and to engineer starches with improved functionalities. With respect to the latter, two generic technologies with great potential have been developed: (i) introduction of new linkage types in starch polymers (1,3- and 1,6-linkages), and (ii) engineering granule-boundness. The toolbox to engineer this new generation of starch polymers is discussed.

The conformation of Pluronic block copolymers adsorbed on carbon nanotubes and their interaction with water studied by small-angle neutron scattering

NASA Astrophysics Data System (ADS)

Cohen, Yachin; Granite, Meirav; Pyckhout-Hintzen, Wim; Radulescu, Aurel

2010-03-01

Amphiphilic block copolymers are particularly useful in dispersing single-walled carbon nanotubes (SWCNT) in water. Small-angle neutron scattering measurements conducted at different D2O/H2O content of the dispersing medium provide quantitative information on the adsorption density and conformation of the polymer interacting with the nanotube surface. Data is presented on Pluronic F108 - (EO)132(PO)50(EO)132 and F127 (EO)100(PO)65(EO)100, where EO-ethylene oxide and PO-propylene oxide, well below the critical micellization temperature of the polymer. A dense coating of the PPO blocks on the nanotube surface is determined with the PEO chains extended from the cylindrical core-shell structure. The data from the two Pluronic systems show minimal scattering at about 70% D2O in the dispersing water, which exhibit a q -1 power law of the scattering vector (q ). This indicates near matching of the polymer chains at a surprisingly high scattering length density. The model fit required considerations of tight association of water molecules around PEO chains and slight isotopic selectivity.

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

PubMed

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

2017-04-19

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

Polyelectrolyte brushes grafted from cellulose nanocrystals using Cu-mediated surface-initiated controlled radical polymerization.

PubMed

Majoinen, Johanna; Walther, Andreas; McKee, Jason R; Kontturi, Eero; Aseyev, Vladimir; Malho, Jani Markus; Ruokolainen, Janne; Ikkala, Olli

2011-08-08

Herein we report the synthesis of cellulose nanocrystals (CNCs) grafted with poly(acrylic acid) (PAA) chains of different lengths using Cu-mediated surface initiated-controlled radical polymerization (SI-CRP). First, poly(tert-butylacrylate) (PtBA) brushes were synthesized; then, subsequent acid hydrolysis was used to furnish PAA brushes tethered onto the CNC surfaces. The CNCs were chemically modified to create initiator moieties on the CNC surfaces using chemical vapor deposition (CVD) and continued in solvent phase in DMF. A density of initiator groups of 4.6 bromine ester groups/nm(2) on the CNC surface was reached, suggesting a dense functionalization and a promising starting point for the controlled/living radical polymerization. The SI-CRP of tert-butylacrylate proceeded in a well-controlled manner with the aid of added sacrificial initiator, yielding polymer brushes with polydispersity values typically well below 1.12. We calculated the polymer brush grafting density to almost 0.3 chains/nm(2), corresponding to high grafting densities and dense polymer brush formation on the nanocrystals. Successful rapid acid hydrolysis to remove the tert-butyl groups yielded pH-responsive PAA-polyelectrolyte brushes bound to the CNC surface. Individually dispersed rod-like nanoparticles with brushes of PtBA or PAA were clearly visualized by AFM and TEM imaging.

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

Ishige, Ryohei; Williams, Gregory A.; Higaki, Yuji

A molded film of single-component polymer-grafted nanoparticles (SPNP), consisting of a spherical silica core and densely grafted polymer chains bearing hydrogen-bonding side groups capable of physical crosslinking, was investigated byin situultra-small-angle X-ray scattering (USAXS) measurement during a uniaxial stretching process. Static USAXS revealed that the molded SPNP formed a highly oriented twinned face-centered cubic (f.c.c.) lattice structure with the [11-1] plane aligned nearly parallel to the film surface in the initial state. Structural analysis ofin situUSAXS using a model of uniaxial deformation induced by rearrangement of the nanoparticles revealed that the f.c.c. lattice was distorted in the stretching direction inmore » proportion to the macroscopic strain until the strain reached 35%, and subsequently changed into other f.c.c. lattices with different orientations. The lattice distortion and structural transition behavior corresponded well to the elastic and plastic deformation regimes, respectively, observed in the stress–strain curve. The attractive interaction of the hydrogen bond is considered to form only at the top surface of the shell and then plays an effective role in cross-linking between nanoparticles. The rearrangement mechanism of the nanoparticles is well accounted for by a strong repulsive interaction between the densely grafted polymer shells of neighboring particles.« less

Ordering nanoparticles with polymer brushes

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

Cheng, Shengfeng; Stevens, Mark J.; Grest, Gary S.

Ordering nanoparticles into a desired super-structure is often crucial for their technological applications. We use molecular dynamics simulations to study the assembly of nanoparticles in a polymer brush randomly grafted to a planar surface as the solvent evaporates. Initially, the nanoparticles are dispersed in a solvent that wets the polymer brush. After the solvent evaporates, the nanoparticles are either inside the brush or adsorbed at the surface of the brush, depending on the strength of the nanoparticle-polymer interaction. For strong nanoparticle-polymer interactions, a 2-dimensional ordered array is only formed when the brush density is finely tuned to accommodate a singlemore » layer of nanoparticles. When the brush density is higher or lower than this optimal value, the distribution of nanoparticles shows large fluctuations in space and the packing order diminishes. For weak nanoparticle-polymer interactions, the nanoparticles order into a hexagonal array on top of the polymer brush as long as the grafting density is high enough to yield a dense brush. As a result, an interesting healing effect is observed for a low-grafting-density polymer brush that can become more uniform in the presence of weakly adsorbed nanoparticles.« less

From intermediate anisotropic to isotropic friction at large strain rates to account for viscosity thickening in polymer solutions

NASA Astrophysics Data System (ADS)

Stephanou, Pavlos S.; Kröger, Martin

2018-05-01

The steady-state extensional viscosity of dense polymeric liquids in elongational flows is known to be peculiar in the sense that for entangled polymer melts it monotonically decreases—whereas for concentrated polymer solutions it increases—with increasing strain rate beyond the inverse Rouse time. To shed light on this issue, we solve the kinetic theory model for concentrated polymer solutions and entangled melts proposed by Curtiss and Bird, also known as the tumbling-snake model, supplemented by a variable link tension coefficient that we relate to the uniaxial nematic order parameter of the polymer. As a result, the friction tensor is increasingly becoming isotropic at large strain rates as the polymer concentration decreases, and the model is seen to capture the experimentally observed behavior. Additional refinements may supplement the present model to capture very strong flows. We furthermore derive analytic expressions for small rates and the linear viscoelastic behavior. This work builds upon our earlier work on the use of the tumbling-snake model under shear and demonstrates its capacity to improve our microscopic understanding of the rheology of entangled polymer melts and concentrated polymer solutions.

Ordering nanoparticles with polymer brushes

DOE PAGES

Cheng, Shengfeng; Stevens, Mark J.; Grest, Gary S.

2017-12-08

Ordering nanoparticles into a desired super-structure is often crucial for their technological applications. We use molecular dynamics simulations to study the assembly of nanoparticles in a polymer brush randomly grafted to a planar surface as the solvent evaporates. Initially, the nanoparticles are dispersed in a solvent that wets the polymer brush. After the solvent evaporates, the nanoparticles are either inside the brush or adsorbed at the surface of the brush, depending on the strength of the nanoparticle-polymer interaction. For strong nanoparticle-polymer interactions, a 2-dimensional ordered array is only formed when the brush density is finely tuned to accommodate a singlemore » layer of nanoparticles. When the brush density is higher or lower than this optimal value, the distribution of nanoparticles shows large fluctuations in space and the packing order diminishes. For weak nanoparticle-polymer interactions, the nanoparticles order into a hexagonal array on top of the polymer brush as long as the grafting density is high enough to yield a dense brush. As a result, an interesting healing effect is observed for a low-grafting-density polymer brush that can become more uniform in the presence of weakly adsorbed nanoparticles.« less

A method for generating reliable atomistic models of amorphous polymers based on a random search of energy minima

NASA Astrophysics Data System (ADS)

Curcó, David; Casanovas, Jordi; Roca, Marc; Alemán, Carlos

2005-07-01

A method for generating atomistic models of dense amorphous polymers is presented. The method is organized in a two-steps procedure. First, structures are generated using an algorithm that minimizes the torsional strain. After this, a relaxation algorithm is applied to minimize the non-bonding interactions. Two alternative relaxation methods, which are based simple minimization and Concerted Rotation techniques, have been implemented. The performance of the method has been checked by simulating polyethylene, polypropylene, nylon 6, poly(L,D-lactic acid) and polyglycolic acid.

Environmental influence on the bond between a polymer concrete overlay and an aluminum substrate.

DOT National Transportation Integrated Search

2000-04-01

Chloride-ion-induced corrosion of reinforcing steel in concrete bridge decks has become a major problem in the United States. : Latex-modified concrete, low-slump dense concrete, and hot-mix asphalt membrane overlays are some of the most used : rehab...

Design and synthesis of two luminescent Zn(II)-based coordination polymers with different structures regulated by different solvent system

NASA Astrophysics Data System (ADS)

Wu, Wei-Ping; Wen, Gui-Lin; Liao, Yi; Wang, Jun; Lu, Lu; Wu, Yu; Xie, Bin

2016-08-01

Two new coordination polymers (CPs) [Zn(HL)(H2O)]n (1) and [Zn3(L)2(H2O)2]n·(H2O)n (2), based on a multifunctional ligand combined carboxylate groups and a nitrogen donor group 5-(6-carboxypyridin-2-yl)isophthalic acid (H3L), have been synthesized under different solvent media and fully characterized by powder X-ray diffraction (PXRD), infrared (IR) spectra, elemental analyses (EA) and thermogravimetric analyses (TGA). Single-crystal X-ray diffraction analysis reveals that 1 shows 1D dimeric chain structure, while 2 gives a 3D dense packing framework. Topology analysis illustrates that 2 can be simplified as a 3-nodal net (4, 5, 6-connected net) with the point symbol of {44·62}{46·64}2{48·66·8}. In addition, solid state luminescent properties of two complexes have also been studied in detail, which may act as the potential optical materials.

Crowding-facilitated macromolecular transport in attractive micropost arrays.

PubMed

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

2017-05-02

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

Recent progress in InP/polymer-based devices for telecom and data center applications

NASA Astrophysics Data System (ADS)

Kleinert, Moritz; Zhang, Ziyang; de Felipe, David; Zawadzki, Crispin; Maese Novo, Alejandro; Brinker, Walter; Möhrle, Martin; Keil, Norbert

2015-02-01

Recent progress on polymer-based photonic devices and hybrid photonic integration technology using InP-based active components is presented. High performance thermo-optic components, including compact polymer variable optical attenuators and switches are powerful tools to regulate and control the light flow in the optical backbone. Polymer arrayed waveguide gratings integrated with InP laser and detector arrays function as low-cost optical line terminals (OLTs) in the WDM-PON network. External cavity tunable lasers combined with C/L band thinfilm filter, on-chip U-groove and 45° mirrors construct a compact, bi-directional and color-less optical network unit (ONU). A tunable laser integrated with VOAs, TFEs and two 90° hybrids builds the optical front-end of a colorless, dual-polarization coherent receiver. Multicore polymer waveguides and multi-step 45°mirrors are demonstrated as bridging devices between the spatialdivision- multiplexing transmission technology using multi-core fibers and the conventional PLCbased photonic platforms, appealing to the fast development of dense 3D photonic integration.

From Comb-like Polymers to Bottle-Brushes

NASA Astrophysics Data System (ADS)

Liang, Heyi; Cao, Zhen; Dobrynin, Andrey; Sheiko, Sergei

We use a combination of the coarse-grained molecular dynamics simulations and scaling analysis to study conformations of bottle-brushes and comb-like polymers in a melt. Our analysis show that bottle-brushes and comb-like polymers can be in four different conformation regimes depending on the number of monomers between grafted side chains and side chain degree of polymerization. In loosely-grafted comb regime (LC) the degree of polymerization between side chains is longer than side chain degree of polymerization, such that the side chains belonging to the same macromolecule do not overlap. Crossover to a new densely-grafted comb regime (DC) takes place when side chains begin to overlap reducing interpenetration of side chains belonging to different macromolecules. In these two regimes both side-chains and backbone behave as unperturbed linear chains with the effective Kuhn length of the backbone being close to that of linear chain. Further decrease spacer degree of polymerization results in crossover to loosely-grafted bottle-brush regime (LB). In this regime, the bottle-brush backbone is stretched while the side-chains still maintain ideal chain conformation. Finally, for even shorter spacer between grafted side chains, which corresponds to densely-grafted bottle-brush regime (DB), the backbone adopts a fully extended chain conformation, and side-chains begin to stretch to maintain a constant monomer density. NSF DMR-1409710, DMR-1407645, DMR-1624569, DMR-1436201.

Investigation of polymer membranes modified by fullerenol for dehydration of organic mixtures

NASA Astrophysics Data System (ADS)

Dmitrenko, Mariia E.; Penkova, Anastasia V.; Kuzminova, Anna I.; Ermakov, Sergey S.; Roizard, Denis

2017-07-01

This study focuses on the development of novel dense and supported mixed-matrix membranes based on chitosan and poly(2,6-dimethyl-1,4-phenylenoxide) (PPO) with low-hydroxylated fullerenol C60(OH)12. These novel membranes containing nano-carbon particles were prepared to reach high membrane performances for further integration in a dehydration process like distillation coupled with pervaporation. SEM microscopy was used to visualize the internal morphology of the membrane. It was found that all membranes were well stable and highly water-selective in spite of the different nature of polymers.

Measurements of Submicron Particle Adsorption and Particle Film Elasticity at Oil-Water Interfaces.

PubMed

Manga, Mohamed S; Hunter, Timothy N; Cayre, Olivier J; York, David W; Reichert, Matthew D; Anna, Shelly L; Walker, Lynn M; Williams, Richard A; Biggs, Simon R

2016-05-03

The influence of particle adsorption on liquid/liquid interfacial tension is not well understood, and much previous research has suggested conflicting behaviors. In this paper we investigate the surface activity and adsorption kinetics of charge stabilized and pH-responsive polymer stabilized colloids at oil/water interfaces using two tensiometry techniques: (i) pendant drop and (ii) microtensiometer. We found, using both techniques, that charge stabilized particles had little or no influence on the (dynamic) interfacial tension, although dense silica particles affected the "apparent" measured tension in the pendent drop, due to gravity driven elongation of the droplet profile. Nevertheless, this apparent change additionally allowed the study of adsorption kinetics, which was related qualitatively between particle systems by estimated diffusion coefficients. Significant and real interfacial tension responses were measured using ∼53 nm core-shell latex particles with a pH-responsive polymer stabilizer of poly(methyl methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate) (pMMA-b-pDMAEMA) diblock copolymer. At pH 2, where the polymer is strongly charged, behavior was similar to that of the bare charge-stabilized particles, showing little change in the interfacial tension. At pH 10, where the polymer is discharged and poorly soluble in water, a significant decrease in the measured interfacial tension commensurate with strong adsorption at the oil-water interface was seen, which was similar in magnitude to the surface activity of the free polymer. These results were both confirmed through droplet profile and microtensiometry experiments. Dilational elasticity measurements were also performed by oscillation of the droplet; again, changes in interfacial tension with droplet oscillation were only seen with the responsive particles at pH 10. Frequency sweeps were performed to ascertain the dilational elasticity modulus, with measured values being significantly higher than previously reported for nanoparticle and surfactant systems, and similar in magnitude to protein stabilized droplets.

High rate lithium-sulfur battery enabled by sandwiched single ion conducting polymer electrolyte

PubMed Central

Sun, Yubao; Li, Gai; Lai, Yuanchu; Zeng, Danli; Cheng, Hansong

2016-01-01

Lithium-sulfur batteries are highly promising for electric energy storage with high energy density, abundant resources and low cost. However, the battery technologies have often suffered from a short cycle life and poor rate stability arising from the well-known “polysulfide shuttle” effect. Here, we report a novel cell design by sandwiching a sp3 boron based single ion conducting polymer electrolyte film between two carbon films to fabricate a composite separator for lithium-sulfur batteries. The dense negative charges uniformly distributed in the electrolyte membrane inherently prohibit transport of polysulfide anions formed in the cathode inside the polymer matrix and effectively blocks polysulfide shuttling. A battery assembled with the composite separator exhibits a remarkably long cycle life at high charge/discharge rates. PMID:26898772

Growth Of Oriented Crystals At Polymerized Membranes

DOEpatents

Charych, Deborah H. , Berman, Amir

2000-01-25

The present invention relates to methods and compositions for the growth and alignment of crystals at biopolymeric films. The methods and compositions of the present invention provide means to generate a variety of dense crystalline ceramic films, with totally aligned crystals, at low temperatures and pressures, suitable for use with polymer and plastic substrates.

The chemical modification and characterization of polypropylene membrane with environment response by in-situ chlorinating graft copolymerization

NASA Astrophysics Data System (ADS)

Zhang, Yue; Liu, Jiankai; Hu, Wenjie; Feng, Ying; Zhao, Jiruo

2017-08-01

In this study, a novel chemical surface modification method of polyolefin membranes is applied following the in-situ chlorinating graft copolymerization (ISCGC). Polypropylene (PP)/methyl methacrylate (MMA) system was used as an example. A unique structure was formed by the modification process on the original membrane surface and the product exhibited an environmental response. Chlorine free radicals were generated using ultraviolet and heat and were used to capture the hydrogen in the polymer chains on the substrate surface. The formed macromolecular radicals could react with MMA over 2 h to achieve a high coverage ratio polymer on the PP membrane surface. The graft copolymers were characterized using FTIR, 1H-NMR, DSC, and XPS, which all proved the feasibility of chemically modifying the PP membrane surface by ISCGC. The surface morphology of the grafted PP membrane was characterized using SEM and AFM. The results showed that the grafted product presents a uniform, neat, and dense mastoid structure with an average thickness of 4.44 μm, which was expected to be similar to the brush-like surface structure. The contact angle and AFM tests indicated that the product surface is responsive to solvent and pH. The experimental results showed that the PP membrane surface structure can be reconstructed using ISCGC, a method that can be used for environment-responsive polymer materials. Moreover, the product has the characteristics of polymer interfacial brush.

Tethered Lubricants

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

Archer, Lynden

We have performed extensive experimental and theoretical studies of interfacial friction, relaxation dynamics, and thermodynamics of polymer chains tethered to points, planes, and particles. A key result from our tribology studies using lateral force microscopy (LFM) measurements of polydisperse brushes of linear and branched chains densely grafted to planar substrates is that there are exceedingly low friction coefficients for these systems. Specific project achievements include: (1) Synthesis of three-tiered lubricant films containing controlled amounts of free and pendent PDMS chains, and investigated the effect of their molecular weight and volume fraction on interfacial friction. (2.) Detailed studies of a familymore » of hairy particles termed nanoscale organic hybrid materials (NOHMs) and demonstration of their use as lubricants.« less

Artificial Informational Polymers and Nanomaterials from Ring-Opening Metathesis Polymerization

NASA Astrophysics Data System (ADS)

James, Carrie Rae

Inspired by naturally occurring polymers (DNA, polypeptides, polysaccharides, etc.) that can self-assemble on the nanoscale into complex, information-rich architectures, we have synthesized nucleic acid based polymers using ROMP. These polymers were synthesized using a graft-through strategy, whereby nucleic acids bearing a strained cyclic olefin were directly polymerized. This is the first example of the graft-through polymerization of nucleic acids. Our approach takes advantage of non-charged peptide nucleic acids (PNAs) as elements to incorporate into ROMP polymer backbones. PNA is a synthetic nucleic acid analogue known for its increased affinity and specificity for complementary DNA or RNA. To accomplish the graft-through polymerization of PNA, we conjugated PNA to strained cyclic olefins using solid phase peptide conjugation chemistry. These PNA monomers were then directly polymerized into homo and block copolymers forming brushes, or comb-like arrangements, of information. Block copolymer amphiphiles of these materials, where the PNA brush served as the hydrophilic portion, were capable of self-assembly into spherical nanoparticles (PNA NPs). These PNA NPs were then studied with respect to their ability to hybridize complementary DNA sequences, as well as their ability to undergo cellular internalization. PNA NPs consisting of densely packed brushes of nucleic acids possessed increased thermal stability when mixed with their complementary DNA sequence, indicating a greater DNA binding affinity over their unpolymerized PNA counterparts. In addition, by arranging the PNA into dense brushes at the surface of the nanoparticle, Cy5.5 labeled PNA NPs were able to undergo cellular internalization into HeLa cells without the need for an additional cellular delivery device. Importantly, cellular internalization of PNA has remained a significant challenge in the literature due to the neutrally charged amino-ethyl glycine backbone of PNA. Therefore, this represents a novel way of facilitating cellular uptake of PNA. This materials strategy represents the first direct polymerization of nucleic acids, and presents a novel method for arranging biological information on the nanoscale at high density in order to confer novel attributes.

Stress and structure development in polymeric coatings

NASA Astrophysics Data System (ADS)

Vaessen, Diane Melissa

2002-09-01

The main goal of this research is to measure the stress evolution in various polymer coating systems to establish the mechanisms responsible for stress development, stress relaxation, and defect formation. Investigated systems include ultraviolet (UV)-curable coatings, dense and porous coatings from polymer solutions, and latex coatings. Coating stress was measured using a controlled environment stress apparatus based on a cantilever deflection principle. For acrylate coatings, it was found that by cycling a UV-lamp on and off, keeping the total dose constant, coating stress was lowered by 60% by decreasing the cycle period. A stress minimum was also found to exist for a given dose of radiation. The lower stress is attributed to stress relaxation and/or slower reaction during dark periods. A viscoelastic stress model of this process was formulated and predicted stress values close to those observed experimentally. During drying of cellulose acetate (CA) coatings cast in acetone, final stress increased from 10 to 45 MPa as coating thickness decreased from 60 to 10 mum. This thickness dependent coating stress for a solvent-cast polymer coating is a new finding and is attributed to (1) less shrinkage in thicker coatings due to more trapped solvent (from skinning) and (2) greater amounts of polymer stress relaxation in thicker coatings. For porous CA coatings prepared by dry-cast phase separation, final in-plane stresses ranged from 20 MPa for coatings containing small pores (˜1 mum) to 5 MPa for coatings containing small pores and macrovoids (˜200 mum). For these coatings, a small amount of stress relaxation occurs due to capillary pressure relief. A stress plateau for the macrovoid-containing coating is likely caused by stress-induced rupture of the polymer-rich phase. Measured stress in pigment-free latex coatings was much lower (˜0.3 MPa) than UV-curable and solvent-cast polymer coatings and was found to increase with increasing latex glass transition temperature. Observations from infrared spectroscopy, scanning electron microscopy, camera imaging, and indentation were also studied to correlate coating properties to measured stresses. The results obtained in this thesis will lead to strategies for material selection, process optimization, and defect elimination in polymeric coatings.

Wafer Scale Fabrication of Dense and High Aspect Ratio Sub-50 nm Nanopillars from Phase Separation of Cross-Linkable Polysiloxane/Polystyrene Blend.

PubMed

Li, Yang; Hao, Yuli; Huang, Chunyu; Chen, Xingyao; Chen, Xinyu; Cui, Yushuang; Yuan, Changsheng; Qiu, Kai; Ge, Haixiong; Chen, Yanfeng

2017-04-19

We demonstrated a simple and effective approach to fabricate dense and high aspect ratio sub-50 nm pillars based on phase separation of a polymer blend composed of a cross-linkable polysiloxane and polystyrene (PS). In order to obtain the phase-separated domains with nanoscale size, a liquid prepolymer of cross-linkable polysiloxane was employed as one moiety for increasing the miscibility of the polymer blend. After phase separation via spin-coating, the dispersed domains of liquid polysiloxane with sub-50 nm size could be solidified by UV exposure. The solidified polysiloxane domains took the role of etching mask for formation of high aspect ratio nanopillars by O 2 reactive ion etching (RIE). The aspect ratio of the nanopillars could be further amplified by introduction of a polymer transfer layer underneath the polymer blend film. The effects of spin speeds, the weight ratio of the polysiloxane/PS blend, and the concentration of polysiloxane/PS blend in toluene on the characters of the nanopillars were investigated. The gold-coated nanopillar arrays exhibited a high Raman scattering enhancement factor in the range of 10 8 -10 9 with high uniformity across over the wafer scale sample. A superhydrophobic surface could be realized by coating a self-assembled monolayers (SAM) of fluoroalkyltrichlorosilane on the nanopillar arrays. Sub-50 nm silicon nanowires (SiNWs) with high aspect ratio of about 1000 were achieved by using the nanopillars as etching mask through a metal-assisted chemical etching process. They showed an ultralow reflectance of approximately 0.1% for wavelengths ranging from 200 to 800 nm.

Novel dense CO2 technique for beta-galactosidase immobilization in polystyrene microchannels.

PubMed

Leclair Ellis, Jeffrey; Tomasko, David L; Dehghani, Fariba

2008-03-01

In this study we design new fabrication techniques and demonstrate the potential of using dense CO2 for facilitating crucial steps in the fabrication of polymeric lab-on-a-chip microdevices by embedding biomolecules at temperatures well below the polymer's glass transition temperature (T(g)). These new techniques are environmentally friendly and done without the use of a clean room. Carbon dioxide at 40 degrees C and between 4.48 and 6.89 MPa was used to immobilize the biologically active molecule, beta-galactosidase (beta-gal), on the surface of polystyrene microchannels. To our knowledge, this is the first time dense CO2 has been used to directly immobilize an enzyme in a microchannel. beta-gal activity was maintained and shown via a fluorescent reaction product, after enzyme immobilization and microchannel capping by the designed fabrication steps at 40 degrees C and pressures up to 6.89 MPa.

Methane Hydrate in Confined Spaces: An Alternative Storage System.

PubMed

Borchardt, Lars; Casco, Mirian Elizabeth; Silvestre-Albero, Joaquin

2018-06-05

Methane hydrate inheres the great potential to be a nature-inspired alternative for chemical energy storage, as it allows to store large amounts of methane in a dense solid phase. The embedment of methane hydrate in the confined environment of porous materials can be capitalized for potential applications as its physicochemical properties, such as the formation kinetics or pressure and temperature stability, are significantly changed compared to the bulk system. We review this topic from a materials scientific perspective by considering porous carbons, silica, clays, zeolites, and polymers as host structures for methane hydrate formation. We discuss the contribution of advanced characterization techniques and theoretical simulations towards the elucidation of the methane hydrate formation and dissociation process within the confined space. We outline the scientific challenges this system is currently facing and look on possible future applications for this technology. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient Energy Conversion by Grafting Nanochannels with End-charged Stimuli-responsive Polyelectrolyte Brush

NASA Astrophysics Data System (ADS)

Chen, Guang; Das, Siddhartha

2017-11-01

Polyelectrolyte (PE) brushes have aroused increasing attention in applications in energy conversion and chemical sensing due to the environmentally-responsive and designable nature. PE brushes are charged polymer chains densely grafted on solid-liquid interfaces. By designing copolymeric systems, one can localize the ionizable sites at the brush tip in order to get end-charged PE brushes. Such brushes demonstrate anomalous shrinking/swelling behaviors with tunable environmental parameters such as pH and salt concentration. In this study, we probe the conformation and electrostatics of such PE brush systems with various size, grafting density and charge distribution, and exploit the electrochemomechanical energy conversion capabilities of nanochannels grafted with such PE brush systems. Our results indicate that the presence of the end-charged PE brush layer can massively enhance the streaming potential mediated energy conversion efficiency, and the improvement is more significant in strongly ionic solution.

Polymer-Based Protein Engineering: Synthesis and Characterization of Armored, High Graft Density Polymer-Protein Conjugates.

PubMed

Carmali, Sheiliza; Murata, Hironobu; Cummings, Chad; Matyjaszewski, Krzysztof; Russell, Alan J

2017-01-01

Atom transfer radical polymerization (ATRP) from the surface of a protein can generate remarkably dense polymer shells that serve as armor and rationally tune protein function. Using straightforward chemistry, it is possible to covalently couple or display multiple small molecule initiators onto a protein surface. The chemistry is fine-tuned to be sequence specific (if one desires a single targeted site) at controlled density. Once the initiator is anchored on the protein surface, ATRP is used to grow polymers on protein surface, in situ. The technique is so powerful that a single-protein polymer conjugate molecule can contain more than 90% polymer coating by weight. If desired, stimuli-responsive polymers can be "grown" from the initiated sites to prepare enzyme conjugates that respond to external triggers such as temperature or pH, while still maintaining enzyme activity and stability. Herein, we focus mainly on the synthesis of chymotrypsin-polymer conjugates. Control of the number of covalently coupled initiator sites by changing the stoichiometric ratio between enzyme and the initiator during the synthesis of protein-initiator complexes allowed fine-tuning of the grafting density. For example, very high grafting density chymotrypsin conjugates were prepared from protein-initiator complexes to grow the temperature-responsive polymers, poly(N-isopropylacrylamide), and poly[N,N'-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate]. Controlled growth of polymers from protein surfaces enables one to predictably manipulate enzyme kinetics and stability without the need for molecular biology-dependent mutagenesis. © 2017 Elsevier Inc. All rights reserved.

Dynamic response of ultrathin highly dense ZIF-8 nanofilms.

PubMed

Cookney, Joanna; Ogieglo, Wojciech; Hrabanek, Pavel; Vankelecom, Ivo; Fila, Vlastimil; Benes, Nieck E

2014-10-11

Ultrathin ZIF-8 nanofilms are prepared by facile step-by-step dip coating. A critical withdrawal speed allows for films with a very uniform minimum thickness. The high refractive index of the films denotes the absence of mesopores. The dynamic response of the films to CO2 exposure resembles behaviour observed for non-equilibrium organic polymers.

25th anniversary article: CVD polymers: a new paradigm for surface modification and device fabrication.

PubMed

Coclite, Anna Maria; Howden, Rachel M; Borrelli, David C; Petruczok, Christy D; Yang, Rong; Yagüe, Jose Luis; Ugur, Asli; Chen, Nan; Lee, Sunghwan; Jo, Won Jun; Liu, Andong; Wang, Xiaoxue; Gleason, Karen K

2013-10-11

Well-adhered, conformal, thin (<100 nm) coatings can easily be obtained by chemical vapor deposition (CVD) for a variety of technological applications. Room temperature modification with functional polymers can be achieved on virtually any substrate: organic, inorganic, rigid, flexible, planar, three-dimensional, dense, or porous. In CVD polymerization, the monomer(s) are delivered to the surface through the vapor phase and then undergo simultaneous polymerization and thin film formation. By eliminating the need to dissolve macromolecules, CVD enables insoluble polymers to be coated and prevents solvent damage to the substrate. CVD film growth proceeds from the substrate up, allowing for interfacial engineering, real-time monitoring, and thickness control. Initiated-CVD shows successful results in terms of rationally designed micro- and nanoengineered materials to control molecular interactions at material surfaces. The success of oxidative-CVD is mainly demonstrated for the deposition of organic conducting and semiconducting polymers. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pressure polymerization of polyester

DOEpatents

Maurer, Charles J.; Shaw, Gordon; Smith, Vicky S.; Buelow, Steven J.; Tumas, William; Contreras, Veronica; Martinez, Ronald J.

2000-08-29

A process is disclosed for the preparation of a polyester polymer or polyester copolymer under superatmospheric pressure conditions in a pipe or tubular reaction under turbannular flow conditions. Reaction material having a glycol equivalents to carboxylic acid equivalents mole ratio of from 1.0:1 to 1.2:1, together with a superatmospheric dense gaseous medium are fed co-currently to the reactor. Dicarboxylic acid and/or diol raw materials may be injected into any of the reaction zones in the process during operation to achieve the overall desired mole ratio balance. The process operates at temperatures of from about 220.degree. C. to about 320.degree. C., with turbannular flow achieved before the polymer product and gas exit the reactor process. The pressure in the reaction zones can be in the range from 15 psia to 2500 psia. A polymer product having a DP of a greater than 40, more preferably at least about 70, is achieved by the transfer of water from the reacting material polymer melt to the gaseous medium in the reactor.

Expansion microscopy: development and neuroscience applications.

PubMed

Karagiannis, Emmanouil D; Boyden, Edward S

2018-06-01

Many neuroscience questions center around understanding how the molecules and wiring in neural circuits mechanistically yield behavioral functions, or go awry in disease states. However, mapping the molecules and wiring of neurons across the large scales of neural circuits has posed a great challenge. We recently developed expansion microscopy (ExM), a process in which we physically magnify biological specimens such as brain circuits. We synthesize throughout preserved brain specimens a dense, even mesh of a swellable polymer such as sodium polyacrylate, anchoring key biomolecules such as proteins and nucleic acids to the polymer. After mechanical homogenization of the specimen-polymer composite, we add water, and the polymer swells, pulling biomolecules apart. Due to the larger separation between molecules, ordinary microscopes can then perform nanoscale resolution imaging. We here review the ExM technology as well as applications to the mapping of synapses, cells, and circuits, including deployment in species such as Drosophila, mouse, non-human primate, and human. Copyright © 2017 Elsevier Ltd. All rights reserved.

Flow induced migration in polymer melts – Theory and simulation

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

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

2015-04-28

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

Entropic organization of interphase chromosomes

PubMed Central

Marenduzzo, Davide

2009-01-01

Chromosomes are not distributed randomly in nuclei. Appropriate positioning can activate (or repress) genes by bringing them closer to active (or inactive) compartments like euchromatin (or heterochromatin), and this is usually assumed to be driven by specific local forces (e.g., involving H bonds between nucleosomes or between nucleosomes and the lamina). Using Monte Carlo simulations, we demonstrate that nonspecific (entropic) forces acting alone are sufficient to position and shape self-avoiding polymers within a confining sphere in the ways seen in nuclei. We suggest that they can drive long flexible polymers (representing gene-rich chromosomes) to the interior, compact/thick ones (and heterochromatin) to the periphery, looped (but not linear) ones into appropriately shaped (ellipsoidal) territories, and polymers with large terminal beads (representing centromeric heterochromatin) into peripheral chromocenters. Flexible polymers tend to intermingle less than others, which is in accord with observations that gene-dense (and so flexible) chromosomes make poor translocation partners. Thus, entropic forces probably participate in the self-organization of chromosomes within nuclei. PMID:19752020

Tuning the density profile of surface-grafted hyaluronan and the effect of counter-ions.

PubMed

Berts, Ida; Fragneto, Giovanna; Hilborn, Jöns; Rennie, Adrian R

2013-07-01

The present paper investigates the structure and composition of grafted sodium hyaluronan at a solid-liquid interface using neutron reflection. The solvated polymer at the surface could be described with a density profile that decays exponentially towards the bulk solution. The density profile of the polymer varied depending on the deposition protocol. A single-stage deposition resulted in denser polymer layers, while layers created with a two-stage deposition process were more diffuse and had an overall lower density. Despite the diffuse density profile, two-stage deposition leads to a higher surface excess. Addition of calcium ions causes a strong collapse of the sodium hyaluronan chains, increasing the polymer density near the surface. This effect is more pronounced on the sample prepared by two-stage deposition due to the initial less dense profile. This study provides an understanding at a molecular level of how surface functionalization alters the structure and how surface layers respond to changes in calcium ions in the solvent.

Fabrication of semiconductor-polymer compound nonlinear photonic crystal slab with highly uniform infiltration based on nano-imprint lithography technique.

PubMed

Qin, Fei; Meng, Zi-Ming; Zhong, Xiao-Lan; Liu, Ye; Li, Zhi-Yuan

2012-06-04

We present a versatile technique based on nano-imprint lithography to fabricate high-quality semiconductor-polymer compound nonlinear photonic crystal (NPC) slabs. The approach allows one to infiltrate uniformly polystyrene materials that possess large Kerr nonlinearity and ultrafast nonlinear response into the cylindrical air holes with diameter of hundred nanometers that are perforated in silicon membranes. Both the structural characterization via the cross-sectional scanning electron microscopy images and the optical characterization via the transmission spectrum measurement undoubtedly show that the fabricated compound NPC samples have uniform and dense polymer infiltration and are of high quality in optical properties. The compound NPC samples exhibit sharp transmission band edges and nondegraded high quality factor of microcavities compared with those in the bare silicon PC. The versatile method can be expanded to make general semiconductor-polymer hybrid optical nanostructures, and thus it may pave the way for reliable and efficient fabrication of ultrafast and ultralow power all-optical tunable integrated photonic devices and circuits.

New High Temperature Cross Linking Monomers

NASA Technical Reports Server (NTRS)

Scola, Daniel A.

1978-01-01

This report describes the results of a one-year program designed to synthesize new, nonvolatile crosslinking monomers and to prove their feasibility in the development of lower temperature curing PMR-polyimide resins with high temperature capability. The objective of this program is to develop PMR-polyimide resins capable of being processed at a maximum temperature of 232C to 288C (450F to 500F) without sacrifice of the high temperature 316C (600F) capability of the state-of-the-art PMR-15 polyimide resin. Four monomethyl esters were synthesized and characterized for use in the crosslinking studies. It was found that all four crosslinkers were capable of entering into a crosslinking reaction to produce polymer specimens which were strong, dense and free of voids. The infrared and DSC studies of each crosslinker with monomers 4,4'-methylenedianiline (MDA) and the dimethyl ester of 3,3',4,4'-benzophenonetetracarboxylic acid (BTDE) comprising the resin systems, crosslinker/MDA/BTDE suggested that curing could be accomplished at 288C (550F). However, fabrication of dense, void free polymer specimens required a temperature of 316C (600F) and a pressure of 0.69 MPa (100 psi). The crosslinkers, monomethyl ester of 2,5-bicyclo[2.2.1]heptadiene-2,3-dicarboxylic acid (NDE) and monomethyl ester of maleic acid (MAE) were selected for evaluation in Celion 6000/PMR polyimide composites. These composites were characterized at RT, 288C (550F) and 316C (600F) initially and after isothermal aging at 288C (550F) and 316C (600F) for several hundred hours. The results of the isothermal aging studies suggested that both PMR systems NDE-MDA-BTDE and MAE-MDA-BTDE are promising candidates as matrices for addition type polyimide composites. These studies demonstrated that alternate crosslinkers to NE/MDA/BTDE are feasible, but mechanisms to lower the crosslinking temperature must be developed to provide lower temperature processing PMR-type polyimides.

Advanced Materials by Atom Transfer Radical Polymerization.

PubMed

Matyjaszewski, Krzysztof

2018-06-01

Atom transfer radical polymerization (ATRP) has been successfully employed for the preparation of various advanced materials with controlled architecture. New catalysts with strongly enhanced activity permit more environmentally benign ATRP procedures using ppm levels of catalyst. Precise control over polymer composition, topology, and incorporation of site specific functionality enables synthesis of well-defined gradient, block, comb copolymers, polymers with (hyper)branched structures including stars, densely grafted molecular brushes or networks, as well as inorganic-organic hybrid materials and bioconjugates. Examples of specific applications of functional materials include thermoplastic elastomers, nanostructured carbons, surfactants, dispersants, functionalized surfaces, and biorelated materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of a Crack-Free, Hybrid Skin Layer with Tunable Surface Topography and Improved Gas Permeation Selectivity on Elastomers Using Gel–Liquid Infiltration Polymerization

DOE PAGES

Wang, Mengyuan; Gorham, Justin M.; Killgore, Jason P.; ...

2017-07-31

Surface modifications of elastomers and gels are crucial for emerging applications such as soft robotics and flexible electronics, in large part because they provide a platform to control wettability, adhesion, and permeability. Current surface modification methods via ultraviolet-ozone (UVO) and/or O2 plasma, atomic layer deposition (ALD), plasmas deposition, and chemical treatment impart a dense polymer or inorganic layer on the surface that is brittle and easy to fracture at low strain levels. This paper presents a new method, based on gel–liquid infiltration polymerization, to form hybrid skin layers atop elastomers. The method is unique in that it allows for controlmore » of the skin layer topography, with tunable feature sizes and aspect ratios as high as 1.8 without fracture. Unlike previous techniques, the skin layer formed here dramatically improves the barrier properties of the elastomer, while preserving skin layer flexibility. Furthermore, the method is versatile and likely applicable to most interfacial polymerization systems and network polymers on flat and patterned surfaces.« less

Formation of a Crack-Free, Hybrid Skin Layer with Tunable Surface Topography and Improved Gas Permeation Selectivity on Elastomers Using Gel–Liquid Infiltration Polymerization

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

Wang, Mengyuan; Gorham, Justin M.; Killgore, Jason P.

Surface modifications of elastomers and gels are crucial for emerging applications such as soft robotics and flexible electronics, in large part because they provide a platform to control wettability, adhesion, and permeability. Current surface modification methods via ultraviolet-ozone (UVO) and/or O2 plasma, atomic layer deposition (ALD), plasmas deposition, and chemical treatment impart a dense polymer or inorganic layer on the surface that is brittle and easy to fracture at low strain levels. This paper presents a new method, based on gel–liquid infiltration polymerization, to form hybrid skin layers atop elastomers. The method is unique in that it allows for controlmore » of the skin layer topography, with tunable feature sizes and aspect ratios as high as 1.8 without fracture. Unlike previous techniques, the skin layer formed here dramatically improves the barrier properties of the elastomer, while preserving skin layer flexibility. Furthermore, the method is versatile and likely applicable to most interfacial polymerization systems and network polymers on flat and patterned surfaces.« less

FCC-HCP coexistence in dense thermo-responsive microgel crystals

NASA Astrophysics Data System (ADS)

Karthickeyan, D.; Joshi, R. G.; Tata, B. V. R.

2017-06-01

Analogous to hard-sphere suspensions, monodisperse thermo-responsive poly (N-isopropyl acrylamide) (PNIPAM) microgel particles beyond a volume fraction (ϕ) of 0.5 freeze into face centered cubic (FCC)-hexagonal close packed (HCP) coexistence under as prepared conditions and into an FCC structure upon annealing. We report here FCC-HCP coexistence to be stable in dense PNIPAM microgel crystals (ϕ > 0.74) with particles in their deswollen state (referred to as osmotically compressed microgel crystals) and the FCC structure with particles in their swollen state by performing annealing studies with different cooling rates. The structure of PNIPAM microgel crystals is characterized using static light scattering technique and UV-Visible spectroscopy and dynamics by dynamic light scattering (DLS). DLS studies reveal that the particle motion is diffusive at short times in crystals with ϕ < 0.74 and sub-diffusive at short times in PNIPAM crystals with ϕ > 0.74. The observed sub-diffusive behavior at short times is due to the overlap (interpenetration) of the dangling polymer chains between the shells of neighbouring PNIPAM microgel particles. Overlap is found to disappear upon heating the crystals well above their melting temperature, Tm due to reduction in the particle size. Annealing studies confirm that the overlap of dangling polymer chains between the shells of neighbouring PNIPAM spheres is responsible for the stability of FCC-HCP coexistence observed in osmotically compressed PNIPAM microgel crystals. Results are discussed in the light of recent reports of stabilizing the HCP structure in hard sphere crystals by adding interacting polymer chains.

Directed Self-Organization of Polymer-Grafted Nanoparticles in Polymer Thin Films

NASA Astrophysics Data System (ADS)

Zhang, Ren

The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. Surface modification of NPs with grafted polymer ligands has emerged as a versatile means to control the interaction and organization of particle constituents in polymer-matrix composite materials. In this study, by incorporating polymer-grafted nanoparticles (PGNPs) into polymeric thin films, we aim to understand and control the spatial organization of PGNPs through the interactions between polymer brush layer and matrix chains. As model systems, we investigate thermodynamic behaviors of polystyrene-tethered gold nanoparticles (denoted as AuPS) dispersed in polymer thin film matrices with identical and different chemical compositions (PS and PMMA, respectively), and evaluate the influence of external perturbation fields on directed organization of nanofillers. With the presence of unfavorable enthalpic interactions between grafted and free polymer chains (i.e. AuPS/ PMMA blend thin films), phase-separated structures are generated upon thermal annealing, characterized with morphologies ranging from discrete droplets to spinodal structures, which is consistent with composition-dependent classic binary polymer blends phase separation. The phase separation kinetics of AuPS/ PMMA blends exhibit distinct features compared to the parent PS/ PMMA homopolymer blends. We further illustrate phase-separated AuPS-rich domains can be directed into unidirectionally aligned anisotropic structures through soft-shear dynamic zone annealing (DZA-SS) process with tunable domain aspect ratios. To exert exquisite control over the shape, size and location of phase-separated PGNP domains, topographically patterned elastomer confinement is introduced to PGNP/ polymer blend thin films during thermal annealing. When the phase-separated lengthscale coincides with confined pattern dimension, long-range ordered submicron-sized AuPS domains are generated in PMMA matrices with dense and well-dispersed nanoparticle distribution. Furthermore, preferential segregation of AuPS nanoparticles at patterned mesa regions can be induced in PS matrices where enthalpic interactions are absent. This selective segregation is achieved due to the local perturbation of grafted chains when confined in a restricted space. The efficiency of this particle segregation process within patterned mesa-trench films can be tuned by changing the relative entropic confinement effects on grafted and matrix chains. This physical pattern directed PGNP organization strategy is applicable to versatile pattern geometries and nanoparticle compositions.

Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states.

PubMed

Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W; Edmondson, Steve; Malmström, Eva

2016-08-21

We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.

Charactrisation of particle assemblies by 3D cross correlation light scattering and diffusing wave spectroscopy

NASA Astrophysics Data System (ADS)

Scheffold, Frank

2014-08-01

To characterize the structural and dynamic properties of soft materials and small particles, information on the relevant mesoscopic length scales is required. Such information is often obtained from traditional static and dynamic light scattering (SLS/DLS) experiments in the single scattering regime. In many dense systems, however, these powerful techniques frequently fail due to strong multiple scattering of light. Here I will discuss some experimental innovations that have emerged over the last decade. New methods such as 3D static and dynamic light scattering (3D LS) as well as diffusing wave spectroscopy (DWS) can cover a much extended range of experimental parameters ranging from dilute polymer solutions, colloidal suspensions to extremely opaque viscoelastic emulsions.

Modeling phase separation in mixtures of intrinsically-disordered proteins

NASA Astrophysics Data System (ADS)

Gu, Chad; Zilman, Anton

Phase separation in a pure or mixed solution of intrinsically-disordered proteins (IDPs) and its role in various biological processes has generated interest from the theoretical biophysics community. Phase separation of IDPs has been implicated in the formation of membrane-less organelles such as nucleoli, as well as in a mechanism of selectivity in transport through the nuclear pore complex. Based on a lattice model of polymers, we study the phase diagram of IDPs in a mixture and describe the selective exclusion of soluble proteins from the dense-phase IDP aggregates. The model captures the essential behaviour of phase separation by a minimal set of coarse-grained parameters, corresponding to the average monomer-monomer and monomer-protein attraction strength, as well as the protein-to-monomer size ratio. Contrary to the intuition that strong monomer-monomer interaction increases exclusion of soluble proteins from the dense IDP aggregates, our model predicts that the concentration of soluble proteins in the aggregate phase as a function of monomer-monomer attraction is non-monotonic. We corroborate the predictions of the lattice model using Langevin dynamics simulations of grafted polymers in planar and cylindrical geometries, mimicking various in-vivo and in-vitro conditions.

Microstructured Electrolyte Membranes to Improve Fuel Cell Performance

NASA Astrophysics Data System (ADS)

Wei, Xue

Fuel cells, with the advantages of high efficiency, low greenhouse gas emission, and long lifetime are a promising technology for both portable power and stationary power sources. The development of efficient electrolyte membranes with high ionic conductivity, good mechanical durability and dense structure at low cost remains a challenge to the commercialization of fuel cells. This thesis focuses on exploring novel composite polymer membranes and ceramic electrolytes with the microstructure engineered to improve performance in direct methanol fuel cells (DMFCs) and solid oxide fuel cells (SOFCs), respectively. Polymer/particle composite membranes hold promise to meet the demands of DMFCs at lower cost. The structure of composite membranes was controlled by aligning proton conducting particles across the membrane thickness under an applied electric field. The field-induced structural changes caused the membranes to display an enhanced water uptake, proton conductivity, and methanol permeability in comparison to membranes prepared without an applied field. Although both methanol permeability and proton conductivity are enhanced by the applied field, the permeability increase is relatively lower than the proton conductivity improvement, which results in enhanced proton/methanol selectivity and improved DMFC performance. Apatite ceramics are a new class of fast ion conductors being studied as alternative SOFC electrolytes in the intermediate temperature range. An electrochemical/hydrothermal deposition method was developed to grow fully dense apatite membranes containing well-developed crystals with c-axis alignment to promote ion conductivity. Hydroxyapatite seed crystals were first deposited onto a metal substrate electrochemically. Subsequent ion substitution during the hydrothermal growth process promoted the formation of dense, fully crystalline films with microstructure optimal for ion transport. The deposition parameters were systematically investigated, such as reactant type, reagent concentration, solution pH, and reaction time. Dense apatite films were formed on palladium substrates that can serve as intermediate temperature fuel cell anodes. The novel apatite membrane structure is promising for fuel cell applications, as well as in improving the biocompatibility of orthopedic implants when coated on stainless steel or titanium substrates.

Gas Separation Properties of Polyimide Thin Films on Ceramic Supports for High Temperature Applications

PubMed Central

Escorihuela, Sara; Brinkmann, Torsten

2018-01-01

Novel selective ceramic-supported thin polyimide films produced in a single dip coating step are proposed for membrane applications at elevated temperatures. Layers of the polyimides P84®, Matrimid 5218®, and 6FDA-6FpDA were successfully deposited onto porous alumina supports. In order to tackle the poor compatibility between ceramic support and polymer, and to get defect-free thin films, the effect of the viscosity of the polymer solution was studied, giving the entanglement concentration (C*) for each polymer. The C* values were 3.09 wt. % for the 6FDA-6FpDA, 3.52 wt. % for Matrimid®, and 4.30 wt. % for P84®. A minimum polymer solution concentration necessary for defect-free film formation was found for each polymer, with the inverse order to the intrinsic viscosities (P84® ≥ Matrimid® >> 6FDA-6FpDA). The effect of the temperature on the permeance of prepared membranes was studied for H2, CH4, N2, O2, and CO2. As expected, activation energy of permeance for hydrogen was higher than for CO2, resulting in H2/CO2 selectivity increase with temperature. More densely packed polymers lead to materials that are more selective at elevated temperatures. PMID:29518942

A new class of tunable hypersonic phononic crystals based on polymer-tethered colloids.

PubMed

Alonso-Redondo, E; Schmitt, M; Urbach, Z; Hui, C M; Sainidou, R; Rembert, P; Matyjaszewski, K; Bockstaller, M R; Fytas, G

2015-09-22

The design and engineering of hybrid materials exhibiting tailored phononic band gaps are fundamentally relevant to innovative material technologies in areas ranging from acoustics to thermo-optic devices. Phononic hybridization gaps, originating from the anti-crossing between local resonant and propagating modes, have attracted particular interest because of their relative robustness to structural disorder and the associated benefit to 'manufacturability'. Although hybridization gap materials are well known, their economic fabrication and efficient control of the gap frequency have remained elusive because of the limited property variability and expensive fabrication methodologies. Here we report a new strategy to realize hybridization gap materials by harnessing the 'anisotropic elasticity' across the particle-polymer interface in densely polymer-tethered colloidal particles. Theoretical and Brillouin scattering analysis confirm both the robustness to disorder and the tunability of the resulting hybridization gap and provide guidelines for the economic synthesis of new materials with deliberately controlled gap position and width frequencies.

Biofunctional polymer nanoparticles for intra-articular targeting and retention in cartilage

NASA Astrophysics Data System (ADS)

Rothenfluh, Dominique A.; Bermudez, Harry; O'Neil, Conlin P.; Hubbell, Jeffrey A.

2008-03-01

The extracellular matrix of dense, avascular tissues presents a barrier to entry for polymer-based therapeutics, such as drugs encapsulated within polymeric particles. Here, we present an approach by which polymer nanoparticles, sufficiently small to enter the matrix of the targeted tissue, here articular cartilage, are further modified with a biomolecular ligand for matrix binding. This combination of ultrasmall size and biomolecular binding converts the matrix from a barrier into a reservoir, resisting rapid release of the nanoparticles and clearance from the tissue site. Phage display of a peptide library was used to discover appropriate targeting ligands by biopanning on denuded cartilage. The ligand WYRGRL was selected in 94 of 96 clones sequenced after five rounds of biopanning and was demonstrated to bind to collagen II α1. Peptide-functionalized nanoparticles targeted articular cartilage up to 72-fold more than nanoparticles displaying a scrambled peptide sequence following intra-articular injection in the mouse.

Effect of Core-shell Ceria/Poly(Vinylpyrrolidone) (PVP) Nanoparticles Incorporated in Polymer Films and Their Optical Properties (2): Increasing the Refractive Index

PubMed Central

Itoh, Toshio; Uchida, Toshio; Izu, Noriya; Shin, Woosuck

2017-01-01

We investigated the preparation of well-dispersed core-shell ceria-poly(vinylpyrrolidone) (PVP) nanoparticles with an average particle size of around 20 nm which were used to produce a hybrid film with a polymer coating of dipentaerythritol hexaacrylate (DPHA). We obtained good dispersion of the nanoparticles in a mixed solvent of 48% 1-methoxy-2-propanol (MP), 32% 3-methoxy-3-methyl-1-butanol (MMB), and 20% methyl i-butyl ketone (MIBK). An ink of the polymer coating consisting of 68.7 wt% nanoparticles and 31.3 wt% DPHA with a polymerization initiator was prepared using this solvent mixture. The surface of the hybrid film showed low roughness and the nanoparticles formed a densely packed structure in the DPHA matrix. The resulting coating possessed excellent transparency and a high refractive index of 1.69. PMID:28773070

Pressure-assisted synthesis of HKUST-1 thin film on polymer hollow fiber at room temperature toward gas separation.

PubMed

Mao, Yiyin; Li, Junwei; Cao, Wei; Ying, Yulong; Sun, Luwei; Peng, Xinsheng

2014-03-26

The scalable fabrication of continuous and defect-free metal-organic framework (MOF) films on the surface of polymeric hollow fibers, departing from ceramic supported or dense composite membranes, is a huge challenge. The critical way is to reduce the growth temperature of MOFs in aqueous or ethanol solvents. In the present work, a pressure-assisted room temperature growth strategy was carried out to fabricate continuous and well-intergrown HKUST-1 films on a polymer hollow fiber by using solid copper hydroxide nanostrands as the copper source within 40 min. These HKUST-1 films/polyvinylidenefluoride (PVDF) hollow fiber composite membranes exhibit good separation performance for binary gases with selectivity 116% higher than Knudsen values via both inside-out and outside-in modes. This provides a new way to enable for scale-up preparation of HKUST-1/polymer hollow fiber membranes, due to its superior economic and ecological advantages.

Poly(cyclohexylethylene)- block-poly(ethylene oxide) block polymers for metal oxide templating

DOE PAGES

Schulze, Morgan W.; Sinturel, Christophe; Hillmyer, Marc A.

2015-09-01

A series of poly(cyclohexylethylene)- block-poly(ethylene oxide) (CEO) diblock copolymers were synthesized through tandem anionic polymerizations and heterogeneous catalytic hydrogenation. Solvent-annealed CEO diblock films were used to template dense arrays of inorganic oxide nanodots via simple spin coating of an inorganic precursor solution atop the ordered film. The substantial chemical dissimilarity of the two blocks enables (i) selective inclusion of the inorganic precursor within the PEO domain and (ii) the formation of exceptionally small feature sizes due to a relatively large interaction parameter estimated from mean-field analysis of the order–disorder transition temperatures of compositionally symmetric samples. UV/ozone treatment following incorporation producesmore » an ordered arrangement of oxide nanodots and simultaneously removes the block polymer template. However, we report the smallest particles (6 ± 1 nm) templated from a selective precursor insertion method to date using a block polymer scaffold.« less

Monitoring the degrafting of polyelectrolyte brushes by using surface gradients

NASA Astrophysics Data System (ADS)

Ko, Yeongun; Genzer, Jan

Polymer brushes comprise densely grafted polymer chains on surfaces, which possess high stability and high concentration of reactive centers per unit area compared to physisorbed polymer film. Polymer brushes are employed in many applications, including anti-fouling surfaces, cell adhesive surfaces, responsive surfaces, low-friction surfaces, etc. Recently, researchers reported that charged (or chargeable) polymer brushes can be degrafted from substrate while incubated in buffer solutions. Based on previous experiments conducted in our group and by others, we assume that chain degrafting results from the hydrolysis of Si-O groups in head-group of the initiator and/or the ester groups in main body of the initiator. The kinetic of hydrolysis is affected by mechanical forces acting on the initiator. Those forces depend on the molecular weight and the grafting density of the brush, and the concentration and distribution of charges along the macromolecule (tuned by pH - for weak electrolytes - and concentration of external salt). In this work, we study the stability of poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) brushes in two solvents (ethanol and water) at various pH values in water and under different levels of external salt concentration. National Science Foundation.

Improved long-term electrical stability of pulsed high-power diodes using dense carbon fiber velvet cathodes

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

Yang Jie; Shu Ting; Wang Hui

2012-07-15

The influence of fibrous velvet cathodes on the electrical stability of a planar high-power diode powered by a {approx}230 kV, {approx}110 ns pulse has been investigated. The current density was on the order of {approx}123 A/cm{sup 2}. A combination of time-resolved electrical and optical diagnostics has been employed to study the basic phenomenology of the temporal and spatial evolution of the diode plasmas. Additionally, an impedance model was used to extract information about this plasma from voltage and current profiles. The results from the two diagnostics were compared. By comparison with commercial polymer velvet cathode, the dense carbon fiber velvetmore » cathode showed superior long-term electrical stability as judged by the change in cathode turn-on field, ignition delays, diode impedance, and surface plasma characteristics during the voltage flattop, a promising result for applications where reliable operation at high power is required. Finally, it was shown that the interaction of the electron beam with the stainless steel anode did not lead to the formation of anode plasma. These results may be of interest to the high power microwave systems with cold cathodes.« less

Nucleation of ordered solid phases of proteins via a disordered high-density state: Phenomenological approach

NASA Astrophysics Data System (ADS)

Pan, Weichun; Kolomeisky, Anatoly B.; Vekilov, Peter G.

2005-05-01

Nucleation of ordered solid phases of proteins triggers numerous phenomena in laboratory, industry, and in healthy and sick organisms. Recent simulations and experiments with protein crystals suggest that the formation of an ordered crystalline nucleus is preceded by a disordered high-density cluster, akin to a droplet of high-density liquid that has been observed with some proteins; this mechanism allowed a qualitative explanation of recorded complex nucleation kinetics curves. Here, we present a simple phenomenological theory that takes into account intermediate high-density metastable states in the nucleation process. Nucleation rate data at varying temperature and protein concentration are reproduced with high fidelity using literature values of the thermodynamic and kinetic parameters of the system. Our calculations show that the growth rate of the near-critical and supercritical ordered clusters within the dense intermediate is a major factor for the overall nucleation rate. This highlights the role of viscosity within the dense intermediate for the formation of the ordered nucleus. The model provides an understanding of the action of additives that delay or accelerate nucleation and presents a framework within which the nucleation of other ordered protein solid phases, e.g., the sickle cell hemoglobin polymers, can be analyzed.

Novel fluoro copolymers for 157-nm photoresists: a progress report

NASA Astrophysics Data System (ADS)

Hohle, Christoph; Hien, Stefan; Eschbaumer, Christian; Rottstegge, Joerg; Sebald, Michael

2002-07-01

Several fluoro-substituted polymers consisting of acid cleavable methacryoic or cinnamic acid tert.-butyl ester compounds copolymerized with maleic acid anhydride derivatives were synthesized by radical copolymerization. Vacuum ultraviolet transmission measurements of the samples reveal absorbances down to 5micrometers -1 despite of the strongly absorbing anhydride moiety which serves as silylation anchor for the application of the Chemical Amplification of Resist Lines (CARL) process, one of the promising approaches for sub-90nm pattern fabrication. Some of the samples exhibit resolutions down to 110nm dense at 157nm exposure using an alternating phase shift mask. The feasibility of the CARL principle including the silylation reaction after development has been demonstrated with selected fluorinated polymer samples.

A unified multicomponent stress-diffusion model of drug release from non-biodegradable polymeric matrix tablets.

PubMed

Salehi, Ali; Zhao, Jin; Cabelka, Tim D; Larson, Ronald G

2016-02-28

We propose a new transport model of drug release from hydrophilic polymeric matrices, based on Stefan-Maxwell flux laws for multicomponent transport. Polymer stress is incorporated in the total mixing free energy, which contributes directly to the diffusion driving force while leading to time-dependent boundary conditions at the tablet interface. Given that hydrated matrix tablets are dense multicomponent systems, extended Stefan-Maxwell (ESM) flux laws are adopted to ensure consistency with the Onsager reciprocity principle and the Gibbs-Duhem thermodynamic constraint. The ESM flux law for any given component takes into account the friction exerted by all other species and is invariant with respect to reference velocity, thus satisfying Galilean translational invariance. Our model demonstrates that penetrant-induced plasticization of polymer chains partially or even entirely offsets the steady decline of chemical potential gradients at the tablet-medium interface that drive drug release. Utilizing a Flory-Huggins thermodynamic model, a modified form of the upper convected Maxwell constitutive equation for polymer stress and a Fujita-type dependence of mutual diffusivities on composition, depending on parameters, Fickian, anomalous or case II drug transport arises naturally from the model, which are characterized by quasi-power-law release profiles with exponents ranging from 0.5 to 1, respectively. A necessary requirement for non-Fickian release in our model is that the matrix stress relaxation time is comparable to the time scale for water diffusion. Mutual diffusivities and their composition dependence are the most decisive factors in controlling drug release characteristics in our model. Regression of the experimental polymer dissolution and drug release profiles in a system of Theophylline/cellulose (K15M) demonstrate that API-water mutual diffusivity in the presence of excipient cannot generally be taken as a constant. Copyright © 2016 Elsevier B.V. All rights reserved.

Structural relaxation processes in polyethylene glycol/CCl4 solutions by Brillouin scattering.

PubMed

Pochylski, M; Aliotta, F; Błaszczak, Z; Gapiński, J

2005-03-10

We present results of a Brillouin scattering experiment on solutions of poly(ethylene glycol) of mean molecular mass 600 g/mol (PEG600) in CCl4. The relaxation process detected has been assigned to conformational rearrangements of the polymeric chains, triggered by reorientation of the side groups. The concentration dependencies of the hypersound velocity and normalized absorption are compared against the indications from several models proposed in the literature. The concentration evolution of the system is described in terms of two distinct regimes. At high polymer content, the system is dominated by the structure of the dense polymer, where polymer-polymer interactions, together with excluded volume effects, induce the existence of a preferred local arrangement resulting in a narrow distribution of the relaxation times, with the average value of the relaxation time following a simple Arrhenius temperature dependence. As the concentration decreases, the original structure of the hydrogen bonded polymer network is destroyed, and a number of different local configuration coexist, giving rise to a wider distribution of relaxation times or to a multiple relaxation. At low concentrations, the experimental data are well fitted assuming a Vogel-Fulker-Tammon behavior for the average relaxation time. In addition, the observed deviation from the ideal behavior for the refractive index and the density suggests that CCl4 does not behave as an inert solvent, and due to polarization effects, it can develop local hetero-associated structures via electrostatic interaction with the O-H end groups of the polymeric chains. The hypothesis has been successfully tested by fitting the concentration behavior of the hypersonic velocity to a recent three-component model, suitable to describe the concentration dependence of sound velocity in moderately interacting fluids. The indication of the model furnishes a very high value for the association constant of the PEG600, confirming the literature indication that, in polymeric systems capable of developing long liner aggregates via hydrogen bonding interaction, the Brillouin probe is insensitive to the true length of the polymeric chains. The Brillouin scattering experiment just sees an effective hydrogen bonded aggregate that is huge relative to the length of the single polymeric chain and becomes sensitive only to the density fluctuations of the local segmental motions.

Bioinspired hybrid materials from spray-formed ceramic templates.

PubMed

Dwivedi, Gopal; Flynn, Katherine; Resnick, Michael; Sampath, Sanjay; Gouldstone, Andrew

2015-05-20

Thermally sprayed ceramics, when infiltrated with polymer, exhibit synergistic increases in strength and toughness. The structure of such composites-a dense, brick-mortar arrangement-is strikingly similar to that of nacre, as are the mechanisms underlying the robust mechanical behavior. This industrial-scale process thus presents an exciting tool for bio-mimetic exploration. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Predictive Methods for Dense Polymer Networks: Combating Bias with Bio-Based Structures

DTIC Science & Technology

2016-03-16

Informatics Tools Acknowledgements: Air Force Office of Scientific Research, Air Force Research Laboratory, Office of Naval Research, Strategic...Sources and Methods • Bio-based cyanate esters have been made from anethole, resveratrol, eugenol, cresol, lignin, vanillin, and even creosote oils ...not large by informatics standards, it nonetheless represents a significant amount of synthetic effort. Because the data is limited, minimizing

Simulations of Biomechanical Phenomena

NASA Astrophysics Data System (ADS)

Gonzalez, Jose Cruz

Recent studies have published breakthroughs in the application of finite element (FEA) studies in the design and analysis of advanced orthodontics. However, FEA has not captured bone remodeling responses to advanced orthodontics. The results of these simulations report unrealistic displacement around the nasal bridge, which impeded correlation with clinical data. Bone remodeling has been previously documented in FEA and has shown bone response to mechanical stimulus in femur bone models. However, the relationship between mechanical stimulus and bone remodeling has not been reported in orthodontic studies due to the complexity of the skull. In the current study, strain energy is used as the mechanical stimulus to control remodeling, from which density and modulus evolve. Due to the localization of forces in orthodontics, current remodeling algorithms have limited application. In turn, we developed an algorithm that dynamically collects, sorts, and bins stresses in all elements for regional remodeling based on the proximity of the element to the load. The results demonstrate that bone response to orthodontic appliances is different than that of an FEA without bone remodeling, due to load path changes based upon evolution of the bone properties. It was also found that density and moduli proximal to the load application site exhibit faster remodeling than those located remotely. Modeling another biomechanical phenomena, a 3D simulation was created to simulate recent experimental results that discovered a difference in impact mitigation properties of dense-polymer/foam bilayer structure based on the orientation of the dense-polymer with respect to the impact site. The impact energy transmitted varied in time of arrival and amplitude depending on the orientation of the structure (thin layer up or down). By creating a 3D explicit dynamic FEA simulation, it is expected to reduce costly experiments and time consumed in set up, and offer opportunities for optimization for future applications in armor. The results agreed with the experimental results, displaying a delay in impact wave arrival, depending on the orientation of the structure. The FEA revealed also revealed that mid-body strains showed an increase at different time intervals, indicating the dense polymer's engagement and impact mitigation.

Anisotropic membranes for gas separation

DOEpatents

Gollan, A.Z.

1987-07-21

A gas separation membrane has a dense separating layer about 10,000 Angstroms or less thick and a porous support layer 10 to 400 microns thick that is an integral unit with gradually and continuously decreasing pore size from the base of the support layer to the surface of the thin separating layer and is made from a casting solution comprising ethyl cellulose and ethyl cellulose-based blends, typically greater than 47.5 ethoxyl content ethyl cellulose blended with compatible second polymers, such as nitrocellulose. The polymer content of the casting solution is from about 10% to about 35% by weight of the total solution with up to about 50% of this polymer weight a compatible second polymer to the ethyl cellulose in a volatile solvent such as isopropanol, methylacetate, methanol, ethanol, and acetone. Typical nonsolvents for the casting solutions include water and formamide. The casting solution is cast in air from about zero to 10 seconds to allow the volatile solvent to evaporate and then quenched in a coagulation bath, typically water, at a temperature of 7--25 C and then air dried at ambient temperature, typically 10--30 C. 2 figs.

Multiscale structure, interfacial cohesion, adsorbed layers, miscibility and properties in dense polymer-particle mixtures

NASA Astrophysics Data System (ADS)

Schweizer, Ken

2012-02-01

A major goal in polymer nanocomposite research is to understand and predict how the chemical and physical nature of individual polymers and nanoparticles, and thermodynamic state (temperature, composition, solvent dilution, filler loading), determine bulk assembly, miscibility and properties. Microscopic PRISM theory provides a route to this goal for equilibrium disordered mixtures. A major prediction is that by manipulating the net polymer-particle interfacial attraction, miscibility is realizable via the formation of thin thermodynamically stable adsorbed layers, which, however, are destroyed by entropic depletion and bridging attraction effects if interface cohesion is too weak or strong, respectively. This and related issues are quantitatively explored for miscible mixtures of hydrocarbon polymers, silica nanospheres, and solvent using x-ray scattering, neutron scattering and rheology. Under melt conditions, quantitative agreement between theory and silica scattering experiments is achieved under both steric stabilization and weak depletion conditions. Using contrast matching neutron scattering to characterize the collective structure factors of polymers, particles and their interface, the existence and size of adsorbed polymer layers, and their consequences on microstructure, is determined. Failure of the incompressible RPA, accuracy of PRISM theory, the nm thickness of adsorbed layers, and qualitative sensitivity of the bulk modulus to interfacial cohesion and particle size are demonstrated for concentrated PEO-silica-ethanol nanocomposites. Temperature-dependent complexity is discovered when water is the solvent, and nonequilibrium effects emerge for adsorbing entangled polymers that strongly impact structure. By varying polymer chemistry, the effect of polymer-particle attraction on the intrinsic viscosity is explored with striking non-classical effects observed. This work was performed in collaboration with S.Y.Kim, L.M.Hall, C.Zukoski and B.Anderson.

Microanalysis of vitrous char and associated polymers: reference and ancient assemblages

NASA Astrophysics Data System (ADS)

Allue, E.; Bonnamy, S.; Courty, M. M.; Gispert I Guirado, F.

2012-12-01

Formation of vitrous char that occur in ancient charcoal assemblages have remained unsolved. Laboratory experiments refuted vitrification to resulting from high temperature charring of green or resinous wood. This puzzling problem has been refreshed by showing the association to the charcoal and vitrous char of plastics that were originally supposed to only be produced by petroleum industry. Extraction of similar polymers within geological glassy products from cosmic airbursts has suggested impact processes to possibly forming the carbonaceous polymorphs. The pulverisation at the ground in the Angles village (French Eastern Pyrenees) following the 2011 August 2nd high altitude meteor explosion of exotic debris with vitrous char and polymers, just alike the puzzling ones of the geological and archaeological records, has provided potential reference materials. We present here their microanalysis by Environmental SEM with EDS, Raman micro-spectrometry and FTIR, XRD, TEM, ICP-MS and isotope analyses. The characterization helps elucidating how the carbonaceous polymorphs formed by transient heating and transient high pressure of atmospheric aerosols. Under TEM the vesicular, dense, vitrous char show high structural organization with a dense pattern of nano-sized graphitized domains, metals and mineral inclusions. The coupled Raman-ESEM has allowed identifying a complex pattern at micro scales of ordered "D" peak at 1320-1350 cm-1 and the graphitic, ordered peak at 1576-1590 cm-1, in association to amorphous and poorly graphitic ordered carbon. The later occurs within plant cells that have been extracted from the dense vitrous char by performing controlled combustion under nitrogen up to 1000°C. In contrast, the brittle, vesicular vitrous char and the polymers encountered at the rear of the pulverised airburst debris reveal to be formed of agglutinated micro spherules of amorphous carbon with rare crystallized carbon nano-domains and scattered mineral inclusions. They completely vaporised at 300°C under stepped-heating without leaving extractable residues. The link established between the structure of these exceptional carbon polymorphs and their forming processes provide diagnostic keys for interpreting vitrous carbon in ancient charcoal assemblage. The hardest ones offer reliable impact markers with their distinctive nanostructure produced by the transient high pressure and heating of carbonaceous aerosols by cosmic airbursts. In contrast, the weakly graphitised ones with distinctive plant structures would possibly express moderate effects of the airburst shock wave on vegetation at the ground. Thus micro-structural characterization of charcoal in archaeological assemblages would help tracing possible exploitation of blasted wood forest and related fossil fuel produced by ancient cosmic airbursts.

Recreating the synthesis of starch granules in yeast

PubMed Central

Pfister, Barbara; Sánchez-Ferrer, Antoni; Diaz, Ana; Lu, Kuanjen; Otto, Caroline; Holler, Mirko; Shaik, Farooque Razvi; Meier, Florence; Mezzenga, Raffaele; Zeeman, Samuel C

2016-01-01

Starch, as the major nutritional component of our staple crops and a feedstock for industry, is a vital plant product. It is composed of glucose polymers that form massive semi-crystalline granules. Its precise structure and composition determine its functionality and thus applications; however, there is no versatile model system allowing the relationships between the biosynthetic apparatus, glucan structure and properties to be explored. Here, we expressed the core Arabidopsis starch-biosynthesis pathway in Saccharomyces cerevisiae purged of its endogenous glycogen-metabolic enzymes. Systematic variation of the set of biosynthetic enzymes illustrated how each affects glucan structure and solubility. Expression of the complete set resulted in dense, insoluble granules with a starch-like semi-crystalline organization, demonstrating that this system indeed simulates starch biosynthesis. Thus, the yeast system has the potential to accelerate starch research and help create a holistic understanding of starch granule biosynthesis, providing a basis for the targeted biotechnological improvement of crops. DOI: http://dx.doi.org/10.7554/eLife.15552.001 PMID:27871361

Comparative study between REAP 200 and FEP171 CAR with 50-kV raster e-beam system for sub-100-nm technology

NASA Astrophysics Data System (ADS)

Baik, Ki-Ho; Lem, Homer Y.; Dean, Robert L.; Osborne, Stephen; Mueller, Mark; Abboud, Frank E.

2003-08-01

In this paper, a process established with a positive-tone chemically amplified resist (CAR) from TOK REAP200 and Fujifilm Arch FEP171 and 50kV MEBES system is discussed. This TOK resist is developed for raster scan 50 kV e-beam systems. It has high contrast, good coating characteristics, good dry etch selectivity, and high environmental stability. In the mask industries, the most popular positive tone CAR is FEP171, which is a high activation energy type CAR. REAP (Raster E-beam Advanced Process) 200 is low activation energy type and new acetal protecting polymer. In this study, we compared to these different type resists in terms of contrast, PAB and PEB latitude, resist profile, footing, T-topping, PED stability, LER, Global CDU (Critical Dimension Uniformity) and resolution. The REAP200 Resist obtained 75nm isolated lines and spaces, 90nm dense patterns with vertical profile, and a good stability of delay time.

A comparison of physicochemical methods for the remediation of porous medium systems contaminated with tar

NASA Astrophysics Data System (ADS)

Hauswirth, Scott C.; Miller, Cass T.

2014-10-01

The remediation of former manufactured gas plant (FMGP) sites contaminated with tar DNAPLs (dense non-aqueous phase liquids) presents a significant challenge. The tars are viscous mixtures of thousands of individual compounds, including known and suspected carcinogens. This work investigates the use of combinations of mobilization, solubilization, and chemical oxidation approaches to remove and degrade tars and tar components in porous medium systems. Column experiments were conducted using several flushing solutions, including an alkaline-polymer (AP) solution containing NaOH and xanthan gum (XG), a surfactant-polymer (SP) solution containing Triton X-100 surfactant (TX100) and XG, an alkaline-surfactant-polymer (ASP) solution containing NaOH, TX100, and XG, and base-activated sodium persulfate both with and without added TX100. The effectiveness of the flushing solutions was assessed based on both removal of polycyclic aromatic hydrocarbon (PAH) mass and on the reduction of dissolved-phase PAH concentrations. SP flushes of 6.6 to 20.9 PV removed over 99% of residual PAH mass and reduced dissolved-phase concentrations by up to two orders of magnitude. ASP flushing efficiently removed 95-96% of residual PAH mass within about 2 PV, and significantly reduced dissolved-phase concentrations of several low molar mass compounds, including naphthalene, acenaphthene, fluorene, and phenanthrene. AP flushing removed a large portion of the residual tar (77%), but was considerably less effective than SP and ASP in terms of the effect on dissolved PAH concentrations. Persulfate was shown to oxidize tar components, primarily those with low molar mass, however, the overall degradation was relatively low (30-50% in columns with low initial tar saturations), and the impact on dissolved-phase concentrations was minimal.

Aging, memory, and nonhierarchical energy landscape of spin jam

NASA Astrophysics Data System (ADS)

Samarakoon, Anjana; Sato, Taku J.; Chen, Tianran; Chern, Gai-Wei; Yang, Junjie; Klich, Israel; Sinclair, Ryan; Zhou, Haidong; Lee, Seung-Hun

2016-10-01

The notion of complex energy landscape underpins the intriguing dynamical behaviors in many complex systems ranging from polymers, to brain activity, to social networks and glass transitions. The spin glass state found in dilute magnetic alloys has been an exceptionally convenient laboratory frame for studying complex dynamics resulting from a hierarchical energy landscape with rugged funnels. Here, we show, by a bulk susceptibility and Monte Carlo simulation study, that densely populated frustrated magnets in a spin jam state exhibit much weaker memory effects than spin glasses, and the characteristic properties can be reproduced by a nonhierarchical landscape with a wide and nearly flat but rough bottom. Our results illustrate that the memory effects can be used to probe different slow dynamics of glassy materials, hence opening a window to explore their distinct energy landscapes.

Molecular Dynamics Study on the Photothermal Actuation of a Glassy Photoresponsive Polymer Reinforced with Gold Nanoparticles with Size Effect.

PubMed

Choi, Joonmyung; Chung, Hayoung; Yun, Jung-Hoon; Cho, Maenghyo

2016-09-14

We investigated the optical and thermal actuation behavior of densely cross-linked photoresponsive polymer (PRP) and polymer nanocomposites containing gold nanoparticles (PRP/Au) using all-atom molecular dynamics (MD) simulations. The modeled molecular structures contain a large number of photoreactive mesogens with linear orientation. Flexible side chains are interconnected through covalent bonds under periodic boundary conditions. A switchable dihedral potential was applied on a diazene moiety to describe the photochemical trans-to-cis isomerization. To quantify the photoinduced molecular reorientation and its effect on the macroscopic actuation of the neat PRP and PRP/Au materials, we characterized the photostrain and other material properties including elastic stiffness and thermal stability according to the photoisomerization ratio of the reactive groups. We particularly examined the effect of nanoparticle size on the photothermal actuation by varying the diameter of the nanofiller (10-20 Å) under the same volume fraction of 1.62%. The results indicated that the insertion of the gold nanoparticles enlarges the photostrain of the material while enhancing its mechanical stiffness and thermal stability. When the diameter of the nanoparticle reaches a size similar to or smaller than the length of the mesogen, the interfacial energy between the nanofiller and the surrounding polymer matrix does not significantly affect the alignment of the mesogens, but rather the adsorption energy at the interface generates a stable interphase layer. Hence, these improvements were more effective as the size of the gold nanoparticle decreased. The present findings suggest a wider analysis of the nanofiller-reinforced PRP composites and could be a guide for the mechanical design of the PRP actuator system.

Structure-induced switching of interpolymer adhesion at a solid-polymer melt interface.

PubMed

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo; Chen, Zhizhao; Cheung, Justin M; Morimitsu, Yuma; Endoh, Maya K; Koga, Tadanori; Fukuto, Masafumi; Yuan, Guangcui; Satija, Sushil K; Carrillo, Jan-Michael Y; Sumpter, Bobby G

2018-02-14

Here we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: "flattened chains" which lie flat on the solid and are densely packed, and "loosely adsorbed polymer chains" which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer-adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as "connector molecules", bridging the free chains and substrate surface and improving the interfacial adhesion. These findings not only shed light on the structure-property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.

Investigating the effects of polymer molecular weight and non-solvent content on the phase separation, surface morphology and hydrophobicity of polyvinyl chloride films

NASA Astrophysics Data System (ADS)

Khoryani, Zahra; Seyfi, Javad; Nekoei, Mehdi

2018-01-01

The main aim of this research is to study the effects of polymer molecular weight as well as non-solvent concentration on the phase separation, surface morphology and wettability of polyvinyl chloride (PVC) films. Gel permeation chromatography (GPC) results showed that the Mn of the used PVC grades is 6 × 104, 8.7 × 104 and 1.26 × 105 g/mol. It was found that a proper combination of polymer molecular weight and non-solvent content could result in superhydrophobic and self-cleaning behaviors. Scanning electron microscopy (SEM) results demonstrated that addition of ethanol causes the polymer chains to be severely aggregated at the films' surface forming strand-like structures decorated by nano-scale polymer spheres. The polymer molecular weight was found to affect the degree of porosity which is highly influential on the hydrophobicity of the films. The mechanism of phase separation process was also discussed and it was found that the instantaneous demixing is the dominant mechanism once higher contents of non-solvent were used. However, a delayed demixing mechanism was detected when the lower molecular weight PVC has been used which resulted in a pore-less and dense skin layer. Differential scanning calorimetry was also utilized to study the crystallization and glass transition behavior of samples.

Template-Assisted Hydrothermal Growth of Aligned Zinc Oxide Nanowires for Piezoelectric Energy Harvesting Applications

PubMed Central

2016-01-01

A flexible and robust piezoelectric nanogenerator (NG) based on a polymer-ceramic nanocomposite structure has been successfully fabricated via a cost-effective and scalable template-assisted hydrothermal synthesis method. Vertically aligned arrays of dense and uniform zinc oxide (ZnO) nanowires (NWs) with high aspect ratio (diameter ∼250 nm, length ∼12 μm) were grown within nanoporous polycarbonate (PC) templates. The energy conversion efficiency was found to be ∼4.2%, which is comparable to previously reported values for ZnO NWs. The resulting NG is found to have excellent fatigue performance, being relatively immune to detrimental environmental factors and mechanical failure, as the constituent ZnO NWs remain embedded and protected inside the polymer matrix. PMID:27172933

Applications of functional polymer brushes for nanoparticle uptake and prevention of protein adsorption

NASA Astrophysics Data System (ADS)

Arifuzzaman, Shafi M.

The central theme of this Ph.D. dissertation is to develop novel multifunctional polymer coatings for understanding partition of proteins and nanoparticles on polymers grafted to flat surfaces (so-called brushes). Systematic investigation of the adsorption phenomena is accomplished by utilizing surface-anchored assemblies comprising grafted polymers with variation in physical properties (i.e., length or/and grafting density) and chemical functionality. The chemical composition of the brush is tailored by either "chemical coloring" of a parent homopolymer brush with selective chemical moieties or by sequential growth of two chemically dissimilar polymer blocks. We present preparation of two types of tailor-made, surface-grafted copolymers: (1) those composed of hydrophilic and hydrophobic blocks (so-called amphiphilic polymer brushes), and (2) those comprising of anionic and cationic polymer segments (so-called polyampholyte brushes). We describe the organization of functionality in the grafted polymer brushes and the partitioning of proteins and nanoparticles using a battery of complementary analytical probes. Specifically, we address how varying the molecular weight, grafting density, and chemical composition of the brush affects adsorbtion and desorbtion of model proteins and gold nanoparticles. Our observations indicate densely-populated responsive amphiphilic polymers are very efficient in suppressing protein adsorption. In addition, we have established that the length of poly(ethylene glycol) spacers attached to a parent homopolymer brush is a key factor governing uptake of gold nanoparticles. Both grafting density and molecular weight of the coating are important in controlling the kinetics and thermodynamics of protein adsorption on surfaces. Our findings and methodologies can lead to the development of next generation environmentally friendly antifouling surfaces and will find application in medical devices, antifouling coatings and anti reflection finishes.

Like-charge attraction and opposite-charge decomplexation between polymers and DNA molecules

NASA Astrophysics Data System (ADS)

Buyukdagli, Sahin

2017-02-01

We scrutinize the effect of polyvalent ions on polymer-DNA interactions. We extend a recently developed test-charge theory [S. Buyukdagli et al., Phys. Rev. E 94, 042502 (2016), 10.1103/PhysRevE.94.042502] to the case of a stiff polymer interacting with a DNA molecule in an electrolyte mixture. The theory accounts for one-loop level electrostatic correlation effects such as the ionic cloud deformation around the strongly charged DNA molecule as well as image-charge forces induced by the low DNA permittivity. Our model can reproduce and explain various characteristics of the experimental phase diagrams for polymer solutions. First, the addition of polyvalent cations to the electrolyte solution results in the attraction of the negatively charged polymer by the DNA molecule. The glue of the like-charge attraction is the enhanced shielding of the polymer charges by the dense counterion layer at the DNA surface. Second, through the shielding of the DNA-induced electrostatic potential, mono- and polyvalent cations of large concentration both suppress the like-charge attraction. Within the same formalism, we also predict a new opposite-charge repulsion effect between the DNA molecule and a positively charged polymer. In the presence of polyvalent anions such as sulfate or phosphate, their repulsion by the DNA charges leads to the charge screening deficiency of the region around the DNA molecule. This translates into a repulsive force that results in the decomplexation of the polymer from DNA. This opposite-charge repulsion phenomenon can be verified by current experiments and the underlying mechanism can be beneficial to gene therapeutic applications where the control over polymer-DNA interactions is the key factor.

High-performance 193-nm photoresist materials based on ROMA polymers: sub-90-nm contact hole application with resist reflow

NASA Astrophysics Data System (ADS)

Joo, Hyun S.; Seo, Dong C.; Kim, Chang M.; Lim, Young T.; Cho, Seong D.; Lee, Jong B.; Song, Ji Y.; Kim, Kyoung M.; Park, Joo H.; Jung, Jae Chang; Shin, Ki S.; Bok, Cheol Kyu; Moon, Seung C.

2004-05-01

There are numerous methods being explored by lithographers to achieve the patterning of sub-90nm contact hole features. Regarding optical impact on contact imaging, various optical extension techniques such as assist features, focus drilling, phase shift masks, and off-axis illumination are being employed to improve the aerial image. One possible option for improving of the process window in contact hole patterning is resist reflow. We have already reported the resist using a ring opened polymer of maleic anhydride unit(ROMA) during the past two years in this conference. It has several good properties such as UV transmittance, PED stability, solubility and storage stability. The resist using ROMA polymer as a matrix resin showed a good lithographic performance at C/H pattern and one of the best characteristics in a ROMA polymer is the property of thermal shrinkage. It has a specific glass transition temperature(Tg) each polymers, so they made a applying of resist reflow technique to print sub-90nm C/H possible. Recently, we have researched about advanced ROMA polymer(ROMA II), which is composed of cycloolefine derivatives with existing ROMA type polymer(ROMA I), for dry etch resistance increasing, high resolution, and good thermal shrinkage property. In this paper, we will present the structure, thermal shrinkage properties, Tg control, material properties for ROMA II polymer and will show characteristics, the lithographic performance for iso and dense C/H applications of the resist using ROMA II polymer. In addition, we will discuss resist reflow data gained at C/H profile of sub-90nm sizes, which has good process window.

Ultrathin Composite Polymeric Membranes for CO2 /N2 Separation with Minimum Thickness and High CO2 Permeance.

PubMed

Benito, Javier; Sánchez-Laínez, Javier; Zornoza, Beatriz; Martín, Santiago; Carta, Mariolino; Malpass-Evans, Richard; Téllez, Carlos; McKeown, Neil B; Coronas, Joaquín; Gascón, Ignacio

2017-10-23

The use of ultrathin films as selective layers in composite membranes offers significant advantages in gas separation for increasing productivity while reducing the membrane size and energy costs. In this contribution, composite membranes have been obtained by the successive deposition of approximately 1 nm thick monolayers of a polymer of intrinsic microporosity (PIM) on top of dense membranes of the ultra-permeable poly[1-(trimethylsilyl)-1-propyne] (PTMSP). The ultrathin PIM films (30 nm in thickness) demonstrate CO 2 permeance up to seven times higher than dense PIM membranes using only 0.04 % of the mass of PIM without a significant decrease in CO 2 /N 2 selectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new class of tunable hypersonic phononic crystals based on polymer-tethered colloids

PubMed Central

Alonso-Redondo, E.; Schmitt, M.; Urbach, Z.; Hui, C. M.; Sainidou, R.; Rembert, P.; Matyjaszewski, K.; Bockstaller, M. R.; Fytas, G.

2015-01-01

The design and engineering of hybrid materials exhibiting tailored phononic band gaps are fundamentally relevant to innovative material technologies in areas ranging from acoustics to thermo-optic devices. Phononic hybridization gaps, originating from the anti-crossing between local resonant and propagating modes, have attracted particular interest because of their relative robustness to structural disorder and the associated benefit to ‘manufacturability'. Although hybridization gap materials are well known, their economic fabrication and efficient control of the gap frequency have remained elusive because of the limited property variability and expensive fabrication methodologies. Here we report a new strategy to realize hybridization gap materials by harnessing the ‘anisotropic elasticity' across the particle–polymer interface in densely polymer-tethered colloidal particles. Theoretical and Brillouin scattering analysis confirm both the robustness to disorder and the tunability of the resulting hybridization gap and provide guidelines for the economic synthesis of new materials with deliberately controlled gap position and width frequencies. PMID:26390851

Hydroxyapatite scaffolds processed using a TBA-based freeze-gel casting/polymer sponge technique.

PubMed

Yang, Tae Young; Lee, Jung Min; Yoon, Seog Young; Park, Hong Chae

2010-05-01

A novel freeze-gel casting/polymer sponge technique has been introduced to fabricate porous hydroxyapatite scaffolds with controlled "designer" pore structures and improved compressive strength for bone tissue engineering applications. Tertiary-butyl alcohol (TBA) was used as a solvent in this work. The merits of each production process, freeze casting, gel casting, and polymer sponge route were characterized by the sintered microstructure and mechanical strength. A reticulated structure with large pore size of 180-360 microm, which formed on burn-out of polyurethane foam, consisted of the strut with highly interconnected, unidirectional, long pore channels (approximately 4.5 microm in dia.) by evaporation of frozen TBA produced in freeze casting together with the dense inner walls with a few, isolated fine pores (<2 microm) by gel casting. The sintered porosity and pore size generally behaved in an opposite manner to the solid loading, i.e., a high solid loading gave low porosity and small pore size, and a thickening of the strut cross section, thus leading to higher compressive strengths.

Anomalous critical behavior in the polymer collapse transition of three-dimensional lattice trails.

PubMed

Bedini, Andrea; Owczarek, Aleksander L; Prellberg, Thomas

2012-07-01

Trails (bond-avoiding walks) provide an alternative lattice model of polymers to self-avoiding walks, and adding self-interaction at multiply visited sites gives a model of polymer collapse. Recently a two-dimensional model (triangular lattice) where doubly and triply visited sites are given different weights was shown to display a rich phase diagram with first- and second-order collapse separated by a multicritical point. A kinetic growth process of trails (KGTs) was conjectured to map precisely to this multicritical point. Two types of low-temperature phases, a globule phase and a maximally dense phase, were encountered. Here we investigate the collapse properties of a similar extended model of interacting lattice trails on the simple cubic lattice with separate weights for doubly and triply visited sites. Again we find first- and second-order collapse transitions dependent on the relative sizes of the doubly and triply visited energies. However, we find no evidence of a low-temperature maximally dense phase with only the globular phase in existence. Intriguingly, when the ratio of the energies is precisely that which separates the first-order from the second-order regions anomalous finite-size scaling appears. At the finite-size location of the rounded transition clear evidence exists for a first-order transition that persists in the thermodynamic limit. This location moves as the length increases, with its limit apparently at the point that maps to a KGT. However, if one fixes the temperature to sit at exactly this KGT point, then only a critical point can be deduced from the data. The resolution of this apparent contradiction lies in the breaking of crossover scaling and the difference in the shift and transition width (crossover) exponents.

Evaluation of moisture-induced damage of dense graded and gap graded asphalt mixture with nanopolymer modified binder

NASA Astrophysics Data System (ADS)

Shaffie, E.; Arshad, A. K.; Ahmad, J.; Hashim, W.

2018-04-01

The purpose of this research is to study the moisture induce damage performance of dense graded (AC14) and stone mastic asphalt (SMA14) asphalt pavement using Nanolyacrylate polymer modified asphalt binder. The physical properties of aggregate, volumetric and performance of asphalt mixes were assessed and evaluated with the laboratory tests. The study investigates fourteenth different asphalt mixtures consisting of NP modified asphalt binder formulations at 2%, 4% and 6%. Two types of asphalt binder, penetration grade PEN 80-100 and performance grade PG 76 were added with Nanopolyacrylate as asphalt modifier. The modified asphalt binder was prepared by adding 6 percent of Nanopolyacrylate (NP) to the asphalt binder. Both AC14 and SMA14 mixtures passed the Marshall requirements which indicate that these mixtures were good with respect to durability and flexibility. In terms of moisture induce damage, it was observed that the strength of the asphalt mixes increased with the addition of NP polymer modified asphalt binder. Similar trend could also be seen for SMA14 mixes, where the ITS value of SMA14 showed a significant difference compared to AC14 and all the mixtures exceeded the minimum requirement value as specified in the specification. Thus, addition of nanopolyacrylate polymer to the asphalt binder has significantly improved the cohesion as well as adhesion properties of the asphalt binder, and hence the stripping performance. Therefore, it can be concluded that the nanopolyacylate is suitable to be used as a modifier to the modified asphalt binder in order to enhance the properties of the asphalt binder and thus improving the performance of asphalt in both AC14 and SMA14 mixes.

Fabrication of highly dense isotropic Nd-Fe-B nylon bonded magnets via extrusion-based additive manufacturing [Fabrication of highly dense isotropic Nd-Fe-B bonded magnets via extrusion-based additive manufacturing

DOE PAGES

Li, Ling; Jones, Kodey E.; Sales, Brian C.; ...

2018-04-03

Magnetically isotropic bonded magnets with a high loading fraction of 70 vol.% Nd-Fe-B are fabricated via an extrusion-based additive manufacturing, or 3D printing system that enables rapid production of large parts. The density of the printed magnet is ~5.2 g/cm 3. The room temperature magnetic properties are: intrinsic coercivity Hci = 8.9 kOe (708.2 kA/m), remanence Br = 5.8 kG (0.58 T), and energy product (BH)max = 7.3 MGOe (58.1 kJ/m 3). The as-printed magnets are then coated with two types of polymers, both of which improve the thermal stability as revealed by flux aging loss measurements. Tensile tests performedmore » at 25 °C and 100 °C show that the ultimate tensile stress (UTS) increases with increasing loading fraction of the magnet powder, and decreases with increasing temperature. AC magnetic susceptibility and resistivity measurements show that the 3D printed Nd-Fe-B bonded magnets exhibit extremely low eddy current loss and high resistivity. Lastly, we demonstrate the performance of the 3D printed magnets in a DC motor configuration via back electromotive force measurements.« less

Fabrication of highly dense isotropic Nd-Fe-B nylon bonded magnets via extrusion-based additive manufacturing [Fabrication of highly dense isotropic Nd-Fe-B bonded magnets via extrusion-based additive manufacturing

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

Li, Ling; Jones, Kodey E.; Sales, Brian C.

Magnetically isotropic bonded magnets with a high loading fraction of 70 vol.% Nd-Fe-B are fabricated via an extrusion-based additive manufacturing, or 3D printing system that enables rapid production of large parts. The density of the printed magnet is ~5.2 g/cm 3. The room temperature magnetic properties are: intrinsic coercivity Hci = 8.9 kOe (708.2 kA/m), remanence Br = 5.8 kG (0.58 T), and energy product (BH)max = 7.3 MGOe (58.1 kJ/m 3). The as-printed magnets are then coated with two types of polymers, both of which improve the thermal stability as revealed by flux aging loss measurements. Tensile tests performedmore » at 25 °C and 100 °C show that the ultimate tensile stress (UTS) increases with increasing loading fraction of the magnet powder, and decreases with increasing temperature. AC magnetic susceptibility and resistivity measurements show that the 3D printed Nd-Fe-B bonded magnets exhibit extremely low eddy current loss and high resistivity. Lastly, we demonstrate the performance of the 3D printed magnets in a DC motor configuration via back electromotive force measurements.« less

Anisotropic membranes for gas separation

DOEpatents

Gollan, Arye Z.

1987-01-01

A gas separation membrane has a dense separating layer about 10,000 Angstroms or less thick and a porous support layer 10 to 400 microns thick that is an integral unit with gradually and continuously decreasing pore size from the base of the support layer to the surface of the thin separating layer and is made from a casting solution comprising ethyl cellulose and ethyl cellulose-based blends, typically greater than 47.5 ethoxyl content ethyl cellulose blended with compatible second polymers, such as nitrocellulose. The polymer content of the casting solution is from about 10% to about 35% by weight of the total solution with up to about 50% of this polymer weight a compatible second polymer to the ethyl cellulose in a volatile solvent such as isopropanol, methylacetate, methanol, ethanol, and acetone. Typical nonsolvents for the casting solutions include water and formamide. The casting solution is cast in air from about zero to 10 seconds to allow the volatile solvent to evaporate and then quenched in a coagulation bath, typically water, at a temperature of 7.degree.-25.degree. C. and then air dried at ambient temperature, typically 10.degree.-30.degree. C.

Process and Microstructure to Achieve Ultra-high Dielectric Constant in Ceramic-Polymer Composites.

PubMed

Zhang, Lin; Shan, Xiaobing; Bass, Patrick; Tong, Yang; Rolin, Terry D; Hill, Curtis W; Brewer, Jeffrey C; Tucker, Dennis S; Cheng, Z-Y

2016-10-21

Influences of process conditions on microstructure and dielectric properties of ceramic-polymer composites are systematically studied using CaCu 3 Ti 4 O 12 (CCTO) as filler and P(VDF-TrFE) 55/45 mol.% copolymer as the matrix by combining solution-cast and hot-pressing processes. It is found that the dielectric constant of the composites can be significantly enhanced-up to about 10 times - by using proper processing conditions. The dielectric constant of the composites can reach more than 1,000 over a wide temperature range with a low loss (tan δ ~ 10 -1 ). It is concluded that besides the dense structure of composites, the uniform distribution of the CCTO particles in the matrix plays a key role on the dielectric enhancement. Due to the influence of the CCTO on the microstructure of the polymer matrix, the composites exhibit a weaker temperature dependence of the dielectric constant than the polymer matrix. Based on the results, it is also found that the loss of the composites at low temperatures, including room temperature, is determined by the real dielectric relaxation processes including the relaxation process induced by the mixing.

Process and Microstructure to Achieve Ultra-high Dielectric Constant in Ceramic-Polymer Composites

NASA Astrophysics Data System (ADS)

Zhang, Lin; Shan, Xiaobing; Bass, Patrick; Tong, Yang; Rolin, Terry D.; Hill, Curtis W.; Brewer, Jeffrey C.; Tucker, Dennis S.; Cheng, Z.-Y.

2016-10-01

Influences of process conditions on microstructure and dielectric properties of ceramic-polymer composites are systematically studied using CaCu3Ti4O12 (CCTO) as filler and P(VDF-TrFE) 55/45 mol.% copolymer as the matrix by combining solution-cast and hot-pressing processes. It is found that the dielectric constant of the composites can be significantly enhanced-up to about 10 times - by using proper processing conditions. The dielectric constant of the composites can reach more than 1,000 over a wide temperature range with a low loss (tan δ ~ 10-1). It is concluded that besides the dense structure of composites, the uniform distribution of the CCTO particles in the matrix plays a key role on the dielectric enhancement. Due to the influence of the CCTO on the microstructure of the polymer matrix, the composites exhibit a weaker temperature dependence of the dielectric constant than the polymer matrix. Based on the results, it is also found that the loss of the composites at low temperatures, including room temperature, is determined by the real dielectric relaxation processes including the relaxation process induced by the mixing.

Process and Microstructure to Achieve Ultra-high Dielectric Constant in Ceramic-Polymer Composites

PubMed Central

Zhang, Lin; Shan, Xiaobing; Bass, Patrick; Tong, Yang; Rolin, Terry D.; Hill, Curtis W.; Brewer, Jeffrey C.; Tucker, Dennis S.; Cheng, Z.-Y.

2016-01-01

Influences of process conditions on microstructure and dielectric properties of ceramic-polymer composites are systematically studied using CaCu3Ti4O12 (CCTO) as filler and P(VDF-TrFE) 55/45 mol.% copolymer as the matrix by combining solution-cast and hot-pressing processes. It is found that the dielectric constant of the composites can be significantly enhanced–up to about 10 times – by using proper processing conditions. The dielectric constant of the composites can reach more than 1,000 over a wide temperature range with a low loss (tan δ ~ 10−1). It is concluded that besides the dense structure of composites, the uniform distribution of the CCTO particles in the matrix plays a key role on the dielectric enhancement. Due to the influence of the CCTO on the microstructure of the polymer matrix, the composites exhibit a weaker temperature dependence of the dielectric constant than the polymer matrix. Based on the results, it is also found that the loss of the composites at low temperatures, including room temperature, is determined by the real dielectric relaxation processes including the relaxation process induced by the mixing. PMID:27767184

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

NASA Astrophysics Data System (ADS)

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.

Robust surface coating for a fast, facile fluorine-18 labeling of iron oxide nanoparticles for PET/MR dual-modality imaging

DOE PAGES

Sun, Ziyan; Cheng, Kai; Wu, Fengyu; ...

2016-10-31

Grafting a robust organic shell around inorganic nanoparticles can optimize their colloidal features to dramatically improve their physicochemical properties. Here, we have developed a polymer coating procedure for providing colloidal stability to the nanoparticles and, more importantly, for applying a fast, facile fluorine-18 labeling of iron oxide nanoparticles (IONPs) for positron emission tomography (PET)/magnetic resonance (MR) dual-modality imaging. The structure of the amphiphilic polymer is based on a backbone of polyacrylic acid, conjugated with multiple oleylamines to form a comb-like branched structure. The dense polymer shell provides high colloidal stability to the IONPs against harsh conditions such as high temperature,more » low pH value, and high ion strength. By incorporating a 1,4,7-triazacyclononane (NOTA) chelator to the comb-like amphiphilic polymer for the chelation of aluminum fluoride ions, we applied a one-step radiolabeling approach for a fast, facile radiofluorination of magnetic nanoparticles. The new strategy can significantly reduce the procedure time and radiation exposure. In conclusion, the PET/MR dual modality imaging was successfully achieved in living subjects by using 18F labeled magnetic nanoparticles.« less

Robust surface coating for a fast, facile fluorine-18 labeling of iron oxide nanoparticles for PET/MR dual-modality imaging

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

Sun, Ziyan; Cheng, Kai; Wu, Fengyu

Grafting a robust organic shell around inorganic nanoparticles can optimize their colloidal features to dramatically improve their physicochemical properties. Here, we have developed a polymer coating procedure for providing colloidal stability to the nanoparticles and, more importantly, for applying a fast, facile fluorine-18 labeling of iron oxide nanoparticles (IONPs) for positron emission tomography (PET)/magnetic resonance (MR) dual-modality imaging. The structure of the amphiphilic polymer is based on a backbone of polyacrylic acid, conjugated with multiple oleylamines to form a comb-like branched structure. The dense polymer shell provides high colloidal stability to the IONPs against harsh conditions such as high temperature,more » low pH value, and high ion strength. By incorporating a 1,4,7-triazacyclononane (NOTA) chelator to the comb-like amphiphilic polymer for the chelation of aluminum fluoride ions, we applied a one-step radiolabeling approach for a fast, facile radiofluorination of magnetic nanoparticles. The new strategy can significantly reduce the procedure time and radiation exposure. In conclusion, the PET/MR dual modality imaging was successfully achieved in living subjects by using 18F labeled magnetic nanoparticles.« less

Antifouling Thin-Film Composite Membranes by Controlled Architecture of Zwitterionic Polymer Brush Layer.

PubMed

Liu, Caihong; Lee, Jongho; Ma, Jun; Elimelech, Menachem

2017-02-21

In this study, we demonstrate a highly antifouling thin-film composite (TFC) membrane by grafting a zwitterionic polymer brush via atom-transfer radical-polymerization (ATRP), a controlled, environmentally benign chemical process. Initiator molecules for polymerization were immobilized on the membrane surface by bioinspired catechol chemistry, leading to the grafting of a dense zwitterionic polymer brush layer. Surface characterization revealed that the modified membrane exhibits reduced surface roughness, enhanced hydrophilicity, and lower surface charge. Chemical force microscopy demonstrated that the modified membrane displayed foulant-membrane interaction forces that were 1 order of magnitude smaller than those of the pristine TFC membrane. The excellent fouling resistance imparted by the zwitterionic brush layer was further demonstrated by significantly reduced adsorption of proteins and bacteria. In addition, forward osmosis fouling experiments with a feed solution containing a mixture of organic foulants (bovine-serum albumin, alginate, and natural organic matter) indicated that the modified membrane exhibited significantly lower water flux decline compared to the pristine TFC membrane. The controlled architecture of the zwitterionic polymer brush via ATRP has the potential for a facile antifouling modification of a wide range of water treatment membranes without compromising intrinsic transport properties.

An Energy Dense-AI-NaBH4-PEMFC Based Power Generator for Unmanned Undersea Vehicles

DTIC Science & Technology

2016-03-01

1]. Although different types of batteries involving lithium , e.g., primary (Li-SOCb) and rechargeable (Li- ion , Li-polymer) batteries , potentially...development of innovative beyond battery -only technological capabilities would be necessary. The main objective of the proposed work is to develop an...increasing the endurance of UUVs. Lithium is commonly used in battery technology because it is the lightest metal , so higher energy densities are possible

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

Shen, Yong; Desseaux, Solenne; Aden, Bethany

We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modifiedmore » L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG 2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.« less

Novel adhesive properties of poly(ethylene-oxide) adsorbed nanolayers

NASA Astrophysics Data System (ADS)

Zeng, Wenduo

Solid-polymer interfaces play crucial roles in the multidisciplinary field of nanotechnology and are the confluence of physics, chemistry, biology, and engineering. There is now growing evidence that polymer chains irreversibly adsorb even onto weakly attractive solid surfaces, forming a nanometer-thick adsorbed polymer layer ("adsorbed polymer nanolayers"). It has also been reported that the adsorbed layers greatly impact on local structures and properties of supported polymer thin films. In this thesis, I aim to clarify adhesive and tribological properties of adsorbed poly(ethylene-oxide) (PEO) nanolayers onto silicon (Si) substrates, which remain unsolved so far. The adsorbed nanolayers were prepared by the established protocol: one has to equilibrate the melt or dense solution against a solid surface; the unadsorbed chains can be then removed by a good solvent, while the adsorbed chains are assumed to maintain the same conformation due to the irreversible freezing through many physical solid-segment contacts. I firstly characterized the formation process and the surface/film structures of the adsorbed nanolayers by using X-ray reflectivity, grazing incidence X-ray diffraction, and atomic force microscopy. Secondly, to compare the surface energy of the adsorbed layers with the bulk, static contact angle measurements with two liquids (water and glycerol) were carried out using a optical contact angle meter equipped with a video camera. Thirdly, I designed and constructed a custom-built adhesion-testing device to quantify the adhesive property. The experimental results provide new insight into the microscopic structure - macroscopic property relationship at the solid-polymer interface.

Aging, memory, and nonhierarchical energy landscape of spin jam

PubMed Central

Samarakoon, Anjana; Sato, Taku J.; Chen, Tianran; Chern, Gai-Wei; Yang, Junjie; Klich, Israel; Sinclair, Ryan; Zhou, Haidong; Lee, Seung-Hun

2016-01-01

The notion of complex energy landscape underpins the intriguing dynamical behaviors in many complex systems ranging from polymers, to brain activity, to social networks and glass transitions. The spin glass state found in dilute magnetic alloys has been an exceptionally convenient laboratory frame for studying complex dynamics resulting from a hierarchical energy landscape with rugged funnels. Here, we show, by a bulk susceptibility and Monte Carlo simulation study, that densely populated frustrated magnets in a spin jam state exhibit much weaker memory effects than spin glasses, and the characteristic properties can be reproduced by a nonhierarchical landscape with a wide and nearly flat but rough bottom. Our results illustrate that the memory effects can be used to probe different slow dynamics of glassy materials, hence opening a window to explore their distinct energy landscapes. PMID:27698141

Ultrahigh Ionic Conduction in Water-Stable Close-Packed Metal-Carbonate Frameworks.

PubMed

Manna, Biplab; Desai, Aamod V; Illathvalappil, Rajith; Gupta, Kriti; Sen, Arunabha; Kurungot, Sreekumar; Ghosh, Sujit K

2017-08-21

Utilization of the robust metal-carbonate backbone in a series of water-stable, anionic frameworks has been harnessed for the function of highly efficient solid-state ion-conduction. The compact organization of hydrophilic guest ions facilitates water-assisted ion-conduction in all the compounds. The dense packing of the compounds imparts high ion-conducting ability and minimizes the possibility of fuel crossover, making this approach promising for design and development of compounds as potential components of energy devices. This work presents the first report of evaluating ion-conduction in a purely metal-carbonate framework, which exhibits high ion-conductivity on the order of 10 -2 S cm -1 along with very low activation energy, which is comparable to highly conducting well-known crystalline coordination polymers or commercialized organic polymers like Nafion.

Purification of biomaterials by phase partitioning

NASA Technical Reports Server (NTRS)

Harris, J. M.

1984-01-01

A technique which is particularly suited to microgravity environments and which is potentially more powerful than electrophoresis is phase partitioning. Phase partitioning is purification by partitioning between the two immiscible aqueous layers formed by solution of the polymers poly(ethylene glycol) and dextran in water. This technique proved to be very useful for separations in one-g but is limited for cells because the cells are more dense than the phase solutions thus tend to sediment to the bottom of the container before reaching equilibrium with the preferred phase. There are three phases to work in this area: synthesis of new polymers for affinity phase partitioning; development of automated apparatus for ground-based separations; and design of apparatus for performing simple phase partitioning space experiments, including examination of mechanisms for separating phases in the absence of gravity.

Interpenetrating and non-interpenetrating 3-dimensional coordination polymer frameworks from multiple building blocks

NASA Astrophysics Data System (ADS)

Bradshaw, Darren; Rosseinsky, Matthew J.

2005-12-01

Reaction of Co(NO3)2ṡ6H2O with the multidentate ligands benzene-1,3,5-tricarboxylate (btc) and the flexible bipyridyl ligand 1,2-bis(4-pyridyl)ethane (bpe) affords the 3-dimensional coordination polymers [Co3(btc)2(bpe)3(eg)2]ṡ(guests) 1, where eg = ethylene glycol, and [Co2(Hbtc)2(bpe)2]ṡ(bpe) 2. Both phases are comprised of infinite metal-carboxylate dimer chains, linked into 2-dimensional sheets by the bpe ligands. These sheets are further linked to adjacent sheets through covalent interactions, 1, or through hydrogen-bonding interactions, 2, to yield the 3-dimensional structures. Phase 1 exhibits solvent filled 1-dimensional pores, whereas 2 is triply-interpenetrated to form a dense solid array.

One-pot biosynthesis of polymer-inorganic nanocomposites

NASA Astrophysics Data System (ADS)

Geng, Jiaqing; Yang, Dong; Zhu, Yong; Cao, Lichao; Jiang, Zhongyi; Sun, Yan

2011-06-01

A biological method is demonstrated to fabricate the polymer-inorganic nanocomposites (PINCs) utilizing bacterium as an efficient and versatile biofactory. Gluconacetobacter xylinum that can produce bacterial cellulose is incubated in the culture medium containing titanium or silica precursor. The PINCs can be acquired under the elaborate control of the culturing condition of G. xylinum, in which the formation of inorganic nanoparticles about several tens of nanometers in size synchronizes the fabrication of reticulated bacterial cellulose membrane composed of dense and finely branched nanofibers about 60-120 nm in diameter. The composition and chemical states, morphology, thermal stability of the inorganic nanoparticles, and nanocomposites were extensively characterized. A tentative mechanism for the formation of PINCs is proposed. It is hoped that this study may establish a generic platform toward facile and green synthesis of nanocomposite materials.

Size Dependent Mechanical Properties of Monolayer Densely Arranged Polystyrene Nanospheres.

PubMed

Huang, Peng; Zhang, Lijing; Yan, Qingfeng; Guo, Dan; Xie, Guoxin

2016-12-13

In contrast to macroscopic materials, the mechanical properties of polymer nanospheres show fascinating scientific and application values. However, the experimental measurements of individual nanospheres and quantitative analysis of theoretical mechanisms remain less well performed and understood. We provide a highly efficient and accurate method with monolayer densely arranged honeycomb polystyrene (PS) nanospheres for the quantitatively mechanical characterization of individual nanospheres on the basis of atomic force microscopy (AFM) nanoindentation. The efficiency is improved by 1-2 orders, and the accuracy is also enhanced almost by half-order. The elastic modulus measured in the experiments increases with decreasing radius to the smallest nanospheres (25-35 nm in radius). A core-shell model is introduced to predict the size dependent elasticity of PS nanospheres, and the theoretical prediction agrees reasonably well with the experimental results and also shows a peak modulus value.

Method of remediation of contaminants in porous media through minimization of bouyancy effects

DOEpatents

Shook, G. Michael; Pope, Gary A.

1999-01-01

A method for controlling vertical migration of contaminants in an aquifer includes introduction of a solubilizing solution having a surfactant and an alcohol or other light co-solvent. The surfactant is selected to solubilize the contaminant. The alcohol or other solvent is selected to provide the microemulsion with a substantially neutral buoyancy with respect to groundwater. The neutral buoyancy of the microemulsion prevents the normal downward movement which is typical of the solubilized dense non-aqueous phase liquid in surfactant-enhanced aquifer remediation. Thus, the risk that any significant amount of the solubilized dense non-aqueous contaminants will migrate vertically can be controlled. The relative tendency for vertical migration may also be reduced by increasing the injection rate or injected fluid viscosity (by adding polymer), or by reducing the well spacing.

Fluorinated bottlebrush polymers based on poly(trifluoroethyl methacrylate): Synthesis and characterizations

DOE PAGES

Xu, Yuewen; Wang, Weiyu; Wang, Yangyang; ...

2015-11-25

Bottlebrush polymers are densely grafted polymers with long side-chains attached to a linear polymeric backbone. Their unusual structures endow them with a number of unique and potentially useful properties in solution, in thin films, and in bulk. Despite the many studies of bottlebrushes that have been reported, the structure–property relationships for this class of materials are still poorly understood. In this contribution, we report the synthesis and characterization of fluorinated bottlebrush polymers based on poly(2,2,2-trifluoroethyl methacrylate). The synthesis was achieved by atom transfer radical polymerization (ATRP) using an α-bromoisobutyryl bromide functionalized norbornene initiator, followed by ring-opening metathesis polymerization (ROMP) usingmore » a third generation Grubbs’ catalyst (G3). Rheological characterization revealed that the bottlebrush polymer backbones remained unentangled as indicated by the lack of a rubbery plateau in the modulus. By tuning the size of the backbone of the bottlebrush polymers, near-spherical and elongated particles representing single brush molecular morphologies were observed in a good solvent as evidenced by TEM imaging, suggesting a semi-flexible nature of their backbones in dilute solutions. Thin films of bottlebrush polymers exhibited noticeably higher static water contact angles as compared to that of the macromonomer reaching the hydrophobic regime, where little differences were observed between each bottlebrush polymer. Further investigation by AFM revealed that the surface of the macromonomer film was relatively smooth; in contrast, the surface of bottlebrush polymers displayed certain degrees of nano-scale roughness (R q = 0.8–2.4 nm). The enhanced hydrophobicity of these bottlebrushes likely results from the preferential enrichment of the fluorine containing end groups at the periphery of the molecules and the film surface due to the side chain crowding effect. Furthermore, our results provide key information towards the design of architecturally tailored fluorinated polymers with desirable properties.« less

Water Sorption in Electron-Beam Evaporated SiO2 on QCM Crystals and Its Influence on Polymer Thin Film Hydration Measurements.

PubMed

Kushner, Douglas I; Hickner, Michael A

2017-05-30

Spectroscopic ellipsometry (SE) and quartz crystal microbalance (QCM) measurements are two critical characterization techniques routinely employed for hydration studies of polymer thin films. Water uptake by thin polymer films is an important area of study to investigate antifouling surfaces, to probe the swelling of thin water-containing ionomer films, and to conduct fundamental studies of polymer brush hydration and swelling. SiO 2 -coated QCM crystals, employed as substrates in many of these hydration studies, show porosity in the thin electron-beam (e-beam) evaporated SiO 2 layer. The water sorption into this porous SiO 2 layer requires correction of the optical and mass characterization of the hydrated polymer due to changes in the SiO 2 layer as it sorbs water. This correction is especially important when experiments on SiO 2 -coated QCM crystals are compared to measurements on Si wafers with dense native SiO 2 layers. Water adsorption filling void space during hydration in ∼200-260 nm thick SiO 2 layers deposited on a QCM crystal resulted in increased refractive index of the layer during water uptake experiments. The increased refractive index led to artificially higher polymer swelling in the optical modeling of the hydration experiments. The SiO 2 -coated QCM crystals showed between 6 and 8% void as measured by QCM and SE, accounting for 60%-85% of the measured polymer swelling in the low humidity regime (<20% RH) and 25%-40% of the polymer swelling in the high humidity regime (>70% RH) from optical modeling for 105 and 47 nm thick sulfonated polymer films. Correcting the refractive index of the SiO 2 layer for its water content resulted in polymer swelling that successfully resembled swelling measured on a silicon wafer with nonporous native oxide.

Evolution of carboxymethyl cellulose layer morphology on hydrophobic mineral surfaces: variation of polymer concentration and ionic strength.

PubMed

Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka; Beattie, David A

2010-06-15

The adsorption of carboxymethyl cellulose (CMC) on the basal planes of talc and molybdenite has been studied using in situ atomic force microscope (AFM) imaging. These experiments were partnered with quantitative adsorption isotherm determinations on particulate samples. The isotherms revealed a clear increase of the CMC adsorbed amount upon increasing the solution ionic strength for adsorption on both minerals. In addition, the shapes of the isotherms changed in response to the change in the electrolyte concentration, with CMC on talc displaying stepped (10(-3) M KCl), Langmuir (10(-2) M KCl), then Freundlich isotherm shapes (10(-1) M KCl), and CMC on molybdenite displaying stepped (10(-3) M KCl), Freundlich (10(-2) M KCl), then Langmuir isotherm shapes (10(-1) M KCl). AFM imaging of the polymer layer on the mineral surfaces with varying solution conditions mirrored and confirmed the conclusions from the isotherms: as the polymer solution concentration increased, coverage on the basal plane increased; as the ionic strength increased, coverage on the basal plane increased and the morphology of the layer changed from isolated well-distributed polymer domains to extensive adsorption and formation of dense, uneven polymer domains/features. In addition, comparison of the talc and molybdenite datasets points toward the presence of different binding mechanisms for CMC adsorption on the talc and molybdenite basal plane surfaces. 2010 Elsevier Inc. All rights reserved.

Small-Angle Neutron Scattering Study of Interplay of Attractive and Repulsive Interactions in Nanoparticle-Polymer System.

PubMed

Kumar, Sugam; Aswal, Vinod K; Kohlbrecher, Joachim

2016-02-16

The phase behavior of nanoparticle (silica)-polymer (polyethylene glycol) system without and with an electrolyte (NaCl) has been studied. It is observed that nanoparticle-polymer system behaves very differently in the presence of electrolyte. In the absence of electrolyte, the nanoparticle-polymer system remains in one-phase even at very high polymer concentrations. On the other hand, a re-entrant phase behavior is found in the presence of electrolyte, where one-phase (individual) system undergoes two-phase (nanoparticle aggregation) and then back to one-phase with increasing polymer concentration. The regime of two-phase system has been tuned by varying the electrolyte concentration. The polymer concentration range over which the two-phase system exists is significantly enhanced with the increase in the electrolyte concentration. These systems have been characterized by small-angle neutron scattering (SANS) experiments of contrast-marching the polymer to the solvent. The data are modeled using a two-Yukawa potential accounting for both attractive and repulsive parts of the interaction between nanoparticles. The phase behavior of nanoparticle-polymer system is explained by interplay of attractive (polymer-induced attractive depletion between nanoparticles) and repulsive (nanoparticle-nanoparticle electrostatic repulsion and polymer-polymer repulsion) interactions present in the system. In the absence of electrolyte, the strong electrostatic repulsion between nanoparticles dominates over the polymer-induced depletion attraction and the nanoparticle system remains in one-phase. With addition of electrolyte, depletion attraction overcomes electrostatic repulsion at some polymer concentration, resulting into nanoparticle aggregation and two-phase system. Further addition of polymer increases the polymer-polymer repulsion which eventually reduces the strength of depletion and hence re-entrant phase behavior. The effects of varying electrolyte concentration on the phase behavior of nanoparticle-polymer system are understood in terms of modifications in nanoparticle-nanoparticle and polymer-polymer interactions. The nanoparticle aggregates in two-phase systems are found to have surface fractal morphology.

Rapid, Efficient and Versatile Strategies for Functionally Sophisticated Polymers and Nanoparticles: Degradable Polyphosphoesters and Anisotropic Distribution of Chemical Functionalities

NASA Astrophysics Data System (ADS)

Zhang, Shiyi

The overall emphasis of this dissertation research included two kinds of asymmetrically-functionalized nanoparticles with anisotropic distributions of chemical functionalities, three degradable polymers synthesized by organocatalyzed ring-opening polymerizations, and two polyphosphoester-based nanoparticle systems for various biomedical applications. Inspired by the many hierarchical assembly processes that afford complex materials in Nature, the construction of asymmetrically-functionalized nanoparticles with efficient surface chemistries and the directional organization of those building blocks into complex structures have attracted much attention. The first method generated a Janus-faced polymer nanoparticle that presented two orthogonally click-reactive surface chemistries, thiol and azido. This robust method involved reactive functional group transfer by templating against gold nanoparticle substrates. The second method produced nanoparticles with sandwich-like distribution of crown ether functionalities through a stepwise self-assembly process that utilized crown ether-ammonium supramolecular interactions to mediate inter-particle association and the local intra-particle phase separation of unlike hydrophobic polymers. With the goal to improve the efficiency of the production of degradable polymers with tunable chemical and physical properties, a new type of reactive polyphosphoester was synthesized bearing alkynyl groups by an organocatalyzed ring-opening polymerization, the chemical availability of the alkyne groups was investigated by employing "click" type azide-alkyne Huisgen cycloaddition and thiol-yne radical-mediated reactions. Based on this alkyne-functionalized polyphosphoester polymer and its two available "click" type reactions, two degradable nanoparticle systems were developed. To develop the first system, the well defined poly(ethylene oxide)-block-polyphosphester diblock copolymer was transformed into a multifunctional Paclitaxel drug conjugate by densely attaching the polyphosphoester block with azide-functionalized Paclitaxel by azide-alkyne Huisgen cycloaddition. This Paclitaxel drug conjugate provides a powerful platform for combinational cancer therapy and bioimaging due to its ultra-high Paclitaxel loading (> 65 wt%), high water solubility (>6.2 mg/mL for PTX) and easy functionalization. Another polyphosphoester-based nanoparticle system has been developed by a programmable process for the rapid and facile preparation of a family of nanoparticles with different surface charges and functionalities. The non-ionic, anionic, cationic and zwitterionic nanoparticles with hydrodynamic diameters between 13 nm to 21 nm and great size uniformity could be rapidly prepared from small molecules in 6 h or 2 days. The anionic and zwitterionic nanoparticles were designed to load silver ions to treat pulmonary infections, while the cationic nanoparticles are being applied to regulate lung injuries by serving as a degradable iNOS inhibitor conjugates. In addition, a direct synthesis of acid-labile polyphosphoramidate by organobase-catalyzed ring-opening polymerization and an improved two-step preparation of polyphosphoester ionomer by acid-assisted cleavage of phosphoramidate bonds on polyphosphoramidate were developed. Polyphosphoramidate and polyphosphoester ionomers may be applied to many applications, due to their unique chemical and physical properties.

Fabrication of microscale materials with programmable composition gradients.

PubMed

Laval, Cédric; Bouchaudy, Anne; Salmon, Jean-Baptiste

2016-04-07

We present an original microfluidic technique coupling pervaporation and the use of Quake valves to fabricate microscale materials (∼10 × 100 μm(2) × 1 cm) with composition gradients along their longest dimension. Our device exploits pervaporation of water through a thin poly(dimethylsiloxane) (PDMS) membrane to continuously pump solutions (or dispersions) contained in different reservoirs connected to a microfluidic channel. This pervaporation-induced flow concentrates solutes (or particles) at the tip of the channel up to the formation of a dense material. The latter invades the channel as it is constantly enriched by an incoming flux of solutes/particles. Upstream Quake valves are used to select which reservoir is connected to the pervaporation channel and thus which solution (or dispersion) enriches the material during its growth. The microfluidic configuration of the pervaporation process is used to impose controlled growth along the channel thus enabling one to program spatial composition gradients using appropriate actuations of the valves. We demonstrate the possibilities offered by our technique through the fabrication of dense assemblies of nanoparticles and polymer composites with programmed gradients of fluorescent dyes. We also address the key issue of the spatial resolution of our gradients and we show that well-defined spatial modulations down to ≈50 μm can be obtained within colloidal materials, whereas gradients within polymer materials are resolved on length scales down to ≈1 mm due to molecular diffusion.

Changes in ionic selectivity with changes in density of water in gels and cells

PubMed Central

Wiggins, Philippa M.; van Ryn, René T.

1990-01-01

Gels equilibrated with aqueous solutions of impermeant solutes reached a steady state in which, in the absence of a pressure difference, the activity of water in the pores of the gel was higher than that of water in the external solution. The chemical potential of water in the gel/polymer solution slurry was higher than that in the supernatant polymer solution removed from the gel. Water in the pores of the gel decreased in density to 0.96 as increasing osmotic stress was applied. It is argued that at constant temperature and pressure water can equilibrate between two compartments of unequal osmolality only by adjusting its molar volume. Experiments showed that when gel water had a higher activity than external water it was K+ selective; when it had a lower activity it was Na+ selective. It is proposed that a continuous spectrum of water structures can exist in these two compartment systems from dense, reactive, weakly-bonded water which selects highly hydrated ions, to expanded, stretched, unreactive, viscous water which is strongly hydrogen bonded and selects K+ and univalent anions. These findings are related to the state and properties of cytoplasmic water which is probably held under osmotic stress by the activity of the sodium pump. PMID:19431765

Fe3O4 nanoparticles modified by CD-containing star polymer for MRI and drug delivery.

PubMed

Cha, Ruitao; Li, Juanjuan; Liu, Yang; Zhang, Yifan; Xie, Qian; Zhang, Mingming

2017-10-01

Fe 3 O 4 nanoparticles with ultrasmall sizes show good T 1 or T 1 +T 2 contrast abilities, and have attracted considerable interest in the field of magnetic resonance imaging (MRI) contrast agents. For effective biomedical applications, the colloidal stability and biocompatibility of the Fe 3 O 4 nanoparticles need to be improved without reducing MRI relaxivity. In this paper, star polymers were used as coating materials to modify Fe 3 O 4 nanoparticles in view of their dense molecular architecture with moderate flexibility. The star polymer was composed of a β-cyclodextrin (β-CD) core and poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) arms. Meanwhile, reduced glutathione (GSH), as a model drug, was also associated with the star polymer. Thus, a new platform for simultaneous diagnosis and treatment was achieved. Compared to the Fe 3 O 4 nanoparticles coated with linear polymers, the Fe 3 O 4 nanoparticles coated with star polymers (Fe 3 O 4 @GCP) possessed higher GSH association capacity and better stability in serum-containing solution. GSH could be released from Fe 3 O 4 @GCP nanoparticles in response to pH value of the solution. Since the sulfhydryl group on GSH is able to combine free radicals, Fe 3 O 4 @GCP nanoparticles exhibited less cytotoxicity compared to the Fe 3 O 4 nanoparticles without including GSH. Furthermore, the nanoparticles could also serve as good T 1 MRI contrast agent, and the MRI relaxivity of Fe 3 O 4 @GCP nanoparticles did not decrease after coated with the star polymer. These results indicate that the precisely designed Fe 3 O 4 @GCP nanoparticles could be used as a versatile promising theranostic nano-platform. Copyright © 2017 Elsevier B.V. All rights reserved.

Real-Time Large-Scale Dense Mapping with Surfels

PubMed Central

Fu, Xingyin; Zhu, Feng; Wu, Qingxiao; Sun, Yunlei; Lu, Rongrong; Yang, Ruigang

2018-01-01

Real-time dense mapping systems have been developed since the birth of consumer RGB-D cameras. Currently, there are two commonly used models in dense mapping systems: truncated signed distance function (TSDF) and surfel. The state-of-the-art dense mapping systems usually work fine with small-sized regions. The generated dense surface may be unsatisfactory around the loop closures when the system tracking drift grows large. In addition, the efficiency of the system with surfel model slows down when the number of the model points in the map becomes large. In this paper, we propose to use two maps in the dense mapping system. The RGB-D images are integrated into a local surfel map. The old surfels that reconstructed in former times and far away from the camera frustum are moved from the local map to the global map. The updated surfels in the local map when every frame arrives are kept bounded. Therefore, in our system, the scene that can be reconstructed is very large, and the frame rate of our system remains high. We detect loop closures and optimize the pose graph to distribute system tracking drift. The positions and normals of the surfels in the map are also corrected using an embedded deformation graph so that they are consistent with the updated poses. In order to deal with large surface deformations, we propose a new method for constructing constraints with system trajectories and loop closure keyframes. The proposed new method stabilizes large-scale surface deformation. Experimental results show that our novel system behaves better than the prior state-of-the-art dense mapping systems. PMID:29747450

Glass-like dynamics in confined and congested ant traffic.

PubMed

Gravish, Nick; Gold, Gregory; Zangwill, Andrew; Goodisman, Michael A D; Goldman, Daniel I

2015-09-07

The collective movement of animal groups often occurs in confined spaces. As animal groups are challenged to move at high density, their mobility dynamics may resemble the flow of densely packed non-living soft materials such as colloids, grains, or polymers. However, unlike inert soft-materials, self-propelled collective living systems often display social interactions whose influence on collective mobility are only now being explored. In this paper, we study the mobility of bi-directional traffic flow in a social insect (the fire ant Solenopsis invicta) as we vary the diameter of confining foraging tunnels. In all tunnel diameters, we observe the emergence of spatially heterogeneous regions of fast and slow traffic that are induced through two phenomena: physical obstruction, arising from the inability of individual ants to interpenetrate, and time-delay resulting from social interaction in which ants stop to briefly antennate. Density correlation functions reveal that the relaxation dynamics of high density traffic fluctuations scale linearly with fluctuation size and are sensitive to tunnel diameter. We separate the roles of physical obstruction and social interactions in traffic flow using cellular automata based simulation. Social interaction between ants is modeled as a dwell time (Tint) over which interacting ants remain stationary in the tunnel. Investigation over a range of densities and Tint reveals that the slowing dynamics of collective motion in social living systems are consistent with dynamics near a fragile glass transition in inert soft-matter systems. In particular, flow is relatively insensitive to density until a critical density is reached. As social interaction affinity is increased (increasing Tint) traffic dynamics change and resemble a strong glass transition. Thus, social interactions play an important role in the mobility of collective living systems at high density. Our experiments and model demonstrate that the concepts of soft-matter physics aid understanding of the mobility of collective living systems, and motivate further inquiry into the dynamics of densely confined social living systems.

Biochemical separations by continuous-bed chromatography.

PubMed

Tisch, T L; Frost, R; Liao, J L; Lam, W K; Remy, A; Scheinpflug, E; Siebert, C; Song, H; Stapleton, A

1998-08-07

Innovations in column-packing media for biomolecule purification have progressed from large spherical, porous polysaccharide beads to advanced polymeric supports. Continuous-bed technology is a radical new technology for chromatography based on the polymerization of advanced monomers and ionomers directly in the chromatographic column. The polymer chains form aggregates which coalesce into a dense, homogeneous network of interconnected nodules consisting of microparticles with an average diameter of 3000 A. The voids or channels between the nodules are large enough to permit a high hydrodynamic flow. Due to the high cross-linking of the polymer matrix, the surface of each nodule is nonporous yet the polymeric microparticles provide a very large surface area for high binding capacity. This paper will demonstrate the properties and advantages of using a continuous bed support for high resolution biomolecule separations at high flow-rates without sacrificing capacity.

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

NASA Astrophysics Data System (ADS)

Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua; Lokitz, Bradley S.; Ruther, Rose E.; Yang, Guang; Lou, Kun; Nanda, Jagjit; Delnick, Frank M.; Dudney, Nancy J.

2018-06-01

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. A remarkable Li+ transference number of 0.79 is discovered for the composite electrolyte.

Viscoelasticity of Depletion-Induced Emulsion Gels

NASA Astrophysics Data System (ADS)

Meller, Amit; Stavans, Joel; Gisler, Thomas; Weitz, David A.

1997-03-01

The presence of non-adsorbing polymer in an oil-in-water emulsion results in a depletion attraction between the emulsion droplets, causing a phase separation into an droplet-rich phase and a polymer-rich phase largely devoid of emulsion droplets. At high enough droplet concentration, however, this phase separation is kinetically arrested to a gel-like state where large (diameter>50 μm) clusters of droplets are weakly connected via ramifications, leading to a measurable elastic modulus. We measure the mean-square displacement <Δ r ^2 (t)> of a droplet of size a inside a cluster using diffusing wave spectroscopy (DWS); by means of a generalized Stokes-Einstein relation we obtain frequency dependent storage and loss moduli G'(ω) and G''(ω), respectively. G'(ω) reaches a plateau at frequencies between 1 rad/s and 100 rad/s; this plateau modulus is found to scale with the hard-sphere energy density k_BT/a^3; within the clusters the droplets are densely packed, yet remain undeformed, the droplet volume fraction being determined by the osmotic pressure exerted by the polymer.

Polymer-Sorted Semiconducting Carbon Nanotube Networks for High-Performance Ambipolar Field-Effect Transistors

PubMed Central

2014-01-01

Efficient selection of semiconducting single-walled carbon nanotubes (SWNTs) from as-grown nanotube samples is crucial for their application as printable and flexible semiconductors in field-effect transistors (FETs). In this study, we use atactic poly(9-dodecyl-9-methyl-fluorene) (a-PF-1-12), a polyfluorene derivative with asymmetric side-chains, for the selective dispersion of semiconducting SWNTs with large diameters (>1 nm) from plasma torch-grown SWNTs. Lowering the molecular weight of the dispersing polymer leads to a significant improvement of selectivity. Combining dense semiconducting SWNT networks deposited from an enriched SWNT dispersion with a polymer/metal-oxide hybrid dielectric enables transistors with balanced ambipolar, contact resistance-corrected mobilities of up to 50 cm2·V–1·s–1, low ohmic contact resistance, steep subthreshold swings (0.12–0.14 V/dec) and high on/off ratios (106) even for short channel lengths (<10 μm). These FETs operate at low voltages (<3 V) and show almost no current hysteresis. The resulting ambipolar complementary-like inverters exhibit gains up to 61. PMID:25493421

Titania Deposition on PMR-15

NASA Technical Reports Server (NTRS)

Meador, Mary B.; Sutter, James K.; Pizem, Hillel; Gershevitz, Olga; Goffer, Yossi; Frimer, Aryeh A.; Sukenik, Chaim N.; Sampathkumaran, Uma; Milhet, Xavier; McIlwain, Alan

2005-01-01

The formation, degree of crystallinity and adherence of dense titania (TiO2) thin film coatings on a high-temperature polyimide resin (PMR-15) can be influenced by the chemical composition of the polymer surface. Furthermore, solution deposition conditions can be adjusted to provide additional control over the morphology and crystallinity of the titania films. Recipes for solution-based titania deposition that used a slowly-hydrolyzing titanium fluoride salt in the presence of boric acid as a fluoride scavenger allowed growth of films up to 750 nm thick in 22 h. By adjusting solution pH and temperature, either amorphous titania or oriented crystalline anatase films could be formed. Surface sulfonate groups enhance the adhesion of solution-deposited oxide thin film coatings. While most sulfonation procedures severely damaged the PMR-15 surface, the use of chlorosulfonic acid followed by hydrolysis of the installed chlorosulfonyl groups provided effective surface sulfonation without significant surface damage. In some cases, the oxide deposition solution caused partial hydrolysis of the polymer surface, which itself was sufficient to allow adhesion of the titania film through chelation of titanium ions by exposed benzoic acid groups on the polymer surface.

Experimental and Modeling Study of Solvent Diffusion in PDMS for Nanoparticle-Polymer Cosuspension Imprint Lithography.

PubMed

Gervasio, Michelle; Lu, Kathy; Davis, Richey

2015-09-15

This study is the first that focuses on solvent migration in a polydimethylsiloxane (PDMS) stamp during the imprint lithography of ZnO-poly(methyl methacrylate) (PMMA) hybrid suspensions. Using suspensions with varying solids loading levels and ZnO/PMMA ratios, the uptake of the anisole solvent in the stamp is evaluated as a function of time. Laser confocal microscopy is employed as a unique technique to measure the penetration depth of the solvent into the stamp. The suspension solids loading affects the anisole saturation depth in the PDMS stamp. For the suspensions with low solids loading, the experimental data agree with the model for non-Fickian diffusion through a rubbery-elastic polymer. For the suspensions with high solids loading, the data agree more with a sigmoidal diffusion curve, reflecting the rubbery-viscous behavior of a swelling polymer. This difference is due to the degree of swelling in the PDMS. Higher solids loadings induce more swelling because the rate of anisole diffusing into the stamp is increased, likely due to the less dense buildup of the solids as the suspension dries.

Structure-induced switching of interpolymer adhesion at a solid–polymer melt interface

DOE PAGES

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo; ...

2018-01-11

In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesionmore » testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chains and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.« less

Property control of graphene aerogels by in situ growth of silicone polymer

NASA Astrophysics Data System (ADS)

Zhou, Shuai; Zhou, Xiang; Hao, Gazi; Jiang, Wei; Wang, Tianhe

2018-05-01

Modulation of the density (from 3.5 to 64 mg cm-3), hydrophobicity and oil-uptake capability of graphene aerogels in extensive ranges were achieved by reacting (3-Mercaptopropyl)trimethoxysilane (MPS) with graphene oxide solutions under heating. The reaction allowed a characteristic silicone substructure to be formed on graphene and joint the graphene layers firmly together. With the increase of MPS concentrations (≤ca. 0.2 vol%), the nano silicone polymer grown on graphene functioned as a "linker" and "spacer", leading to a substantial decrease of the aerogel density. Because of the formation of silicone polymer and the characteristic nano-micro substructures on the backbones of graphene aerogels, the graphene aerogels exhibited a high hydrophobicity with the water contact angle consistently exceeding 142 degrees. Functionalized graphene aerogels with a density of 3.5 mg cm-3 were conveniently fabricated that displayed an extraordinary oil absorption capacity, 182 times for lubricating oil and 143 times for n-hexane of its own weight. Furthermore, the aerogels maintained their ultra-high absorption capability even after 20 absorption-distillation cycles, due to structural integrity held by the strong interfacial adhesion between graphene sheets and polymer chains of aerogels. This study offers a promising graphene aerogels and also provides a strategy for fabricating extra low dense functional materials.

In situ growth of well-dispersed CdS nanocrystals in semiconducting polymers

PubMed Central

2013-01-01

A straight synthetic route to fabricate hybrid nanocomposite films of well-dispersed CdS nanocrystals (NCs) in poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) is reported. A soluble cadmium complex [Cd(SBz)2]2·MI, obtained by incorporating a Lewis base (1-methylimidazole, MI) on the cadmium bis(benzyl)thiol, is used as starting reagent in an in situ thermolytic process. CdS NCs with spherical shape nucleate and grow well below 200°C in a relatively short time (30 min). Photoluminescence spectroscopy measurements performed on CdS/MEH-PPV nanocomposites show that CdS photoluminescence peaks are totally quenched inside MEH-PPV, if compared to CdS/PMMA nanocomposites, as expected due to overlapping of the polymer absorption and CdS emission spectra. The CdS NCs are well-dispersed in size and homogeneously distributed within MEH-PPV matrix as proved by transmission electron microscopy. Nanocomposites with different precursor/polymer weight ratios were prepared in the range from 1:4 to 4:1. Highly dense materials, without NCs clustering, were obtained for a weight/weight ratio of 2:3 between precursor and polymer, making these nanocomposites particularly suitable for optoelectronic and solar energy conversion applications. PMID:24015753

Preparation of a bonelike apatite-polymer fiber composite using a simple biomimetic process.

PubMed

Yokoyama, Yoshiro; Oyane, Ayako; Ito, Atsuo

2008-08-01

A bonelike apatite-polymer fiber composite may be useful as an implant material to replace bone, the enthesis of a tendon, and the joint part of a ligament. We treated an ethylene-vinyl alcohol copolymer (EVOH) plate and knitted EVOH fibers with an oxygen plasma to produce oxygen-containing functional groups on their surfaces. The plasma-treated samples were alternately dipped in alcoholic calcium and phosphate ion solutions three times to deposit apatite precursors onto their surfaces. The surface-modified samples formed a dense and uniform bonelike surface apatite layer after immersion for 24 h in a simulated body fluid with ion concentrations approximately equal to those of human blood plasma. The adhesive strength between the apatite layer and the sample's surface increased with increasing power density of the oxygen plasma. The apatite-EVOH fiber composite obtained by our process has similarities to natural bone in that apatite crystals are deposited on organic polymer fibers. The resulting composite would possess osteoconductivity due to the apatite phase. With proper polymer selection and optimized synthesis techniques, a composite could be made that would have bonelike mechanical properties. Hence, the present surface modification and coating process would be a promising route to obtain new implant materials with bonelike mechanical properties and osteoconductivity. (c) 2007 Wiley Periodicals, Inc.

Molding of strength testing samples using modern PDCPD material for purpose of automotive industry

NASA Astrophysics Data System (ADS)

Grabowski, L.; Baier, A.; Sobek, M.

2017-08-01

The casting of metal materials is widely known but the molding of composite polymer materials is not well-known method still. The initial choice of method for producing composite bodies was the method of casting of PDCPD material. For purpose of performing casting of polymer composite material, a special mold was made. Firstly, the 3D printed, using PLA material, mold was used. After several attempts of casting PDCPD many problems were encountered. The second step was to use mold milled from a firm and dense isocyanate foam. After several attempts research shown that this solution is more resistant to high-temperature peak, but this material is too fragile to use it several times. This solution also prevents mold from using external heating, which can be necessary for performing correct molding process. The last process was to use the aluminum mold, which is dedicated to PDCPD polymer composite, because of low adhesiveness. This solution leads to perform correct PDCPD polymer composite material injection. After performing casting operation every PDCPD testing samples were tested. These results were compared together. The result of performed work was to archive correct properties of injection of composite material. Research and results were described in detail in this paper.

Flexible composite radiation detector

DOEpatents

Cooke, D Wayne [Santa Fe, NM; Bennett, Bryan L [Los Alamos, NM; Muenchausen, Ross E [Los Alamos, NM; Wrobleski, Debra A [Los Alamos, NM; Orler, Edward B [Los Alamos, NM

2006-12-05

A flexible composite scintillator was prepared by mixing fast, bright, dense rare-earth doped powdered oxyorthosilicate (such as LSO:Ce, LSO:Sm, and GSO:Ce) scintillator with a polymer binder. The binder is transparent to the scintillator emission. The composite is seamless and can be made large and in a wide variety of shapes. Importantly, the composite can be tailored to emit light in a spectral region that matches the optimum response of photomultipliers (about 400 nanometers) or photodiodes (about 600 nanometers), which maximizes the overall detector efficiency.

The Contribution of Prohibitin 1 to Prostate Cancer Chemoresistance

DTIC Science & Technology

2015-10-01

ceramide-PEG5K in normal BALB/c mice after i.v. injection. The siRNA was labeled with near infrared (NIR) dye DY647. (B) Ex vivo fluorescence image of...ceramide-PEG5K (Right) siRNA NPs at 18 h. The siRNA was labeled with dye DY547. (Scale bar, 10 μm.) Zhu et al. PNAS | June 23, 2015 | vol. 112 | no...Woodrow KA, et al. (2009) Intravaginal gene silencing using biodegradable polymer nanoparticles densely loaded with small-interfering RNA. Nat Mater

Numerical Simulation of Ballistic Impact of Layered Aluminum Nitride Ceramic

DTIC Science & Technology

2015-09-01

tile(s) Aluminum nitride (AlN) 163 a Polymer layers Polyurethane foam 18 b Backing metal Aluminum 6061-T6 (Al) 23 c Projectile Tungsten heavy alloy...larger (a factor of 3.8) than the most dense polyurethane foam of the available constitutive models. Default options for element failure were imposed in...AlN), a polycrystalline ceramic. The total thickness of the tile(s) is 38.1 mm in all cases. A thin polyurethane laminate separates neighboring tiles

Single-source-precursor synthesis of dense SiC/HfC(x)N(1-x)-based ultrahigh-temperature ceramic nanocomposites.

PubMed

Wen, Qingbo; Xu, Yeping; Xu, Binbin; Fasel, Claudia; Guillon, Olivier; Buntkowsky, Gerd; Yu, Zhaoju; Riedel, Ralf; Ionescu, Emanuel

2014-11-21

A novel single-source precursor was synthesized by the reaction of an allyl hydrido polycarbosilane (SMP10) and tetrakis(dimethylamido)hafnium(iv) (TDMAH) for the purpose of preparing dense monolithic SiC/HfC(x)N(1-x)-based ultrahigh temperature ceramic nanocomposites. The materials obtained at different stages of the synthesis process were characterized via Fourier transform infrared (FT-IR) as well as nuclear magnetic resonance (NMR) spectroscopy. The polymer-to-ceramic transformation was investigated by means of MAS NMR and FT-IR spectroscopy as well as thermogravimetric analysis (TGA) coupled with in situ mass spectrometry. Moreover, the microstructural evolution of the synthesized SiHfCN-based ceramics annealed at different temperatures ranging from 1300 °C to 1800 °C was characterized by elemental analysis, X-ray diffraction, Raman spectroscopy and transmission electron microscopy (TEM). Based on its high temperature behavior, the amorphous SiHfCN-based ceramic powder was used to prepare monolithic SiC/HfC(x)N(1-x)-based nanocomposites using the spark plasma sintering (SPS) technique. The results showed that dense monolithic SiC/HfC(x)N(1-x)-based nanocomposites with low open porosity (0.74 vol%) can be prepared successfully from single-source precursors. The average grain size of both HfC0.83N0.17 and SiC phases was found to be less than 100 nm after SPS processing owing to a unique microstructure: HfC0.83N0.17 grains were embedded homogeneously in a β-SiC matrix and encapsulated by in situ formed carbon layers which acted as a diffusion barrier to suppress grain growth. The segregated Hf-carbonitride grains significantly influenced the electrical conductivity of the SPS processed monolithic samples. While Hf-free polymer-derived SiC showed an electrical conductivity of ca. 1.8 S cm(-1), the electrical conductivity of the Hf-containing material was analyzed to be ca. 136.2 S cm(-1).

Brush-Like Polymers: New Design Platforms for Soft, Dry Materials with Unique Property Relations

NASA Astrophysics Data System (ADS)

Daniel, William Francis McKemie, Jr.

Elastomers represent a unique class of engineering materials due to their light weight, low cost, and desirable combination of softness (105 -107 Pa) and large extensibilities (up to 1000%). Despite these advantages, there exist applications that require many times softer modulus, greater extensibility, and stronger strain hardening for the purpose of mimicking the mechanical properties of systems such as biological tissues. Until recently, only liquid-filled gels were suitable materials for such applications, including soft robotics and implants. A considerable amount of work has been done to create gels with superior properties, but despite unique strengths they also suffer from unique weaknesses. This class of material displays fundamental limitations in the form of heterogeneous structures, solvent loss and phase transitions at extreme temperatures, and loss of liquid fraction upon high deformations. In gels the solvent fraction also introduces a large solvent/polymer interaction parameter which must be carefully considered when designing the final mechanical properties. These energetic considerations further exaggerate the capacity for inconstant mechanical properties caused by fluctuations of the solvent fraction. In order to overcome these weaknesses, a new platform for single component materials with low modulus (<105 Pa) must be developed. Single component systems do not suffer from compositional changes over time and display more stable performance in a wider variety of temperatures and humidity conditions. A solvent-free system also has the potential to be homogeneous which replaces the large energetic interactions with comparatively small architectural interaction parameters. If a solvent-free alternative to liquid-filled gels is to be created, we must first consider the fundamental barrier to softer elastomers, i.e. entanglements - intrinsic topological restrains which define a lower limit of modulus ( 105 Pa). These entanglements are determined by chemistry specific parameters (repeat unit volume and Kuhn segment size) in the polymer liquid (melt) prior to crosslinking. Previous solvent free replacements for gels include elastomers end-linked in semidilute conditions. These materials are generated through crosslinking telechelic polymer chains in semidilute solutions at the onset of chain overlap. At such low polymer concentrations entanglements are greatly diluted and once the resulting gel is dried it creates a supersoft and super-elastic network. Although such methods have successfully generated materials with moduli below the 105 Pa limit and high extensibilities ( 1000%) they present their own limitations. Firstly, the semidilute crosslinking methods uses an impractically large volume of solvent which is unattractive in industry. Second, producing and crosslinking large monodisperse telechelic chains is a nontrivial process leading to large uncertainties in the final network architecture and properties. Specifically, telechelics have a distribution of end-to-end distances and in semidilute solutions with extremely low fraction of chain ends the crosslink reaction is diffusion limited, very slow, and imprecise. In order to achieve a superior solvent-free platform, we propose alteration of mechanical properties through the architectural disentanglement of brush-like polymer structures. In recent year there has been an increase in the synthetic conditions and crosslinking schemes available for producing brush-like structures. This makes brush-like materials an attractive alternative to more restrictive methods such as end-linking. Standard networks have one major control factor outside of chemistry, the network stand length. Brush-like architectures are created from long strands with regularly grafted side chains creating three characteristic length scales which may be independently manipulated. In collaboration with M. Rubinstein, we have utilized bottlebrush polymer architectures (a densely grafted brush-like polymer) to experimentally verify theoretical predictions of disentangled bottlebrush melts. By attaching well-defined side chains onto long polymer backbones, individual polymer strands are separated in space (similar to dilution with solvent) accompanied by a comparatively small increase in the rigidity of the strands. The end result is an architectural disentangled melt with an entanglement plateau modulus as much as three orders of magnitude lower than typical linear polymers and a broadly expanded potential for extensibility once crosslinked.

Massively Parallel Simulations of Diffusion in Dense Polymeric Structures

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

Faulon, Jean-Loup, Wilcox, R.T.

1997-11-01

An original computational technique to generate close-to-equilibrium dense polymeric structures is proposed. Diffusion of small gases are studied on the equilibrated structures using massively parallel molecular dynamics simulations running on the Intel Teraflops (9216 Pentium Pro processors) and Intel Paragon(1840 processors). Compared to the current state-of-the-art equilibration methods this new technique appears to be faster by some orders of magnitude.The main advantage of the technique is that one can circumvent the bottlenecks in configuration space that inhibit relaxation in molecular dynamics simulations. The technique is based on the fact that tetravalent atoms (such as carbon and silicon) fit in themore » center of a regular tetrahedron and that regular tetrahedrons can be used to mesh the three-dimensional space. Thus, the problem of polymer equilibration described by continuous equations in molecular dynamics is reduced to a discrete problem where solutions are approximated by simple algorithms. Practical modeling applications include the constructing of butyl rubber and ethylene-propylene-dimer-monomer (EPDM) models for oxygen and water diffusion calculations. Butyl and EPDM are used in O-ring systems and serve as sealing joints in many manufactured objects. Diffusion coefficients of small gases have been measured experimentally on both polymeric systems, and in general the diffusion coefficients in EPDM are an order of magnitude larger than in butyl. In order to better understand the diffusion phenomena, 10, 000 atoms models were generated and equilibrated for butyl and EPDM. The models were submitted to a massively parallel molecular dynamics simulation to monitor the trajectories of the diffusing species.« less

Novel self-assembled gels and materials synthesis in unconventional environments

NASA Astrophysics Data System (ADS)

Irvin, Glen Clifford, Jr.

This thesis deals specifically with the fabrication of novel nanophase and polymer materials using novel microstructured mediums. Enzymatic polymerization in a new microemulsion system using dense carbon dioxide and fluorinated surfactants was carried out. The morphology, molecular weight, and chemical structure of the polymer are characterized through electron microscopy, HPLC, FTIR, and 1HNMR. Structural characteristics indicate similarity to polymers formed in AOT-inverse micelles. Spectroscopic information of the polymerization system on a molecular level has been performed. The results indicate strong hydrogen bonding interactions between the monomer, water, and perfluorinated surfactant implying the partitioning of the monomer to the surfactant headgroup region. An extension of the microemulsion environment is found with novel microemulsion based gels. The gels contain both lecithin and AOT surfactants where roughly equal volumes of hydrocarbon and water forms a three-dimensional gel network. This microemulsion system is unique from a fundamental scientific and practical interest. Analysis of the system microstructures using 1HNMR, 13CNMR 31PNNM, Rheology, SAXS, SANS, and conductivity is presented. Nanomaterial templated syntheses were conducted and are discussed. A new technique was developed for the rapid production of clathrate hydrates either in aqueous or water-in-microemulsion environments. The systems devised for this technology have significantly greater interfacial contact between water and gas molecules (clathrate hydrate constituents). The rapid clathrate hydrate technique was utilized for synthesis of nanoclusters in aqueous and reverse micelle based systems using the remarkable phenomenon of clathrate hydrate formation. Conversion of water to crystalline ice-like (clathrate hydrate) form is exploited to arrest particle growth, thereby restricting particle size to the nanometer range. The technique is used to generate high synthesis rates of nanoclusters (specifically ferrites) in aqueous solution. By controlling process conditions, ferrite particles with spherical or high aspect ratio acicular morphologies are obtained. Characterization of magnetic materials produced using this new technique was detailed with XRD, SQUID, and TEM. An extension of the rapid hydrate technique to AOT/water/Isooctane microemulsions found that for the same [water]/[AOT] ratio, nanoclusters of smaller size could be formed simply by subjecting the reversed micelles to hydrate forming conditions. Analysis of a model semiconductor (PbS) is presented using UV-VIS, XRD, EDAX, TEM, and Electron Diffraction.

Boundary layers of aqueous surfactant and block copolymer solutions against hydrophobic and hydrophilic solid surfaces

NASA Astrophysics Data System (ADS)

Steitz, Roland; Schemmel, Sebastian; Shi, Hongwei; Findenegg, Gerhard H.

2005-03-01

The boundary layer of aqueous surfactants and amphiphilic triblock copolymers against flat solid surfaces of different degrees of hydrophobicity was investigated by neutron reflectometry (NR), grazing incidence small angle neutron scattering (GISANS) and atomic force microscopy (AFM). Solid substrates of different hydrophobicities were prepared by appropriate surface treatment or by coating silicon wafers with polymer films of different chemical natures. For substrates coated with thin films (20-30 nm) of deuterated poly(styrene) (water contact angle \\theta_{\\mathrm {w}} \\approx 90^\\circ ), neutron reflectivity measurements on the polymer/water interface revealed a water depleted liquid boundary layer of 2-3 nm thickness and a density about 90% of the bulk water density. No pronounced depletion layer was found at the interface of water against a less hydrophobic polyelectrolyte coating (\\theta_{\\mathrm {w}} \\approx 63^\\circ ). It is believed that the observed depletion layer at the hydrophobic polymer/water interface is a precursor of the nanobubbles which have been observed by AFM at this interface. Decoration of the polymer coatings by adsorbed layers of nonionic CmEn surfactants improves their wettability by the aqueous phase at surfactant concentrations well below the critical micellar concentration (CMC) of the surfactant. Here, GISANS experiments conducted on the system SiO2/C8E4/D2O reveal that there is no preferred lateral organization of the C8E4 adsorption layers. For amphiphilic triblock copolymers (PEO-PPO-PEO) it is found that under equilibrium conditions they form solvent-swollen brushes both at the air/water and the solid/water interface. In the latter case, the brushes transform to uniform, dense layers after extensive rinsing with water and subsequent solvent evaporation. The primary adsorption layers maintain properties of the precursor brushes. In particular, their thickness scales with the number of ethylene oxide units (EO) of the block copolymer. In the case of dip-coating without subsequent rinsing, surface patterns of the presumably crystalline polymer on top of the primary adsorption layer develop upon drying under controlled conditions. The morphology depends mainly on the nominal surface coverage with the triblock copolymer. Similar morphologies are found on bare and polystyrene-coated silicon substrates, indicating that the surface patterning is mainly driven by segregation forces within the polymer layers and not by interactions with the substrate.

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

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo

In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesionmore » testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chains and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.« less

Embedded optical interconnect technology in data storage systems

NASA Astrophysics Data System (ADS)

Pitwon, Richard C. A.; Hopkins, Ken; Milward, Dave; Muggeridge, Malcolm

2010-05-01

As both data storage interconnect speeds increase and form factors in hard disk drive technologies continue to shrink, the density of printed channels on the storage array midplane goes up. The dominant interconnect protocol on storage array midplanes is expected to increase to 12 Gb/s by 2012 thereby exacerbating the performance bottleneck in future digital data storage systems. The design challenges inherent to modern data storage systems are discussed and an embedded optical infrastructure proposed to mitigate this bottleneck. The proposed solution is based on the deployment of an electro-optical printed circuit board and active interconnect technology. The connection architecture adopted would allow for electronic line cards with active optical edge connectors to be plugged into and unplugged from a passive electro-optical midplane with embedded polymeric waveguides. A demonstration platform has been developed to assess the viability of embedded electro-optical midplane technology in dense data storage systems and successfully demonstrated at 10.3 Gb/s. Active connectors incorporate optical transceiver interfaces operating at 850 nm and are connected in an in-plane coupling configuration to the embedded waveguides in the midplane. In addition a novel method of passively aligning and assembling passive optical devices to embedded polymer waveguide arrays has also been demonstrated.

Shape-Persistent, Thermoresponsive Polypeptide Brushes Prepared by Vapor Deposition Surface-Initiated Ring-Opening Polymerization of α-Amino Acid N -Carboxyanhydrides

DOE PAGES

Shen, Yong; Desseaux, Solenne; Aden, Bethany; ...

2015-04-20

We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modifiedmore » L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG 2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.« less

Behavior of grafted polymers on nanofillers and their influence on polymer nanocomposite properties

NASA Astrophysics Data System (ADS)

Dukes, Douglas Michael

Polymer nanocomposites continue to receive wide-spread acclaim for their potential to improve composite materials beyond conventional macroscale fillers. The improvement lies both in the altered properties of the particle itself and in the interaction region surrounding the filler. As the surface area of the filler increases, a greater volume fraction of this interphase region is present in the composite. However, simply minimizing the particle size to maximize surface area introduces additional problems; the larger specific surface area promotes aggregation to reduce the surface energy. Since the composite's properties are largely tied to the morphology, aggregation prevents control over the dispersion state of the filler, and thus the properties. Therefore, disaggregation and morphology control are vital to achieving designable nanocomposites. To accomplish both tasks, this thesis focuses on the behavior of grafted polymer coatings on nanoparticles and their in uence on the macroscopic properties. Grafted chains play an integral role in both morphology control and reinforcement. To investigate the behavior of polymer brushes on nanoparticles, polystyrene was grafted on 15 nm silica particles at varying graft densities and molecular weights. Dynamic light scattering studies in dilute solution were performed to obtain the brush height as a function of both graft density and molecular weight. Three distinct regimes of behavior exist, the "mushroom", the semi-dilute polymer brush (SDPB), and the concentrated polymer brush (CPB) regimes. In the CPB regime, which is an extraordinary configuration of highly-stretched chains on densely grafted surfaces, the brush height h was found to scale as h ∝ N4/5, where N is the degree of polymerization. This result is contrary to the observed scaling of the CPB in flat interface systems, where h ∝ N1. To explore the behavior of grafted chains in the melt, molecular dynamics simulations were performed on grafted nanoparticles grafted with varying amounts of polymer chains at different curvatures. Particles as small as 15 monomers in size were found to already be in the large particle limit, a result that has many implications regarding the dispersibility of grafted fillers in composites. At low graft densities, melt chains were found to form entanglements with the brush all the way to the particle surface, implying the particle is not effectively screened by the grafted chains. The mechanical properties of these grafted silica composites were studied as a function of matrix polymer fraction. As more matrix polymer is introduced, the dominant contribution to the behavior shifts from the grafted chains to the matrix chains. This elucidates the role of grafted chains on the mechanical properties of grafted nanoparticle composites. As the graft density is increased, the wettability of grafted chains was shown to decrease, causing fewer entanglements between grafted chains and matrix chains, resulting in poorer reinforcement. Interesting behavior was observed at low graft densities; a pronounced shape memory effect occurred at high particle concentrations. It is proposed that the grafted chains entangle with adjacent grafted chains, forming a three-dimensional network of entangled brushes attached to silica cores. This structure effectively forms "cross-links" as in elastomeric systems, giving an entropic restorative force to stretched chains. Thus, above Tg, when chains have a higher degree of mobility, the composites can be stretched to over 800%. When cooled to below Tg, they retain the deformed geometry. Upon reheating above Tg, the composite is restored to its original dimensions. This work has identified means of improving theoretical models to better guide future experiments and lead to predictability in polymer composite design. Grafted chains have the demonstrated ability to control the morphology and reinforcement in polymer composites. The behavior of grafted chains were shown to demonstrate drastically different properties from their bulk polymer counterparts.

Rutting resistance of asphalt mixture with cup lumps modified binder

NASA Astrophysics Data System (ADS)

Shaffie, E.; Hanif, W. M. M. Wan; Arshad, A. K.; Hashim, W.

2017-11-01

Rutting is the most common pavement distress in pavement structures which occurs mainly due to several factors such as increasing of traffic volume, climatic conditions and also due to construction design errors. This failure reduced the service life of the pavement, reduced driver safety and increase cost of maintenance. Polymer Modified Binder has been observed for a long time in improving asphalt pavement performance. Research shows that the use of polymer in bituminous mix not only improve the resistance to rutting but also increase the life span of the pavement. This research evaluates the physical properties and rutting performance of dense graded Superpave-designed HMA mix. Two different types of dense graded Superpave HMA mix were developed consists of unmodified binder mix (UMB) and cup lumps rubber (liquid form) modified binder mix (CLMB). Natural rubber polymer modified binder was prepared from addition of 8 percent of cup lumps into binder. Results showed that all the mixes passed the Superpave volumetric properties criteria which indicate that these mixtures were good with respect to durability and flexibility. Furthermore, rutting results from APA rutting test was determined to evaluate the performance of these mixtures. The rutting result of CLMB demonstrates better resistance to rutting than those prepared using UMB mix. Addition of cup lumps rubber in asphalt mixture was found to be significant, where the cup lumps rubber has certainly improves the binder properties and enhanced its rutting resistance due to greater elasticity offered by the cup lumps rubber particles. It shows that the use of cup lumps rubber can significantly reduce the rut depth of asphalt mixture by 41% compared to the minimum rut depth obtained for the UMB mix. Therefore, it can be concluded that the cup lumps rubber is suitable to be used as a modifier to modified binder in order to enhance the properties of the binder and thus improves the performance of asphalt mixes.

Analysis of CD44-Hyaluronan Interactions in an Artificial Membrane System

PubMed Central

Wolny, Patricia M.; Banerji, Suneale; Gounou, Céline; Brisson, Alain R.; Day, Anthony J.; Jackson, David G.; Richter, Ralf P.

2010-01-01

CD44 is a major cell surface receptor for the large polydisperse glycosaminoglycan hyaluronan (HA). Binding of the long and flexible HA chains is thought to be stabilized by the multivalent nature of the sugar molecule. In addition, high and low molecular weight forms of HA provoke distinct proinflammatory and anti-inflammatory effects upon binding to CD44 and can deliver either proliferative or antiproliferative signals in appropriate cell types. Despite the importance of such interactions, however, neither the stoichiometry of multivalent HA binding at the cell surface nor the molecular basis for functional distinction between different HA size categories is understood. Here we report on the design of a supported lipid bilayer system that permits quantitative analysis of multivalent binding through presentation of CD44 in a stable, natively oriented manner and at controlled density. Using this system in combination with biophysical techniques, we show that the amount of HA binding to bilayers that are densely coated with CD44 increases as a function of HA size, with half-maximal saturation at ∼30 kDa. Moreover, reversible binding was confined to the smaller HA species (molecular weight of ≤10 kDa), whereas the interaction was essentially irreversible with larger polymers. The amount of bound HA decreased with decreasing receptor surface density, but the stability of binding was not affected. From a physico-chemical perspective, the binding properties of HA share many similarities with the typical behavior of a flexible polymer as it adsorbs onto a homogeneously attractive surface. These findings provide new insight into the multivalent nature of CD44-HA interactions and suggest a molecular basis for the distinct biological properties of different size fractions of hyaluronan. PMID:20663884

DNA-Templated Polymerization of Side-Chain-Functionalized Peptide Nucleic Acid Aldehydes

PubMed Central

Kleiner, Ralph E.; Brudno, Yevgeny; Birnbaum, Michael E.; Liu, David R.

2009-01-01

The DNA-templated polymerization of synthetic building blocks provides a potential route to the laboratory evolution of sequence-defined polymers with structures and properties not necessarily limited to those of natural biopolymers. We previously reported the efficient and sequence-specific DNA-templated polymerization of peptide nucleic acid (PNA) aldehydes. Here, we report the enzyme-free, DNA-templated polymerization of side-chain-functionalized PNA tetramer and pentamer aldehydes. We observed that the polymerization of tetramer and pentamer PNA building blocks with a single lysine-based side chain at various positions in the building block could proceed efficiently and sequence-specifically. In addition, DNA-templated polymerization also proceeded efficiently and in a sequence-specific manner with pentamer PNA aldehydes containing two or three lysine side chains in a single building block to generate more densely functionalized polymers. To further our understanding of side-chain compatibility and expand the capabilities of this system, we also examined the polymerization efficiencies of 20 pentamer building blocks each containing one of five different side-chain groups and four different side-chain regio- and stereochemistries. Polymerization reactions were efficient for all five different side-chain groups and for three of the four combinations of side-chain regio- and stereochemistries. Differences in the efficiency and initial rate of polymerization correlate with the apparent melting temperature of each building block, which is dependent on side-chain regio- and stereochemistry, but relatively insensitive to side-chain structure among the substrates tested. Our findings represent a significant step towards the evolution of sequence-defined synthetic polymers and also demonstrate that enzyme-free nucleic acid-templated polymerization can occur efficiently using substrates with a wide range of side-chain structures, functionalization positions within each building block, and functionalization densities. PMID:18341334

Live-cell imaging of neurofilament transport in cultured neurons.

PubMed

Uchida, Atsuko; Monsma, Paula C; Fenn, J Daniel; Brown, Anthony

2016-01-01

Neurofilaments, which are the intermediate filaments of nerve cells, are space-filling cytoskeletal polymers that contribute to the growth of axonal caliber. In addition to their structural role, neurofilaments are cargos of axonal transport that move along microtubule tracks in a rapid, intermittent, and bidirectional manner. Though they measure just 10nm in diameter, which is well below the diffraction limit of optical microscopes, these polymers can reach 100 μm or more in length and are often packed densely, just tens of nanometers apart. These properties of neurofilaments present unique challenges for studies on their movement. In this article, we describe several live-cell fluorescence imaging strategies that we have developed to image neurofilament transport in axons of cultured neurons on short and long timescales. Together, these methods form a powerful set of complementary tools with which to study the axonal transport of these unique intracellular cargos. Copyright © 2016 Elsevier Inc. All rights reserved.

Structural Evolution of Low-Molecular-Weight Poly(ethylene oxide)-block-polystyrene Diblock Copolymer Thin Film

PubMed Central

Huang, Xiaohua

2013-01-01

The structural evolution of low-molecular-weight poly(ethylene oxide)-block-polystyrene (PEO-b-PS) diblock copolymer thin film with various initial film thicknesses on silicon substrate under thermal annealing was investigated by atomic force microscopy, optical microscopy, and contact angle measurement. At film thickness below half of the interlamellar spacing of the diblock copolymer (6.2 nm), the entire silicon is covered by a polymer brush with PEO blocks anchored on the Si substrate due to the substrate-induced effect. When the film is thicker than 6.2 nm, a dense polymer brush which is equal to half of an interlamellar layer was formed on the silicon, while the excess material dewet this layer to form droplets. The droplet surface was rich with PS block and the PEO block crystallized inside the bigger droplet to form spherulite. PMID:24302862

Tape method of forming a thin layer of doped lanthanum chromite particles and of bonding such on an electrode

DOEpatents

Richards, Von L.; Singhal, Subhash C.; Pal, Uday B.

1992-01-01

A combustible polymer film, useful for application of an interconnection on an electrode is made by: (1) providing doped LaCro.sub.3 particles; (2) dispersing doped LaCrO.sub.3 particles in a solvent, to provide a dispersion; (3) screening the dispersion to provide particles in the range of from 30 micrometers to 80 micrometers; (4) admixing a fugitive polymer with the particles; (5) casting the dispersion to provide a film; (6) drying the film; and (7) stripping the film. The film can then be applied to a porous, preheated electrode top surface, and then electrochemical vapor depositing a dense skeletal LaCrO.sub.3 structure, between and around the doped LaCrO.sub.3 particles. Additional solid oxide electrolyte and fuel electrode layers can then be added to provide a fuel cell.

Tape method of forming a thin layer of doped lanthanum chromite particles and of bonding such on an electrode

DOEpatents

Richards, V.L.; Singhal, S.C.; Pal, U.B.

1992-07-21

A combustible polymer film, useful for application of an interconnection on an electrode is made by: (1) providing doped LaCro[sub 3] particles; (2) dispersing doped LaCrO[sub 3] particles in a solvent, to provide a dispersion; (3) screening the dispersion to provide particles in the range of from 30 micrometers to 80 micrometers; (4) admixing a fugitive polymer with the particles; (5) casting the dispersion to provide a film; (6) drying the film; and (7) stripping the film. The film can then be applied to a porous, preheated electrode top surface, and then a dense skeletal LaCrO[sub 3] structure is electrochemically vapor deposited between and around the doped LaCrO[sub 3] particles. Additional solid oxide electrolyte and fuel electrode layers can then be added to provide a fuel cell. 4 figs.

Effect of tethering on the surface dynamics of a thin polymer melt layer

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

Uğur, Gökçe; Akgun, Bulent; Jiang, Zhang

The surface height fluctuations of a layer of low molecular weight (2.2k) untethered perdeuterated polystyrene (dPS) chains adjacent to a densely grafted polystyrene brush are slowed dramatically. Due to the interpenetration of the brush with the layer of “untethered chains” a hydrodynamic continuum theory can only describe the fluctuations when the effective thickness of the film is taken to be that which remains above the swollen brush. Furthermore, the portion of the film of initially untethered chains that interpenetrates with the brush becomes so viscous as to effectively play the role of a rigid substrate. They provide a route formore » tailoring polymer layer surface properties such as wetting, adhesion and friction, since these hybrid samples contain a covalently tethered layer at the bottom, does not readily dewet, and are more robust than thin layers of untethered short chains on rigid substrates.« less

Hemispherical array of sensors with contractively wrapped polymer petals for flow sensing

NASA Astrophysics Data System (ADS)

Kanhere, Elgar; Wang, Nan; Kottapalli, Ajay Giri Prakash; Miao, Jianmin; Triantafyllou, Michael

2017-11-01

Hemispherical arrays have inherent advantages that allow simultaneous detection of flow speed and direction due to their shape. Though MEMS technology has progressed leaps and bounds, fabrication of array of sensors on a hemispherical surface is still a challenge. In this work, a novel approach of constructing hemispherical array is presented which employs a technique of contractively wrapping a hemispherical surface with flexible liquid crystal polymer petals. This approach also leverages the offerings from rapid prototyping technology and established standard MEMS fabrication processes. Hemispherical arrays of piezoresistive sensors are constructed with two types of petal wrappings, 4-petals and 8-petals, on a dome. The flow sensing and direction detection abilities of the dome are evaluated through experiments in wind tunnel. Experimental results demonstrate that a dome equipped with a dense array of sensors can provide information pertaining to the stimulus, through visualization of output profile over the entire surface.

Molecular characterization of the plant biopolyester cutin by AFM and spectroscopic techniques.

PubMed

Benítez, José J; Matas, Antonio J; Heredia, Antonio

2004-08-01

Atomic force microscopy, FT-IR spectroscopy, and solid-state nuclear magnetic resonance have been used to improve our current knowledge on the molecular characteristics of the biopolyester cutin, the main component of the plant cuticle. After comparison of samples of cutin isolated from young and mature tomato fruit cuticles has been possible to establish different degrees of cross-linking in the biopolymer and that the polymer is mainly formed after esterification of secondary hydroxyl groups of the monomers that form this type of cutin. Atomic force microscopy gave useful structural information on the molecular topography of the outer surface of the isolated samples. The texture of these samples is a consequence of the cross-linking degree or chemical status of the polymer. Thus, the more dense and cross-linked cutin from ripe or mature tomato fruit is characterized by a flatter and more globular texture in addition to the development of elongated and orientated superstructures.

Effect of tethering on the surface dynamics of a thin polymer melt layer

DOE PAGES

Uğur, Gökçe; Akgun, Bulent; Jiang, Zhang; ...

2016-05-13

The surface height fluctuations of a layer of low molecular weight (2.2k) untethered perdeuterated polystyrene (dPS) chains adjacent to a densely grafted polystyrene brush are slowed dramatically. Due to the interpenetration of the brush with the layer of “untethered chains” a hydrodynamic continuum theory can only describe the fluctuations when the effective thickness of the film is taken to be that which remains above the swollen brush. Furthermore, the portion of the film of initially untethered chains that interpenetrates with the brush becomes so viscous as to effectively play the role of a rigid substrate. They provide a route formore » tailoring polymer layer surface properties such as wetting, adhesion and friction, since these hybrid samples contain a covalently tethered layer at the bottom, does not readily dewet, and are more robust than thin layers of untethered short chains on rigid substrates.« less

Fibrillar films obtained from sodium soap fibers and polyelectrolyte multilayers.

PubMed

Zawko, Scott A; Schmidt, Christine E

2011-08-01

An objective of tissue engineering is to create synthetic polymer scaffolds with a fibrillar microstructure similar to the extracellular matrix. Here, we present a novel method for creating polymer fibers using the layer-by-layer method and sacrificial templates composed of sodium soap fibers. Soap fibers were prepared from neutralized fatty acids using a sodium chloride crystal dissolution method. Polyelectrolyte multilayers (PEMs) of polystyrene sulfonate and polyallylamine hydrochloride were deposited onto the soap fibers, crosslinked with glutaraldehyde, and then the soap fibers were leached with warm water and ethanol. The morphology of the resulting PEM structures was a dense network of fibers surrounded by a nonfibrillar matrix. Microscopy revealed that the PEM fibers were solid structures, presumably composed of polyelectrolytes complexed with residual fatty acids. These fibrillar PEM films were found to support the attachment of human dermal fibroblasts. Copyright © 2011 Wiley Periodicals, Inc.

System Applies Polymer Powder To Filament Tow

NASA Technical Reports Server (NTRS)

Baucom, Robert M.; Snoha, John J.; Marchello, Joseph M.

1993-01-01

Polymer powder applied uniformly and in continuous manner. Powder-coating system applies dry polymer powder to continuous fiber tow. Unique filament-spreading technique, combined with precise control of tension on fibers in system, ensures uniform application of polymer powder to web of spread filaments. Fiber tows impregnated with dry polymer powders ("towpregs") produced for preform-weaving and composite-material-molding applications. System and process valuable to prepreg industry, for production of flexible filament-windable tows and high-temperature polymer prepregs.

Mineralogical signatures of stone formation mechanisms.

PubMed

Gower, Laurie B; Amos, Fairland F; Khan, Saeed R

2010-08-01

The mechanisms involved in biomineralization are modulated through interactions with organic matrix. In the case of stone formation, the role of the organic macromolecules in the complex urinary environment is not clear, but the presence of mineralogical 'signatures' suggests that some aspects of stone formation may result from a non-classical crystallization process that is induced by acidic proteins. An amorphous precursor has been detected in many biologically controlled mineralization reactions, which is thought to be regulated by non-specific interactions between soluble acidic proteins and mineral ions. Using in vitro model systems, we find that a liquid-phase amorphous mineral precursor induced by acidic polypeptides can lead to crystal textures that resemble those found in Randall's plaque and kidney stones. This polymer-induced liquid-precursor process leads to agglomerates of coalesced mineral spherules, dense-packed spherulites with concentric laminations, mineral coatings and 'cements', and collagen-associated mineralization. Through the use of in vitro model systems, the mechanisms involved in the formation of these crystallographic features may be resolved, enhancing our understanding of the potential role(s) that proteins play in stone formation.

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

Jee, S.S.; DiMasi, E.; Kasinath, R.K.

Bone is a hierarchically structured composite which imparts it with unique mechanical properties and bioresorptive potential. These properties are primarily influenced by the underlying nanostructure of bone, which consists of nanocrystals of hydroxyapatite embedded and uniaxially aligned within collagen fibrils. There is also a small fraction of non-collagenous proteins in bone, and these are thought to play an important role in bone's formation. In our in vitro model system of bone formation, polyanionic peptides are used to mimic the role of the non-collagenous proteins. In our prior studies, we have shown that intrafibrillar mineralization can be achieved in synthetic reconstitutedmore » collagen sponges using a polymer-induced liquid-precursor (PILP) mineralization process. This led to a nanostructured arrangement of hydroxyapatite crystals within the individual fibrils which closely mimics that of bone. This report demonstrates that biogenic collagen scaffolds obtained from turkey tendon, which consist of densely packed and oriented collagen fibrils, can also be mineralized by the PILP process. Synchrotron X-ray diffraction studies show that the mineralization process leads to a high degree of crystallographic orientation at the macroscale, thus emulating that found in the biological system of naturally mineralizing turkey tendon.« less

Polymeric membrane systems of potential use for battery separators

NASA Technical Reports Server (NTRS)

Philipp, W. H.

1977-01-01

Two membrane systems were investigated that may have potential use as alkaline battery separators. One system comprises two miscible polymers: a support polymer (e.g., polyvinyl formal) and an ion conductor such as polyacrylic acid. The other system involves a film composed of two immiscible polymers: a conducting polymer (e.g., calcium polyacrylate) suspended in an inert polymer support matrix, polyphenylene oxide. Resistivities in 45-percent potassium hydroxide and qualitative mechanical properties are presented for films comprising various proportions of conducting and support polymers. In terms of these parameters, the results are encouraging for optimum ratios of conducting to support polymers.

Molecular-Level Processing of Si-(B)-C Materials with Tailored Nano/Microstructures.

PubMed

Schmidt, Marion; Durif, Charlotte; Acosta, Emanoelle Diz; Salameh, Chrystelle; Plaisantin, Hervé; Miele, Philippe; Backov, Rénal; Machado, Ricardo; Gervais, Christel; Alauzun, Johan G; Chollon, Georges; Bernard, Samuel

2017-12-01

The design of Si-(B)-C materials is investigated, with detailed insight into the precursor chemistry and processing, the precursor-to-ceramic transformation, and the ceramic microstructural evolution at high temperatures. In the early stage of the process, the reaction between allylhydridopolycarbosilane (AHPCS) and borane dimethyl sulfide is achieved. This is investigated in detail through solid-state NMR and FTIR spectroscopy and elemental analyses for Si/B ratios ranging from 200 to 30. Boron-based bridges linking AHPCS monomeric fragments act as crosslinking units, extending the processability range of AHPCS and suppressing the distillation of oligomeric fragments during the low-temperature pyrolysis regime. Polymers with low boron contents display appropriate requirements for facile processing in solution, leading to the design of monoliths with hierarchical porosity, significant pore volume, and high specific surface area after pyrolysis. Polymers with high boron contents are more appropriate for the preparation of dense ceramics through direct solid shaping and pyrolysis. We provide a comprehensive study of the thermal decomposition mechanisms, and a subsequent detailed study of the high-temperature behavior of the ceramics produced at 1000 °C. The nanostructure and microstructure of the final SiC-based ceramics are intimately linked to the boron content of the polymers. B 4 C/C/SiC nanocomposites can be obtained from the polymer with the highest boron content. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2017-07-06

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

Permeability of uncharged organic molecules in reverse osmosis desalination membranes.

PubMed

Dražević, Emil; Košutić, Krešimir; Svalina, Marin; Catalano, Jacopo

2017-06-01

Reverse osmosis (RO) membranes are primarily designed for removal of salts i.e. for desalination of brackish and seawater, but they have also found applications in removal of organic molecules. While it is clear that steric exclusion is the dominant removal mechanism, the fundamental explanation for how and why the separation occurs remains elusive. Until recently there was no strong microscopic evidences elucidating the structure of the active polyamide layers of RO membranes, and thus they have been conceived as "black boxes"; or as an array of straight capillaries with a distribution of radii; or as polymers with a small amount of polymer free domains. The knowledge of diffusion and sorption coefficients is a prerequisite for understanding the intrinsic permeability of any organic solute in any polymer. At the same time, it is technically challenging to accurately measure these two fundamental parameters in very thin (20-300 nm) water-swollen active layers. In this work we have measured partition and diffusion coefficients and RO permeabilities of ten organic solutes in water-swollen active layers of two types of RO membranes, low (SWC4+) and high flux (XLE). We deduced from our results and recent microscopic studies that the solute flux of organic molecules in polyamide layer of RO membranes occurs in two domains, dense polymer (the key barrier layer) and the water filled domains. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Youm, Sang Gil; Hwang, Euiyong; Chavez, Carlos A.

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe themore » development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.« less

Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies

DOE PAGES

Youm, Sang Gil; Hwang, Euiyong; Chavez, Carlos A.; ...

2016-06-15

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe themore » development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.« less

A Preliminary Study on the Toxic Combustion Products Testing of Polymers Used in High-Pressure Oxygen Systems

NASA Technical Reports Server (NTRS)

Hshieh, Fu-Yu; Beeson, Harold D.

2004-01-01

One likely cause of polymer ignition in a high-pressure oxygen system is adiabatic-compression heating of polymers caused by pneumatic impact. Oxidative _ pyrolysis or combustion of polymers in a high-pressure oxygen system could generate toxic gases. This paper reports the preliminary results of toxic combustion product testing of selected polymers in a pneumatic-impact test system. Five polymers commonly used in high-pressure oxygen systems, Nylon 6/6, polychlorotrifluoroethylene (CTFE), polytetrafluoroethylene (PTFE), fluoroelastomer (Viton(TradeMark) A), and nitrile rubber (Buna N), were tested in a pneumatic-impact test system at 2500- or 3500-psia oxygen pressure. The polymers were ignited and burned, then combustion products were collected in a stainless-steel sample bottle and analyzed by GC/MS/IRD, GC/FID, and GC/Methanizer/FID. The results of adiabatic-compression tests show that combustion of hydrocarbon polymers, nitrogen-containing polymers, and halogenated polymers in high-pressure oxygen systems are relatively complete. Toxicity of the combustion product gas is presumably much lower than the combustion product gas generated from ambient-pressure oxygen (or air) environments. The NASA-Lewis equilibrium code was used to determine the composition of combustion product gas generated from a simulated, adiabatic-compression test of nine polymers. The results are presented and discussed.

Molecularly Engineered Polymer-Based Systems in Drug Delivery and Regenerative Medicine.

PubMed

Piluso, Susanna; Soultan, Al Halifa; Patterson, Jennifer

2017-01-01

Polymer-based systems are attractive in drug delivery and regenerative medicine due to the possibility of tailoring their properties and functions to a specific application. The present review provides several examples of molecularly engineered polymer systems, including stimuli responsive polymers and supramolecular polymers. The advent of controlled polymerization techniques has enabled the preparation of polymers with controlled molecular weight and well-defined architecture. By using these techniques coupled to orthogonal chemical modification reactions, polymers can be molecularly engineered to incorporate functional groups able to respond to small changes in the local environment or to a specific biological signal. This review highlights the properties and applications of stimuli-responsive systems and polymer therapeutics, such as polymer-drug conjugates, polymer-protein conjugates, polymersomes, and hyperbranched systems. The applications of polymeric membranes in regenerative medicine are also discussed. The examples presented in this review suggest that the combination of membranes with polymers that are molecularly engineered to respond to specific biological functions could be relevant in the field of regenerative medicine. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

PubMed

Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

2013-04-10

Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now.

Polarization independent polymer waveguide tunable receivers incorporating a micro-optic circulator

NASA Astrophysics Data System (ADS)

Wu, Xiaoping; Park, Tae-Hyun; Park, Su-Hyun; Seo, Jun-Kyu; Oh, Min-Cheol

2018-06-01

In order to simplify the receiver configuration in a wavelength division multiplexed optical fiber network, compact wavelength tunable filters have long been expected to be used as channel selectors. Bragg reflector inherently has the most suitable reflection spectrum for filtering a single wavelength from the densely multiplexed wavelength signal. Polymer has high thermo-optic coefficient and good thermal insulation property compared to the other optical waveguide materials such as silicon and silica materials. This can be used to broadly tune the reflection spectrum of Bragg reflector using a simple micro-heater. In this work, a micro-optic circulator component and a polymeric Bragg reflector device are assembled to produce a small form factor tunable receiver. Compared to the integrated-optical versions, the micro-optics are based on well-developed manufacturing processes and can achieve competitive production yields. The device exhibits high reflectivity with a flat top passband, and a polarization dependence of 0.06 nm achieved by virtue of the low birefringence of LFR polymer, which make a significant contribution to the implementation of polarization independent tunable receiver. The wavelength tuning range of 40 nm is demonstrated by using a bottom located heater with a groove for heat isolation.

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

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

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

DOE PAGES

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua; ...

2018-04-24

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Mechanical properties of porous and cellular materials

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

Sieradzki, K.; Green, D.J.; Gibson, L.J.

1991-01-01

This symposium successfully brought scientists together from a wide variety of disciplines to focus on the mechanical behavior of porous and cellular solids composed of metals, ceramics, polymers, or biological materials. For cellular materials, papers ranged from processing techniques through microstructure-mechanical property relationships to design. In an overview talk, Mike Ashby (Cambridge Univ.) showed how porous cellular materials can be more efficient than dense materials in designs that require minimum weight. He indicated that many biological materials have been able to accomplish such efficiency but there exists an opportunity to design even more efficient, manmade materials controlling microstructures at differentmore » scale levels. In the area of processing, James Aubert (Sandia National Laboratories) discussed techiques for manipulating polymersolvent phase equilibria to control the microstructure of microcellular foams. Other papers on processing discussed the production of cellular ceramics by CVD, HIPing and sol- gel techniques. Papers on the mechanical behavior of cellular materials considered various ceramics microcellular polymers, conventional polymer foams and apples. There were also contributions that considered optimum design procedures for cellular materials. Steven Cowin (City Univ. of New York) discussed procedures to match the discrete microstructural aspects of cellular materials with the continuum mechanics approach to their elastic behavior.« less

Unified force-level theory of multiscale transient localization and emergent elasticity in polymer solutions and melts

NASA Astrophysics Data System (ADS)

Dell, Zachary E.; Schweizer, Kenneth S.

A unified, microscopic, theoretical understanding of polymer dynamics in concentrated liquids from segmental to macromolecular scales remains an open problem. We have formulated a statistical mechanical theory for this problem that explicitly accounts for intra- and inter-molecular forces at the Kuhn segment level. The theory is self-consistently closed at the level of a matrix of dynamical second moments of a tagged chain. Two distinct regimes of isotropic transient localization are predicted. In semidilute solutions, weak localization is predicted on a mesoscopic length scale between segment and chain scales which is a power law function of the invariant packing length. This is consistent with the breakdown of Rouse dynamics and the emergence of entanglements. The chain structural correlations in the dynamically arrested state are also computed. In dense melts, strong localization is predicted on a scale much smaller than the segment size which is weakly dependent on chain connectivity and signals the onset of glassy dynamics. Predictions of the dynamic plateau shear modulus are consistent with the known features of emergent rubbery and glassy elasticity. Generalizations to treat the effects of chemical crosslinking and physical bond formation in polymer gels are possible.

Cellular mechanics and motility

NASA Astrophysics Data System (ADS)

Hénon, Sylvie; Sykes, Cécile

2015-10-01

The term motility defines the movement of a living organism. One widely known example is the motility of sperm cells, or the one of flagellar bacteria. The propulsive element of such organisms is a cilium(or flagellum) that beats. Although cells in our tissues do not have a flagellum in general, they are still able to move, as we will discover in this chapter. In fact, in both cases of movement, with or without a flagellum, cell motility is due to a dynamic re-arrangement of polymers inside the cell. Let us first have a closer look at the propulsion mechanism in the case of a flagellum or a cilium, which is the best known, but also the simplest, and which will help us to define the hydrodynamic general conditions of cell movement. A flagellum is sustained by cellular polymers arranged in semi-flexible bundles and flagellar beating generates cell displacement. These polymers or filaments are part of the cellular skeleton, or "cytoskeleton", which is, in this case, external to the cellular main body of the organism. In fact, bacteria move in a hydrodynamic regime in which viscosity dominates over inertia. The system is thus in a hydrodynamic regime of low Reynolds number (Box 5.1), which is nearly exclusively the case in all cell movements. Bacteria and their propulsion mode by flagella beating are our unicellular ancestors 3.5 billion years ago. Since then, we have evolved to form pluricellular organisms. However, to keep the ability of displacement, to heal our wounds for example, our cells lost their flagellum, since it was not optimal in a dense cell environment: cells are too close to each other to leave enough space for the flagella to accomplish propulsion. The cytoskeleton thus developed inside the cell body to ensure cell shape changes and movement, and also mechanical strength within a tissue. The cytoskeleton of our cells, like the polymers or filaments that sustain the flagellum, is also composed of semi-flexible filaments arranged in bundles, and also in cross-linked or branched networks. It is a highly dynamical system in which filaments are able to elongate or slide one on the other with the contribution of very active cellular proteins like molecular motors. The versatile properties of this cytoskeleton ensure the diversity of mechanical behaviors to explain cell rigidity as well as cell motility.

High-Pressure CO2 Sorption in Polymers of Intrinsic Microporosity under Ultrathin Film Confinement.

PubMed

Ogieglo, Wojciech; Ghanem, Bader; Ma, Xiaohua; Wessling, Matthias; Pinnau, Ingo

2018-04-04

Ultrathin microporous polymer films are pertinent to the development and further spread of nanotechnology with very promising potential applications in molecular separations, sensors, catalysis, or batteries. Here, we report high-pressure CO 2 sorption in ultrathin films of several chemically different polymers of intrinsic microporosity (PIMs), including the prototypical PIM-1. Films with thicknesses down to 7 nm were studied using interference-enhanced in situ spectroscopic ellipsometry. It was found that all PIMs swell much more than non-microporous polystyrene and other high-performance glassy polymers reported previously. Furthermore, chemical modifications of the parent PIM-1 strongly affected the swelling magnitude. By investigating the behavior of relative refractive index, n rel , it was possible to study the interplay between micropores filling and matrix expansion. Remarkably, all studied PIMs showed a maximum in n rel at swelling of 2-2.5% indicating a threshold point above which the dissolution in the dense matrix started to dominate over sorption in the micropores. At pressures above 25 bar, all PIMs significantly plasticized in compressed CO 2 and for the ones with the highest affinity to the penetrant, a liquidlike mixing typical for rubbery polymers was observed. Reduction of film thickness below 100 nm revealed pronounced nanoconfinement effects and resulted in a large swelling enhancement and a quick loss of the ultrarigid character. On the basis of the partial molar volumes of the dissolved CO 2 , the effective reduction of the T g was estimated to be ∼200 °C going from 128 to 7 nm films.

Flexible packaging for PV modules

NASA Astrophysics Data System (ADS)

Dhere, Neelkanth G.

2008-08-01

Economic, flexible packages that provide needed level of protection to organic and some other PV cells over >25-years have not yet been developed. However, flexible packaging is essential in niche large-scale applications. Typical configuration used in flexible photovoltaic (PV) module packaging is transparent frontsheet/encapsulant/PV cells/flexible substrate. Besides flexibility of various components, the solder bonds should also be flexible and resistant to fatigue due to cyclic loading. Flexible front sheets should provide optical transparency, mechanical protection, scratch resistance, dielectric isolation, water resistance, UV stability and adhesion to encapsulant. Examples are Tefzel, Tedlar and Silicone. Dirt can get embedded in soft layers such as silicone and obscure light. Water vapor transmittance rate (WVTR) of polymer films used in the food packaging industry as moisture barriers are ~0.05 g/(m2.day) under ambient conditions. In comparison, light emitting diodes employ packaging components that have WVTR of ~10-6 g/(m2.day). WVTR of polymer sheets can be improved by coating them with dense inorganic/organic multilayers. Ethylene vinyl acetate, an amorphous copolymer used predominantly by the PV industry has very high O2 and H2O diffusivity. Quaternary carbon chains (such as acetate) in a polymer lead to cleavage and loss of adhesional strength at relatively low exposures. Reactivity of PV module components increases in presence of O2 and H2O. Adhesional strength degrades due to the breakdown of structure of polymer by reactive, free radicals formed by high-energy radiation. Free radical formation in polymers is reduced when the aromatic rings are attached at regular intervals. This paper will review flexible packaging for PV modules.

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

PubMed

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.

Single-source-precursor synthesis of dense SiC/HfCxN1-x-based ultrahigh-temperature ceramic nanocomposites

NASA Astrophysics Data System (ADS)

Wen, Qingbo; Xu, Yeping; Xu, Binbin; Fasel, Claudia; Guillon, Olivier; Buntkowsky, Gerd; Yu, Zhaoju; Riedel, Ralf; Ionescu, Emanuel

2014-10-01

A novel single-source precursor was synthesized by the reaction of an allyl hydrido polycarbosilane (SMP10) and tetrakis(dimethylamido)hafnium(iv) (TDMAH) for the purpose of preparing dense monolithic SiC/HfCxN1-x-based ultrahigh temperature ceramic nanocomposites. The materials obtained at different stages of the synthesis process were characterized via Fourier transform infrared (FT-IR) as well as nuclear magnetic resonance (NMR) spectroscopy. The polymer-to-ceramic transformation was investigated by means of MAS NMR and FT-IR spectroscopy as well as thermogravimetric analysis (TGA) coupled with in situ mass spectrometry. Moreover, the microstructural evolution of the synthesized SiHfCN-based ceramics annealed at different temperatures ranging from 1300 °C to 1800 °C was characterized by elemental analysis, X-ray diffraction, Raman spectroscopy and transmission electron microscopy (TEM). Based on its high temperature behavior, the amorphous SiHfCN-based ceramic powder was used to prepare monolithic SiC/HfCxN1-x-based nanocomposites using the spark plasma sintering (SPS) technique. The results showed that dense monolithic SiC/HfCxN1-x-based nanocomposites with low open porosity (0.74 vol%) can be prepared successfully from single-source precursors. The average grain size of both HfC0.83N0.17 and SiC phases was found to be less than 100 nm after SPS processing owing to a unique microstructure: HfC0.83N0.17 grains were embedded homogeneously in a β-SiC matrix and encapsulated by in situ formed carbon layers which acted as a diffusion barrier to suppress grain growth. The segregated Hf-carbonitride grains significantly influenced the electrical conductivity of the SPS processed monolithic samples. While Hf-free polymer-derived SiC showed an electrical conductivity of ca. 1.8 S cm-1, the electrical conductivity of the Hf-containing material was analyzed to be ca. 136.2 S cm-1.A novel single-source precursor was synthesized by the reaction of an allyl hydrido polycarbosilane (SMP10) and tetrakis(dimethylamido)hafnium(iv) (TDMAH) for the purpose of preparing dense monolithic SiC/HfCxN1-x-based ultrahigh temperature ceramic nanocomposites. The materials obtained at different stages of the synthesis process were characterized via Fourier transform infrared (FT-IR) as well as nuclear magnetic resonance (NMR) spectroscopy. The polymer-to-ceramic transformation was investigated by means of MAS NMR and FT-IR spectroscopy as well as thermogravimetric analysis (TGA) coupled with in situ mass spectrometry. Moreover, the microstructural evolution of the synthesized SiHfCN-based ceramics annealed at different temperatures ranging from 1300 °C to 1800 °C was characterized by elemental analysis, X-ray diffraction, Raman spectroscopy and transmission electron microscopy (TEM). Based on its high temperature behavior, the amorphous SiHfCN-based ceramic powder was used to prepare monolithic SiC/HfCxN1-x-based nanocomposites using the spark plasma sintering (SPS) technique. The results showed that dense monolithic SiC/HfCxN1-x-based nanocomposites with low open porosity (0.74 vol%) can be prepared successfully from single-source precursors. The average grain size of both HfC0.83N0.17 and SiC phases was found to be less than 100 nm after SPS processing owing to a unique microstructure: HfC0.83N0.17 grains were embedded homogeneously in a β-SiC matrix and encapsulated by in situ formed carbon layers which acted as a diffusion barrier to suppress grain growth. The segregated Hf-carbonitride grains significantly influenced the electrical conductivity of the SPS processed monolithic samples. While Hf-free polymer-derived SiC showed an electrical conductivity of ca. 1.8 S cm-1, the electrical conductivity of the Hf-containing material was analyzed to be ca. 136.2 S cm-1. Electronic supplementary information (ESI) available: Raman spectroscopy characterization of the SiHfCN-based ceramics. See DOI: 10.1039/c4nr03376k

Resolving the chemical nature of nanodesigned silica surface obtained via a bottom-up approach.

PubMed

Rahma, Hakim; Buffeteau, Thierry; Belin, Colette; Le Bourdon, Gwenaëlle; Degueil, Marie; Bennetau, Bernard; Vellutini, Luc; Heuzé, Karine

2013-08-14

The covalent grafting on silica surfaces of a functional dendritic organosilane coupling agent inserted, in a long alkyl chain monolayer, is described. In this paper, we show that depending on experimental parameters, particularly the solvent, it is possible to obtain a nanodesigned surface via a bottom-up approach. Thus, we succeed in the formation of both homogeneous dense monolayer and a heterogeneous dense monolayer, the latter being characterized by a nanosized volcano-type pattern (4-6 nm of height, 100 nm of width, and around 3 volcanos/μm(2)) randomly distributed over the surface. The dendritic attribute of the grafted silylated coupling agent affords enough anchoring sites to immobilize covalently functional gold nanoparticles (GNPs), coated with amino PEG polymer to resolve the chemical nature of the surfaces and especially the volcano type nanopattern structures of the heterogeneous monolayer. Thus, the versatile surface chemistry developed herein is particularly challenging as the nanodesign is straightforward achieved in a bottom-up approach without any specific lithography device.

Unbinding transition from fluid membranes with associated polymers.

PubMed

Benhamou, M; Kaidi, H

2013-10-01

We consider two neighboring fluid membranes that are associated with long flexible polymers (proteins or other macromolecules). We are interested in two physical systems consisting of i) two adjacent membranes with end-grafted (or adsorbed) polymers (system I), or ii) two membranes confining a polymer solution (system II). In addition to the pure interactions between membranes, the presence of polymers gives rise to new induced mediated interactions, which are repulsive, for system I, and attractive, for system II. In fact, repulsive induced interactions are caused by the excluded-volume forces between grafted polymers, while attractive ones, by entropy loss, due to free motion of polymers between membranes. The main goal is a quantitative study of the unbinding transition thermodynamics that is drastically affected by the associated polymers. For system I, the repulsive polymer-mediated force delays this transition that can happen at low temperature. To investigate the unbinding phenomenon, we first present an exact mathematical analysis of the total potential that is the sum of the primitive and induced potentials. This mathematical study enables us to classify the total interaction potentials, in terms of all parameters of the problem. Second, use is made of the standard variational method to calculate the first moments of the membrane separation. Special attention is paid to the determination of the unbinding temperature. In particular, we discuss its dependence on the extra parameters related to the associated polymers, which are the surface coverage and the polymer layer thickness on each membrane (for system I) or the polymer density and the gyration radius of coils (for system II). Third, we compute the disjoining pressure upon membrane separation. Finally, we emphasize that the presence of polymers may be a mechanism to delay or to accentuate the appearance of the unbinding transition between fluid membranes.

Antibiotic-containing polymers for localized, sustained drug delivery

PubMed Central

Stebbins, Nicholas D.; Ouimet, Michelle A.; Uhrich, Kathryn E.

2014-01-01

Many currently used antibiotics suffer from issues such as systemic toxicity, short half-life, and increased susceptibility to bacterial resistance. Although most antibiotic classes are administered systemically through oral or intravenous routes, a more efficient delivery system is needed. This review discusses the chemical conjugation of antibiotics to polymers, achieved by forming covalent bonds between antibiotics and a pre-existing polymer or by developing novel antibiotic-containing polymers. Through conjugating antibiotics to polymers, unique polymer properties can be taken advantage of. These polymeric antibiotics display controlled, sustained drug release and vary in antibiotic class type, synthetic method, polymer composition, bond lability, and antibacterial activity. The polymer synthesis, characterization, drug release, and antibacterial activities, if applicable, will be presented to offer a detailed overview of each system. PMID:24751888

Competition between excluded-volume and electrostatic interactions for nanogel swelling: effects of the counterion valence and nanogel charge.

PubMed

Adroher-Benítez, Irene; Martín-Molina, Alberto; Ahualli, Silvia; Quesada-Pérez, Manuel; Odriozola, Gerardo; Moncho-Jordá, Arturo

2017-03-01

In this work the equilibrium distribution of ions around a thermo-responsive charged nanogel particle in an electrolyte aqueous suspension is explored using coarse-grained Monte Carlo computer simulations and the Ornstein-Zernike integral equation theory. We explicitly consider the ionic size in both methods and study the interplay between electrostatic and excluded-volume effects for swollen and shrunken nanogels, monovalent and trivalent counterions, and for two different nanogel charges. We find good quantitative agreement between the ionic density profiles obtained using both methods when the excluded repulsive force exerted by the cross-linked polymer network is taken into account. For the shrunken conformation, the electrostatic repulsion between the charged groups provokes a heterogeneous polymer density profile, leading to a nanogel structure with an internal low density hole surrounded by a dense corona. The results show that the excluded-volume repulsion strongly hinders the ion permeation for shrunken nanogels, where volume exclusion is able to significantly reduce the concentration of counterions in the more dense regions of the nanogel. In general, we demonstrate that the thermosensitive behaviour of nanogels, as well as their internal structure, is strongly influenced by the valence of the counterions and also by the charge of the particles. On the one hand, an increase of the counterion valence moves the swelling transition to lower temperatures, and induces a major structuring of the charged monomers into internal and external layers around the crown for shrunken nanogels. On the other hand, increasing the particle charge shifts the swelling curve to larger values of the effective radius of the nanogel.

Nanoparticle packing within block copolymer micelles prepared by the interfacial instability method.

PubMed

Nabar, Gauri M; Winter, Jessica O; Wyslouzil, Barbara E

2018-05-02

The interfacial instability method has emerged as a viable approach for encapsulating high concentrations of nanoparticles (NPs) within morphologically diverse micelles. In this method, transient interfacial instabilities at the surface of an emulsion droplet guide self-assembly of block co-polymers and NP encapsulants. Although used by many groups, there are no systematic investigations exploring the relationship between NP properties and micelle morphology. Here, the effect of quantum dot (QD) and superparamagnetic iron oxide NP (SPION) concentration on the shape, size, and surface deformation of initially spherical poly(styrene-b-ethylene oxide) (PS-b-PEO) micelles was examined. Multi-NP encapsulation and uniform dispersion within micelles was obtained even at low NP concentrations. Increasing NP concentration initially resulted in larger numbers of elongated micelles and cylinders with tightly-controlled diameters smaller than those of spherical micelles. Beyond a critical NP concentration, micelle formation was suppressed; the dominant morphology became densely-loaded NP structures that were coated with polymer and exhibited increased polydispersity. Transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) revealed that NPs in densely-loaded structures can be well-ordered, with packing volume fractions of up to 24%. These effects were enhanced in magnetic composites, possibly by dipole interactions. Mechanisms governing phase transitions triggered by NP loading in the interfacial instability process were proposed. The current study helps establish and elucidate the active role played by NPs in directing block copolymer assembly in the interfacial instability process, and provides important guiding principles for the use of this approach in generating NP-loaded block copolymer composites.

Application of CFRP with High Hydrogen Gas Barrier Characteristics to Fuel Tanks of Space Transportation System

NASA Astrophysics Data System (ADS)

Yonemoto, Koichi; Yamamoto, Yuta; Okuyama, Keiichi; Ebina, Takeo

In the future, carbon fiber reinforced plastics (CFRPs) with high hydrogen gas barrier performance will find wide applications in all industrial hydrogen tanks that aim at weight reduction; the use of such materials will be preferred to the use of conventional metallic materials such as stainless steel or aluminum. The hydrogen gas barrier performance of CFRP will become an important issue with the introduction of hydrogen-fuel aircraft. It will also play an important role in realizing fully reusable space transportation system that will have high specific tensile CFRP structures. Such materials are also required for the manufacture of high-pressure hydrogen gas vessels for use in the fuel cell systems of automobiles. This paper introduces a new composite concept that can be used to realize CFRPs with high hydrogen gas barrier performance for applications in the cryogenic tanks of fully reusable space transportation system by the incorporation of a nonmetallic crystal layer, which is actually a dense and highly oriented clay crystal laminate. The preliminary test results show that the hydrogen gas barrier characteristics of this material after cryogenic heat shocks and cyclic loads are still better than those of other polymer materials by approximately two orders of magnitude.

Evolution of material properties during free radical photopolymerization

NASA Astrophysics Data System (ADS)

Wu, Jiangtao; Zhao, Zeang; Hamel, Craig M.; Mu, Xiaoming; Kuang, Xiao; Guo, Zaoyang; Qi, H. Jerry

2018-03-01

Photopolymerization is a widely used polymerization method in many engineering applications such as coating, dental restoration, and 3D printing. It is a complex chemical and physical process, through which a liquid monomer solution is rapidly converted to a solid polymer. In the most common free-radical photopolymerization process, the photoinitiator in the solution is exposed to light and decomposes into active radicals, which attach to monomers to start the polymerization reaction. The activated monomers then attack Cdbnd C double bonds of unsaturated monomers, which leads to the growth of polymer chains. With increases in the polymer chain length and the average molecular weight, polymer chains start to connect and form a network structure, and the liquid polymer solution becomes a dense solid. During this process, the material properties of the cured polymer change dramatically. In this paper, experiments and theoretical modeling are used to investigate the free-radical photopolymerization reaction kinetics, material property evolution and mechanics during the photopolymerization process. The model employs the first order chemical reaction rate equations to calculate the variation of the species concentrations. The degree of monomer conversion is used as an internal variable that dictates the mechanical properties of the cured polymer at different curing states, including volume shrinkage, glass transition temperature, and nonlinear viscoelastic properties. To capture the nonlinear behavior of the cured polymer under low temperature and finite deformation, a multibranch nonlinear viscoelastic model is developed. A phase evolution model is used to describe the mechanics of the coupling between the crosslink network evolution and mechanical loading during the curing process. The comparison of the model and the experimental results indicates that the model can capture property changes during curing. The model is further applied to investigate the internal stress of a thick sample caused by volume shrinkage during photopolymerization. Changes in the conversion degree gradient and the internal stress during photopolymerization are determined using FEM simulation. The model can be extended to many photocuring processes, such as photopolymerization 3D printing, surface coating and automotive part curing processes.

Using adaptive-mesh refinement in SCFT simulations of surfactant adsorption

NASA Astrophysics Data System (ADS)

Sides, Scott; Kumar, Rajeev; Jamroz, Ben; Crockett, Robert; Pletzer, Alex

2013-03-01

Adsorption of surfactants at interfaces is relevant to many applications such as detergents, adhesives, emulsions and ferrofluids. Atomistic simulations of interface adsorption are challenging due to the difficulty of modeling the wide range of length scales in these problems: the thin interface region in equilibrium with a large bulk region that serves as a reservoir for the adsorbed species. Self-consistent field theory (SCFT) has been extremely useful for studying the morphologies of dense block copolymer melts. Field-theoretic simulations such as these are able to access large length and time scales that are difficult or impossible for particle-based simulations such as molecular dynamics. However, even SCFT methods can be difficult to apply to systems in which small spatial regions might require finer resolution than most of the simulation grid (eg. interface adsorption and confinement). We will present results on interface adsorption simulations using PolySwift++, an object-oriented, polymer SCFT simulation code aided by the Tech-X Chompst library that enables via block-structured AMR calculations with PETSc.

A Brief Study on Toxic Combustion Products of the Polymers Used in High-Pressure Oxygen Systems

NASA Technical Reports Server (NTRS)

Hshieh, Fu-Yu; Beeson, Harold D.

2005-01-01

One likely cause of polymer ignition in a high-pressure oxygen system is the adiabatic-compression heating of polymers caused by pneumatic impact. Oxidative pyrolysis or combustion of polymers in a high-pressure oxygen system could generate toxic gases. This paper investigates the feasibility of using the NASA pneumatic-impact system to conduct adiabatic-compression combustion tests and determines the toxic combustion products produced from the burning of five selected polymers. Five polymers commonly used in high-pressure oxygen systems, Zytel(Registered TradeMark) 42 (Nylon 6/6), Buna N (nitrile rubber), Witon(Registered TradeMark) A (copolymer of vinylidene fluoride and hexafluoropropylene), Neoflon(Registered TradeMark) (polychlorotrifluoroethylene), and Teflon(Registered TradeMark) (polytetrafluoroethylene), were tested in the NASA pneumatic-impact test system at 17.2-MPa oxygen pressure. The polymers were ignited and burned; combustion products were collected in a stainless-steel sample bottle and analyzed using various methods. The results show that the NASA pneumatic-impact system is an appropriate test system to conduct adiabatic-compression combustion tests and to collect combustion products for further chemical analysis. The composition of the combustion product gas generated from burning the five selected polymers are presented and discussed.

Turbulence Modulation and Dense-Spray Structure

DTIC Science & Technology

1988-08-01

system ............................................. 10 6 Particle size distribution (dp = 0.5 mm) .................................... 13 7 Particle size...54 27 Sketch of the pressurized test apparatus .................................... 55 28 Sketch of the double-pulse holocamera system ...58 29 Sketch of the hologram reconstruction system ............................ 59 30 Typical hologram reconstruction in the dense

Characterization of Composite Fan Case Resins

NASA Technical Reports Server (NTRS)

Dvoracek, Charlene M.

2004-01-01

The majority of commercial turbine engines that power today s aircraft use a large fan driven by the engine core to generate thrust which dramatically increases the engine s efficiency. However, if one of these fan blades fails during flight, it becomes high energy shrapnel, potentially impacting the engine or puncturing the aircraft itself and thus risking the lives of passengers. To solve this problem, the fan case must be capable of containing a fan blade should it break off during flight. Currently, all commercial fan cases are made of either just a thick metal barrier or a thinner metal wall surrounded by Kevlar-an ultra strong fiber that elastically catches the blade. My summer 2004 project was to characterize the resins for a composite fan case that will be lighter and more efficient than the current metal. The composite fan case is created by braiding carbon fibers and injecting a polymer resin into the braid. The resin holds the fibers together, so at first using the strongest polymer appears to logically lead to the strongest fan case. Unfortunately, the stronger polymers are too viscous when melted. This makes the manufacturing process more difficult because the polymer does not flow as freely through the braid, and the final product is less dense. With all of this in mind, it is important to remember that the strength of the polymer is still imperative; the case must still contain blades with high impact energy. The research identified which polymer had the right balance of properties, including ease of fabrication, toughness, and ability to transfer the load to the carbon fibers. Resin deformation was studied to better understand the composite response during high speed impact. My role in this research was the testing of polymers using dynamic mechanical analysis and tensile, compression, and torsion testing. Dynamic mechanical analysis examines the response of materials under cyclic loading. Two techniques were used for dynamic mechanical analysis. The ARES Instrument analyzed the material through torsion. The second machine, TA Instruments apparatus, applied a bending force to the specimen. These experiments were used to explore the effects of temperature and strain rate on the stiffness and strength of the resins. The two different types of loading allowed us to verify our results. An axial-torsional load frame, manufactured by MTS Systems, Inc., was used to conduct the tensile, compression, and torsional testing. These tests were used to determine the stress-strain curves for the resins. The elastic and plastic deformation data was provided to another team member for characterization of high fidelity material property predictions. This information was useful in having a better understanding of the polymers so that the fan cases could be as sturdy as possible. Deformation studies are the foundation for the computational modeling that provides the structural design of a composite engine case as well as detailed analysis of the blade impact event.

Preparation Process and Dielectric Properties of Ba(0.5)Sr(0.5)TiO3-P(VDF-CTFE) Nanocomposites

NASA Technical Reports Server (NTRS)

Zhang, Lin; Wu, Peixuang; Li, Yongtang; Cheng, Z. -Y.; Brewer, Jeffrey C.

2014-01-01

Ceramic-polymer 0-3 nanocomposites, in which nanosized Ba(0.5)Sr(0.5)TiO3 (BST) powders were used as ceramic filler and P(VDF-CTFE) 88/12 mol% [poly(vinylidene fluoridechlorotrifluoroethylene)] copolymer was used as matrix, were studied over a concentration range from 0 to 50 vol.% of BST powders. It is found that the solution cast composites are porous and a hot-press process can eliminate the porosity, which results in a dense composite film. Two different configurations used in the hot-press process are studied. Although there is no clear difference in the uniformity and microstructure of the composites prepared using these two configurations, the composite prepared using one configuration exhibit a higher dielectric constant with a lower loss. For the composite with 40 vol. BST, a dielectric constant of 70 with a loss of 0.07 at 1 kHz is obtained at room temperature. The composites exhibit a lower dielectric loss than the polymer matrix at high frequency. However, at low frequency, the composites exhibit a higher loss than the polymer matrix due to a low frequency relaxation process that appears in the composites. It is believed that this relaxation process is related to the interfacial layer formed between BST particle and the polymer matrix. The temperature dependence of the dielectric property of the composites was studied. It is found that the dielectric constant of these composites is almost independent of the temperature over a temperature range from 20 to 120 C. Key words: A. Polymer-matrix composites (PMCs); B. Electrical Properties; E. Casting; E. Heat treatment; Dielectric properties.

Gas Permeation in Thin Glassy Polymer Films

NASA Astrophysics Data System (ADS)

Paul, Donald

2011-03-01

The development of asymmetric and composite membranes with very thin dense ``skins'' needed to achieve high gas fluxes enabled the commercial use of membranes for molecular level separations. It has been generally assumed that these thin skins, with thicknesses of the order of 100 nm, have the same permeation characteristics as films with thicknesses of 25 microns or more. Thick films are easily made in the laboratory and have been used extensively for measuring permeation characteristics to evaluate the potential of new polymers for membrane applications. There is now evidence that this assumption can be in very significant error, and use of thick film data to select membrane materials or predict performance should be done with caution. This presentation will summarize our work on preparing films of glassy polymers as thin as 20 nm and characterizing their behavior by gas permeation, ellipsometry and positron annihilation lifetime spectroscopy. Some of the most important polymers used commercially as gas separation membranes, i.e., Matrimid polyimide, polysulfone (PSF) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), have been made into well-defined thin films in our laboratories by spin casting techniques and their properties studied using the techniques we have developed. These thin films densify (or physically age) much faster than thicker films, and, as result, the permeability decreases, sometimes by several-fold over weeks or months for thin films. This means that the properties of these thin films can be very different from bulk films. The techniques, interpretations and implications of these observations will be discussed. In a broader sense, gas permeation measurements can be a powerful way of developing a better understanding of the effects of polymer chain confinement and/or surface mobility on the behavior of thin films.

Dynamical theory of dense groups of galaxies

NASA Technical Reports Server (NTRS)

Mamon, Gary A.

1990-01-01

It is well known that galaxies associate in groups and clusters. Perhaps 40% of all galaxies are found in groups of 4 to 20 galaxies (e.g., Tully 1987). Although most groups appear to be so loose that the galaxy interactions within them ought to be insignificant, the apparently densest groups, known as compact groups appear so dense when seen in projection onto the plane of the sky that their members often overlap. These groups thus appear as dense as the cores of rich clusters. The most popular catalog of compact groups, compiled by Hickson (1982), includes isolation among its selection critera. Therefore, in comparison with the cores of rich clusters, Hickson's compact groups (HCGs) appear to be the densest isolated regions in the Universe (in galaxies per unit volume), and thus provide in principle a clean laboratory for studying the competition of very strong gravitational interactions. The $64,000 question here is then: Are compact groups really bound systems as dense as they appear? If dense groups indeed exist, then one expects that each of the dynamical processes leading to the interaction of their member galaxies should be greatly enhanced. This leads us to the questions: How stable are dense groups? How do they form? And the related question, fascinating to any theorist: What dynamical processes predominate in dense groups of galaxies? If HCGs are not bound dense systems, but instead 1D change alignments (Mamon 1986, 1987; Walke & Mamon 1989) or 3D transient cores (Rose 1979) within larger looser systems of galaxies, then the relevant question is: How frequent are chance configurations within loose groups? Here, the author answers these last four questions after comparing in some detail the methods used and the results obtained in the different studies of dense groups.

Develop a PWL System for Dense Graded Hot Mix Asphalt Construction, Including Pay Factors

DOT National Transportation Integrated Search

2015-01-01

This research project developed a PWL system that the Nevada DOT can effectively implement on the construction of dense graded HMA mixtures. The PWL system includes pay factors that are based on pavement performance indicators such as rutting and cra...

Bioinspired air-retaining nanofur for drag reduction.

PubMed

Kavalenka, Maryna N; Vüllers, Felix; Lischker, Simone; Zeiger, Claudia; Hopf, Andreas; Röhrig, Michael; Rapp, Bastian E; Worgull, Matthias; Hölscher, Hendrik

2015-05-27

Bioinspired nanofur, covered by a dense layer of randomly distributed high aspect ratio nano- and microhairs, possesses superhydrophobic and air-retaining properties. Nanofur is fabricated using a highly scalable hot pulling method in which softened polymer is elongated with a heated sandblasted plate. Here we investigate the stability of the underwater air layer retained by the irregular nanofur topography by applying hydraulic pressure to the nanofur kept underwater, and evaluate the gradual changes in the air-covered area. Furthermore, the drag reduction resulting from the nanofur air retention is characterized by measuring the pressure drop across channels with and without nanofur.

Variable-Resistivity Material For Memory Circuits

NASA Technical Reports Server (NTRS)

Nagasubramanian, Ganesan; Distefano, Salvador; Moacanin, Jovan

1989-01-01

Nonvolatile memory elements packed densely. Electrically-erasable, programmable, read-only memory matrices made with newly-synthesized organic material of variable electrical resistivity. Material, polypyrrole doped with tetracyanoquinhydrone (TCNQ), changes reversibly between insulating or higher-resistivity state and conducting or low-resistivity state. Thin film of conductive polymer separates layer of row conductors from layer of column conductors. Resistivity of film at each intersection and, therefore, resistance of memory element defined by row and column, increased or decreased by application of suitable switching voltage. Matrix circuits made with this material useful for experiments in associative electronic memories based on models of neural networks.

Rheological Enhancement of Pork Myofibrillar Protein-Lipid Emulsion Composite Gels via Glucose Oxidase Oxidation/Transglutaminase Cross-Linking Pathway.

PubMed

Wang, Xu; Xiong, Youling L; Sato, Hiroaki

2017-09-27

Porcine myofibrillar protein (MP) was modified with glucose oxidase (GluOx)-iron that produces hydroxyl radicals then subjected to microbial transglutaminase (TGase) cross-linking in 0.6 M NaCl at 4 °C. The resulting aggregation and gel formation of MP were examined. The GluOx-mediated oxidation promoted the formation of both soluble and insoluble protein aggregates via disulfide bonds and occlusions of hydrophobic groups. The subsequent TGase treatment converted protein aggregates into highly cross-linked polymers. MP-lipid emulsion composite gels formed with such polymers exhibited markedly enhanced gelling capacity: up to 4.4-fold increases in gel firmness and 3.5-fold increases in gel elasticity over nontreated protein. Microstructural examination showed small oil droplets dispersed in a densely packed gel matrix when MP was oxidatively modified, and the TGase treatment further contributed to such packing. The enzymatic GluOx oxidation/TGase treatment shows promise to improve the textural properties of emulsified meat products.

Structural diversity in binary superlattices self-assembled from polymer-grafted nanocrystals

DOE PAGES

Ye, Xingchen; Zhu, Chenhui; Ercius, Peter; ...

2015-12-02

Multicomponent nanocrystal superlattices represent an interesting class of material that derives emergent properties from mesoscale structure, yet their programmability can be limited by the alkyl-chain-based ligands decorating the surfaces of the constituent nanocrystals. Polymeric ligands offer distinct advantages, as they allow for more precise tuning of the effective size and ‘interaction softness’ through changes to the polymer’s molecular weight, chemical nature, architecture, persistence length and surrounding solvent. Here we show the formation of 10 different binary nanocrystal superlattices (BNSLs) with both two- and three-dimensional order through independent adjustment of the core size of spherical nanocrystals and the molecular weight ofmore » densely grafted polystyrene ligands. These polymer-brush-based ligands introduce new energetic contributions to the interparticle potential that stabilizes various BNSL phases across a range of length scales and interparticle spacings. In conclusion, our study opens the door for nanocrystals to become modular elements in the design of functional particle brush solids with controlled nanoscale interfaces and mesostructures.« less

Neutral glycans from sandfish skin can reduce friction of polymers

PubMed Central

Vihar, Boštjan; Hanisch, Franz Georg; Baumgartner, Werner

2016-01-01

The lizard Scincus scincus, also known as sandfish, can move through aeolian desert sand in a swimming-like manner. A prerequisite for this ability is a special integument, i.e. scales with a very low friction for sand and a high abrasion resistance. Glycans in the scales are causally related to the low friction. Here, we analysed the glycans and found that neutral glycans with five to nine mannose residues are important. If these glycans were covalently bound to acrylic polymers like poly(methyl methacrylate) or acrylic car coatings at a density of approximately one molecule per 4 nm², friction for and adhesion of sand particles could be reduced to levels close to those observed with sandfish scales. This was also found true, if the glycans were isolated from sources other than sandfish scales like plants such as almonds or mistletoe. We speculate that these neutral glycans act as low density spacers separating sand particles from the dense scales thereby reducing van der Waals forces. PMID:27030038

Influence of Resin Composition on the Defect Formation in Alumina Manufactured by Stereolithography

PubMed Central

Johansson, Emil; Lidström, Oscar; Johansson, Jan; Lyckfeldt, Ola; Adolfsson, Erik

2017-01-01

Stereolithography (SL) is a technique allowing additive manufacturing of complex ceramic parts by selective photopolymerization of a photocurable suspension containing photocurable monomer, photoinitiator, and a ceramic powder. The manufactured three-dimensional object is cleaned and converted into a dense ceramic part by thermal debinding of the polymer network and subsequent sintering. The debinding is the most critical and time-consuming step, and often the source of cracks. In this study, photocurable alumina suspensions have been developed, and the influence of resin composition on defect formation has been investigated. The suspensions were characterized in terms of rheology and curing behaviour, and cross-sections of sintered specimens manufactured by SL were evaluated by SEM. It was found that the addition of a non-reactive component to the photocurable resin reduced polymerization shrinkage and altered the thermal decomposition of the polymer matrix, which led to a reduction in both delamination and intra-laminar cracks. Using a non-reactive component that decomposed rather than evaporated led to less residual porosity. PMID:28772496

Intravaginal gene silencing using biodegradable polymer nanoparticles densely loaded with small-interfering RNA

NASA Astrophysics Data System (ADS)

Woodrow, Kim A.; Cu, Yen; Booth, Carmen J.; Saucier-Sawyer, Jennifer K.; Wood, Monica J.; Mark Saltzman, W.

2009-06-01

Vaginal instillation of small-interfering RNA (siRNA) using liposomes has led to silencing of endogenous genes in the genital tract and protection against challenge from infectious disease. Although siRNA lipoplexes are easily formulated, several of the most effective transfection agents available commercially may be toxic to the mucosal epithelia and none are able to provide controlled or sustained release. Here, we demonstrate an alternative approach using nanoparticles composed entirely of FDA-approved materials. To render these materials effective for gene silencing, we developed novel approaches to load them with high amounts of siRNA. A single dose of siRNA-loaded nanoparticles to the mouse female reproductive tract caused efficient and sustained gene silencing. Knockdown of gene expression was observed proximal (in the vaginal lumen) and distal (in the uterine horns) to the site of topical delivery. In addition, nanoparticles penetrated deep into the epithelial tissue. This is the first report demonstrating that biodegradable polymer nanoparticles are effective delivery vehicles for siRNA to the vaginal mucosa.

Creation of high-refractive-index amorphous titanium oxide thin films from low-fractal-dimension polymeric precursors synthesized by a sol-gel technique with a hydrazine monohydrochloride catalyst.

PubMed

Shimizu, Wataru; Nakamura, Satoshi; Sato, Takaaki; Murakami, Yasushi

2012-08-21

Amorphous titanium dioxide (TiO(2)) thin films exhibiting high refractive indices (n ≈ 2.1) and high transparency were fabricated by spin-coating titanium oxide liquid precursors having a weakly branched polymeric structure. The precursor solution was prepared from titanium tetra-n-butoxide (TTBO) via the catalytic sol-gel process with hydrazine monohydrochloride used as a salt catalyst, which serves as a conjugate acid-base pair catalyst. Our unique catalytic sol-gel technique accelerated the overall polycondensation reaction of partially hydrolyzed alkoxides, which facilitated the formation of liner polymer-like titanium oxide aggregates having a low fractal dimension of ca. (5)/(3), known as a characteristic of the so-called "expanded polymer chain". Such linear polymeric features are essential to the production of highly dense amorphous TiO(2) thin films; mutual interpenetration of the linear polymeric aggregates avoided the creation of void space that is often generated by the densification of high-fractal-dimension (particle-like) aggregates produced in a conventional sol-gel process. The mesh size of the titanium oxide polymers can be tuned either by water concentration or the reaction time, and the smaller mesh size in the liquid precursor led to a higher n value of the solid thin film, thanks to its higher local electron density. The reaction that required no addition of organic ligand to stabilize titanium alkoxides was advantageous to overcoming issues from organic residues such as coloration. The dense amorphous film structure suppressed light scattering loss owing to its extremely smooth surface and the absence of inhomogeneous grains or particles. Furthermore, the fabrication can be accomplished at a low heating temperature of <80 °C. Indeed, we successfully obtained a transparent film with a high refractive index of n = 2.064 (at λ = 633 nm) on a low-heat-resistance plastic, poly(methyl methacrylate), at 60 °C. The result offers an efficient route to high-refractive-index amorphous TiO(2) films as well as base materials for a wider range of applications.

Hybrid organic-inorganic rotaxanes and molecular shuttles.

PubMed

Lee, Chin-Fa; Leigh, David A; Pritchard, Robin G; Schultz, David; Teat, Simon J; Timco, Grigore A; Winpenny, Richard E P

2009-03-19

The tetravalency of carbon and its ability to form covalent bonds with itself and other elements enables large organic molecules with complex structures, functions and dynamics to be constructed. The varied electronic configurations and bonding patterns of inorganic elements, on the other hand, can impart diverse electronic, magnetic, catalytic and other useful properties to molecular-level structures. Some hybrid organic-inorganic materials that combine features of both chemistries have been developed, most notably metal-organic frameworks, dense and extended organic-inorganic frameworks and coordination polymers. Metal ions have also been incorporated into molecules that contain interlocked subunits, such as rotaxanes and catenanes, and structures in which many inorganic clusters encircle polymer chains have been described. Here we report the synthesis of a series of discrete rotaxane molecules in which inorganic and organic structural units are linked together mechanically at the molecular level. Structural units (dialkyammonium groups) in dumb-bell-shaped organic molecules template the assembly of essentially inorganic 'rings' about 'axles' to form rotaxanes consisting of various numbers of rings and axles. One of the rotaxanes behaves as a 'molecular shuttle': the ring moves between two binding sites on the axle in a large-amplitude motion typical of some synthetic molecular machine systems. The architecture of the rotaxanes ensures that the electronic, magnetic and paramagnetic characteristics of the inorganic rings-properties that could make them suitable as qubits for quantum computers-can influence, and potentially be influenced by, the organic portion of the molecule.

Polymer-lipid hybrid systems: merging the benefits of polymeric and lipid-based nanocarriers to improve oral drug delivery.

PubMed

Rao, Shasha; Prestidge, Clive A

2016-01-01

A number of biobarriers limit efficient oral drug absorption; both polymer-based and lipid-based nanocarriers have demonstrated properties and delivery mechanisms to overcome these biobarriers in preclinical settings. Moreover, in order to address the multifaceted oral drug delivery challenges, polymer-lipid hybrid systems are now being designed to merge the beneficial features of both polymeric and lipid-based nanocarriers. Recent advances in the development of polymer-lipid hybrids with a specific focus on their viability in oral delivery are reviewed. Three classes of polymer-lipid hybrids have been identified, i.e. lipid-core polymer-shell systems, polymer-core lipid-shell systems, and matrix-type polymer-lipid hybrids. We focus on their application to overcome the various biological barriers to oral drug absorption, as exemplified by selected preclinical studies. Numerous studies have demonstrated the superiority of polymer-lipid hybrid systems to their non-hybrid counterparts in providing improved drug encapsulation, modulated drug release, and improved cellular uptake. These features have encouraged their applications in the delivery of chemotherapeutics, proteins, peptides, and vaccines. With further research expected to optimize the manufacturing and scaling up processes and in-depth pre-clinical pharmacological and toxicological assessments, these multifaceted drug delivery systems will have significant clinical impact on the oral delivery of pharmaceuticals and biopharmaceuticals.

Polymer mediated layer-by-layer assembly of different shaped gold nanoparticles.

PubMed

Budy, Stephen M; Hamilton, Desmond J; Cai, Yuheng; Knowles, Michelle K; Reed, Scott M

2017-02-01

Gold nanoparticles (GNPs) have a wide range of properties with potential applications in electronics, optics, catalysis, and sensing. In order to demonstrate that dense, stable, and portable samples could be created for these applications, multiple layers of GNPs were assembled via drop casting on glass substrates by layer-by-layer (LBL) techniques. Two cationic polyelectrolytes, poly(diallyldimethylammonium chloride) and polyethyleneimine, one anionic polyelectrolyte, poly(sodium 4-styrene sulfonate), and one neutral polymer, polyvinylpyrrolidone, were combined with four different shapes of GNPs (spherical, rod, triangular prismatic, and octahedral) to prepare thin films. A subset of these polymer nanoparticle combinations were assembled into thin films. Synthesized GNPs were characterized via dynamic light scattering, UV-vis spectroscopy, and transmission electron microscopy and the LBL thin films were characterized using UV-vis spectroscopy and atomic force microscopy. Sensing applications of the nanoparticles in solution and thin films were tested by monitoring the localized surface plasmon resonance of the GNPs. LBL thin films were prepared ranging from 25 to 100 layers with optical densities at plasmon from 0.5 to 3.0. Sensitivity in solutions ranged from 14 to 1002nm/refractive index units (RIU) and films ranged from 18.8 to 135.1nm/RIU suggesting reduced access to the GNPs within the films. Copyright © 2016 Elsevier Inc. All rights reserved.

Interfacial friction and adhesion of cross-linked polymer thin films swollen with linear chains.

PubMed

Zhang, Qing; Archer, Lynden A

2007-07-03

The preparation and interfacial properties of a new type of tethered, thin-film lubricant coating are presented. These coatings are composed of three components: a dense self-assembled monolayer (SAM) underlayer that presents reactive vinyl groups at its surface; a cross-linked polydimethylsiloxane (PDMS) overlayer that is covalently tethered to the SAM; and free, mobile linear PDMS chains dispersed in the network. We investigate the influence of the molecular weight (Ms) and concentration of the free PDMS chains on the structure and equilibrium swelling properties of the cross-linked films. Using a bead-probe lateral force microscopy measurement technique, we also quantify the interfacial friction and adhesion characteristics of surfaces functionalized with these coatings. We find that both the volume fraction and the molecular weight of free PDMS molecules in the coatings influence their interfacial friction and adhesion properties. For example, the addition of short PDMS chains in dry, cross-linked PDMS thin films yields tethered surface coatings with ultralow friction coefficients (mu = 5.2 x 10(-3)). An analysis based on classical lubrication theory suggests that the reduction in friction force produced by free polymer is a consequence of the gradual separation of asperities on opposing surfaces and the consequent substitution of solid-solid friction by viscous drag of the free polymer chains in the network.

Super-hydrophobic coatings based on non-solvent induced phase separation during electro-spraying.

PubMed

Gao, Jiefeng; Huang, Xuewu; Wang, Ling; Zheng, Nan; Li, Wan; Xue, Huaiguo; Li, Robert K Y; Mai, Yiu-Wing

2017-11-15

The polymer solution concentration determines whether electrospinning or electro-spraying occurs, while the addition of the non-solvent into the polymer solution strongly influences the surface morphology of the obtained products. Both smooth and porous surfaces of the electro-sprayed microspheres can be harvested by choosing different non-solvent and its amount as well as incorporating polymeric additives. The influences of the solution concentration, weight ratio between the non-solvent and the copolymer, and the polymeric additives on the surface morphology and the wettability of the electro-sprayed products were systematically studied. Surface pores and/or asperities on the microsphere surface were mainly caused by the non-solvent induced phase separation (NIPS) and subsequent evaporation of the non-solvent during electro-spraying. With increasing polymer solution concentration, the microsphere was gradually changed to the bead-on-string geometry and finally to a nanofiber form, leading to a sustained decrease of the contact angle (CA). It was found that the substrate coatings derived from the microspheres possessing hierarchical surface pores or dense asperities had high surface roughness and super-hydrophobicity with CAs larger than 150° while sliding angles smaller than 10°; but coatings composed of microspheres with smooth surfaces gave relatively low CAs. Copyright © 2017 Elsevier Inc. All rights reserved.

Model systems for single molecule polymer dynamics

PubMed Central

Latinwo, Folarin

2012-01-01

Double stranded DNA (dsDNA) has long served as a model system for single molecule polymer dynamics. However, dsDNA is a semiflexible polymer, and the structural rigidity of the DNA double helix gives rise to local molecular properties and chain dynamics that differ from flexible chains, including synthetic organic polymers. Recently, we developed single stranded DNA (ssDNA) as a new model system for single molecule studies of flexible polymer chains. In this work, we discuss model polymer systems in the context of “ideal” and “real” chain behavior considering thermal blobs, tension blobs, hydrodynamic drag and force–extension relations. In addition, we present monomer aspect ratio as a key parameter describing chain conformation and dynamics, and we derive dynamical scaling relations in terms of this molecular-level parameter. We show that asymmetric Kuhn segments can suppress monomer–monomer interactions, thereby altering global chain dynamics. Finally, we discuss ssDNA in the context of a new model system for single molecule polymer dynamics. Overall, we anticipate that future single polymer studies of flexible chains will reveal new insight into the dynamic behavior of “real” polymers, which will highlight the importance of molecular individualism and the prevalence of non-linear phenomena. PMID:22956980

An Analog Macroscopic Technique for Studying Molecular Hydrodynamic Processes in Dense Gases and Liquids.

PubMed

Dahlberg, Jerry; Tkacik, Peter T; Mullany, Brigid; Fleischhauer, Eric; Shahinian, Hossein; Azimi, Farzad; Navare, Jayesh; Owen, Spencer; Bisel, Tucker; Martin, Tony; Sholar, Jodie; Keanini, Russell G

2017-12-04

An analog, macroscopic method for studying molecular-scale hydrodynamic processes in dense gases and liquids is described. The technique applies a standard fluid dynamic diagnostic, particle image velocimetry (PIV), to measure: i) velocities of individual particles (grains), extant on short, grain-collision time-scales, ii) velocities of systems of particles, on both short collision-time- and long, continuum-flow-time-scales, iii) collective hydrodynamic modes known to exist in dense molecular fluids, and iv) short- and long-time-scale velocity autocorrelation functions, central to understanding particle-scale dynamics in strongly interacting, dense fluid systems. The basic system is composed of an imaging system, light source, vibrational sensors, vibrational system with a known media, and PIV and analysis software. Required experimental measurements and an outline of the theoretical tools needed when using the analog technique to study molecular-scale hydrodynamic processes are highlighted. The proposed technique provides a relatively straightforward alternative to photonic and neutron beam scattering methods traditionally used in molecular hydrodynamic studies.

Biodegradable polymers for targeted delivery of anti-cancer drugs.

PubMed

Doppalapudi, Sindhu; Jain, Anjali; Domb, Abraham J; Khan, Wahid

2016-06-01

Biodegradable polymers have been used for more than three decades in cancer treatment and have received increased interest in recent years. A range of biodegradable polymeric drug delivery systems designed for localized and systemic administration of therapeutic agents as well as tumor-targeting macromolecules has entered into the clinical phase of development, indicating the significance of biodegradable polymers in cancer therapy. This review elaborates upon applications of biodegradable polymers in the delivery and targeting of anti-cancer agents. Design of various drug delivery systems based on biodegradable polymers has been described. Moreover, the indication of polymers in the targeted delivery of chemotherapeutic drugs via passive, active targeting, and localized drug delivery are also covered. Biodegradable polymer-based drug delivery systems have the potential to deliver the payload to the target and can enhance drug availability at desired sites. Systemic toxicity and serious side effects observed with conventional cancer therapeutics can be significantly reduced with targeted polymeric systems. Still, there are many challenges that need to be met with respect to the degradation kinetics of the system, diffusion of drug payload within solid tumors, targeting tumoral tissue and tumor heterogeneity.

Polymer therapeutics: concepts and applications.

PubMed

Haag, Rainer; Kratz, Felix

2006-02-13

Polymer therapeutics encompass polymer-protein conjugates, drug-polymer conjugates, and supramolecular drug-delivery systems. Numerous polymer-protein conjugates with improved stability and pharmacokinetic properties have been developed, for example, by anchoring enzymes or biologically relevant proteins to polyethylene glycol components (PEGylation). Several polymer-protein conjugates have received market approval, for example the PEGylated form of adenosine deaminase. Coupling low-molecular-weight anticancer drugs to high-molecular-weight polymers through a cleavable linker is an effective method for improving the therapeutic index of clinically established agents, and the first candidates have been evaluated in clinical trials, including, N-(2-hydroxypropyl)methacrylamide conjugates of doxorubicin, camptothecin, paclitaxel, and platinum(II) complexes. Another class of polymer therapeutics are drug-delivery systems based on well-defined multivalent and dendritic polymers. These include polyanionic polymers for the inhibition of virus attachment, polycationic complexes with DNA or RNA (polyplexes), and dendritic core-shell architectures for the encapsulation of drugs. In this Review an overview of polymer therapeutics is presented with a focus on concepts and examples that characterize the salient features of the drug-delivery systems.

Spherical Nucleic Acids: A New Form of DNA

NASA Astrophysics Data System (ADS)

Cutler, Joshua Isaac

Spherical Nucleic Acids (SNAs) are a new class of nucleic acid-based nanomaterials that exhibit unique properties currently being explored in the contexts of gene-based cancer therapies and in the design of programmable nanoparticle-based materials. The properties of SNAs differ from canonical, linear nucleic acids by virtue of their dense packing into an oriented 3-dimensional array. SNAs can be synthesized from a number of useful nanoparticle templates, such as plasmonic gold and silver, magnetic oxides, luminescent semi-conductor quantum dots, and silica. In addition, by crosslinking the oligonucleotides and dissolving the core, they can be made in a hollow form as well. This dissertation describes the evolution of SNAs from initial studies of inorganic nanoparticle-based materials densely functionalized with oligonucleotides to the proving of a hypothesis that their unique properties can be observed in a core-less structure if the nucleic acids are densely packed and highly oriented. Chapter two describes the synthesis of densely functionalized polyvalent oligonucleotide superparamagnetic iron oxide nanoparticles using the copper-catalyzed azide-alkyne cycloaddition reaction. These particles are shown to exhibit cooperative binding in a density- and salt concentration-dependent fashion, with nearly identical behaviors to those of SNA-functionalized gold nanoparticles. Importantly, these particles are the first non-gold particles shown to be capable of entering cells in high numbers via the SNA-mediated cellular uptake pathway, and provided the first evidence that SNA-mediated cellular uptake is core-independent. In the third chapter, a gold nanoparticle catalyzed alkyne cross-linking reaction is described that is capable of forming hollow organic nanoparticles using polymers with alkyne-functionalized backbones. With this method, the alkyne-modified polymers adsorb to the particle surfaces, cross-link on the surface, allowing the gold nanoparticle to be subsequently dissolved oxidatively with KCN or Iodine. The reaction pathway is analyzed through characterization of the reaction progression and resulting products, and a mechanistic pathway is proposed. This is the first report of a gold nanoparticle catalyzed reaction involving the conversion of propargyl ethers to terminal alcohols, which can subsequently cross-link if densely arranged on a gold nanoparticle surface. Importantly, these structures can be synthesized using gold nanoparticles of a range of sizes, thereby providing control over the size and properties of the resulting crosslinked particle. Chapter four returns to the topic of SNAs and builds upon the chemistry of chapter three culminating in the synthesis of cross-linked hollow SNA nanoparticles. These structures are formed by the cross-linking of synthetically modified alkyne-bearing oligonucleotides through the pathway described in chapter three. When the gold core is dissolved, the resulting hollow SNAs exhibit nearly identical binding, nuclease resistance, cellular uptake, and gene regulation properties of SNA-gold nanoparticle conjugates. Indeed, this chapter demonstrates that the unique properties of SNA-nanoparticle conjugates are core-independent and stem solely from the dense ensemble of oligonucleotides arranged on their surfaces. The fifth chapter further asserts the synthetic achievements made in chapter four by showing how hollow SNAs can be substituted for SNA-gold nanoparticles in the context of DNA-programmable assembly. In this case, they can be used as building blocks within binary synthetic schemes to synthesize unique nanoparticle superlattices. It bolsters the design rules of DNA-programmable assembly by showing that the predicted structures form based on the behavior of SNA hybridization, and are universal for any SNA-functionalized nanoparticle.

Modeling and measuring non-Newtonian shear flows of soft interfaces

NASA Astrophysics Data System (ADS)

Lopez, Juan; Raghunandan, Aditya; Underhill, Patrick; Hirsa, Amir

2017-11-01

Soft interfaces of polymers, particles, and proteins between fluid phases are ubiquitous in industrial and natural processes. The flow response of such systems to deformation is often not linear, as one would expect for Newtonian interfaces. The resistance to (pure shear) flow of interfaces is generally characterized by a single intrinsic material property, the surface shear viscosity. Predicted shear responses of Newtonian interfaces have achieved consensus across a wide range of flow conditions and measurement devices, when the nonlinear hydrodynamic coupling to the bulk phase is correctly accounted for. However, predicting the flows of sheared non-Newtonian interfaces remains a challenge. Here, we introduce a computational model that incorporates a non-Newtonian constitutive equation for the sheared interface and properly accounts for the coupled interfacial and bulk phase flows. We compare predictions to experiments performed with a model phospholipid system, DPPC - the main constituent of mammalian lung surfactant. Densely packed films of DPPC are directly sheared in a knife-edge surface viscometer. Yield-stress and shear thinning behaviors are shown to be accurately captured across hydrodynamic regimes straddling the Stokes flow limit to inertia dominated flows. Supported by NASA Grant NNX13AQ22G.

Viscosity of the oil-in-water Pickering emulsion stabilized by surfactant-polymer and nanoparticle-surfactant-polymer system

NASA Astrophysics Data System (ADS)

Sharma, Tushar; Kumar, G. Suresh; Chon, Bo Hyun; Sangwai, Jitendra S.

2014-11-01

Information on the viscosity of Pickering emulsion is required for their successful application in upstream oil and gas industry to understand their stability at extreme environment. In this work, a novel formulation of oil-in-water (o/w) Pickering emulsion stabilized using nanoparticle-surfactant-polymer (polyacrylamide) system as formulated in our earlier work (Sharma et al., Journal of Industrial and Engineering Chemistry, 2014) is investigated for rheological stability at high pressure and high temperature (HPHT) conditions using a controlled-strain rheometer. The nanoparticle (SiO2 and clay) concentration is varied from 1.0 to 5.0 wt%. The results are compared with the rheological behavior of simple o/w emulsion stabilized by surfactant-polymer system. Both the emulsions exhibit non-Newtonian shear thinning behavior. A positive shift in this behavior is observed for surfactant-polymer stabilized emulsion at high pressure conditions. Yield stress is observed to increase with pressure for surfactant-polymer emulsion. In addition, increase in temperature has an adverse effect on the viscosity of emulsion stabilized by surfactant-polymer system. In case of nanoparticle-surfactant-polymer stabilized o/w emulsion system, the viscosity and yield stress are predominantly constant for varying pressure and temperature conditions. The viscosity data for both o/w emulsion systems are fitted by the Herschel-Bulkley model and found to be satisfactory. In general, the study indicates that the Pickering emulsion stabilized by nanoparticle-surfactant-polymer system shows improved and stable rheological properties as compared to conventional emulsion stabilized by surfactant-polymer system indicating their successful application for HPHT environment in upstream oil and gas industry.

Engineered Polymers for Advanced Drug Delivery

PubMed Central

Kim, Sungwon; Kim, Jong-Ho; Jeon, Oju; Kwon, Ick Chan; Park, Kinam

2009-01-01

Engineered polymers have been utilized for developing advanced drug delivery systems. The development of such polymers has caused advances in polymer chemistry, which, in turn, has resulted in smart polymers that can respond to changes in environmental condition, such as temperature, pH, and biomolecules. The responses vary widely from swelling/deswelling to degradation. Drug-polymer conjugates and drug-containing nano/micro-particles have been used for drug targeting. Engineered polymers and polymeric systems have also been used in new areas, such as molecular imaging as well as in nanotechnology. This review examines the engineered polymers that have been used as traditional drug delivery and as more recent applications in nanotechnology. PMID:18977434

Shape memory polymer medical device

DOEpatents

Maitland, Duncan [Pleasant Hill, CA; Benett, William J [Livermore, CA; Bearinger, Jane P [Livermore, CA; Wilson, Thomas S [San Leandro, CA; Small, IV, Ward; Schumann, Daniel L [Concord, CA; Jensen, Wayne A [Livermore, CA; Ortega, Jason M [Pacifica, CA; Marion, III, John E.; Loge, Jeffrey M [Stockton, CA

2010-06-29

A system for removing matter from a conduit. The system includes the steps of passing a transport vehicle and a shape memory polymer material through the conduit, transmitting energy to the shape memory polymer material for moving the shape memory polymer material from a first shape to a second and different shape, and withdrawing the transport vehicle and the shape memory polymer material through the conduit carrying the matter.

Processing and properties of ceramic matrix-polymer composites for dental applications

NASA Astrophysics Data System (ADS)

Huang, Hsuan Yao

The basic composite structure of natural hard tissue was used to guide the design and processing of dental restorative materials. The design incorporates the methodology of using inorganic minerals as the main structural phase reinforced with a more ductile but tougher organic phase. Ceramic-polymer composites were prepared by slip casting a porous ceramic structure, heating and chemical treating the porous preform, infiltrating with monomer and then curing. The three factors that determined the mechanical properties of alumina-polymer composites were the type of polymer used, the method of silane treatments, and the type of bond between particles in the porous preforms. Without the use of silane coupling agents, the composites were measured to have a lower strength. The composite with a more "flexible" porous alumina network had a greater ability to plastically dissipate the energy of propagating cracks. However, the aggressive nature of the alumina particles on opposing enamel requires that these alumina-polymer composites have a wear compatible coating for practical application. A route to dense bioactive apatite wollastonite glass ceramics (AWGC)-polymer composites was developed. The problems associated with glass dissolution into the aqueous medium for slip casting were overcome with the use of silane. The role of heating rate and development of ceramic compact microstructure on composite properties was explored. In general, if isothermal heating was not applied, decreasing heating rate increased glass crystallinity and particle-particle fusion, but decreased pore volume. Also composite strength and fracture toughness decreased while modulus and hardness increased with decreasing heating rate. If isothermal heating was applied, glass crystallinity, pore content, and composite mechanical properties showed relatively little change regardless of the initial heating rate. The potential of AWGC-polymer composites for dental and implant applications was explored. Strengths and toughnesses were not severely degraded by immersion in simulated body fluids up to 30 days. The composite elastic modulus approached that of hard tissues and its wear behavior with opposing tooth was excellent. Growth of apatite over the entire composite surface was achieved in SBF. Growth of apatite in human whole saliva was achieved on the bioactive glass surface, but not on the composite surface.

Effects of Phase Separation Behavior on Morphology and Performance of Polycarbonate Membranes.

PubMed

Idris, Alamin; Man, Zakaria; Maulud, Abdulhalim S; Khan, Muhammad Saad

2017-04-05

The phase separation behavior of bisphenol-A-polycarbonate (PC), dissolved in N -methyl-2-pyrrolidone and dichloromethane solvents in coagulant water, was studied by the cloud point method. The respective cloud point data were determined by titration against water at room temperature and the characteristic binodal curves for the ternary systems were plotted. Further, the physical properties such as viscosity, refractive index, and density of the solution were measured. The critical polymer concentrations were determined from the viscosity measurements. PC/NMP and PC/DCM membranes were fabricated by the dry-wet phase inversion technique and characterized for their morphology, structure, and thermal stability using field emission scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis, respectively. The membranes' performances were tested for their permeance to CO₂, CH₄, and N₂ gases at 24 ± 0.5 °C with varying feed pressures from 2 to 10 bar. The PC/DCM membranes appeared to be asymmetric dense membrane types with appreciable thermal stability, whereas the PC/NMP membranes were observed to be asymmetric with porous structures exhibiting 4.18% and 9.17% decrease in the initial and maximum degradation temperatures, respectively. The ideal CO₂/N₂ and CO₂/CH₄ selectivities of the PC/NMP membrane decreased with the increase in feed pressures, while for the PC/DCM membrane, the average ideal CO₂/N₂ and CO₂/CH₄ selectivities were found to be 25.1 ± 0.8 and 21.1 ± 0.6, respectively. Therefore, the PC/DCM membranes with dense morphologies are appropriate for gas separation applications.

Novel method for measuring a dense 3D strain map of robotic flapping wings

NASA Astrophysics Data System (ADS)

Li, Beiwen; Zhang, Song

2018-04-01

Measuring dense 3D strain maps of the inextensible membranous flapping wings of robots is of vital importance to the field of bio-inspired engineering. Conventional high-speed 3D videography methods typically reconstruct the wing geometries through measuring sparse points with fiducial markers, and thus cannot obtain the full-field mechanics of the wings in detail. In this research, we propose a novel system to measure a dense strain map of inextensible membranous flapping wings by developing a superfast 3D imaging system and a computational framework for strain analysis. Specifically, first we developed a 5000 Hz 3D imaging system based on the digital fringe projection technique using the defocused binary patterns to precisely measure the dynamic 3D geometries of rapidly flapping wings. Then, we developed a geometry-based algorithm to perform point tracking on the precisely measured 3D surface data. Finally, we developed a dense strain computational method using the Kirchhoff-Love shell theory. Experiments demonstrate that our method can effectively perform point tracking and measure a highly dense strain map of the wings without many fiducial markers.

Designing polymers with sugar-based advantages for bioactive delivery applications.

PubMed

Zhang, Yingyue; Chan, Jennifer W; Moretti, Alysha; Uhrich, Kathryn E

2015-12-10

Sugar-based polymers have been extensively explored as a means to increase drug delivery systems' biocompatibility and biodegradation. Here,we review he use of sugar-based polymers for drug delivery applications, with a particular focus on the utility of the sugar component(s) to provide benefits for drug targeting and stimuli responsive systems. Specifically, numerous synthetic methods have been developed to reliably modify naturally-occurring polysaccharides, conjugate sugar moieties to synthetic polymer scaffolds to generate glycopolymers, and utilize sugars as a multifunctional building block to develop sugar-linked polymers. The design of sugar-based polymer systems has tremendous implications on both the physiological and biological properties imparted by the saccharide units and are unique from synthetic polymers. These features include the ability of glycopolymers to preferentially target various cell types and tissues through receptor interactions, exhibit bioadhesion for prolonged residence time, and be rapidly recognized and internalized by cancer cells. Also discussed are the distinct stimuli-sensitive properties of saccharide-modified polymers to mediate drug release under desired conditions. Saccharide-based systems with inherent pH- and temperature-sensitive properties, as well as enzyme-cleavable polysaccharides for targeted bioactive delivery, are covered. Overall, this work emphasizes inherent benefits of sugar-containing polymer systems for bioactive delivery.

Electrically conducting polymers for aerospace applications

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Gaier, James R.; Good, Brian S.; Sharp, G. R.; Meador, Michael A.

1991-01-01

Current research on electrically conducting polymers from 1974 to the present is reviewed focusing on the development of materials for aeronautic and space applications. Problems discussed include extended pi-systems, pyrolytic polymers, charge-transfer systems, conductive matrix resins for composite materials, and prospects for the use of conducting polymers in space photovoltaics.

Ultra fast polymer network blue phase liquid crystals

NASA Astrophysics Data System (ADS)

Hussain, Zakir; Masutani, Akira; Danner, David; Pleis, Frank; Hollfelder, Nadine; Nelles, Gabriele; Kilickiran, Pinar

2011-06-01

Polymer-stabilization of blue phase liquid crystal systems within a host polymer network are reported, which enables ultrafast switching flexible displays. Our newly developed method to stabilize the blue phase in an existing polymer network (e.g., that of a polymer network liquid crystal; PNLC) has shown wide temperature stability and fast response speeds. Systems where the blue phase is stabilized in an already existing polymer network are attractive candidates for ultrafast LCDs. The technology also promises to be applied to flexible PNLC and/or polymer dispersed liquid crystal (PDLC) displays using plastic substrate such as polyethylene terephthalate (PET).

Polymers for hydrogen infrastructure and vehicle fuel systems :

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

Barth, Rachel Reina; Simmons, Kevin L.; San Marchi, Christopher W.

2013-10-01

This document addresses polymer materials for use in hydrogen service. Section 1 summarizes the applications of polymers in hydrogen infrastructure and vehicle fuel systems and identifies polymers used in these applications. Section 2 reviews the properties of polymer materials exposed to hydrogen and/or high-pressure environments, using information obtained from published, peer-reviewed literature. The effect of high pressure on physical and mechanical properties of polymers is emphasized in this section along with a summary of hydrogen transport through polymers. Section 3 identifies areas in which fuller characterization is needed in order to assess material suitability for hydrogen service.

Polymers for Drug Delivery Systems

PubMed Central

Liechty, William B.; Kryscio, David R.; Slaughter, Brandon V.; Peppas, Nicholas A.

2012-01-01

Polymers have played an integral role in the advancement of drug delivery technology by providing controlled release of therapeutic agents in constant doses over long periods, cyclic dosage, and tunable release of both hydrophilic and hydrophobic drugs. From early beginnings using off-the-shelf materials, the field has grown tremendously, driven in part by the innovations of chemical engineers. Modern advances in drug delivery are now predicated upon the rational design of polymers tailored for specific cargo and engineered to exert distinct biological functions. In this review, we highlight the fundamental drug delivery systems and their mathematical foundations and discuss the physiological barriers to drug delivery. We review the origins and applications of stimuli-responsive polymer systems and polymer therapeutics such as polymer-protein and polymer-drug conjugates. The latest developments in polymers capable of molecular recognition or directing intracellular delivery are surveyed to illustrate areas of research advancing the frontiers of drug delivery. PMID:22432577

Polymer surfaces structured with random or aligned electrospun nanofibers to promote the adhesion of blood platelets.

PubMed

Wan, Ling-Shu; Xu, Zhi-Kang

2009-04-01

Fibrous membranes (nonwoven meshes) prepared via electrospinning technique have great potential in tissue engineering. This work is the first study on the behaviors of blood platelets at the nanostructured surface generated by electrospinning. Poly[acrylonitrile-co-(N-vinyl-2-pyrrolidone)] (PANCNVP) that shows excellent antiplatelet adhesion ability was directly electrospun onto its dense membrane surface. Polyacrylonitrile (PAN) samples were used as controls. The depth as well as the density of the nanofibers can be easily controlled. The results showed that the PANCNVP dense membrane certainly suppressed the activation and adhesion of platelets. However, whether the nanofibers and underlying membranes were composed of PAN or PANCNVP, the nanostructured surfaces promoted the activation, adhesion, and orientation of platelets. It was also found that, if the space between fibers was too large or the depth of fibers was too small, the nanostructured surface did not change the property of antiplatelet adhesion of PANCNVP. The promotion of activation and adhesion of platelets was obviously due to the presence of nanofibers, which induced the changes of surface topography and charge. Copyright 2008 Wiley Periodicals, Inc.

Propulsion and Power Generation Capabilities of a Dense Plasma Focus (DPF) Fusion System for Future Military Aerospace Vehicles (POSTPRINT)

DTIC Science & Technology

2005-10-06

The objective of this study was to perform a parametric evaluation of the performance and interface characteristics of a dense plasma focus (DPF...dense plasma focus (DPF) fusion power and propulsion technology, with advanced waverider-like airframe configurations utilizing air-breathing MHD

Real-time detection of moving objects from moving vehicles using dense stereo and optical flow

NASA Technical Reports Server (NTRS)

Talukder, Ashit; Matthies, Larry

2004-01-01

Dynamic scene perception is very important for autonomous vehicles operating around other moving vehicles and humans. Most work on real-time object tracking from moving platforms has used sparse features or assumed flat scene structures. We have recently extended a real-time, dense stereo system to include realtime, dense optical flow, enabling more comprehensive dynamic scene analysis. We describe algorithms to robustly estimate 6-DOF robot egomotion in the presence of moving objects using dense flow and dense stereo. We then use dense stereo and egomotion estimates to identify & other moving objects while the robot itself is moving. We present results showing accurate egomotion estimation and detection of moving people and vehicles under general 6-DOF motion of the robot and independently moving objects. The system runs at 18.3 Hz on a 1.4 GHz Pentium M laptop, computing 160x120 disparity maps and optical flow fields, egomotion, and moving object segmentation. We believe this is a significant step toward general unconstrained dynamic scene analysis for mobile robots, as well as for improved position estimation where GPS is unavailable.

Real-time detection of moving objects from moving vehicles using dense stereo and optical flow

NASA Technical Reports Server (NTRS)

Talukder, Ashit; Matthies, Larry

2004-01-01

Dynamic scene perception is very important for autonomous vehicles operating around other moving vehicles and humans. Most work on real-time object tracking from moving platforms has used sparse features or assumed flat scene structures. We have recently extended a real-time, dense stereo system to include real-time, dense optical flow, enabling more comprehensive dynamic scene analysis. We describe algorithms to robustly estimate 6-DOF robot egomotion in the presence of moving objects using dense flow and dense stereo. We then use dense stereo and egomotion estimates to identity other moving objects while the robot itself is moving. We present results showing accurate egomotion estimation and detection of moving people and vehicles under general 6-DOF motion of the robot and independently moving objects. The system runs at 18.3 Hz on a 1.4 GHz Pentium M laptop, computing 160x120 disparity maps and optical flow fields, egomotion, and moving object segmentation. We believe this is a significant step toward general unconstrained dynamic scene analysis for mobile robots, as well as for improved position estimation where GPS is unavailable.

Real-time Detection of Moving Objects from Moving Vehicles Using Dense Stereo and Optical Flow

NASA Technical Reports Server (NTRS)

Talukder, Ashit; Matthies, Larry

2004-01-01

Dynamic scene perception is very important for autonomous vehicles operating around other moving vehicles and humans. Most work on real-time object tracking from moving platforms has used sparse features or assumed flat scene structures. We have recently extended a real-time. dense stereo system to include realtime. dense optical flow, enabling more comprehensive dynamic scene analysis. We describe algorithms to robustly estimate 6-DOF robot egomotion in the presence of moving objects using dense flow and dense stereo. We then use dense stereo and egomotion estimates to identify other moving objects while the robot itself is moving. We present results showing accurate egomotion estimation and detection of moving people and vehicles under general 6DOF motion of the robot and independently moving objects. The system runs at 18.3 Hz on a 1.4 GHz Pentium M laptop. computing 160x120 disparity maps and optical flow fields, egomotion, and moving object segmentation. We believe this is a significant step toward general unconstrained dynamic scene analysis for mobile robots, as well as for improved position estimation where GPS is unavailable.

Effect of attractive interactions between polymers on the effective force acting between colloids immersed in a polymer system: Analytic liquid-state theory.

PubMed

Chervanyov, A I

2016-12-28

By making use of the polymer reference interaction site model, we analytically study the effect of attractive interactions between polymers on the effective forces acting between colloids immersed in a polymer system. The performed theoretical analysis has no restrictions with respect to the polymer density and relative sizes of the colloids and polymers. The polymer mediated (PM) potential acting between colloids is shown to significantly depend on the strength and range of the polymer-polymer interactions. In the nano-particle limit, where the colloid radius is much smaller than the polymer gyration radius, the presence of attractive polymer-polymer interactions causes only quantitative changes to the PM potential. In the opposite limit of relatively large colloids, the polymer-polymer interactions revert the sign of the total effective force acting between colloids so that this force becomes attractive at sufficiently large polymer densities. With the objective to study an intricate interplay between the attractive PM forces and steric repulsion in different polymer density regimes, we calculate the second virial coefficient B of the total effective potential acting between colloids. The dependence of B on the polymer density is discussed in detail, revealing several novel features of the PM interactions caused by the presence of attractive polymer-polymer interactions.

New way to produce dense double-antikaonic dibaryon system, 𝐾̄𝐾̄NN, through Λ(1405)-doorway sticking in p + p collisions

PubMed Central

YAMAZAKI, Toshimitsu; AKAISHI, Yoshinori; HASSANVAND, Maryam

2011-01-01

A recent successful observation of a dense and deeply bound 𝐾̄ nuclear system, K−pp, in the p + p → K+ + K−pp reaction in a DISTO experiment indicates that the double-𝐾̄ dibaryon, K−K−pp, which was predicted to be a dense nuclear system, can also be formed in p + p collisions. We find theoretically that the K−-K− repulsion plays no significant role in reducing the density and binding energy of K−K−pp and that, when two Λ(1405) resonances are produced simultaneously in a short-range p + p collision, they act as doorways to copious formation of K−K−pp, if and only if K−K−pp is a dense object, as predicted. PMID:21670568

Polymers for 3D Printing and Customized Additive Manufacturing.

PubMed

Ligon, Samuel Clark; Liska, Robert; Stampfl, Jürgen; Gurr, Matthias; Mülhaupt, Rolf

2017-08-09

Additive manufacturing (AM) alias 3D printing translates computer-aided design (CAD) virtual 3D models into physical objects. By digital slicing of CAD, 3D scan, or tomography data, AM builds objects layer by layer without the need for molds or machining. AM enables decentralized fabrication of customized objects on demand by exploiting digital information storage and retrieval via the Internet. The ongoing transition from rapid prototyping to rapid manufacturing prompts new challenges for mechanical engineers and materials scientists alike. Because polymers are by far the most utilized class of materials for AM, this Review focuses on polymer processing and the development of polymers and advanced polymer systems specifically for AM. AM techniques covered include vat photopolymerization (stereolithography), powder bed fusion (SLS), material and binder jetting (inkjet and aerosol 3D printing), sheet lamination (LOM), extrusion (FDM, 3D dispensing, 3D fiber deposition, and 3D plotting), and 3D bioprinting. The range of polymers used in AM encompasses thermoplastics, thermosets, elastomers, hydrogels, functional polymers, polymer blends, composites, and biological systems. Aspects of polymer design, additives, and processing parameters as they relate to enhancing build speed and improving accuracy, functionality, surface finish, stability, mechanical properties, and porosity are addressed. Selected applications demonstrate how polymer-based AM is being exploited in lightweight engineering, architecture, food processing, optics, energy technology, dentistry, drug delivery, and personalized medicine. Unparalleled by metals and ceramics, polymer-based AM plays a key role in the emerging AM of advanced multifunctional and multimaterial systems including living biological systems as well as life-like synthetic systems.

Polymers for 3D Printing and Customized Additive Manufacturing

PubMed Central

2017-01-01

Additive manufacturing (AM) alias 3D printing translates computer-aided design (CAD) virtual 3D models into physical objects. By digital slicing of CAD, 3D scan, or tomography data, AM builds objects layer by layer without the need for molds or machining. AM enables decentralized fabrication of customized objects on demand by exploiting digital information storage and retrieval via the Internet. The ongoing transition from rapid prototyping to rapid manufacturing prompts new challenges for mechanical engineers and materials scientists alike. Because polymers are by far the most utilized class of materials for AM, this Review focuses on polymer processing and the development of polymers and advanced polymer systems specifically for AM. AM techniques covered include vat photopolymerization (stereolithography), powder bed fusion (SLS), material and binder jetting (inkjet and aerosol 3D printing), sheet lamination (LOM), extrusion (FDM, 3D dispensing, 3D fiber deposition, and 3D plotting), and 3D bioprinting. The range of polymers used in AM encompasses thermoplastics, thermosets, elastomers, hydrogels, functional polymers, polymer blends, composites, and biological systems. Aspects of polymer design, additives, and processing parameters as they relate to enhancing build speed and improving accuracy, functionality, surface finish, stability, mechanical properties, and porosity are addressed. Selected applications demonstrate how polymer-based AM is being exploited in lightweight engineering, architecture, food processing, optics, energy technology, dentistry, drug delivery, and personalized medicine. Unparalleled by metals and ceramics, polymer-based AM plays a key role in the emerging AM of advanced multifunctional and multimaterial systems including living biological systems as well as life-like synthetic systems. PMID:28756658

Arginine- and lysine-specific polymers for protein recognition and immobilization.

PubMed

Renner, Christian; Piehler, Jacob; Schrader, Thomas

2006-01-18

Free radical polymerization of methacrylamide-based bisphosphonates turns weak arginine binders into powerful polymeric protein receptors. Dansyl-labeled homo- and copolymers with excellent water solubility are accessible through a simple copolymerization protocol. Modeling studies point to a striking structural difference between the stiff rodlike densely packed homopolymer 1 and the flexible copolymer 2 with spatially separated bisphosphonate units. Fluorescence titrations in buffered aqueous solution (pH = 7.0) confirm the superior affinity of the homopolymer toward oligoarginine peptides reaching nanomolar K(D) values for the Tat peptide. Basic proteins are bound almost equally well by 1 and 2 with micromolar affinities, with the latter producing much more soluble complexes. The Arg selectivity of the monomer is transferred to the polymer, which binds Arg-rich proteins 1 order of magnitude tighter than lysine-rich pendants of comparable pI, size, and (Arg/Lys vs Glu/Asp) ratio. Noncovalent deposition of both polymers on glass substrates via polyethyleneimine layers results in new materials suitable for peptide and protein immobilization. RIfS measurements allow calculation of association constants K(a) as well as dissociation kinetics k(D). They generally confirm the trends already found in free solution. Close inspection of electrostatic potential surfaces suggest that basic domains favor protein binding on the flat surface. The high specificity of the bisphosphonate polymers toward basic proteins is demonstrated by comparison with polyvinyl sulfate, which has almost no effect in RIfS experiments. Thus, copolymerization of few different comonomer units without cross-linking enables surface recognition of basic proteins in free solution as well as their effective immobilization on surfaces.

An extended GS method for dense linear systems

NASA Astrophysics Data System (ADS)

Niki, Hiroshi; Kohno, Toshiyuki; Abe, Kuniyoshi

2009-09-01

Davey and Rosindale [K. Davey, I. Rosindale, An iterative solution scheme for systems of boundary element equations, Internat. J. Numer. Methods Engrg. 37 (1994) 1399-1411] derived the GSOR method, which uses an upper triangular matrix [Omega] in order to solve dense linear systems. By applying functional analysis, the authors presented an expression for the optimum [Omega]. Moreover, Davey and Bounds [K. Davey, S. Bounds, A generalized SOR method for dense linear systems of boundary element equations, SIAM J. Comput. 19 (1998) 953-967] also introduced further interesting results. In this note, we employ a matrix analysis approach to investigate these schemes, and derive theorems that compare these schemes with existing preconditioners for dense linear systems. We show that the convergence rate of the Gauss-Seidel method with preconditioner PG is superior to that of the GSOR method. Moreover, we define some splittings associated with the iterative schemes. Some numerical examples are reported to confirm the theoretical analysis. We show that the EGS method with preconditioner produces an extremely small spectral radius in comparison with the other schemes considered.

System for diffusing light from an optical fiber or light guide

DOEpatents

Maitland, Duncan J [Pleasant Hill, CA; Wilson, Thomas S [San Leandro, CA; Benett, William J [Livermore, CA; Small, IV, Ward [

2008-06-10

A system for diffusing light from an optical fiber wherein the optical fiber is coupled to a light source, comprising forming a polymer element adapted to be connected to the optical fiber and incorporating a scattering element with the polymer element wherein the scattering element diffuses the light from the polymer element. The apparatus of the present invention comprises a polymer element operatively connected to the optical fiber and a scattering element operatively connected with the shape polymer element that diffuses the light from the polymer element.

Polymer in a pore: Effect of confinement on the free energy barrier

NASA Astrophysics Data System (ADS)

Kumar, Sanjiv; Kumar, Sanjay

2018-06-01

We investigate the transfer of a polymer chain from cis- side to trans- side through two types of pores: cone-shaped channel and flat-channel. Using the exact enumeration technique, we obtain the free energy landscapes of a polymer chain for such systems. We have also calculated the free-energy barrier of a polymer chain attached to the edge of the pore. The model system allows us to calculate the force required to pull polymer from the pore and stall-force to confine polymer within the pore.

Smart and functional polymer materials for smart and functional microfluidic instruments

NASA Astrophysics Data System (ADS)

Gray, Bonnie L.

2014-04-01

As microfluidic systems evolve from "chip-in-the-lab" to true portable lab-on-a-chip (LoC) or lab-in-a-package (LiP) microinstrumentation, there is a need for increasingly miniaturized sensors, actuators, and integration/interconnect technologies with high levels of functionality and self-direction. Furthermore, as microfluidic instruments are increasingly realized in polymer-based rather than glass- or silicon- based platforms, there is a need to realize these highly functional components in materials that are polymer-compatible. Polymers that are altered to possess basic functionality, and even higher-functioning "smart" polymer materials, may help to realize high-functioning and selfdirecting portable microinstrumentation. Stimuli-responsive hydrogels have been recognized for over a decade as beneficial to the development of smart microfluidics systems and instrumentation. In addition, functional materials such as conductive and magnetic composite polymers are being increasingly employed to push microfluidics systems to greater degrees of functionality, portability, and/or flexibility for wearable/implantable systems. Functional and smart polymer materials can be employed to realize electrodes, electronic routing, heaters, mixers, valves, pumps, sensors, and interconnect structures in polymer-based microfluidic systems. Stimuli for such materials can be located on-chip or in a small package, thus greatly increasing the degree of portability and the potential for mechanical flexibility of such systems. This paper will examine the application of functional polymer materials to the development of high-functioning microfluidics instruments with a goal towards self-direction.

Incorporation of additives into polymers

DOEpatents

McCleskey, T. Mark; Yates, Matthew Z.

2003-07-29

There has been invented a method for incorporating additives into polymers comprising: (a) forming an aqueous or alcohol-based colloidal system of the polymer; (b) emulsifying the colloidal system with a compressed fluid; and (c) contacting the colloidal polymer with the additive in the presence of the compressed fluid. The colloidal polymer can be contacted with the additive by having the additive in the compressed fluid used for emulsification or by adding the additive to the colloidal system before or after emulsification with the compressed fluid. The invention process can be carried out either as a batch process or as a continuous on-line process.

Cell specific, variable density, polymer microspheres

NASA Technical Reports Server (NTRS)

Yen, Shiao-Ping S. (Inventor); Rembaum, Alan (Inventor); Molday, Robert S. (Inventor)

1977-01-01

Biocompatible polymeric microspheres having an average diameter below about 3 microns and having density at least 15% greater or lesser than organic cells and having covalent binding sites are provided in accordance with this invention. The microspheres are obtained by copolymerizing a hydroxy or amine substituted acrylic monomer such as hydroxyethylmethacrylate with a light or dense comonomer such as a fluoromonomer. A lectin or antibody is bound to the hydroxy or amine site of the bead to provide cell specificity. When added to a cell suspension the marked bead will specifically label the cell membrane by binding to specific receptor sites thereon. The labelled membrane can then be separated by density gradient centrifugation.

Comparison of Danish dichotomous and BI-RADS classifications of mammographic density.

PubMed

Hodge, Rebecca; Hellmann, Sophie Sell; von Euler-Chelpin, My; Vejborg, Ilse; Andersen, Zorana Jovanovic

2014-06-01

In the Copenhagen mammography screening program from 1991 to 2001, mammographic density was classified either as fatty or mixed/dense. This dichotomous mammographic density classification system is unique internationally, and has not been validated before. To compare the Danish dichotomous mammographic density classification system from 1991 to 2001 with the density BI-RADS classifications, in an attempt to validate the Danish classification system. The study sample consisted of 120 mammograms taken in Copenhagen in 1991-2001, which tested false positive, and which were in 2012 re-assessed and classified according to the BI-RADS classification system. We calculated inter-rater agreement between the Danish dichotomous mammographic classification as fatty or mixed/dense and the four-level BI-RADS classification by the linear weighted Kappa statistic. Of the 120 women, 32 (26.7%) were classified as having fatty and 88 (73.3%) as mixed/dense mammographic density, according to Danish dichotomous classification. According to BI-RADS density classification, 12 (10.0%) women were classified as having predominantly fatty (BI-RADS code 1), 46 (38.3%) as having scattered fibroglandular (BI-RADS code 2), 57 (47.5%) as having heterogeneously dense (BI-RADS 3), and five (4.2%) as having extremely dense (BI-RADS code 4) mammographic density. The inter-rater variability assessed by weighted kappa statistic showed a substantial agreement (0.75). The dichotomous mammographic density classification system utilized in early years of Copenhagen's mammographic screening program (1991-2001) agreed well with the BI-RADS density classification system.

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

PubMed

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

2016-10-01

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

Normetex Pump Alternatives Study

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

Clark, Elliot A.

2013-04-25

A mainstay pump for tritium systems, the Normetex scroll pump, is currently unavailable because the Normetex company went out of business. This pump was an all-metal scroll pump that served tritium processing facilities very well. Current tritium system operators are evaluating replacement pumps for the Normetex pump and for general used in tritium service. An all-metal equivalent alternative to the Normetex pump has not yet been identified. 1. The ideal replacement tritium pump would be hermetically sealed and contain no polymer components or oils. Polymers and oils degrade over time when they contact ionizing radiation. 2. Halogenated polymers (containing fluorine,more » chlorine, or both) and oils are commonly found in pumps. These materials have many properties that surpass those of hydrocarbon-based polymers and oils, including thermal stability (higher operating temperature) and better chemical resistance. Unfortunately, they are less resistant to degradation from ionizing radiation than hydrocarbon-based materials (in general). 3. Polymers and oils can form gaseous, condensable (HF, TF), liquid, and solid species when exposed to ionizing radiation. For example, halogenated polymers form HF and HCl, which are extremely corrosive upon reaction with water. If a pump containing polymers or oils must be used in a tritium system, the system must be designed to be able to process the unwanted by-products. Design features to mitigate degradation products include filters and chemical or physical traps (eg. cold traps, oil traps). 4. Polymer components can work in tritium systems, but must be replaced regularly. Polymer components performance should be monitored or be regularly tested, and regular replacement of components should be viewed as an expected normal event. A radioactive waste stream must be established to dispose of used polymer components and oil with an approved disposal plan developed based on the facility location and its regulators. Polymers have varying resistances to ionizing radiation - aromatic polymers such as polyimide Vespel (TM) and the elastomer EPDM (ethylene propylene diene monomer) have been found to be more resistant to degradation in tritium than other polymers. This report presents information to help select replacement pumps for Normetex pumps in tritium systems. Several pumps being considered as Normetex replacement pumps are discussed.« less

Effects of low-level hydrophobic substitution on conditioning properties of cationic cellulosic polymers in shampoo systems.

PubMed

Drovetskaya, T V; Kreeger, R L; Amos, J L; Davis, C B; Zhou, S

2004-01-01

A new class of cationic conditioning polymers (Polymer SL) has been prepared and evaluated in shampoo formulations. Polymer SL is a family of high viscosity quaternized hydroxyethyl cellulose (HEC) polymers with cationic substitution of trimethyl ammonium and dimethyldodecyl ammonium (Figure 1). SL compositions benefit from hydrophobic character to deliver superior conditioning performance in hair care applications. At the same time, low levels of hydrophobes have been chosen to assure good compatibility with surfactant systems without the complications of associative thickening. The polymers have been evaluated in clear shampoo formulations and two-in-one silicone containing shampoos using objective lab methods and subjective panel evaluation on hair tresses. Commercial conditioning polymers: Polyquaternium-10 (PQ-10) (UCARE Polymer LR-30M) and Guar Hydroxypro-pyltrimethylammonium Chloride (Jaguar C-13S) were used as performance benchmarks. The new hydrophobically-modified cationic polymers demonstrated superior performance in all major categories of conditioning and showed improved silicone deposition from two-in-one systems. Moreover, they retained other good qualities of their PQ-10 structural analogs such as enabling crystal clear formulations and showing no build-up or volume-down effects on hair. These new olymers were also found to be efficient conditioning agents in different surfactant systems with or without silicones.

High-angle annular dark field scanning transmission electron microscopy on carbon-based functional polymer systems.

PubMed

Sourty, Erwan; van Bavel, Svetlana; Lu, Kangbo; Guerra, Ralph; Bar, Georg; Loos, Joachim

2009-06-01

Two purely carbon-based functional polymer systems were investigated by bright-field conventional transmission electron microscopy (CTEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). For a carbon black (CB) filled polymer system, HAADF-STEM provides high contrast between the CB agglomerates and the polymer matrix so that details of the interface organization easily can be revealed and assignment of the CB phase is straightforward. For a second system, the functional polymer blend representing the photoactive layer of a polymer solar cell, details of its nanoscale organization could be observed that were not accessible with CTEM. By varying the camera length in HAADF-STEM imaging, the contrast can be enhanced between crystalline and amorphous compounds due to diffraction contrast so that nanoscale interconnections between domains are identified. In general, due to its incoherent imaging characteristics HAADF-STEM allows for reliable interpretation of the data obtained.

The Development for Polymer Actuator Active Catheter System

PubMed Central

Sewa, S.; Onishi, K.; Oguro, K.; Asaka, K.; Taki, W.; Toma, N.

2001-01-01

Summary Electric stimuli polymer-metal composite actuator material has been developed for active catheter system and other widely new applications. The polymer actuator is made of ion exchange polymer and gold as electrode, and a pulse voltage of 3 volts on the actuator gave a quick bend 90 degree angle. This composite material is possible to make small size, light and soft actuator. So now we can actually develop an active catheter for the interventional radiology surgery. The prototype polymer actuator active catheter has been developed by using polymer actuator technology and Micro Electronics Mechanical System (MEMS) technologies. The active catheter is controllable from the outside of the body by electric signal. The tip part of the catheter is made of the polymer actuator tube and bends 90 degree angles. The animal tests (dog) showed good actuator performance to control right direction and bending angle at bifurcation of blood vessel and aneurysms. PMID:20663388

Chemistry of the metal-polymer interfacial region.

PubMed

Leidheiser, H; Deck, P D

1988-09-02

In many polymer-metal systems, chemical bonds are formed that involve metal-oxygen-carbon complexes. Infrared and Mössbauer spectroscopic studies indicate that carboxylate groups play an important role in some systems. The oxygen sources may be the polymer, the oxygen present in the oxide on the metal surface, or atmospheric oxygen. Diffusion of metal ions from the substrate into the polymer interphase may occur in some systems that are cured at elevated temperatures. It is unclear whether a similar, less extensive diffusion occurs over long time periods in systems maintained at room temperature. The interfacial region is dynamic, and chemical changes occur with aging at room temperature. Positron annihilation spectroscopy may have application to characterizing the voids at the metal-polymer interface.

Characterization of mono-ethylene-glycol based industrial polyurethanes samples by fast-neutron radiography and neutron tomography

NASA Astrophysics Data System (ADS)

Rogante, Massimo; Söllradl, Stefan

2016-09-01

A complicated structural organization of polyurethanes may have a strong influence on the materials functional properties. Under particular conditions such as mechanical and thermal loading and aging, it leads to the material degradation, even in fresh-prepared bulk polymers and especially if defects are present in the material. Unwanted bubbles can be observed, which form during the expansion of the mixture during its chemical reaction and remain present in the final product. These macro-, micro- and nano-bubbles influence the material's performance. In this work, neutron radiography and tomography have been adopted to characterize at a macro-scale level the bulk of commercially available polyurethane samples, obtained from dissimilar- mixture ratios with different densities and branching levels as well as from different zones of the production mould. The characterisation allowed an estimation of the different dense materials - as they are used, e.g., in soles of shoes - as well as the invisible defects like pores and cracks, responsible for the materials fracture by mechanical loading. The obtained information are expected to be useful for various industrial sectors such as automotive and footwear industry. It will be completed by applying SANS, which has already proved to characterize the microstructure of the bulk-polymer with respect to nano-pores, micro-cracks and their arrangement in the polymer matrix.

Highly selective coextraction of rhodamine B and dibenzyl phthalate based on high-density dual-template imprinted shells on silica microparticles.

PubMed

Long, Zerong; Xu, Weiwei; Peng, Yumei; Lu, Yi; Luo, Qian; Qiu, Hongdeng

2017-01-01

A simple one-pot approach based on molecularly imprinted polymer shells dispersed on the surface of silica for simultaneous determination of rhodamine B and dibenzyl phthalate (DBzP) has been developed. Highly dense molecularly imprinted polymer shells were formed in the mixture of acetonitrile and toluene by the copolymerization of methacrylic acid and ethylene glycol dimethacrylate, as well as two templates, rhodamine B and dibenzyl phthalate, directed by the vinyl end groups functional monolayer at surface silica microspheres after 3-methacryloxypropyl trimethoxysilane modification. The obtained imprinted polymer shells showed large average pore diameter (102.5 nm) and about 100 nm shell thickness. The imprinted particles also showed high imprinting factor (α RhB = 3.52 and α DBzP = 3.94), rapid binding kinetics, and excellent selective affinity capacity for rhodamine B and dibenzyl phthalate containing another three competitors in mixed solution. Moreover, the imprinted particles coupled with ultra high performance liquid chromatography was successfully applied to simultaneous analysis of rhodamine B and dibenzyl phthalate in two spiked beverage samples with average recoveries in the range of 88.0-93.0% for rhodamine B and 84.0-92.0% for dibenzyl phthalate with the relative standard deviation lower than 5.1%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries.

PubMed

Li, Changyi; Ward, Ashleigh L; Doris, Sean E; Pascal, Tod A; Prendergast, David; Helms, Brett A

2015-09-09

Redox flow batteries (RFBs) present unique opportunities for multi-hour electrochemical energy storage (EES) at low cost. Too often, the barrier for implementing them in large-scale EES is the unfettered migration of redox active species across the membrane, which shortens battery life and reduces Coulombic efficiency. To advance RFBs for reliable EES, a new paradigm for controlling membrane transport selectivity is needed. We show here that size- and ion-selective transport can be achieved using membranes fabricated from polymers of intrinsic microporosity (PIMs). As a proof-of-concept demonstration, a first-generation PIM membrane dramatically reduced polysulfide crossover (and shuttling at the anode) in lithium-sulfur batteries, even when sulfur cathodes were prepared as flowable energy-dense fluids. The design of our membrane platform was informed by molecular dynamics simulations of the solvated structures of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) vs lithiated polysulfides (Li2Sx, where x = 8, 6, and 4) in glyme-based electrolytes of different oligomer length. These simulations suggested polymer films with pore dimensions less than 1.2-1.7 nm might incur the desired ion-selectivity. Indeed, the polysulfide blocking ability of the PIM-1 membrane (∼0.8 nm pores) was improved 500-fold over mesoporous Celgard separators (∼17 nm pores). As a result, significantly improved battery performance was demonstrated, even in the absence of LiNO3 anode-protecting additives.

Membranes of Polymers of Intrinsic Microporosity (PIM-1) Modified by Poly(ethylene glycol).

PubMed

Bengtson, Gisela; Neumann, Silvio; Filiz, Volkan

2017-06-05

Until now, the leading polymer of intrinsic microporosity PIM-1 has become quite famous for its high membrane permeability for many gases in gas separation, linked, however, to a rather moderate selectivity. The combination with the hydrophilic and low permeable poly(ethylene glycol) (PEG) and poly(ethylene oxides) (PEO) should on the one hand reduce permeability, while on the other hand enhance selectivity, especially for the polar gas CO₂ by improving the hydrophilicity of the membranes. Four different paths to combine PIM-1 with PEG or poly(ethylene oxide) and poly(propylene oxide) (PPO) were studied: physically blending, quenching of polycondensation, synthesis of multiblock copolymers and synthesis of copolymers with PEO/PPO side chain. Blends and new, chemically linked polymers were successfully formed into free standing dense membranes and measured in single gas permeation of N₂, O₂, CO₂ and CH₄ by time lag method. As expected, permeability was lowered by any substantial addition of PEG/PEO/PPO regardless the manufacturing process and proportionally to the added amount. About 6 to 7 wt % of PEG/PEO/PPO added to PIM-1 halved permeability compared to PIM-1 membrane prepared under similar conditions. Consequently, selectivity from single gas measurements increased up to values of about 30 for CO₂/N₂ gas pair, a maximum of 18 for CO₂/CH₄ and 3.5 for O₂/N₂.

Ion conducting polymers and polymer blends for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

Optimization of neural network for ionic conductivity of nanocomposite solid polymer electrolyte system (PEO-LiPF 6-EC-CNT)

NASA Astrophysics Data System (ADS)

Johan, Mohd Rafie; Ibrahim, Suriani

2012-01-01

In this study, the ionic conductivity of a nanocomposite polymer electrolyte system (PEO-LiPF 6-EC-CNT), which has been produced using solution cast technique, is obtained using artificial neural networks approach. Several results have been recorded from experiments in preparation for the training and testing of the network. In the experiments, polyethylene oxide (PEO), lithium hexafluorophosphate (LiPF 6), ethylene carbonate (EC) and carbon nanotubes (CNT) are mixed at various ratios to obtain the highest ionic conductivity. The effects of chemical composition and temperature on the ionic conductivity of the polymer electrolyte system are investigated. Electrical tests reveal that the ionic conductivity of the polymer electrolyte system varies with different chemical compositions and temperatures. In neural networks training, different chemical compositions and temperatures are used as inputs and the ionic conductivities of the resultant polymer electrolytes are used as outputs. The experimental data is used to check the system's accuracy following the training process. The neural network is found to be successful for the prediction of ionic conductivity of nanocomposite polymer electrolyte system.

Aqueous Solution-Deposited Molybdenum Oxide Films as an Anode Interfacial Layer for Organic Solar Cells.

PubMed

Yi, Qinghua; Zhai, Pengfei; Sun, Yinghui; Lou, Yanhui; Zhao, Jie; Sun, Baoquan; Patterson, Brian; Luo, Hongmei; Zhang, Wenrui; Jiao, Liang; Wang, Haiyan; Zou, Guifu

2015-08-26

In this study, we report the growth of molybdenum oxide (MoOx) film by polymer-assisted deposition (PAD), an environmentally friendly strategy in an aqueous system. The MoOx film has good crystal quality and is dense and smooth. The transparency of the film is >95% in the wavelength range of 300-900 nm. The device based on P3HT:PCBM absorber material was fabricated. The solar cell with PAD-MoOx as an anode interfacial layer exhibits great performance, even better than that of a solar cell with PSS or evaporated MoOx as an anode interfacial layer. More importantly, the solar cells based on the growth of MoOx have a longer term stability than that of solar cells based on PSS. These results demonstrate the aqueous PAD technology provides an alternative strategy not only for the thin films' growth of applied materials but also for the solution processing for the low-cost fabrication of future materials to be applied in the field of solar cells.

Fabrication of Transparent Protective Diamond-Like Carbon Films on Polymer

NASA Astrophysics Data System (ADS)

Baek, Sang-min; Shirafuji, Tatsuru; Saito, Nagahiro; Takai, Osamu

2011-08-01

Si doped hydrogenated amorphous carbon (Si-DLC) films as a candidate protection coating for polycarbonate (PC) were prepared using a pulse-biased inductively coupled plasma chemical vapor deposition (ICP-CVD) system with a gas mixture of acetylene (C2H2) and tetramethylsilane [Si(CH3)4]. The effects of Si incorporation on the structure and optical properties of the Si-DLC films were investigated. In addition, plasma pretreatments with O2, N2, and Ar gases were carried out to enhance the adhesion strength of Si-DLC films on polycarbonate. Structural characterization through Raman and X-ray photoelectron spectroscopy (XPS) analyses showed that the incorporation of Si atoms in DLC films leads to an increase in the optical band gap (Eopt) with the formation of sp3 C-Si bonds. O2 plasma pretreatment improved the strength of adhesion of the Si-DLC films to polycarbonate, while Ar and N2 plasma treatments did not. This can be explained by the formation of an activated dense interfacial layer by O2 plasma pretreatment.

Ultraviolet photochemistry of cyanoacetylene: Application to Titan. [Abstract only

NASA Technical Reports Server (NTRS)

Clarke, D. W.; Ferris, J. P.

1994-01-01

Cyanoacetylene is believed to have had a central role in the formation of the pyrimidines essential for RNA synthesis leading to the origin of life on Earth. Cyanoacetylene has also been detected on Titan, Saturn's largest moon, and the only moon in the solar system that possesses a dense atmosphere. It is generally accepted that photochemistry plays a major role in the formation of the complex organic molecules and aerosols found in Titan's atmosphere. Because of its long wavelength absorption and low dissociation threshold it is expected that cyanoacetylene is an important part of these photochemical processes. Since cyanoacetylene would also have been subject to ultraviolet light in the atmosphere of early Earth, an investigation of cyanoacetylene photochemistry on Titan might lead to a better understanding of both the photochemical reactions occurring on primitive earth and the processes of chemical evolution as they occur in planetary atmospheres. The effects of irradiation wavelength, mixing with Titan's atmospheric gases, reducing the temperature and lowering cyanoacetylene partial pressures on product formation and polymer composition have been determined with the ultimate goal of understanding the chemical transformations taking place in Titan's atmosphere.

Charge segregation in weakly ionized microgels

DOE PAGES

Hyatt, John S.; Douglas, Alison M.; Stanley, Chris; ...

2017-01-19

Here we investigate microgels synthesized from N-isopropylacrylamide (NIPAM) copolymerized with a large mol% of acrylic acid, finding that when the acid groups are partially ionized at high temperatures, competition between ion-induced swelling and hydrophobic deswelling of poly(NIPAM) chains results in microphase separation. In cross-linked microgels, this manifests as a dramatic decrease in the ratio between the radius of gyration and the hydrodynamic radius to ~0.2, indicating that almost all the mass of the microgel is concentrated near the particle center. We also observe a concurrent decrease of the polymer network length scale via small-angle neutron scattering, confirming the presence ofmore » a dense, deswollen core surrounded by a diffuse, charged periphery. We compare these results to those obtained for a system of charged ultralow-cross-linked microgels; the form factor shows a distinct peak at high q when the temperature exceeds a threshold value. Lastly, we successfully fit the form factor to theory developed to describe scattering from weakly charged gels in poor solvents, and we tie this behavior to charge segregation in the case of the cross-linked microgels.« less

Effects of Noise and Vibration on the Solid to Liquid Fluidization Transition in Small Dense Granular Systems Under Shear

NASA Astrophysics Data System (ADS)

Melhus, Martin Frederic

2011-07-01

Granular materials exhibit bulk properties that are distinct from conventional solids, liq- uids, and gases, due to the dissipative nature of the inter-granular forces. Understanding the fundamentals of granular materials draws upon and gives insight into many fields at the current frontiers of physics, such as plasticity of solids, fracture and friction, com- plex systems such as colloids, foams and suspensions, and a variety of biological systems. Particulate flows are widespread in geophysics, and are also essential to many industries. Despite the importance of these phenomena, we lack a theoretical model that explains most behaviors of granular materials. Since granular assemblies are highly dissipative, they are often far from mechanical equilibrium, making most classical analyses inappli- cable. A theory for dilute granular systems exists, but for dense granular systems (by far the majority of granular systems in the real world) no comparable theory is accepted. We approach this problem by examining the fluidization, or transition from solid to liquid, in dense granular systems. In this study, the separate effects of random noise and vibration on the static to flowing transition of a dense granular assembly under planar shear is studied numerically using soft contact particle dynamics simulations in two dimensions. We focus on small systems in a thin planar Couette cell, examining the bistable region while increasing shear, with varying amounts of random noise or vibration, and determine the statistics of the shear required for the onset of flow. We find that the applied power is the key parameter in determining the magnitude of the effects of the noise or vibration, with vibration frequency also having an influence. Similarities and differences between noise and vibration are determined, and the results compare favorably with a two phase model for dense granular flow.

Intravaginal gene silencing using biodegradable polymer nanoparticles densely loaded with small-interfering RNA

PubMed Central

Woodrow, Kim A.; Cu, Yen; Booth, Carmen J.; Saucier-Sawyer, Jennifer K.; Wood, Monica J.; Saltzman, W. Mark

2009-01-01

Vaginal instillation of small-interfering RNA (siRNA) using liposomes has led to silencing of endogenous genes in the genital tract and protected against challenge from infectious disease. Although siRNA lipoplexes are easily formulated, several of the most effective transfection agents available commercially may be toxic to the mucosal epithelia and none are able to provide controlled or sustained release. Here, we demonstrate an alternate approach, using nanoparticles composed entirely of FDA-approved materials. To render these materials effective for gene silencing we developed novel approaches to load them with high amounts of siRNA. A single dose of siRNA-loaded nanoparticles to the mouse female reproductive tract caused efficient and sustained gene silencing. Knockdown of gene expression was observed proximal (in the vaginal lumen) and distal (in the uterine horns) to the site of topical delivery. In addition, nanoparticles penetrated deep into the epithelial tissue. This is the first report demonstrating that biodegradable polymer nanoparticles are effective delivery vehicles for siRNA in the vaginal mucosa. PMID:19404239

Direct Visualization of Conformation and Dense Packing of DNA-Based Soft Colloids

NASA Astrophysics Data System (ADS)

Zhang, Jing; Lettinga, Paul M.; Dhont, Jan K. G.; Stiakakis, Emmanuel

2014-12-01

Soft colloids—such as polymer-coated particles, star polymers, block-copolymer micelles, microgels—constitute a broad class of materials where microscopic properties such as deformability and penetrability of the particle play a key role in tailoring their macroscopic properties which is of interest in many technological areas. The ability to access these microscopic properties is not yet demonstrated despite its great importance. Here we introduce novel DNA-coated colloids with star-shaped architecture that allows accessing the above local structural information by directly visualizing their intramolecular monomer density profile and arm's free-end locations with confocal fluorescent microscopy. Compression experiments on a two-dimensional hexagonal lattice formed by these macromolecular assemblies reveal an exceptional resistance to mutual interpenetration of their charged corona at pressures approaching the MPa range. Furthermore, we find that this lattice, in a close packing configuration, is surprisingly tolerant to particle size variation. We anticipate that these stimuli-responsive materials could aid to get deeper insight in a wide range of problems in soft matter, including the study and design of biomimetic lubricated surfaces.

Formation of Heterogeneous Toroidal-Spiral Particles -- by Drop Sedimentation and Interaction

NASA Astrophysics Data System (ADS)

Liu, Ying; Nitsche, Ludwig; Gemeinhart, Richard; Sharma, Vishal; Szymusiak, Magdalena; Shen, Hao

2013-03-01

We describe self-assembly of polymeric particles, whereby competitive kinetics of viscous sedimentation, diffusion, and cross-linking yield a controllable toroidal-spiral (TS) structure. Precursor polymeric droplets are splashed through the surface of a less dense, miscible solution, after which viscous forces entrain the surrounding bulk solution into the sedimenting polymer drop to form TS channels. The intricate structure forms because low interfacial tension between the two miscible solutions is dominated by viscous forces. The biocompatible polymer, poly(ethylene glycol) diacrylate (PEG-DA), is used to demonstrate the solidification of the TS shapes at various configurational stages by UV-triggered cross-linking. The dimensions of the channels are controlled by Weber number during impact on the surface, and Reynolds number and viscosity ratio during subsequent sedimentation. Within the critical separation distance, interaction of multiple drops generates similar structure with more flexibility. Furthermore, the understanding of multiple drop interaction is essential for mass production of TS particles by using parallel and sequential arrays of drops. This work was supported by NSF CBET Grant CBET-1039531.

Conductive inks for metalization in integrated polymer microsystems

DOEpatents

Davidson, James Courtney [Livermore, CA; Krulevitch, Peter A [Pleasanton, CA; Maghribi, Mariam N [Livermore, CA; Benett, William J [Livermore, CA; Hamilton, Julie K [Tracy, CA; Tovar, Armando R [San Antonio, TX

2006-02-28

A system of metalization in an integrated polymer microsystem. A flexible polymer substrate is provided and conductive ink is applied to the substrate. In one embodiment the flexible polymer substrate is silicone. In another embodiment the flexible polymer substrate comprises poly(dimethylsiloxane).

The Workshop on Conductive Polymers: Final Report

DOE R&D Accomplishments Database

1985-10-01

Reports are made by groups on: polyacetylene, polyphenylene, polyaniline, and related systems; molecular, crystallographic, and defect structures in conducting polymers; heterocyclic polymers; synthesis of new and improved conducting polymers; future applications possibilities for conducting polymers; and challenges for improved understanding of properties. (DLC)

2,4 Diamino benzonitrile

NASA Technical Reports Server (NTRS)

Frost, Lawrence W. (Inventor)

1980-01-01

Deep curable polymers having heterocyclic ring systems such as isoindoloquinazolinedione ring systems prepared from novel cyanoimide polymers, most desirably 2'-cyanoimide polymers. Preferably the cyanoimide polymers are prepared from a diamine having at least one nitrile group in the two position to an amine group and a dianhydride having at least two cyclic anhydride groups. Copolymers may be prepared having other linkages, notably imide linkages, in addition to isoindoloquinazolinedione ring systems and/or other similar heterocyclic ring systems. The copolymers can be prepared by use of diamines containing one or more cyanoimide groupings and/or imide groups in their structure.

Method for separating biological cells. [suspended in aqueous polymer systems

NASA Technical Reports Server (NTRS)

Brooks, D. E. (Inventor)

1980-01-01

A method for separating biological cells by suspending a mixed cell population in a two-phase polymer system is described. The polymer system consists of droplet phases with different surface potentials for which the cell populations exhibit different affinities. The system is subjected to an electrostatic field of sufficient intensity to cause migration of the droplets with an attendant separation of cells.

Energy transfer dynamics in strongly inhomogeneous hot-dense-matter systems

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

Stillman, C. R.; Nilson, P. M.; Sefkow, A. B.

Direct measurements of energy transfer across steep density and temperature gradients in a hot-dense-matter system are presented. Hot dense plasma conditions were generated by high-intensity laser irradiation of a thin-foil target containing a buried metal layer. Energy transfer to the layer was measured using picosecond time-resolved x-ray emission spectroscopy. Here, the data show two x-ray flashes in time. Fully explicit, coupled particle-in-cell and collisional-radiative atomic kinetics model predictions reproduce these observations, connecting the two x-ray flashes with staged radial energy transfer within the target.

Energy transfer dynamics in strongly inhomogeneous hot-dense-matter systems

DOE PAGES

Stillman, C. R.; Nilson, P. M.; Sefkow, A. B.; ...

2018-06-25

Direct measurements of energy transfer across steep density and temperature gradients in a hot-dense-matter system are presented. Hot dense plasma conditions were generated by high-intensity laser irradiation of a thin-foil target containing a buried metal layer. Energy transfer to the layer was measured using picosecond time-resolved x-ray emission spectroscopy. Here, the data show two x-ray flashes in time. Fully explicit, coupled particle-in-cell and collisional-radiative atomic kinetics model predictions reproduce these observations, connecting the two x-ray flashes with staged radial energy transfer within the target.

A study on the dynamic interfacial tension of acidic crude oil/alkali (alkali-polymer) systems--

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

Huang, Y.; Yang, P.; Qin, T.

1989-01-01

This paper describes the investigation of dynamic interfacial tension (DIFT) between the acidic Liao-He crude oil and two types of brine: a simple alkali system and a combined alkali-polymer system. It was found that interfacial tension (IFT) changed markedly with time and that the history of DIFT depended upon the concentration of alkali in the brine. The experimental results also showed that the IFT dropped dramatically as soon as the fresh oil contacted brine causing spontaneous emulsification to occur. The steady-state value of DIFT {gamma} st can be lower with the combined alkali-polymer system than with the simple alkali system.more » The results indicate that biopolymer is more effective than partially hydrolyzed polyacrylamide (PHPAM) for lowering {gamma} st and that Na{sub 2}Co{sub 1} causes a lower {gamma} st than NaOH in the combined alkali-polymer system. Optimized formulations containing Na{sub 2}CO{sub 3} added biopolymer can reduce {gamma} st by two orders of magnitude, and PHPAM can reduce {gamma} st by one order of magnitude. The interaction between alkali and polymer in the combined alkali-polymer system is discussed.« less

Structural health monitoring system/method using electroactive polymer fibers

NASA Technical Reports Server (NTRS)

Scott-Carnell, Lisa A. (Inventor); Siochi, Emilie J. (Inventor)

2013-01-01

A method for monitoring the structural health of a structure of interest by coupling one or more electroactive polymer fibers to the structure and monitoring the electroactive responses of the polymer fiber(s). Load changes that are experienced by the structure cause changes in the baseline responses of the polymer fiber(s). A system for monitoring the structural health of the structure is also provided.

Effect of bidispersity in grafted chain length on grafted chain conformations and potential of mean force between polymer grafted nanoparticles in a homopolymer matrix.

PubMed

Nair, Nitish; Wentzel, Nathaniel; Jayaraman, Arthi

2011-05-21

In efforts to produce polymeric materials with tailored physical properties, significant interest has grown around the ability to control the spatial organization of nanoparticles in polymer nanocomposites. One way to achieve controlled particle arrangement is by grafting the nanoparticle surface with polymers that are compatible with the matrix, thus manipulating the interfacial interactions between the nanoparticles and the polymer matrix. Previous work has shown that the molecular weight of the grafted polymer, both at high grafting density and low grafting density, plays a key role in dictating the effective inter-particle interactions in a polymer matrix. At high grafting density nanoparticles disperse (aggregate) if the graft molecular weight is higher (lower) than the matrix molecular weight. At low grafting density the longer grafts can better shield the nanoparticle surface from direct particle-particle contacts than the shorter grafts and lead to the dispersion of the grafted particles in the matrix. Despite the importance of graft molecular weight, and evidence of non-trivial effects of polydispersity of chains grafted on flat surfaces, most theoretical work on polymer grafted nanoparticles has only focused on monodisperse grafted chains. In this paper, we focus on how bidispersity in grafted chain lengths affects the grafted chain conformations and inter-particle interactions in an implicit solvent and in a dense homopolymer polymer matrix. We first present the effects of bidispersity on grafted chain conformations in a single polymer grafted particle using purely Monte Carlo (MC) simulations. This is followed by calculations of the potential of mean force (PMF) between two grafted particles in a polymer matrix using a self-consistent Polymer Reference Interaction Site Model theory-Monte Carlo simulation approach. Monte Carlo simulations of a single polymer grafted particle in an implicit solvent show that in the bidisperse polymer grafted particles with an equal number of short and long grafts at low to medium grafting density, the short grafts are in a more coiled up conformation (lower radius of gyration) than their monodisperse counterparts to provide a larger free volume to the longer grafts so they can gain conformational entropy. The longer grafts do not show much difference in conformation from their monodisperse counterparts at low grafting density, but at medium grafting density the longer grafts exhibit less stretched conformations (lower radius of gyration) as compared to their monodisperse counterparts. In the presence of an explicit homopolymer matrix, the longer grafts are more compressed by the matrix homopolymer chains than the short grafts. We observe that the potential of mean force between bidisperse grafted particles has features of the PMF of monodisperse grafted particles with short grafts and monodisperse grafted particles with long grafts. The value of the PMF at contact is governed by the short grafts and values at large inter-particle distances are governed by the longer grafts. Further comparison of the PMF for bidisperse and monodisperse polymer grafted particles in a homopolymer matrix at varying parameters shows that the effects of matrix chain length, matrix packing fraction, grafting density, and particle curvature on the PMF between bidisperse polymer grafted particles are similar to those seen between monodisperse polymer grafted particles. © 2011 American Institute of Physics.

Environmental stress cracking of polymers

NASA Technical Reports Server (NTRS)

Mahan, K. I.

1980-01-01

A two point bending method for use in studying the environmental stress cracking and crazing phenomena is described and demonstrated for a variety of polymer/solvent systems. Critical strain values obtained from these curves are reported for various polymer/solvent systems including a considerable number of systems for which critical strain values have not been previously reported. Polymers studied using this technique include polycarbonate (PC), ABS, high impact styrene (HIS), polyphenylene oxide (PPO), and polymethyl methacrylate (PMMA). Critical strain values obtained using this method compared favorably with available existing data. The major advantage of the technique is the ability to obtain time vs. strain curves over a short period of time. The data obtained suggests that over a short period of time the transition in most of the polymer solvent systems is more gradual than previously believed.

Interaction of poly(ethylene-glycols) with air-water interfaces and lipid monolayers: investigations on surface pressure and surface potential.

PubMed Central

Winterhalter, M; Bürner, H; Marzinka, S; Benz, R; Kasianowicz, J J

1995-01-01

We have characterized the surface activity of different-sized poly(ethylene-glycols) (PEG; M(r) 200-100,000 Da) in the presence or absence of lipid monolayers and over a wide range of bulk PEG concentrations (10(-8)-10% w/v). Measurements of the surface potential and surface pressure demonstrate that PEGs interact with the air-water and lipid-water interfaces. Without lipid, PEG added either to the subphase or to the air-water interface forms relatively stable monolayers. Except for very low molecular weight polymers (PEGs < 1000 Da), low concentrations of PEG in the subphase (between 10(-5) and 10(-4)% w/v) increase the surface potential from zero (with respect to the potential of a pure air-water interface) to a plateau value of approximately 440 mV. At much higher polymer concentrations, > 10(-1)% (w/v), depending on the molecular weight of the PEG and corresponding to the concentration at which the polymers in solution are likely to overlap, the surface potential decreases. High concentrations of PEG in the subphase cause a similar decrease in the surface potential of densely packed lipid monolayers spread from either diphytanoyl phosphatidylcholine (DPhPC), dipalmitoyl phosphatidylcholine (DPPC), or dioleoyl phosphatidylserine (DOPS). Adding PEG as a monolayer at the air-water interface also affects the surface activity of DPhPC or DPPC monolayers. At low lipid concentration, the surface pressure and potential are determined by the polymer. For intermediate lipid concentrations, the surface pressure-area and surface potential-area isotherms show that the effects due to lipid and PEG are not always additive and that the polymer's effect is distinct for the two lipids. When PEG-lipid-mixed monolayers are compressed to surface pressures greater than the collapse pressure for a PEG monolayer, the surface pressure-area and surface potential-area isotherms approach that of the lipid alone, suggesting that for this experimental condition PEG is expelled from the interface. PMID:8534807

Compositions, methods, and systems comprising fluorous-soluble polymers

DOEpatents

Swager, Timothy M.; Lim, Jeewoo; Takeda, Yohei

2015-10-13

The present invention generally relates to compositions, methods, and systems comprising polymers that are fluorous-soluble and/or organize at interfaces between a fluorous phase and a non-fluorous phase. In some embodiments, emulsions or films are provided comprising a polymer. The polymers, emulsions, and films can be used in many applications, including for determining, treating, and/or imaging a condition and/or disease in a subject. The polymer may also be incorporated into various optoelectronic device such as photovoltaic cells, organic light-emitting diodes, organic field effect transistors, or the like. In some embodiments, the polymers comprise pi-conjugated backbones, and in some cases, are highly emissive.

Constitutive Modeling of Nanotube-Reinforced Polymer Composite Systems

NASA Technical Reports Server (NTRS)

Odegard, Gregory M.; Harik, Vasyl M.; Wise, Kristopher E.; Gates, Thomas S.

2004-01-01

In this study, a technique has been proposed for developing constitutive models for polymer composite systems reinforced with single-walled carbon nanotubes (SWNT). Since the polymer molecules are on the same size scale as the nanotubes, the interaction at the polymer/nanotube interface is highly dependent on the local molecular structure and bonding. At these small length scales, the lattice structures of the nanotube and polymer chains cannot be considered continuous, and the bulk mechanical properties of the SWNT/polymer composites can no longer be determined through traditional micromechanical approaches that are formulated using continuum mechanics. It is proposed herein that the nanotube, the local polymer near the nanotube, and the nanotube/polymer interface can be modeled as an effective continuum fiber using an equivalent-continuum modeling method. The effective fiber retains the local molecular structure and bonding information and serves as a means for incorporating micromechanical analyses for the prediction of bulk mechanical properties of SWNT/polymer composites with various nanotube sizes and orientations. As an example, the proposed approach is used for the constitutive modeling of two SWNT/polyethylene composite systems, one with continuous and aligned SWNT and the other with discontinuous and randomly aligned nanotubes.

Constitutive Modeling of Nanotube-Reinforced Polymer Composite Systems

NASA Technical Reports Server (NTRS)

Odegard, Gregory M.; Harik, Vasyl M.; Wise, Kristopher E.; Gates, Thomas S.

2001-01-01

In this study, a technique has been proposed for developing constitutive models for polymer composite systems reinforced with single-walled carbon nanotubes (SWNT). Since the polymer molecules are on the same size scale as the nanotubes, the interaction at the polymer/nanotube interface is highly dependent on the local molecular structure and bonding. At these small length scales, the lattice structures of the nanotube and polymer chains cannot be considered continuous, and the bulk mechanical properties of the SWNT/polymer composites can no longer be determined through traditional micromechanical approaches that are formulated using continuum mechanics. It is proposed herein that the nanotube, the local polymer near the nanotube, and the nanotube/polymer interface can be modeled as an effective continuum fiber using an equivalent-continuum modeling method. The effective fiber retains the local molecular structure and bonding information and serves as a means for incorporating micromechanical analyses for the prediction of bulk mechanical properties of SWNT/polymer composites with various nanotube sizes and orientations. As an example, the proposed approach is used for the constitutive modeling of two SWNT/polyethylene composite systems, one with continuous and aligned SWNT and the other with discontinuous and randomly aligned nanotubes.

A concise review on smart polymers for controlled drug release.

PubMed

Aghabegi Moghanjoughi, Arezou; Khoshnevis, Dorna; Zarrabi, Ali

2016-06-01

Design and synthesis of efficient drug delivery systems are of critical importance in health care management. Innovations in materials chemistry especially in polymer field allows introduction of advanced drug delivery systems since polymers could provide controlled release of drugs in predetermined doses over long periods, cyclic and tunable dosages. To this end, researchers have taken advantages of smart polymers since they can undergo large reversible, chemical, or physical fluctuations as responses to small changes in environmental conditions, for instance, in pH, temperature, light, and phase transition. The present review aims to highlight various kinds of smart polymers, which are used in controlled drug delivery systems as well as mechanisms of action and their applications.

Polymer Energy Rechargeable System Battery Being Developed

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

2003-01-01

Long description. Illustrations of discotic liquid crystals, rod-coil polymers, lithium-ion conducting channel dilithium phthalocyanine (Li2Pc) from top and side, novel star polyethylene oxide structures, composite polyethylene oxide materials (showing polyethylene oxide + lithium salt, carbon atoms and oxygen atoms), homopolyrotaxanes, and diblock copolymers In fiscal year 2000, NASA established a program to develop the next generation, lithium-based, polymer electrolyte batteries for aerospace applications. The goal of this program, known as Polymer Energy Rechargeable Systems (PERS), is to develop a space-qualified, advanced battery system embodying polymer electrolyte and lithium-based electrode technologies and to establish world-class domestic manufacturing capabilities for advanced batteries with improved performance characteristics that address NASA s future aerospace battery requirements.

Single-shot mega-electronvolt ultrafast electron diffraction for structure dynamic studies of warm dense matter

NASA Astrophysics Data System (ADS)

Mo, M. Z.; Shen, X.; Chen, Z.; Li, R. K.; Dunning, M.; Sokolowski-Tinten, K.; Zheng, Q.; Weathersby, S. P.; Reid, A. H.; Coffee, R.; Makasyuk, I.; Edstrom, S.; McCormick, D.; Jobe, K.; Hast, C.; Glenzer, S. H.; Wang, X.

2016-11-01

We have developed a single-shot mega-electronvolt ultrafast-electron-diffraction system to measure the structural dynamics of warm dense matter. The electron probe in this system is featured by a kinetic energy of 3.2 MeV and a total charge of 20 fC, with the FWHM pulse duration and spot size at sample of 350 fs and 120 μm respectively. We demonstrate its unique capability by visualizing the atomic structural changes of warm dense gold formed from a laser-excited 35-nm freestanding single-crystal gold foil. The temporal evolution of the Bragg peak intensity and of the liquid signal during solid-liquid phase transition are quantitatively determined. This experimental capability opens up an exciting opportunity to unravel the atomic dynamics of structural phase transitions in warm dense matter regime.

Revisiting structure-property relationship of pH-responsive polymers for drug delivery applications.

PubMed

Bazban-Shotorbani, Salime; Hasani-Sadrabadi, Mohammad Mahdi; Karkhaneh, Akbar; Serpooshan, Vahid; Jacob, Karl I; Moshaverinia, Alireza; Mahmoudi, Morteza

2017-05-10

pH-responsive polymers contain ionic functional groups as pendants in their structure. The total number of charged groups on polymer chains determines the overall response of the system to changes in the external pH. This article reviews various pH-responsive polymers classified as polyacids (e.g., carboxylic acid based polymers, sulfonamides, anionic polysaccharides, and anionic polypeptides) and polybases (e.g., polyamines, pyridine and imidazole containing polymers, cationic polysaccharides, and cationic polypeptides). We correlate the pH variations in the body at the organ level (e.g., gastrointestinal tract and vaginal environment), tissue level (e.g., cancerous and inflamed tissues), and cellular level (e.g., sub-cellular organelles), with the intrinsic properties of pH-responsive polymers. This knowledge could help to select more effective ('smart') polymeric systems based on the biological target. Considering the pH differences in the body, various drug delivery systems can be designed by utilizing smart biopolymeric compounds with the required pH-sensitivity. We also review the pharmaceutical application of pH-responsive polymeric carriers including hydrogels, polymer-drug conjugates, micelles, dendrimers, and polymersomes. © 2016.

Functional polymers as therapeutic agents: concept to market place.

PubMed

Dhal, Pradeep K; Polomoscanik, Steven C; Avila, Louis Z; Holmes-Farley, S Randall; Miller, Robert J

2009-11-12

Biologically active synthetic polymers have received considerable scientific interest and attention in recent years for their potential as promising novel therapeutic agents to treat human diseases. Although a significant amount of research has been carried out involving polymer-linked drugs as targeted and sustained release drug delivery systems and prodrugs, examples on bioactive polymers that exhibit intrinsic therapeutic properties are relatively less. Several appealing characteristics of synthetic polymers including high molecular weight, molecular architecture, and controlled polydispersity can all be utilized to discover a new generation of therapies. For example, high molecular weight bioactive polymers can be restricted to gastrointestinal tract, where they can selectively recognize, bind, and remove target disease causing substances from the body. The appealing features of GI tract restriction and stability in biological environment render these polymeric drugs to be devoid of systemic toxicity that are generally associated with small molecule systemic drugs. The present article highlights recent developments in the rational design and synthesis of appropriate functional polymers that have resulted in a number of promising polymer based therapies and biomaterials, including some marketed products.

Thiol-vinyl systems as shape memory polymers and novel two-stage reactive polymer systems

NASA Astrophysics Data System (ADS)

Nair, Devatha P.

2011-12-01

The focus of this research was to formulate, characterize and tailor the reaction methodologies and material properties of thiol-vinyl systems to develop novel polymer platforms for a range of engineering applications. Thiol-ene photopolymers were demonstrated to exhibit several advantageous characteristics for shape memory polymer systems for a range of biomedical applications. The thiol-ene shape memory polymer systems were tough and flexible as compared to the acrylic control systems with glass transition temperatures between 30 and 40 °C; ideal for actuation at body temperature. The thiol-ene polymers also exhibited excellent shape fixity and a rapid and distinct shape memory actuation response along with free strain recoveries of greater than 96% and constrained stress recoveries of 100%. Additionally, two-stage reactive thiol-acrylate systems were engineered as a polymer platform technology enabling two independent sets of polymer processing and material properties. There are distinct advantages to designing polymer systems that afford two distinct sets of material properties -- an intermediate polymer that would enable optimum handling and processing of the material (stage 1), while maintaining the ability to tune in different, final properties that enable the optimal functioning of the polymeric material (stage 2). To demonstrate the range of applicability of the two-stage reactive systems, three specific applications were demonstrated; shape memory polymers, lithographic impression materials, and optical materials. The thiol-acrylate reactions exhibit a wide range of application versatility due to the range of available thiol and acrylate monomers as well as reaction mechanisms such as Michael Addition reactions and free radical polymerizations. By designing a series of non-stoichiometeric thiol-acrylate systems, a polymer network is initially formed via a base catalyzed 'click' Michael addition reaction. This self-limiting reaction results in a Stage 1 polymer with excess acrylic functional groups within the network. At a later point in time, the photoinitiated, free radical polymerization of the excess acrylic functional groups results in a highly crosslinked, robust material system. By varying the monomers within the system as well as the stoichiometery of thiol to acrylate functional groups, the ability of the two-stage reactive systems to encompass a wide range of properties at the end of both the stage 1 and stage 2 polymerizations was demonstrated. The thiol-acrylate networks exhibited intermediate Stage 1 rubbery moduli and glass transition temperatures that range from 0.5 MPa and -10 ºC to 22 MPa and 22 ºC respectively. The same polymer networks can then attain glass transition temperatures that range from 5 ºC to 195 ºC and rubbery moduli of up to 200 MPa after the subsequent photocure stage. Two-stage reactive polymer composite systems were also formulated and characterized for thermomechanical and mechanical properties. Thermomechanical analysis showed that the fillers resulted in a significant increase in the modulus at both stage 1 and stage 2 polymerizations without a significant change in the glass transition temperatures (Tg). The two-stage reactive matrix composite formed with a hexafunctional acrylate matrix and 20 volume % silica particles showed a 125% increase in stage 1 modulus and 101% increase in stage 2 modulus, when compared with the modulus of the neat matrix. Finally, the two-stage reactive polymeric devices were formulated and designed as orthopedic suture anchors for arthroscopic surgeries and mechanically characterized. The Stage 1 device was designed to exhibit properties ideal for arthroscopic delivery and device placement with glass transition temperatures 25 -- 30 °C and rubbery moduli ˜ 95 MPa. The subsequent photopolymerization generated Stage 2 polymers designed to match the local bone environment with moduli ranging up to 2 GPa. Additionally, pull-out strengths of 140 N were demonstrated and are equivalent to the pull-strengths achieved by other commercially available suture anchors.

In situ synthesis of metal nanoparticles in polymer matrix and their optical limiting applications.

PubMed

Porel, S; Venkatram, N; Rao, D Narayana; Radhakrishnan, T P

2007-06-01

We present an overview of the simple and environmentally benign protocol we have developed recently, for the in situ generation of metal nanoparticles inside polymer films by mild thermal annealing, leading to free-standing as well as supported thin films of nanoparticle-embedded polymer. The fabrication chemistry is discussed and spectroscopic/microscopic characterizations of silver and gold nanoparticles in poly(vinyl alcohol) film are presented. Optical limiting characteristics of the silver-polymer system are investigated in detail and preliminary results for the gold-polymer system are reported.

Effects of Phase Separation Behavior on Morphology and Performance of Polycarbonate Membranes

PubMed Central

Idris, Alamin; Man, Zakaria; Maulud, Abdulhalim S.; Khan, Muhammad Saad

2017-01-01

The phase separation behavior of bisphenol-A-polycarbonate (PC), dissolved in N-methyl-2-pyrrolidone and dichloromethane solvents in coagulant water, was studied by the cloud point method. The respective cloud point data were determined by titration against water at room temperature and the characteristic binodal curves for the ternary systems were plotted. Further, the physical properties such as viscosity, refractive index, and density of the solution were measured. The critical polymer concentrations were determined from the viscosity measurements. PC/NMP and PC/DCM membranes were fabricated by the dry-wet phase inversion technique and characterized for their morphology, structure, and thermal stability using field emission scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis, respectively. The membranes’ performances were tested for their permeance to CO2, CH4, and N2 gases at 24 ± 0.5 °C with varying feed pressures from 2 to 10 bar. The PC/DCM membranes appeared to be asymmetric dense membrane types with appreciable thermal stability, whereas the PC/NMP membranes were observed to be asymmetric with porous structures exhibiting 4.18% and 9.17% decrease in the initial and maximum degradation temperatures, respectively. The ideal CO2/N2 and CO2/CH4 selectivities of the PC/NMP membrane decreased with the increase in feed pressures, while for the PC/DCM membrane, the average ideal CO2/N2 and CO2/CH4 selectivities were found to be 25.1 ± 0.8 and 21.1 ± 0.6, respectively. Therefore, the PC/DCM membranes with dense morphologies are appropriate for gas separation applications. PMID:28379173

Low-cost Electromagnetic Heating Technology for Polymer Extrusion-based Additive Manufacturing

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

Carter, William G.; Rios, Orlando; Akers, Ronald R.

To improve the flow of materials used in in polymer additive manufacturing, ORNL and Ajax Tocco created an induction system for heating fused deposition modeling (FDM) nozzles used in polymer additive manufacturing. The system is capable of reaching a temperature of 230 C, a typical nozzle temperature for extruding ABS polymers, in 17 seconds. A prototype system was built at ORNL and sent to Ajax Tocco who analyzed the system and created a finalized power supply. The induction system was mounted to a PrintSpace Altair desktop printer and used to create several test parts similar in quality to those createdmore » using a resistive heated nozzle.« less

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

PubMed

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

2016-04-01

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

Interpenetrating Polymer Networks as Innovative Drug Delivery Systems

PubMed Central

Lohani, Alka; Singh, Garima; Bhattacharya, Shiv Sankar; Verma, Anurag

2014-01-01

Polymers have always been valuable excipients in conventional dosage forms, also have shown excellent performance into the parenteral arena, and are now capable of offering advanced and sophisticated functions such as controlled drug release and drug targeting. Advances in polymer science have led to the development of several novel drug delivery systems. Interpenetrating polymer networks (IPNs) have shown superior performances over the conventional individual polymers and, consequently, the ranges of applications have grown rapidly for such class of materials. The advanced properties of IPNs like swelling capacity, stability, biocompatibility, nontoxicity and biodegradability have attracted considerable attention in pharmaceutical field especially in delivering bioactive molecules to the target site. In the past few years various research reports on the IPN based delivery systems showed that these carriers have emerged as a novel carrier in controlled drug delivery. The present review encompasses IPNs, their types, method of synthesis, factors which affects the morphology of IPNs, extensively studied IPN based drug delivery systems, and some natural polymers widely used for IPNs. PMID:24949205

Development of anti-scale poly(aspartic acid-citric acid) dual polymer systems for water treatment.

PubMed

Nayunigari, Mithil Kumar; Gupta, Sanjay Kumar; Kokkarachedu, Varaprasad; Kanny, K; Bux, F

2014-01-01

The formation of calcium sulphate and calcium carbonate scale poses major problems in heat exchangers and water cooling systems, thereby affecting the performance of these types of equipment. In order to inhibit these scale formations, new types of biodegradable water soluble single polymer and dual poly(aspartic acid-citric acid) polymers were developed and tested. The effectiveness of single polymer and four different compositions of poly aspartic acid and citric acid dual polymer systems as scale inhibitors were evaluated. Details of the synthesis, thermal stability, scale inhibition and the morphological characterization of single and dual polymers are presented in this scientific paper. It was found that the calcium sulphate scale inhibition rate was in the range 76.06-91.45%, while the calcium carbonate scale inhibition rate observed was in the range 23.37-30.0% at 65-70 °C. The finding suggests that the water soluble dual polymers are very effective in sulphate scale inhibition in comparison of calcium carbonate scale inhibition.

Effect of blending and nanoparticles on the ionic conductivity of solid polymer electrolyte systems

NASA Astrophysics Data System (ADS)

Manjunatha, H.; Damle, R.; Kumaraswamy, G. N.

2018-05-01

In the present work, a polymer electrolyte blend containing polymers Poly ethylene oxide (PEO) and Poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) was prepared. The polymer blend was complexed with potassium trifluoromethanesulfonate (KCF3SO3), and titanium oxide nanoparticles (TiO2) (10nm size) were dispersed in to the complex at different weight percentages. The conductivity due to ions in the blend is determined by Ac impedance measurements in the frequency range of 10Hz-1MHz. The nano composite polymer blend containing 5wt% of TiO2 shows a conductivity of 7.95×10-5Scm-1, which is almost 1.5 orders more than polymer electrolyte with PEO as a polymer. XRD studies show a decrease in the coherence length of XRD peaks on addition of nanoparticles, which is due to increase the amorphous phase in the systems. Temperature dependence conductivity studies of the systems shows that, activation energy decreases with increase in the percentage of nanoparticles in the blend.

UV-cured polymer optics

NASA Astrophysics Data System (ADS)

Piñón, Victor; Santiago, Freddie; Vogelsberg, Ashten; Davenport, Amelia; Cramer, Neil

2017-10-01

Although many optical-quality glass materials are available for use in optical systems, the range of polymeric materials is limited. Polymeric materials have some advantages over glass when it comes to large-scale manufacturing and production. In smaller scale systems, they offer a reduction in weight when compared to glass counterparts. This is especially important when designing optical systems meant to be carried by hand. We aimed to expand the availability of polymeric materials by exploring both crown-like and flint-like polymers. In addition, rapid and facile production was also a goal. By using UV-cured thiolene-based polymers, we were able to produce optical materials within seconds. This enabled the rapid screening of a variety of polymers from which we down-selected to produce optical flats and lenses. We will discuss problems with production and mitigation strategies in using UV-cured polymers for optical components. Using UV-cured polymers present a different set of problems than traditional injection-molded polymers, and these issues are discussed in detail. Using these produced optics, we integrated them into a modified direct view optical system, with the end goal being the development of drop-in replacements for glass components. This optical production strategy shows promise for use in lab-scale systems, where low-cost methods and flexibility are of paramount importance.

An in-situ infection detection sensor coating for urinary catheters

PubMed Central

Milo, Scarlet; Thet, Naing Tun; Liu, Dan; Nzakizwanayo, Jonathan; Jones, Brian V.; Jenkins, A. Toby A.

2016-01-01

We describe a novel infection-responsive coating for urinary catheters that provides a clear visual early warning of Proteus mirabilis infection and subsequent blockage. The crystalline biofilms of P. mirabilis can cause serious complications for patients undergoing long-term bladder catheterisation. Healthy urine is around pH 6, bacterial urease increases urine pH leading to the precipitation of calcium and magnesium deposits from the urine, resulting in dense crystalline biofilms on the catheter surface that blocks urine flow. The coating is a dual layered system in which the lower poly(vinyl alcohol) layer contains the self-quenching dye carboxyfluorescein. This is capped by an upper layer of the pH responsive polymer poly(methyl methacrylate-co-methacrylic acid) (Eudragit S100®). Elevation of urinary pH (>pH 7) dissolves the Eudragit layer, releasing the dye to provide a clear visual warning of impending blockage. Evaluation of prototype coatings using a clinically relevant in vitro bladder model system demonstrated that coatings provide up to 12 h advanced warning of blockage, and are stable both in the absence of infection, and in the presence of species that do not cause catheter blockage. At the present time, there are no effective methods to control these infections or provide warning of impending catheter blockage. PMID:26945183

Efficient sparse matrix-matrix multiplication for computing periodic responses by shooting method on Intel Xeon Phi

NASA Astrophysics Data System (ADS)

Stoykov, S.; Atanassov, E.; Margenov, S.

2016-10-01

Many of the scientific applications involve sparse or dense matrix operations, such as solving linear systems, matrix-matrix products, eigensolvers, etc. In what concerns structural nonlinear dynamics, the computations of periodic responses and the determination of stability of the solution are of primary interest. Shooting method iswidely used for obtaining periodic responses of nonlinear systems. The method involves simultaneously operations with sparse and dense matrices. One of the computationally expensive operations in the method is multiplication of sparse by dense matrices. In the current work, a new algorithm for sparse matrix by dense matrix products is presented. The algorithm takes into account the structure of the sparse matrix, which is obtained by space discretization of the nonlinear Mindlin's plate equation of motion by the finite element method. The algorithm is developed to use the vector engine of Intel Xeon Phi coprocessors. It is compared with the standard sparse matrix by dense matrix algorithm and the one developed by Intel MKL and it is shown that by considering the properties of the sparse matrix better algorithms can be developed.

Influence of Lipid Membrane Rigidity on Properties of Supporting Polymer

PubMed Central

Jablin, Michael S.; Dubey, Manish; Zhernenkov, Mikhail; Toomey, Ryan; Majewski, Jarosław

2011-01-01

Temperature-sensitive hydrogel polymers are utilized as responsive layers in various applications. Although the polymer's native characteristics have been studied extensively, details concerning its properties during interaction with biorelated structures are lacking. This work investigates the interaction between a thermoresponsive polymer cushion and different lipid membrane capping layers probed by neutron reflectometry. N-isopropylacrylamide copolymerized with methacroylbenzophenone first supported a lipid bilayer composed of 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) and subsequently 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). The polymer-membrane systems were investigated above and below the polymer transition temperature (37 and 25°C). Although the same cushion supported each lipid membrane, the polymer hydration profile and thickness were markedly different for DPPE and DPPC systems. Because DPPE and DPPC have different bending rigidities, these results establish that the polymer-membrane interaction is critically mediated by the mechanics of the membrane, providing better insight into cell-hydrogel interactions. PMID:21723822

Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

PubMed

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

2016-01-11

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

Low density microcellular foams

DOEpatents

Aubert, J.H.; Clough, R.L.; Curro, J.G.; Quintana, C.A.; Russick, E.M.; Shaw, M.T.

1985-10-02

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the reusltant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 ..mu..m and a volume such that the foams have a length greater than 1 cm are provided.

Cell specific, variable density, polymer microspheres

NASA Technical Reports Server (NTRS)

Yen, Shiao-Ping S. (Inventor); Rembaum, Alan (Inventor); Molday, Robert S. (Inventor)

1978-01-01

Biocompatible polymeric microspheres having an average diameter below about 3 microns and having a density at least 15% greater or lesser than organic cells and having covalent binding sites are provided in accordance with this invention. The microspheres are obtained by copolymerizing a hydroxy or amine substituted acrylic monomer such as hydroxyethylmethacrylate with a light or dense comonomer such as a fluoromonomer. A lectin or antibody is bound to the hydroxy or amine site of the bead to provide cell specificity. When added to a cell suspension the marked bead will specifically label the cell membrane by binding to specific receptor sites thereon. The labelled membrane can then be separated by density gradient centrifugation.

Weak correlations between local density and dynamics near the glass transition.

PubMed

Conrad, J C; Starr, F W; Weitz, D A

2005-11-17

We perform experiments on two different dense colloidal suspensions with confocal microscopy to probe the relationship between local structure and dynamics near the glass transition. We calculate the Voronoi volume for our particles and show that this quantity is not a universal probe of glassy structure for all colloidal suspensions. We correlate the Voronoi volume to displacement and find that these quantities are only weakly correlated. We observe qualitatively similar results in a simulation of a polymer melt. These results suggest that the Voronoi volume does not predict dynamical behavior in experimental colloidal suspensions; a purely structural approach based on local single particle volume likely cannot describe the colloidal glass transition.

Effect of formulation and processing variables on the characteristics of microspheres for water-soluble drugs prepared by w/o/o double emulsion solvent diffusion method.

PubMed

Lee, J; Park, T G; Choi, H

2000-02-25

80% except for acetaminophen, due to its lower solubility in water and higher solubility in corn oil. The release profile of the drug was pH dependent. In acidic medium, the release rate was much slower, however, the drug was released quickly at pH 7.4. Tacrine showed unexpected release profiles, probably due to ionic interaction with polymer matrix and the shell structure and the highest release rate was obtained at pH 2.0. The prepared microspheres had a sponge-like inner structure with or without central hollow core and the surface was dense with no apparent pores.

Controlling the degradation kinetics of porous iron by poly(lactic-co-glycolic acid) infiltration for use as temporary medical implants

PubMed Central

Yusop, Abdul Hakim Md; Daud, Nurizzati Mohd; Nur, Hadi; Kadir, Mohammed Rafiq Abdul; Hermawan, Hendra

2015-01-01

Iron and its alloy have been proposed as biodegradable metals for temporary medical implants. However, the formation of iron oxide and iron phosphate on their surface slows down their degradation kinetics in both in vitro and in vivo scenarios. This work presents new approach to tailor degradation behavior of iron by incorporating biodegradable polymers into the metal. Porous pure iron (PPI) was vacuum infiltrated by poly(lactic-co-glycolic acid) (PLGA) to form fully dense PLGA-infiltrated porous iron (PIPI) and dip coated into the PLGA to form partially dense PLGA-coated porous iron (PCPI). Results showed that compressive strength and toughness of the PIPI and PCPI were higher compared to PPI. A strong interfacial interaction was developed between the PLGA layer and the iron surface. Degradation rate of PIPI and PCPI was higher than that of PPI due to the effect of PLGA hydrolysis. The fast degradation of PIPI did not affect the viability of human fibroblast cells. Finally, this work discusses a degradation mechanism for PIPI and the effect of PLGA incorporation in accelerating the degradation of iron. PMID:26057073

Thermosensitive behavior of poly(ethylene glycol)-based block copolymer (PEG-b-PADMO) controlled via self-assembled microstructure.

PubMed

Cui, Qianling; Wu, Feipeng; Wang, Erjian

2011-05-19

Stimuli-responsive, well-defined diblock copolymers (PEG-b-PADMO) comprising poly(ethylene glycol) (PEG, DP (degree of polymerization)=45) as the hydrophilic and temperature-sensitive part and poly(N-acryloyl-2,2-dimethyl-1,3-oxazolidine) (PADMO, DP=18-47) as the hydrophobic and acid-labile part self-assembled in water into spherical micelles with high aggregation number. The micellar structures and thermally induced phase transitions of the copolymers were investigated with (1)H NMR spectroscopy, light scattering, microscopy, turbidimetry, and fluorescence techniques. Thermoresponsive phase transitions of the copolymers in water were controlled via formation of core-shell-type micelles with densely compact PEG corona. Their lower critical solution temperatures (LCSTs) were modulated within the range 40-72 °C by varying PADMO block length. This unusually low LCST was attributed to the densely packed PEG structure in the polymer micelles, which resulted in strong n-clustering attractive interactions and insufficient hydration of PEG chains in the shell and greatly enhanced the thermosensitivity. The LCST behavior can also be modulated by partial acid hydrolysis of PADMO segments through the resulting change of hydrophobicity. © 2011 American Chemical Society

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

PubMed

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

2017-09-15

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

Innovative hybrid optics: combining the thermal stability of glass with low manufacturing cost of polymers

NASA Astrophysics Data System (ADS)

Doushkina, Valentina

2010-08-01

Innovative hybrid glass-polymer optical solutions on a component, module, or system level offer thermal stability of glass with low manufacturing cost of polymers reducing component weight, enhancing the safety and appeal of the products. Narrow choice of polymer materials is compensated by utilizing sophisticated optical surfaces such as refractive, reflective, and diffractive substrates with spherical, aspherical, cylindrical, and freeform prescriptions. Current advancements in polymer technology and injection molding capabilities placed polymer optics in the heart of many high tech devices and applications including Automotive Industry, Defense & Aerospace; Medical/Bio Science; Projection Displays, Sensors, Information Technology, Commercial and Industrial. This paper is about integration of polymer and glass optics for enhanced optical performance with reduced number of components, thermal stability, and low manufacturing cost. The listed advantages are not achievable when polymers or glass optics are used as stand-alone. The author demonstrates that integration of polymer and glass on component or optical system level on one hand offers high resolution and diffraction limited image quality, similar to the glass optics with stable refractive index and stable thermal performance when design is athermalized within the temperature range. On the other hand, the integrated hybrid solution significantly reduces cost, weight, and complexity, just like the polymer optics. The author will describe the design and analyzes process of combining glass and polymer optics for variety of challenging applications such as fast optics with low F/#, wide field of view lenses or systems, free form optics, etc.

Investigation of Alien Wavelength Quality in Live Multi-Domain, Multi-Vendor Link Using Advanced Simulation Tool

NASA Astrophysics Data System (ADS)

Nordal Petersen, Martin; Nuijts, Roeland; Lange Bjørn, Lars

2014-05-01

This article presents an advanced optical model for simulation of alien wavelengths in multi-domain and multi-vendor dense wavelength-division multiplexing networks. The model aids optical network planners with a better understanding of the non-linear effects present in dense wavelength-division multiplexing systems and better utilization of alien wavelengths in future applications. The limiting physical effects for alien wavelengths are investigated in relation to power levels, channel spacing, and other factors. The simulation results are verified through experimental setup in live multi-domain dense wavelength-division multiplexing systems between two national research networks: SURFnet in Holland and NORDUnet in Denmark.

Performance optimization of dense-array concentrator photovoltaic system considering effects of circumsolar radiation and slope error.

PubMed

Wong, Chee-Woon; Chong, Kok-Keong; Tan, Ming-Hui

2015-07-27

This paper presents an approach to optimize the electrical performance of dense-array concentrator photovoltaic system comprised of non-imaging dish concentrator by considering the circumsolar radiation and slope error effects. Based on the simulated flux distribution, a systematic methodology to optimize the layout configuration of solar cells interconnection circuit in dense array concentrator photovoltaic module has been proposed by minimizing the current mismatch caused by non-uniformity of concentrated sunlight. An optimized layout of interconnection solar cells circuit with minimum electrical power loss of 6.5% can be achieved by minimizing the effects of both circumsolar radiation and slope error.

Single-shot mega-electronvolt ultrafast electron diffraction for structure dynamic studies of warm dense matter

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

Mo, M. Z., E-mail: mmo09@slac.stanford.edu; Shen, X.; Chen, Z.

We have developed a single-shot mega-electronvolt ultrafast-electron-diffraction system to measure the structural dynamics of warm dense matter. The electron probe in this system is featured by a kinetic energy of 3.2 MeV and a total charge of 20 fC, with the FWHM pulse duration and spot size at sample of 350 fs and 120 μm respectively. We demonstrate its unique capability by visualizing the atomic structural changes of warm dense gold formed from a laser-excited 35-nm freestanding single-crystal gold foil. The temporal evolution of the Bragg peak intensity and of the liquid signal during solid-liquid phase transition are quantitatively determined.more » This experimental capability opens up an exciting opportunity to unravel the atomic dynamics of structural phase transitions in warm dense matter regime.« less

Single-shot mega-electronvolt ultrafast electron diffraction for structure dynamic studies of warm dense matter

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

Mo, M. Z.; Shen, X.; Chen, Z.

We have developed a single-shot mega-electronvolt ultrafast-electron-diffraction system to measure the structural dynamics of warm dense matter. The electron probe in this system is featured by a kinetic energy of 3.2 MeV and a total charge of 20 fC, with the FWHM pulse duration and spot size at sample of 350 fs and 120 µm respectively. We demonstrate its unique capability by visualizing the atomic structural changes of warm dense gold formed from a laser-excited 35-nm freestanding single-crystal gold foil. The temporal evolution of the Bragg peak intensity and of the liquid signal during solid-liquid phase transition are quantitatively determined.more » This experimental capability opens up an exciting opportunity to unravel the atomic dynamics of structural phase transitions in warm dense matter regime« less

Universal scaling laws of diffusion in two-dimensional granular liquids.

PubMed

Wang, Chen-Hung; Yu, Szu-Hsuan; Chen, Peilong

2015-06-01

We find, in a two-dimensional air table granular system, that the reduced diffusion constant D* and excess entropy S(2) follow two distinct scaling laws: D*∼e(S(2)*) for dense liquids and D∼e(3S(2)*) for dilute ones. The scaling for dense liquids is very similar to that for three-dimensional liquids proposed previously [M. Dzugutov, Nature (London) 381, 137 (1996); A. Samanta et al., Phys. Rev. Lett. 92, 145901 (2004)]. In the dilute regime, a power law [Y. Rosenfeld, J. Phys.: Condens. Matter 11, 5415 (1999)] also fits our data reasonably well. In our system, particles experience low air drag dissipation and interact with each others through embedded magnets. These near-conservative many-body interactions are responsible for the measured Gaussian velocity distribution functions and the scaling laws. The dominance of cage relaxations in dense liquids leads to the different scaling laws for dense and dilute regimes.

Single-shot mega-electronvolt ultrafast electron diffraction for structure dynamic studies of warm dense matter

DOE PAGES

Mo, M. Z.; Shen, X.; Chen, Z.; ...

2016-08-04

We have developed a single-shot mega-electronvolt ultrafast-electron-diffraction system to measure the structural dynamics of warm dense matter. The electron probe in this system is featured by a kinetic energy of 3.2 MeV and a total charge of 20 fC, with the FWHM pulse duration and spot size at sample of 350 fs and 120 µm respectively. We demonstrate its unique capability by visualizing the atomic structural changes of warm dense gold formed from a laser-excited 35-nm freestanding single-crystal gold foil. The temporal evolution of the Bragg peak intensity and of the liquid signal during solid-liquid phase transition are quantitatively determined.more » This experimental capability opens up an exciting opportunity to unravel the atomic dynamics of structural phase transitions in warm dense matter regime« less

Carboranylmethylene-substituted phosphazenes and polymers thereof

NASA Technical Reports Server (NTRS)

Allcock, H. R.; Scopelianos, A. G. (Inventor)

1984-01-01

Carboranylmethylene-substituted cyclophosphazenes are described which can be thermally polymerized into carboranylmethylene-substituted phosphazene polymers. The polymers are useful as thermally stable coatings. Also, due to the characteristics of these polymers in acting as a ligand for transition metals, metalocarboranylmethylene phosphazene polymers are described which can act as immobilized catalyst systems, and are electrically conductive and superconductive.

The support system of the firefighter's activity by detecting objects in smoke space

NASA Astrophysics Data System (ADS)

Sakai, Masaki; Aoki, Yoshimitsu; Takagi, Mikio

2005-12-01

In recent years, crisis management's response to terrorist attacks and natural disasters, as well as accelerating rescue operations has become an important issue. We aim to make a support system for firefighters using the application of various engineering techniques such as information technology and radar technology. In rescue operations, one of the biggest problems is that the view of firefighters is obstructed by dense smoke. One of the current measures against this condition is the use of search sticks, like a blind man walking in town. The most important task for firefighters is to understand inside situation of a space with dense smoke. Therefore, our system supports firefighters' activity by visualizing the space with dense smoke. First, we scan target space with dense smoke by using millimeter-wave radar combined with a gyro sensor. Then multiple directional scan data can be obtained, and we construct a 3D map from high-reflection point dataset using 3D image processing technologies (3D grouping and labeling processing). In this paper, we introduce our system and report the results of the experiment in the real smoke space situation and practical achievements.

Simulation Studies of LCST-like Phase Transitions in Elastin-like Polypeptides (ELPs) and Conjugates of ELP with Rigid Macromolecules

NASA Astrophysics Data System (ADS)

Condon, Joshua; Martin, Tyler; Jayaraman, Arthi

We use atomistic (AA) and coarse-grained (CG) molecular dynamics simulations to elucidate the thermodynamic driving forces governing lower critical solution temperature (LCST)-like phase transition exhibited by elastin-like peptides (ELPs) and conjugates of ELP with other macromolecules. In the AA simulations, we study ELP oligomers in explicit water, and mark the transition as the temperature at which they undergo a change in ``hydration'' state. While AA simulations are restricted to small systems of short ELPs and do not capture the chain aggregation observed in experiments of ELPs, they guide the phenomenological CG model development by highlighting the solvent induced polymer-polymer effective interactions with changing temperature. In the CG simulations, we capture the LCST polymer aggregation by increasing polymer-polymer effective attractive interactions in an implicit solvent. We examine the impact of conjugating a block of LCST polymer to another rigid unresponsive macromolecular block on the LCST-like transition. We find that when multiple LCST polymers are conjugated to a rigid polymer block, increased crowding of the LCST polymers shifts the onset of chain aggregation to smaller effective polymer-polymer attraction compared to the free LCST polymers. These simulation results provide guidance on the design of conjugated bio-mimetic thermoresponsive materials, and shape the fundamental understanding of the impact of polymer crowding on phase behavior in thermoresponsive LCST polymer systems.

75 FR 53277 - Notice of Workshop on Polymers for Photovoltaic Systems

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-31

... photovoltaic systems; testing, performance, and reliability of polymers in photovoltaic systems; impact of... mentioned topics; presentation of a NIST- developed accelerated aging and service life prediction...

Direct observation of single flexible polymers using single stranded DNA†

PubMed Central

Brockman, Christopher; Kim, Sun Ju

2012-01-01

Over the last 15 years, double stranded DNA (dsDNA) has been used as a model polymeric system for nearly all single polymer dynamics studies. However, dsDNA is a semiflexible polymer with markedly different molecular properties compared to flexible chains, including synthetic organic polymers. In this work, we report a new system for single polymer studies of flexible chains based on single stranded DNA (ssDNA). We developed a method to synthesize ssDNA for fluorescence microscopy based on rolling circle replication, which generates long strands (>65 kb) of ssDNA containing “designer” sequences, thereby preventing intramolecular base pair interactions. Polymers are synthesized to contain amine-modified bases randomly distributed along the backbone, which enables uniform labelling of polymer chains with a fluorescent dye to facilitate fluorescence microscopy and imaging. Using this approach, we synthesized ssDNA chains with long contour lengths (>30 μm) and relatively low dye loading ratios (~1 dye per 100 bases). In addition, we used epifluorescence microscopy to image single ssDNA polymer molecules stretching in flow in a microfluidic device. Overall, we anticipate that ssDNA will serve as a useful model system to probe the dynamics of polymeric materials at the molecular level. PMID:22956981

The Use of Polymer Design in Resorbable Colloids

NASA Astrophysics Data System (ADS)

Finne-Wistrand, Anna; Albertsson, Ann-Christine

2006-08-01

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

Observation of dynamic equilibrium cluster phase in nanoparticle-polymer system

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

Kumar, Sugam, E-mail: sugam@barc.gov.in; Mehan, S.; Aswal, V. K.

2016-05-23

Small-angle neutron scattering (SANS) and dynamic light scattering (DLS) have been used to investigate the existence of a cluster phase in a nanoparticle-polymer system. The nanoparticle-polymer system shows an interesting reentrant phase behavior where the charge stabilized silica nanoparticles undergo particle clustering and back to individual nanoparticles as a function of polymer concentration. This kind of phase behavior is believed to be directed by opposing attractive and repulsive interactions present in the system. The phase behavior shows two narrow regions of polymer concentration immediately before and after the two-phase formation indicating the possibility of the existence of some equilibrium clusters.more » DLS results show a much higher size of particles than individuals in these two regions which remains unchanged even after dilution. The SANS data show the evolution of attraction with increased volume fraction of the particles supporting the dynamic nature of these clusters.« less

A synthetic polymer system with repeatable chemical recyclability

NASA Astrophysics Data System (ADS)

Zhu, Jian-Bo; Watson, Eli M.; Tang, Jing; Chen, Eugene Y.-X.

2018-04-01

The development of chemically recyclable polymers offers a solution to the end-of-use issue of polymeric materials and provides a closed-loop approach toward a circular materials economy. However, polymers that can be easily and selectively depolymerized back to monomers typically require low-temperature polymerization methods and also lack physical properties and mechanical strengths required for practical uses. We introduce a polymer system based on γ-butyrolactone (GBL) with a trans-ring fusion at the α and β positions. Such trans-ring fusion renders the commonly considered as nonpolymerizable GBL ring readily polymerizable at room temperature under solvent-free conditions to yield a high–molecular weight polymer. The polymer has enhanced thermostability and can be repeatedly and quantitatively recycled back to its monomer by thermolysis or chemolysis. Mixing of the two enantiomers of the polymer generates a highly crystalline supramolecular stereocomplex.

Artificially Engineered Protein Polymers.

PubMed

Yang, Yun Jung; Holmberg, Angela L; Olsen, Bradley D

2017-06-07

Modern polymer science increasingly requires precise control over macromolecular structure and properties for engineering advanced materials and biomedical systems. The application of biological processes to design and synthesize artificial protein polymers offers a means for furthering macromolecular tunability, enabling polymers with dispersities of ∼1.0 and monomer-level sequence control. Taking inspiration from materials evolved in nature, scientists have created modular building blocks with simplified monomer sequences that replicate the function of natural systems. The corresponding protein engineering toolbox has enabled the systematic development of complex functional polymeric materials across areas as diverse as adhesives, responsive polymers, and medical materials. This review discusses the natural proteins that have inspired the development of key building blocks for protein polymer engineering and the function of these elements in material design. The prospects and progress for scalable commercialization of protein polymers are reviewed, discussing both technology needs and opportunities.

Dense range map reconstruction from a versatile robotic sensor system with an active trinocular vision and a passive binocular vision.

PubMed

Kim, Min Young; Lee, Hyunkee; Cho, Hyungsuck

2008-04-10

One major research issue associated with 3D perception by robotic systems is the creation of efficient sensor systems that can generate dense range maps reliably. A visual sensor system for robotic applications is developed that is inherently equipped with two types of sensor, an active trinocular vision and a passive stereo vision. Unlike in conventional active vision systems that use a large number of images with variations of projected patterns for dense range map acquisition or from conventional passive vision systems that work well on specific environments with sufficient feature information, a cooperative bidirectional sensor fusion method for this visual sensor system enables us to acquire a reliable dense range map using active and passive information simultaneously. The fusion algorithms are composed of two parts, one in which the passive stereo vision helps active vision and the other in which the active trinocular vision helps the passive one. The first part matches the laser patterns in stereo laser images with the help of intensity images; the second part utilizes an information fusion technique using the dynamic programming method in which image regions between laser patterns are matched pixel-by-pixel with help of the fusion results obtained in the first part. To determine how the proposed sensor system and fusion algorithms can work in real applications, the sensor system is implemented on a robotic system, and the proposed algorithms are applied. A series of experimental tests is performed for a variety of configurations of robot and environments. The performance of the sensor system is discussed in detail.

Adsorption and flocculation by polymers and polymer mixtures.

PubMed

Gregory, John; Barany, Sandor

2011-11-14

Polymers of various types are in widespread use as flocculants in several industries. In most cases, polymer adsorption is an essential prerequisite for flocculation and kinetic aspects are very important. The rates of polymer adsorption and of re-conformation (relaxation) of adsorbed chains are key factors that influence the performance of flocculants and their mode of action. Polyelectrolytes often tend to adopt a rather flat adsorbed configuration and in this state their action is mainly through charge effects, including 'electrostatic patch' attraction. When the relaxation rate is quite low, particle collisions may occur while the adsorbed chains are still in an extended state and flocculation by polymer bridging may occur. These effects are now well understood and supported by much experimental evidence. In recent years there has been considerable interest in the use of multi-component flocculants, especially dual-polymer systems. In the latter case, there can be significant advantages over the use of single polymers. Despite some complications, there is a broad understanding of the action of dual polymer systems. In many cases the sequence of addition of the polymers is important and the pre-adsorbed polymer can have two important effects: providing adsorption sites for the second polymer or causing a more extended adsorbed conformation as a result of 'site blocking'. Copyright © 2011 Elsevier B.V. All rights reserved.

A Study of Functional Polymer Colloids Prepared Using Thiol-Ene/Yne Click Chemistry

NASA Astrophysics Data System (ADS)

Durham, Olivia Z.

This project demonstrates the first instance of thiol-ene chemistry as the polymerization method for the production of polymer colloids in two-phase heterogeneous suspensions, miniemulsions, and emulsions. This work was also expanded to thiol-yne chemistry for the production of polymer particles containing increased crosslinking density. The utility of thiol-ene and thiol-yne chemistries for polymerization and polymer modification is well established in bulk systems. These reactions are considered 'click' reactions, which can be defined as processes that are both facile and simple, offering high yields with nearly 100% conversion, no side products, easy product separation, compatibility with a diverse variety of commercially available starting materials, and orthogonality with other chemistries. In addition, thiol-ene and thiol-yne chemistry follow a step-growth mechanism for the development of highly uniform polymer networks, where polymer growth is dependent on the coupling of functional groups. These step-growth polymerization systems are in stark contrast to the chain-growth mechanisms of acrylic and styrenic monomers that have dominated the field of conventional heterogeneous polymerizations. Preliminary studies evaluated the mechanism of particle production in suspension and miniemulsion systems. Monomer droplets were compared to the final polymer particles to confirm that particle growth occurred through the polymerization of monomer droplets. Additional parameters examined include homogenization energy (mechanical mixing), diluent species and concentration, and monomer content. These reactions were conducted using photoinitiation to yield particles in a matter of minutes with diameters in the size range of several microns to hundreds of microns in suspensions or submicron particles in miniemulsions. Improved control over the particle size and size distribution was examined through variation of reaction parameters. In addition, a method of seeded suspension polymerization was attempted. This project was further expanded through an extensive evaluation of stabilizers in thiol-ene suspension polymerizations. The scope of stabilizers used included synthetic surfactants (ionic and nonionic), natural gums, and colloidal silica (Pickering stabilization). Suspension polymerizations were further expanded to include thiol-yne chemistry for the evaluation of polymer composition and thermal properties. In addition, polymer particles with excess ene, yne, or thiol functionality were successfully developed to demonstrate the potential for further functionalization. The self-limiting behavior of thiol-ene/yne reactions allows for successful synthesis of functional polymer colloids using off-stoichiometric amounts of monomers. This capacity to control functionality is illustrated through the creation of fluorescent polymer particles using both an in situ thiol-ene polymerization reaction with a vinyl chromophore as well as through post-polymerization modification of thiol-ene and thiol-yne polymers with excess thiol functionality via thiol-isocyanate chemistry. To produce smaller polymer particles without the need for intense homogenization energy or high stabilizer concentrations, an emulsion polymerization system was implemented using a water soluble-thermal initiator. It was found that unlike thiol-ene suspensions, which are limited to crosslinked systems, thiol-ene emulsion polymerizations allowed for the production of polymer particles comprised of either crosslinked or linear polymer networks. For the crosslinked systems, various anionic SDS surfactant concentrations were examined to observe the influence on particle size. In linear polymer systems, variations in polymer composition were examined. Preliminary studies performed with a monomer with an ethylene glycol-like structure indicated that the synthesis of polymer particles with narrower size distributions compared to any of the other emulsion compositions was possible. Finally, thiol-ene chemistry was also employed toward the synthesis of degradable polyanhydride polymer particles. Unlike the aforementioned studies, the approach to particle synthesis was conducted by using a premade thiol-ene polymer. Various linear thiol-ene polyanhydrides were emulsified in water or buffered solutions via sonication. Polymer latex was obtained upon solvent evaporation of the dichloromethane (DCM) solvent used to solubilize the polymer. In this work, variation of polymer composition as well as degradation was examined. Additional experiments included a study of the release of Rhodamine B dye, functionalization of the linear polymers, and studies involving the delay of degradation through the incorporation of crosslinking in the polymer particles. The projects presented herein provide an innovative approach to the synthesis of polymer colloids using thiol-ene and thiol-yne 'click' chemistry in both heterogeneous polymerizations as well as through solvent evaporation of premade polymer solutions. Polymer colloids prove to be an area of great interest for numerous applications that encompass various areas involving biomedical and industrial technologies including paints and coatings, cosmetics, diagnostics, and drug delivery. Improvements in methods of chemical synthesis as well as advances in the tailoring of material properties are of utmost importance for the ever increasing demands of new technologies and educational enlightenment.

The life times of polymer composites in construction

NASA Astrophysics Data System (ADS)

Meier, Urs

2016-05-01

This paper discusses examples that prove the long-term reliability of Fiber Reinforced Polymers (FRP) under extreme loading conditions and outdoor weathering. Results of polymer/steel-composite anchorage systems, Glass Fiber Reinforced Polymer (GFRP) plates and shells, GFRP box girders, Carbon Fiber Reinforced Polymer (CFRP) post-tensioning tendons and CFRP stays are going to be presented.

Phase equilibria in polymer-blend thin films

NASA Astrophysics Data System (ADS)

Clarke, Nigel; Souche, Mireille

2010-03-01

To describe equilibrium concentration profiles in thin films of polymer mixtures, we propose a Hamiltonian formulation of the Flory-Huggins-de Gennes theory describing a polymer blend thin film. We first focus on the case of 50:50 polymer blends confined between anti-symmetric walls. The different phases of the system and the transitions between them, including finite size effects, are systematically studied through their relation with the geometry of the Hamiltonian flow in phase space. This method provides an easy and efficient way, with strong graphical insight, to infer the qualitative physical behavior of polymer blend thin films. The addition of a further degree of freedom in the system, namely a solvent, may result in a chaotic behavior of the system, characterized by the existence of solutions with exponential sensitivity to initial conditions. Such solutions and there subsequent contribution to the out-of-equilibrium dynamics of the system are well described in Hamiltonian formalism. A fully consistent treatment of the Flory-Huggins-de Gennes theory of thin film polymer blend solutions, in the spirit of the Hamiltonian approach will be presented. 1. M. Souche and N. Clarke, J. Chem. Phys., submitted.

New Approach To Produce Water Free of Bacteria, Viruses, and Halogens in a Recyclable System▿

PubMed Central

Ahmed, Abd El-Shafey I.; Cavalli, Gabriel; Bushell, Michael E.; Wardell, John N.; Pedley, Steve; Charles, Katarina; Hay, John N.

2011-01-01

The antimicrobial activity of a new cross-linked N-halamine polymer against bacteria and viruses was evaluated. The polymer achieved a 9-log10 reduction of bacteria (both Escherichia coli and Staphylococcus aureus) in 1.5 h and a 5-log10 reduction of bacteriophage PRD1 in 3 h. At the same time, the ability of the nonhalogenated polymer to trap halide ions was examined. The polymer was incorporated into a multifiltration system to study the ability to produce water free of bacteria, viruses, and halide ions. The antimicrobial activity, useful lifetime, halide ion level, and recycling possibilities of the system were quantified on a laboratory scale. A design for a large-scale multifiltration system based on this polymer is proposed. PMID:21115711

Smart drug release systems based on stimuli-responsive polymers.

PubMed

Qing, Guangyan; Li, Minmin; Deng, Lijing; Lv, Ziyu; Ding, Peng; Sun, Taolei

2013-07-01

Stimuli-responsive polymers could respond to external stimuli, such as temperature, pH, photo-irradiation, electric field, biomolecules in solution, etc., which further induce reversible transformations in the structures and conformations of polymers, providing an excellent platform for controllable drug release, while the accuracy of drug delivery could obtain obvious improvement in this system. In this review, recent progresses in the drug release systems based on stimuli-responsive polymers are summarized, in which drugs can be released in an intelligent mode with high accuracy and efficiency, while potential damages to normal cells and tissues can also be effectively prevented owing to the unique characteristics of materials. Moreover, we introduce some smart nanoparticles-polymers conjugates and drug release devices, which are especially suitable for the long-term sustained drug release.

Low density microcellular foams

DOEpatents

Aubert, James H.; Clough, Roger L.; Curro, John G.; Quintana, Carlos A.; Russick, Edward M.; Shaw, Montgomery T.

1987-01-01

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the resultant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Means for subjecting such a solvent to one-dimensional cooling are also provided. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 .mu.m and a volume such that the foams have a length greater than 1 cm are provided.

Facile preparation of polymer microspheres and fibers with a hollow core and porous shell for oil adsorption and oil/water separation

NASA Astrophysics Data System (ADS)

Gao, Jiefeng; Song, Xin; Huang, Xuewu; Wang, Ling; Li, Bei; Xue, Huaiguo

2018-05-01

Non-solvent assisted electrospinning was proposed for fabricating Polymethylmethacrylate (PMMA) microspheres and fibers with a hollow core and porous shell, which could be used for oil adsorption and oil/water separation. Propanediol was chosen as the non-solvent because of its high surface tension and viscosity as well as large phase separation tendency with polymer, which was beneficial to the formation of both the hollow core and porous shell during the electrospinning. With the increase of the polymer solution concentration, the microsphere gradually evolved to the bead-on-string geometry and finally to a continuous fiber form, indicating the transition from electro-spraying to electrospinning. The hollow core and dense surface pores enhanced the hydrophobicity, oleophilicity, permeability, and specific surface area of the fibers, and hence imparted the fibrous mat a high oil adsorption capacity. When the porous hollow microspheres were electro-sprayed onto the stainless steel mesh followed by the PDMS modification, the modified mesh became super-hydrophobic and super-oleophilic with the contact angle of 153° and sliding angle of 4°. The as-prepared mesh showed rapid oil/water separation with high efficiency and excellent recycling performance. The flux for separation of oil/water mixture could reach as high as 11,000 L m-2 h-1. This facile non-solvent assisted electrospinning method provides a new avenue for preparation of multifunctional porous materials which possess potential applications in large-scale oil/water separation.

Formation of polymeric toroidal-spiral particles.

PubMed

Sharma, Vishal; Szymusiak, Magdalena; Shen, Hao; Nitsche, Ludwig C; Liu, Ying

2012-01-10

Compared to spherical matrices, particles with well-defined internal structure provide large surface to volume ratio and predictable release kinetics for the encapsulated payloads. We describe self-assembly of polymeric particles, whereby competitive kinetics of viscous sedimentation, diffusion, and cross-linking yield a controllable toroidal-spiral (T-S) structure. Precursor polymeric droplets are splashed through the surface of a less dense, miscible solution, after which viscous forces entrain the surrounding bulk solution into the sedimenting polymer drop to form T-S channels. The intricate structure forms because low interfacial tension between the two miscible solutions is dominated by viscous forces. The biocompatible polymer, poly(ethylene glycol) diacrylate (PEG-DA), is used to demonstrate the solidification of the T-S shapes at various configurational stages by UV-triggered cross-linking. The dimensions of the channels are controlled by Weber number during impact on the surface, and Reynolds number and viscosity ratio during subsequent sedimentation. We anticipate applications of the T-S particle in drug delivery, wherein diffusion through these T-S channels and the polymer matrix would offer parallel release pathways for molecules of different sizes. Polyphosphate, as a model macromolecule, is entrained in T-S particles during their formation. The in vitro release kinetics of polyphosphate from the T-S particles with various channel length and width is reported. In addition, self-assembly of T-S particles occurs in a single step under benign conditions for delicate macromolecules, and appears conducive to scaleup.

Three-dimensional ceramic molding process based on microstereolithography for the production of piezoelectric energy harvesters

NASA Astrophysics Data System (ADS)

Maruo, Shoji; Sugiyama, Kenji; Daicho, Yuya; Monri, Kensaku

2014-03-01

A three-dimensional (3-D) molding process using a master polymer mold produced by microstereolithography has been developed for the production of piezoelectric ceramic elements. In this method, ceramic slurry is injected into a 3-D polymer mold via a centrifugal casting process. The polymer master mold is thermally decomposed so that complex 3-D piezoelectric ceramic elements can be produced. As an example of 3-D piezoelectric ceramic elements, we produced a spiral piezoelectric element that can convert multidirectional loads into a voltage. It was confirmed that a prototype of the spiral piezoelectric element could generate a voltage by applying a load in both parallel and lateral directions in relation to the helical axis. The power output of 123 pW was obtained by applying the maximum load of 2.8N at 2 Hz along the helical axis. In addition, to improve the performance of power generation, we utilized a two-step sintering process to obtain dense piezoelectric elements. As a result, we obtained a sintering body with relative density of 92.8%. Piezoelectric constant d31 of the sintered body attained to -40.0 pC/N. Furthermore we analyzed the open-circuit voltage of the spiral piezoelectric element using COMSOL multiphysics. As a result, it was found that use of patterned electrodes according to the surface potential distribution of the spiral piezoelectric element had a potential to provide high output voltage that was 20 times larger than that of uniform electrodes.

Ion distribution in quaternary-ammonium-functionalized aromatic polymers: effects on the ionic clustering and conductivity of anion-exchange membranes.

PubMed

Weiber, E Annika; Jannasch, Patric

2014-09-01

A series of copoly(arylene ether sulfone)s that have precisely two, three, or four quaternary ammonium (QA) groups clustered directly on single phenylene rings along the backbone are studied as anion-exchange membranes. The copolymers are synthesized by condensation polymerizations that involve either di-, tri-, or tetramethylhydroquinone followed by virtually complete benzylic bromination using N-bromosuccinimide and quaternization with trimethylamine. This synthetic strategy allows excellent control and systematic variation of the local density and distribution of QA groups along the backbone. Small-angle X-ray scattering of these copolymers shows extensive ionic clustering, promoted by an increasing density of QA on the single phenylene rings. At an ion-exchange capacity (IEC) of 2.1 meq g(-1), the water uptake decreases with the increasing local density of QA groups. Moreover, at moderate IECs at 20 °C, the Br(-) conductivity of the densely functionalized copolymers is higher than a corresponding randomly functionalized polymer, despite the significantly higher water uptake of the latter. Thus, the location of multiple cations on single aromatic rings in the polymers facilitates the formation of a distinct percolating hydrophilic phase domain with a high ionic concentration to promote efficient anion transport, despite probable limitations by reduced ion dissociation. These findings imply a viable strategy to improve the performance of alkaline membrane fuel cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High performance p-type organic thin film transistors with an intrinsically photopatternable, ultrathin polymer dielectric layer☆

PubMed Central

Petritz, Andreas; Wolfberger, Archim; Fian, Alexander; Krenn, Joachim R.; Griesser, Thomas; Stadlober, Barbara

2013-01-01

A high-performing bottom-gate top-contact pentacene-based oTFT technology with an ultrathin (25–48 nm) and electrically dense photopatternable polymeric gate dielectric layer is reported. The photosensitive polymer poly((±)endo,exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, diphenylester) (PNDPE) is patterned directly by UV-exposure (λ = 254 nm) at a dose typical for conventionally used negative photoresists without the need for any additional photoinitiator. The polymer itself undergoes a photo-Fries rearrangement reaction under UV illumination, which is accompanied by a selective cross-linking of the macromolecules, leading to a change in solubility in organic solvents. This crosslinking reaction and the negative photoresist behavior are investigated by means of sol–gel analysis. The resulting transistors show a field-effect mobility up to 0.8 cm2 V−1 s−1 at an operation voltage as low as −4.5 V. The ultra-low subthreshold swing in the order of 0.1 V dec−1 as well as the completely hysteresis-free transistor characteristics are indicating a very low interface trap density. It can be shown that the device performance is completely stable upon UV-irradiation and development according to a very robust chemical rearrangement. The excellent interface properties, the high stability and the small thickness make the PNDPE gate dielectric a promising candidate for fast organic electronic circuits. PMID:24748853

Electroactive poly(vinylidene fluoride)-based structures for advanced applications.

PubMed

Ribeiro, Clarisse; Costa, Carlos M; Correia, Daniela M; Nunes-Pereira, João; Oliveira, Juliana; Martins, Pedro; Gonçalves, Renato; Cardoso, Vanessa F; Lanceros-Méndez, Senentxu

2018-04-01

Poly(vinylidene fluoride) (PVDF) and its copolymers are the polymers with the highest dielectric constants and electroactive responses, including piezoelectric, pyroelectric and ferroelectric effects. This semicrystalline polymer can crystallize in five different forms, each related to a different chain conformation. Of these different phases, the β phase is the one with the highest dipolar moment and the highest piezoelectric response; therefore, it is the most interesting for a diverse range of applications. Thus, a variety of processing methods have been developed to induce the formation of the polymer β phase. In addition, PVDF has the advantage of being easily processable, flexible and low-cost. In this protocol, we present a number of reproducible and effective methods to produce β-PVDF-based morphologies/structures in the form of dense films, porous films, 3D scaffolds, patterned structures, fibers and spheres. These structures can be fabricated by different processing techniques, including doctor blade, spin coating, printing technologies, non-solvent-induced phase separation (NIPS), temperature-induced phase separation (TIPS), solvent-casting particulate leaching, solvent-casting using a 3D nylon template, freeze extraction with a 3D poly(vinyl alcohol) (PVA) template, replica molding, and electrospinning or electrospray, with the fabrication method depending on the desired characteristics of the structure. The developed electroactive structures have shown potential to be used in a wide range of applications, including the formation of sensors and actuators, in biomedicine, for energy generation and storage, and as filtration membranes.

Tuning of electrostatic vs. depletion interaction in deciding the phase behavior of nanoparticle-polymer system

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

Kumar, Sugam, E-mail: sugam@barc.gov.in; Aswal, V. K.; Kohlbrecher, J.

2015-06-24

Nanoparticle-polymer system interestingly show a re-entrant phase behavior where charge stabilized silica nanoparticles (phase I) undergo particle clustering (phase II) and then back to individual particles (phase I) as a function of polymer concentration. Such phase behavior arises as a result of dominance of various interactions (i) nanoparticle-nanoparticle electrostatic repulsion (ii) polymer induced attractive depletion between nanoparticles and (iii) polymer-polymer repulsion, at different concentration regimes. Small-angle neutron scattering (SANS) has been used to study the evolution of interaction during this re-entrant phase behavior of nanoparticles by contrast-marching the polymer. The SANS data have been modeled using a two-Yukawa potential accountingmore » for both attractive and repulsive parts of the interaction between nanoparticles. The degree of both of these parts has been separately tuned by varying the polymer concentration and ionic strength of the solution. Both of these parts are found to have long-range nature. At low polymer concentrations, the electrostatic repulsion dominates over the depletion attraction. The magnitude and the range of the depletion interaction increase with the polymer concentration leading to nanoparticle clustering. At higher polymer concentrations, the increased polymer-polymer repulsion reduces the strength of depletion leading to re-entrant phase behavior. The clusters formed under depletion attraction are found to have surface fractal morphology.« less

Ballistic near-field heat transport in dense many-body systems

NASA Astrophysics Data System (ADS)

Latella, Ivan; Biehs, Svend-Age; Messina, Riccardo; Rodriguez, Alejandro W.; Ben-Abdallah, Philippe

2018-01-01

Radiative heat transport mediated by near-field interactions is known to be superdiffusive in dilute, many-body systems. Here we use a generalized Landauer theory of radiative heat transfer in many-body planar systems to demonstrate a nonmonotonic transition from superdiffusive to ballistic transport in dense systems. We show that such a transition is associated to a change of the polarization of dominant modes. Our findings are complemented by a quantitative study of the relaxation dynamics of the system in the different regimes of heat transport. This result could have important consequences on thermal management at nanoscale of many-body systems.

A molecular dynamics study of polymer/graphene interfacial systems

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

Rissanou, Anastassia N.; Harmandaris, Vagelis

2014-05-15

Graphene based polymer nanocomposites are hybrid materials with a very broad range of technological applications. In this work, we study three hybrid polymer/graphene interfacial systems (polystyrene/graphene, poly(methyl methacrylate)/graphene and polyethylene/graphene) through detailed atomistic molecular dynamics (MD) simulations. Density profiles, structural characteristics and mobility aspects are being examined at the molecular level for all model systems. In addition, we compare the properties of the hybrid systems to the properties of the corresponding bulk ones, as well as to theoretical predictions.

Potential of polymeric particles as future vaccine delivery systems/adjuvants for parenteral and non-parenteral immunization against tuberculosis: A systematic review.

PubMed

Khademi, Farzad; Derakhshan, Mohammad; Yousefi-Avarvand, Arshid; Tafaghodi, Mohsen

2018-02-01

Production of effective tuberculosis (TB) vaccine is necessity. However, the development of new subunit vaccines is faced with concerns about their weak immunogenicity. To overcome such problems, polymers-based vaccine delivery systems have been proposed to be used via various routes. The purpose of this study was to determine the potential of polymeric particles as future vaccine delivery systems/adjuvants for parenteral and non-parenteral immunization against TB. PubMed, Scopus, Science-Direct, and the ISI web of knowledge databases were searched for related keywords. A total of 420 articles, written up to June 25, 2016, were collected on the potential of polymeric particles as TB vaccine delivery systems after parenteral and non-parenteral immunization. Thirty-one relevant articles were selected by applying inclusion and exclusion criteria. It was shown that the immunogenicity of TB vaccines had been improved by using biodegradable and non-biodegradable synthetic polymers as well as natural polymers and they are better able to enhance the humoral and cellular immune responses, compared to TB vaccines alone. The present study revealed that various polymeric particles, after M. tuberculosis challenge in animal models, provide long-lasting protection against TB. PLGA (poly (lactide-co-glycolide)) and chitosan polymers were widely used as TB vaccine delivery systems/adjuvants. It seems that PLGA and chitosan polymers are well-suited particles for the parenteral and non-parenteral administration of TB vaccines, respectively. Non-biodegradable synthetic polymers in comparison with biodegradable synthetic and natural polymers have been used less frequently. Therefore, further study on this category of polymers is required.

Polymers in separation processes

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina; Staszak, Katarzyna

2017-05-01

Application of polymer materials as membranes and ion-exchange resins was presented with a focus on their use for the recovery of metal ions from aqueous solutions. Several membrane techniques were described including reverse osmosis, nanofiltration, ultrafiltration, diffusion and Donnan dialysis, electrodialysis and membrane extraction system (polymer inclusion and supported membranes). Moreover, the examples of using ion-exchange resins in metal recovery were presented. The possibility of modification of the resin was discussed, including hybrid system with metal cation or metal oxide immobilized on polymer matrices or solvent impregnated resin.

A Simple Analytical Model for Asynchronous Dense WDM/OOK Systems

DTIC Science & Technology

1994-06-01

asynchronous dense WDM systems employing an external OOK modulator. Our model is based upon a close approximation of the optical Fabry - Perot filter in the...receiver as a single-pole RC filter for signals that are bandlimitr i, & -equency band approximately equal to one sixtieth of the Fabry - Perot filter’s...4 A. INPUT SIGNAL ............................................................................................... 4 B. FABRY - PEROT FILTERED OUTPUT

PLGA: a unique polymer for drug delivery.

PubMed

Kapoor, Deepak N; Bhatia, Amit; Kaur, Ripandeep; Sharma, Ruchi; Kaur, Gurvinder; Dhawan, Sanju

2015-01-01

Biodegradable polymers have played an important role in the delivery of drugs in a controlled and targeted manner. Polylactic-co-glycolic acid (PLGA) is one of the extensively researched synthetic biodegradable polymers due to its favorable properties. It is also known as a 'Smart Polymer' due to its stimuli sensitive behavior. A wide range of PLGA-based drug delivery systems have been reported for the treatment or diagnosis of various diseases and disorders. The present review provides an overview of the chemistry, physicochemical properties, biodegradation behavior, evaluation parameters and applications of PLGA in drug delivery. Different drug-polymer combinations developed into drug delivery or carrier systems are enumerated and discussed.

Large photorefractive effect in a thermally decomposed polymer compared with that in molecularly doped systems

NASA Astrophysics Data System (ADS)

Yokoyama, Kenji; Arishima, Koichi; Sukegawa, Ken

1994-07-01

Photorefractive polymers with the same electro-optic effect were fabricated to investigate the photorefractive effects in different photoconductive systems. The photoconduction in the polymers was varied by the addition of squarylium dye to diethylaminobenzaldehyde-diphenylhydrazone (DEH), by the formation of a charge-transfer complex between tetracyanoquinodimethane and DEH, and by the thermal decomposition of DEH. The largest photorefractive effect was observed in the thermally decomposed polymer among these polymers. A diffraction efficiency of 1.1% and a beam-coupling gain coefficient of 10 cm-1 were achieved in a 34.9 V/μm dc electric field.

Water-soluble polymers bearing phosphorylcholine group and other zwitterionic groups for carrying DNA derivatives.

PubMed

Lin, Xiaojie; Ishihara, Kazuhiko

2014-01-01

Water-soluble polymers with equal positive and negative charges in the same monomer unit, such as the phosphorylcholine group and other zwitterionic groups, exhibit promising potential in gene delivery with appreciable transfection efficiency, compared with the traditional poly(ethylene glycol)-based polycation-gene complexes. These zwitterionic polymers with various architectural structures and properties have been synthesized by various polymerization methods, such as conventional radical polymerization, atom-transfer radical-polymerization, reversible addition-fragmentation chain-transfer polymerization, and nitroxide-mediated radical polymerization. These techniques have been used to efficiently facilitate gene therapy by fabrication of non-viral vectors with high cytocompatibility, large gene-carrying capacity, effective cell-membrane permeability, and in vivo gene-loading/releasing functionality. Zwitterionic polymer-based gene delivery vectors systems can be categorized into soluble-polymer/gene mixing, molecular self-assembly, and polymer-gene conjugation systems. This review describes the preparation and characterization of various zwitterionic polymer-based gene delivery vectors, specifically water-soluble phospholipid polymers for carrying gene derivatives.

Constitutive Modeling of Nanotube-Reinforced Polymer Composites

NASA Technical Reports Server (NTRS)

Odegard, G. M.; Gates, T. S.; Wise, K. E.; Park, C.; Siochi, E. J.; Bushnell, Dennis M. (Technical Monitor)

2002-01-01

In this study, a technique is presented for developing constitutive models for polymer composite systems reinforced with single-walled carbon nanotubes (SWNT). Because the polymer molecules are on the same size scale as the nanotubes, the interaction at the polymer/nanotube interface is highly dependent on the local molecular structure and bonding. At these small length scales, the lattice structures of the nanotube and polymer chains cannot be considered continuous, and the bulk mechanical properties can no longer be determined through traditional micromechanical approaches that are formulated by using continuum mechanics. It is proposed herein that the nanotube, the local polymer near the nanotube, and the nanotube/polymer interface can be modeled as an effective continuum fiber using an equivalent-continuum modeling method. The effective fiber serves as a means for incorporating micromechanical analyses for the prediction of bulk mechanical properties of SWNT/polymer composites with various nanotube lengths, concentrations, and orientations. As an example, the proposed approach is used for the constitutive modeling of two SWNT/polyimide composite systems.

Diffusion of residual monomer in polymer resins.

PubMed Central

Piver, W T

1976-01-01

A simplified mathematical model which made use of Fick's laws of diffusion written in spherical coordinates was developed to describe the rate of diffusion of residual monomers from polymer resins. The properties of the monomer-polymer system which influenced the amount of monomer remaining in the polymer as a function of time were the diffusivity and solubility of the monomer in the polymer, and the particle size of the polymer resin. This model was used to analyze literature data on the diffusion of residual vinyl chloride monomer in polyvinyl chloride resins made by the suspension process. It was concluded that particle size of the resin was a significant parameter which should be taken advantage of in process equipment designed to remove residual monomer from PVC resins. The diffusivity of the monomer in the polymer was a function of the solubility of the monomer in the polymer. Monomer solubility can be determined from Henry's law. It was suggested that this model could be adapted to describe diffusion of monomers from any monomer-polymer system, and would be a useful approach to modeling the transport of nonreactive chemical additives from plastics. PMID:1026410

Facile morphology-controlled synthesis of nickel-coated graphite core-shell particles for excellent conducting performance of polymer-matrix composites and enhanced catalytic reduction of 4-nitrophenol

NASA Astrophysics Data System (ADS)

Bian, Juan; Lan, Fang; Wang, Yilong; Ren, Ke; Zhao, Suling; Li, Wei; Chen, Zhihong; Li, Jiangyu; Guan, Jianguo

2018-04-01

We have developed a novel seed-mediated growth method to fabricate nickel-coated graphite composite particles (GP@Ni-CPs) with controllable shell morphology by simply adjusting the concentration of sodium hydroxide ([NaOH]). The fabrication of two kinds of typical GP@Ni-CPs includes adsorption of Ni2+ via electrostatic attraction, sufficient heterogeneous nucleation of Ni atoms by an in situ reduction, and shell-controlled growth by regulating the kinetics of electroless Ni plating in turn. High [NaOH] results in fast kinetics of electroless plating, which causes heterogeneous nuclei to grow isotropically. After fast and uniform growth of Ni nuclei, GP@Ni-CPs with dense shells can be achieved. The first typical GP@Ni-CPs exhibit denser shells, smaller diameters and higher conductivities than the available commercial ones, indicating their important applications in the conducting of polymer-matrix composites. On the other hand, low [NaOH] favors slow kinetics. Thus, the reduction rate of Ni2+ slows down to a relatively low level so that electroless plating is dominated thermodynamically instead of kinetically, leading to an anisotropic crystalline growth of nuclei and finally to the formation of GP@Ni-CPs with nanoneedle-like shells. The second typical samples can effectively catalyze the reduction of p-nitrophenol into p-aminophenol with NaBH4 in comparison with commercial GP@Ni-CPs and RANEY® Ni, owing to the strong charge accumulation effect of needle-like Ni shells. This work proposes a model system for fundamental investigations and has important applications in the fields of electronic interconnection and catalysis.

Biodegradable implants from poly-(alpha-hydroxy acid) polymers for isoniazid delivery.

PubMed

Hurley, L; Andersen, B R

1999-11-01

In vitro and in vivo study of an isoniazid (INH) drug delivery system. To develop a system for the treatment of tuberculosis using a subcutaneous polymer implant with a large drug load released slowly over a long period. INH delivery by biodegradable poly-(alpha-hydroxy acid) polymers was evaluated using ground polymer and compression molded implants. Rate of drug release and structural stability of the implant in an aqueous environment were measured, as were in vivo evaluations of the duration of measurable levels of INH in serum and urine. Factors that influenced the suitability of an implant in an in vitro system included polymer molecular weight and crystallinity, polymer and drug particle size, drug loading dose, and press temperature and pressure. The implant characteristics that most closely approached optimal conditions include a polymer of 100% L-lactide with low intrinsic viscosity, polymer particle size <75 micron, and INH particle = 126-180 micron, INH loading dose not to exceed 46%, and press conditions of 70 degrees C and 345000 kPa. Studies of subcutaneous implants in rabbits and baboons show that INH is released from the implant for 15 to 26 weeks. An INH-containing polymer was developed that was structurally stable in an aqueous environment and that released INH over a period of at least 15 weeks. Studies with infected animals will be necessary to determine the dose required for prophylaxis and treatment of active disease.

Self-Assembled CNT-Polymer Hybrids in Single-Walled Carbon Nanotubes Dispersed Aqueous Triblock Copolymer Solutions

NASA Astrophysics Data System (ADS)

Vijayaraghavan, D.; Manjunatha, A. S.; Poojitha, C. G.

2018-04-01

We have carried out scanning electron microscopy (SEM), differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), electrical conductivity, and 1H NMR studies as a function of temperature on single-walled carbon nanotubes (SWCNTs) dispersed aqueous triblock copolymer (P123) solutions. The single-walled carbon nanotubes in this system aggregate to form bundles, and the bundles aggregate to form net-like structures. Depending on the temperature and phases of the polymer, this system exhibits three different self-assembled CNT-polymer hybrids. We find CNT-unimer hybrid at low temperatures, CNT-micelle hybrid at intermediate temperatures wherein the polymer micelles are adsorbed in the pores of the CNT nets, and another type of CNT-micelle hybrid at high temperatures wherein the polymer micelles are adsorbed on the surface of the CNT bundles. Our DSC thermogram showed two peaks related to these structural changes in the CNT-polymer hybrids. Temperature dependence of the 1H NMR chemical shifts of the molecular groups of the polymer and the AC electrical conductivity of the composite also showed discontinuous changes at the temperatures at which the CNT-polymer hybrid's structural changes are seen. Interestingly, for a higher CNT concentration (0.5 wt.%) in the system, the aggregated polymer micelles adsorbed on the CNTs exhibit cone-like and cube-like morphologies at the intermediate and at high temperatures respectively.

Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

DOEpatents

Skotheim, Terje A.; Okamoto, Yoshiyuki; Lee, Hung S.

1989-01-01

The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10.sup.-4 to 10.sup.-7 S cm.sup.-1 at room temperature.

Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

DOEpatents

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

1989-11-21

The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10[sup [minus]4] to 10[sup [minus]7] S cm[sup [minus]1] at room temperature.

[Use of a novel polymer, the in-situ gelling mucoadhesive thiolated poly(aspartic acid) in ophthalmic drug delivery].

PubMed

Horvát, Gabriella; Budai-Szűcs, Mária; Berkó, Szilvia; Szabóné-Révész, Piroska; Gyarmati, Benjámin; Szilágyi, Barnabas Áron; Szilágyi, András; Csányi Erzsébet

2015-01-01

The bioavailability of drugs used on mucosal surfaces can be increased by the use of mucoadhesive polymers. A new type of mucoadhesive polymers is the group of thiolated polymers with thiol group containing side chains. These polymers are able to form covalent bonds (disulphide linkages) with the mucin glycoproteins. For the formulation of an ocular drug delivery system (DDS) thiolated poly(aspartic acid) polymer (ThioPASP) was used. Our aim was to determine their biocompatibility, mucoadhesion and drug release property. According to the results it can be established that the thiolated poly(aspartic acid) polymers can be a potential vehicle of an ocular drug delivery system due to their biocompatibility, good mucoadhesive property and drug release profile. Thanks to their properties controlled drug delivery can be achieved and bioavailability of the ophthalmic formulation can be increased, while the usage frequency can be decreased.

Self-assembling nucleic acid delivery vehicles via linear, water-soluble, cyclodextrin-containing polymers.

PubMed

Davis, M E; Pun, S H; Bellocq, N C; Reineke, T M; Popielarski, S R; Mishra, S; Heidel, J D

2004-01-01

Non-viral (synthetic) nucleic acid delivery systems have the potential to provide for the practical application of nucleic acid-based therapeutics. We have designed and prepared a tunable, non-viral nucleic acid delivery system that self-assembles with nucleic acids and centers around a new class of polymeric materials; namely, linear, water-soluble cyclodextrin-containing polymers. The relationships between polymer structure and gene delivery are illustrated, and the roles of the cyclodextrin moieties for minimizing toxicity and forming inclusion complexes in the self-assembly processes are highlighted. This vehicle is the first example of a polymer-based gene delivery system formed entirely by self-assembly.

Tripolar vortex formation in dense quantum plasma with ion-temperature-gradients

NASA Astrophysics Data System (ADS)

Qamar, Anisa; Ata-ur-Rahman, Mirza, Arshad M.

2012-05-01

We have derived system of nonlinear equations governing the dynamics of low-frequency electrostatic toroidal ion-temperature-gradient mode for dense quantum magnetoplasma. For some specific profiles of the equilibrium density, temperature, and ion velocity gradients, the nonlinear equations admit a stationary solution in the form of a tripolar vortex. These results are relevant to understand nonlinear structure formation in dense quantum plasmas in the presence of equilibrium ion-temperature and density gradients.

Development of controlled drug release systems based on thiolated polymers.

PubMed

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

2000-05-03

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

Origin of organic matter in the early solar system. VII - The organic polymer in carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Hayatsu, R.; Matsuoka, S.; Anders, E.; Scott, R. G.; Studier, M. H.

1977-01-01

Degradation techniques, including pyrolysis, depolymerization, and oxidation, were used to study the insoluble polymer from the Murchison C2 chondrite. Oxidation with Cr2O7(2-) or O2/UV led to the identification of 15 aromatic ring systems. Of 11 aliphatic acids identified, three dicarboxylic acids presumably came from hydroaromatic portions of the polymer, whereas eight monocarboxylic acids probably derive from bridging groups or ring substituents. Depolymerization with CF3COO4 yielded some of the same ring systems, as well as alkanes (C1 through C8) and alkenes (C2 through C8), alkyl (C1 through C5) benzenes and naphthalenes, and methyl- or dimethyl -indene, -indane, -phenol, -pyrrole, and -pyridine. All these compounds were detected below 200 C, and are therefore probably indigenous constituents. The properties of the meteoritic polymer were compared with the properties of a synthetic polymer produced by the Fischer-Tropsch reaction. It is suggested that the meteoritic polymer was also produced by surface catalysis.

Shape memory polymer actuator and catheter

DOEpatents

Maitland, Duncan J.; Lee, Abraham P.; Schumann, Daniel L.; Matthews, Dennis L.; Decker, Derek E.; Jungreis, Charles A.

2004-05-25

An actuator system is provided for acting upon a material in a vessel. The system includes an optical fiber and a shape memory polymer material operatively connected to the optical fiber. The shape memory polymer material is adapted to move from a first shape for moving through said vessel to a second shape where it can act upon said material.

Shape memory polymer actuator and catheter

DOEpatents

Maitland, Duncan J.; Lee, Abraham P.; Schumann, Daniel L.; Matthews, Dennis L.; Decker, Derek E.; Jungreis, Charles A.

2007-11-06

An actuator system is provided for acting upon a material in a vessel. The system includes an optical fiber and a shape memory polymer material operatively connected to the optical fiber. The shape memory polymer material is adapted to move from a first shape for moving through said vessel to a second shape where it can act upon said material.

Seven years of radionuclide laboratory at IMC - important achievements.

PubMed

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

2016-10-20

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

Experimental study of thin film sensor networks for wind turbine blade damage detection

NASA Astrophysics Data System (ADS)

Downey, A.; Laflamme, S.; Ubertini, F.; Sauder, H.; Sarkar, P.

2017-02-01

Damage detection of wind turbine blades is difficult due to their complex geometry and large size, for which large deployment of sensing systems is typically not economical. A solution is to develop and deploy dedicated sensor networks fabricated from inexpensive materials and electronics. The authors have recently developed a novel skin-type strain gauge for measuring strain over very large surfaces. The skin, a type of large-area electronics, is constituted from a network of soft elastomeric capacitors. The sensing system is analogous to a biological skin, where local strain can be monitored over a global area. In this paper, we propose the utilization of a dense network of soft elastomeric capacitors to detect, localize, and quantify damage on wind turbine blades. We also leverage mature off-the-shelf technologies, in particular resistive strain gauges, to augment such dense sensor network with high accuracy data at key locations, therefore constituting a hybrid dense sensor network. The proposed hybrid dense sensor network is installed inside a wind turbine blade model, and tested in a wind tunnel to simulate an operational environment. Results demonstrate the ability of the hybrid dense sensor network to detect, localize, and quantify damage.

Method of producing an electronic unit having a polydimethylsiloxane substrate and circuit lines

DOEpatents

Davidson, James Courtney [Livermore, CA; Krulevitch, Peter A [Pleasanton, CA; Maghribi, Mariam N [Livermore, CA; Benett, William J [Livermore, CA; Hamilton, Julie K [Tracy, CA; Tovar, Armando R [San Antonio, TX

2012-06-19

A system of metalization in an integrated polymer microsystem. A flexible polymer substrate is provided and conductive ink is applied to the substrate. In one embodiment the flexible polymer substrate is silicone. In another embodiment the flexible polymer substrate comprises poly(dimethylsiloxane).

Head-Tail Asymmetry Determines the Formation of Polymer Cubosomes or Hexasomes in a Rod-Coil Amphiphilic Block Copolymer.

PubMed

Lyu, Xiaolin; Xiao, Anqi; Zhang, Wei; Hou, Pingping; Gu, Kehua; Tang, Zhehao; Pan, Hongbing; Wu, Fan; Shen, Zhihao; Fan, Xinghe

2018-06-08

In this report, Im-3m and Pn-3m polymer cubosomes and p6mm polymer hexasomes are obtained through the self-assembly of a rod-coil amphiphilic block copolymer (ABCP). This is the first time that these structures are observed in a rod-coil system. By varying the hydrophobic chain length, the initial concentration of the polymer solution, or the solubility parameter of the mixed solvent, head-tail asymmetry is adjusted to control the formation of polymer cubosomes or hexasomes. The formation mechanism of the polymer cubosomes was also studied. This research opens up a new way for further study of the bicontinuous and inverse phases in different ABCP systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of the role of flocculation conditions in recuperative thickening on dewatering performance and biogas production.

PubMed

Cobbledick, Jeffrey; Zhang, Victor; Rollings-Scattergood, Sasha; Latulippe, David R

2017-11-01

There is considerable interest in recuperative thickening (RT), the recycling of partially digested solids in an anaerobic digester outlet stream back into the incoming feed, as a 'high-performance' process to increase biogas production, increase system capacity, and improve biosolids stabilization. While polymer flocculation is commonly used in full-scale RT operations, no studies have investigated the effect of flocculation conditions on RT process performance. Our goal was to investigate the effect of polymer type and dosage conditions on dewatering performance and biogas production in a lab-scale RT system. The type of polymer flocculant significantly affected dewatering performance. For example, the 440 LH polymer (low molecular weight (MW) polyacrylamide) demonstrated lower capillary suction time (CST) and filtrate total suspended solids (TSS) values than the C-6267 polymer (high MW polyacrylamide). An examination of the dewatering performance of RT digesters with different polymers found a strong correlation between CST and filtrate TSS. The type of polymer flocculant had no significant effect on biogas productivity or composition; the methane content was greater than 60% in good agreement with typical results. The optimization of the polymer flocculation conditions is a critical task for which the lab-scale RT system used in this work is ideally suited.

Constitutive Modeling of Nanotube-Reinforced Polymer Composites

NASA Technical Reports Server (NTRS)

Odegard, G. M.; Gates, T. S.; Wise, K. E.

2002-01-01

In this study, a technique is presented for developing constitutive models for polymer composite systems reinforced with single-walled carbon nanotubes (SWNT). Because the polymer molecules are on the same size scale as the nanotubes, the interaction at the polymer/nanotube interface is highly dependent on the local molecular structure and bonding. At these small length scales, the lattice structures of the nanotube and polymer chains cannot be considered continuous, and the bulk mechanical properties can no longer be determined through traditional micromechanical approaches that are formulated by using continuum mechanics. It is proposed herein that the nanotube, the local polymer near the nanotube, and the nanotube/polymer interface can be modeled as an effective continuum fiber using an equivalent-continuum modeling method. The effective fiber serves as a means for incorporating micromechanical analyses for the prediction of bulk mechanical properties of SWNT/polymer composites with various nanotube shapes, sizes, concentrations, and orientations. As an example, the proposed approach is used for the constitutive modeling of two SWNT/LaRC-SI (with a PmPV interface) composite systems, one with aligned SWNTs and the other with three-dimensionally randomly oriented SWNTs. The Young's modulus and shear modulus have been calculated for the two systems for various nanotube lengths and volume fractions.

From particle condensation to polymer aggregation

NASA Astrophysics Data System (ADS)

Janke, Wolfhard; Zierenberg, Johannes

2018-01-01

We draw an analogy between droplet formation in dilute particle and polymer systems. Our arguments are based on finite-size scaling results from studies of a two-dimensional lattice gas to three-dimensional bead-spring polymers. To set the results in perspective, we compare with in part rigorous theoretical scaling laws for canonical condensation in a supersaturated gas at fixed temperature, and derive corresponding scaling predictions for an undercooled gas at fixed density. The latter allows one to efficiently employ parallel multicanonical simulations and to reach previously not accessible scaling regimes. While the asymptotic scaling can not be observed for the comparably small polymer system sizes, they demonstrate an intermediate scaling regime also observable for particle condensation. Altogether, our extensive results from computer simulations provide clear evidence for the close analogy between particle condensation and polymer aggregation in dilute systems.

Fundamental molecular design for precise control of thermoresponsiveness of organic polymers by using ternary systems.

PubMed

Amemori, Shogo; Kokado, Kenta; Sada, Kazuki

2012-05-23

The de novo design of thermosensitive polymers in solution has been achieved by using the addition of small organic molecules (or "effectors"). Hydrogen bonding as an attractive polymer-polymer or polymer-effector interaction substantially dominates the responsivity, causing facile switching between LCST-type and UCST-type phase transitions, control of the transition temperature, and further coincidence of the two transitions. Small molecules having a high affinity for the polymer induce UCST-type phase behavior, whereas those having a low affinity for the polymer showed LCST-type phase behavior.

Amylose-Based Cationic Star Polymers for siRNA Delivery.

PubMed

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

2015-01-01

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

Combining quantitative and qualitative breast density measures to assess breast cancer risk.

PubMed

Kerlikowske, Karla; Ma, Lin; Scott, Christopher G; Mahmoudzadeh, Amir P; Jensen, Matthew R; Sprague, Brian L; Henderson, Louise M; Pankratz, V Shane; Cummings, Steven R; Miglioretti, Diana L; Vachon, Celine M; Shepherd, John A

2017-08-22

Accurately identifying women with dense breasts (Breast Imaging Reporting and Data System [BI-RADS] heterogeneously or extremely dense) who are at high breast cancer risk will facilitate discussions of supplemental imaging and primary prevention. We examined the independent contribution of dense breast volume and BI-RADS breast density to predict invasive breast cancer and whether dense breast volume combined with Breast Cancer Surveillance Consortium (BCSC) risk model factors (age, race/ethnicity, family history of breast cancer, history of breast biopsy, and BI-RADS breast density) improves identifying women with dense breasts at high breast cancer risk. We conducted a case-control study of 1720 women with invasive cancer and 3686 control subjects. We calculated ORs and 95% CIs for the effect of BI-RADS breast density and Volpara™ automated dense breast volume on invasive cancer risk, adjusting for other BCSC risk model factors plus body mass index (BMI), and we compared C-statistics between models. We calculated BCSC 5-year breast cancer risk, incorporating the adjusted ORs associated with dense breast volume. Compared with women with BI-RADS scattered fibroglandular densities and second-quartile dense breast volume, women with BI-RADS extremely dense breasts and third- or fourth-quartile dense breast volume (75% of women with extremely dense breasts) had high breast cancer risk (OR 2.87, 95% CI 1.84-4.47, and OR 2.56, 95% CI 1.87-3.52, respectively), whereas women with extremely dense breasts and first- or second-quartile dense breast volume were not at significantly increased breast cancer risk (OR 1.53, 95% CI 0.75-3.09, and OR 1.50, 95% CI 0.82-2.73, respectively). Adding continuous dense breast volume to a model with BCSC risk model factors and BMI increased discriminatory accuracy compared with a model with only BCSC risk model factors (C-statistic 0.639, 95% CI 0.623-0.654, vs. C-statistic 0.614, 95% CI 0.598-0.630, respectively; P < 0.001). Women with dense breasts and fourth-quartile dense breast volume had a BCSC 5-year risk of 2.5%, whereas women with dense breasts and first-quartile dense breast volume had a 5-year risk ≤ 1.8%. Risk models with automated dense breast volume combined with BI-RADS breast density may better identify women with dense breasts at high breast cancer risk than risk models with either measure alone.

Mechanisms of Local Stress Sensing in Multifunctional Polymer Films Using Fluorescent Tetrapod Nanocrystals

DOE PAGES

Raja, Shilpa N.; Zherebetskyy, Danylo; Wu, Siva; ...

2016-07-13

Nanoscale stress-sensing can be used across fields ranging from detection of incipient cracks in structural mechanics to monitoring forces in biological tissues. We demonstrate how tetrapod quantum dots (tQDs) embedded in block copolymers act as sensors of tensile/compressive stress. Remarkably, tQDs can detect their own composite dispersion and mechanical properties with a switch in optomechanical response when tQDs are in direct contact. Using experimental characterizations, atomistic simulations and finite-element analyses, we show that under tensile stress, densely packed tQDs exhibit a photoluminescence peak shifted to higher energies ("blue-shift") due to volumetric compressive stress in their core; loosely packed tQDs exhibitmore » a peak shifted to lower energies ("red-shift") from tensile stress in the core. The stress shifts result from the tQD's unique branched morphology in which the CdS arms act as antennas that amplify the stress in the CdSe core. Our nanocomposites exhibit excellent cyclability and scalability with no degraded properties of the host polymer. Colloidal tQDs allow sensing in many materials to potentially enable autoresponsive, smart structural nanocomposites that self-predict upcoming fracture.« less

Thermodynamic and mechanical properties of epoxy resin DGEBF crosslinked with DETDA by molecular dynamics.

PubMed

Tack, Jeremy L; Ford, David M

2008-06-01

Fully atomistic molecular dynamics (MD) simulations were used to predict the properties of diglycidyl ether of bisphenol F (DGEBF) crosslinked with curing agent diethyltoluenediamine (DETDA). This polymer is a commercially important epoxy resin and a candidate for applications in nanocomposites. The calculated properties were density and bulk modulus (at near-ambient pressure and temperature) and glass transition temperature (at near-ambient pressure). The molecular topology, degree of curing, and MD force-field were investigated as variables. The models were created by densely packing pre-constructed oligomers of different composition and connectivity into a periodic simulation box. For high degrees of curing (greater than 90%), the density was found to be insensitive to the molecular topology and precise value of degree of curing. Of the two force-fields that were investigated, cff91 and COMPASS, the latter clearly gave more accurate values for the density as compared to experiment. In fact, the density predicted by COMPASS was within 6% of reported experimental values for the highly crosslinked polymer. The predictions of both force-fields for glass transition temperature were within the range of reported experimental values, with the predictions of cff91 being more consistent with a highly cured resin.

Corrosion, optical and magnetic properties of flexible iron nitride nano thin films deposited on polymer substrate

NASA Astrophysics Data System (ADS)

Khan, W. Q.; Wang, Qun; Jin, Xin; Yasin, G.

2017-11-01

Iron nitride thin films of different compositions and thicknesses were deposited on flexible polymer substrate in Ar/N2 atmosphere by reactive magnetron sputtering under varying nitrogen flow rates. The nano structured films were characterized by X-ray diffraction, UV-visible spectrophotometer, electrochemical impedance (EIS), atomic force (AFM) and transmission electron microscopies. The dependence of their functional properties on coating and growth conditions was studied in detail. It was found that the thin films show a uniform permeability in the frequency range of 200 MHz to 1 Ghz and can be used in this range without appreciable changes. Decrease of nitrogen flow rate resulted in the smoother surfaces which in turn increase transmittance quality and corrosion resistance. Functional properties are dependent of nature, relative concentration of the iron nitride phases and film thickness. Surface integrity is excellent for180 nm thick sample because the films appear to be very dense and free from open pores. By keeping sputtering power stable at 110 W, nitrogen flow rate of 10 sccm was ideal to develop the ferromagnetic γʹFe4N phase at room temperature.

Patterning highly ordered arrays of complex nanofeatures through EUV directed polarity switching of non chemically amplified photoresist

PubMed Central

Ghosh, Subrata; Satyanarayana, V. S. V.; Pramanick, Bulti; Sharma, Satinder K.; Pradeep, Chullikkattil P.; Morales-Reyes, Israel; Batina, Nikola; Gonsalves, Kenneth E.

2016-01-01

Given the importance of complex nanofeatures in the filed of micro-/nanoelectronics particularly in the area of high-density magnetic recording, photonic crystals, information storage, micro-lens arrays, tissue engineering and catalysis, the present work demonstrates the development of new methodology for patterning complex nanofeatures using a recently developed non-chemically amplified photoresist (n-CARs) poly(4-(methacryloyloxy)phenyl)dimethylsulfoniumtriflate) (polyMAPDST) with the help of extreme ultraviolet lithography (EUVL) as patterning tool. The photosensitivity of polyMAPDST is mainly due to the presence of radiation sensitive trifluoromethanesulfonate unit (triflate group) which undergoes photodegradation upon exposure with EUV photons, and thus brings in polarity change in the polymer structure. Integration of such radiation sensitive unit into polymer network avoids the need of chemical amplification which is otherwise needed for polarity switching in the case of chemically amplified photoresists (CARs). Indeed, we successfully patterned highly ordered wide-raging dense nanofeatures that include nanodots, nanowaves, nanoboats, star-elbow etc. All these developed nanopatterns have been well characterized by FESEM and AFM techniques. Finally, the potential of polyMAPDST has been established by successful transfer of patterns into silicon substrate through adaptation of compatible etch recipes. PMID:26975782

Confined stimuli-responsive polymer gel in inverse opal polymer membrane for colorimetric glucose sensor.

PubMed

Honda, Masaki; Kataoka, Kazunori; Seki, Takahiro; Takeoka, Yukikazu

2009-07-21

We developed a totally synthetic colorimetric glucose-sensing system that is composed of glucose-responsive hydrogel particles confined in an inverse opal polymer membrane. This system exhibits structural color on the basis of Bragg diffraction arising from the 3-D ordered structure with periodicity on the order of the wavelength of visible light. The volume of the hydrogel particles reversibly changes as the glucose concentration varies in the separated pores of the inverse opal polymer membrane; this system reveals a reversible change in the color appearance and the peak intensity of the reflection spectra with the variation in the glucose concentration. By careful design of the system, we can detect the important range of glucose concentration around the threshold value for diagnosing diabetes mellitus by using the colorimetric glucose-sensing system.

Biodegradable polymers as non-viral carriers for plasmid DNA delivery.

PubMed

Luten, Jordy; van Nostrum, Cornelus F; De Smedt, Stefaan C; Hennink, Wim E

2008-03-03

Gene therapy holds a great promise for the treatment of acquired and inherited diseases with a genetic origin that are currently incurable. Non-viral gene delivery systems are gaining recognition as an alternative to viral gene vectors for their potential in avoiding immunogenicity and toxicity problems inherently associated with the use of viral systems. Many cationic polymers have been studied both in vitro and in vivo for gene delivery purposes. However, in recent years there has been a focus on biodegradable carrier systems. The potential advantage of biodegradable carriers as compared to their non-degradable counterparts is their reduced toxicity and the avoidance of accumulation of the polymer in the cells after repeated administration. Also, the degradation of the polymer can be used as a tool to release the plasmid DNA into the cytosol. In this article the recent results obtained with two classes of degradable gene delivery systems, namely those based on water-soluble cationic polymers and on micro- and nanoparticles will be summarized and discussed.

Mechanistic modelling of drug release from polymer-coated and swelling and dissolving polymer matrix systems.

PubMed

Kaunisto, Erik; Marucci, Mariagrazia; Borgquist, Per; Axelsson, Anders

2011-10-10

The time required for the design of a new delivery device can be sensibly reduced if the release mechanism is understood and an appropriate mathematical model is used to characterize the system. Once all the model parameters are obtained, in silico experiments can be performed, to provide estimates of the release from devices with different geometries and compositions. In this review coated and matrix systems are considered. For coated formulations, models describing the diffusional drug release, the osmotic pumping drug release, and the lag phase of pellets undergoing cracking in the coating due to the build-up of a hydrostatic pressure are reviewed. For matrix systems, models describing pure polymer dissolution, diffusion in the polymer and drug release from swelling and eroding polymer matrix formulations are reviewed. Importantly, the experiments used to characterize the processes occurring during the release and to validate the models are presented and discussed. Copyright © 2011 Elsevier B.V. All rights reserved.

Dependence of Ion Dynamics on the Polymer Chain Length in Poly(ethylene oxide)-Based Polymer Electrolytes.

PubMed

Chattoraj, Joyjit; Knappe, Marisa; Heuer, Andreas

2015-06-04

It is known from experiments that in the polymer electrolyte system, which contains poly(ethylene oxide) chains (PEO), lithium-cations (Li(+)), and bis(trifluoromethanesulfonyl)imide-anions (TFSI(-)), the cation and the anion diffusion and the ionic conductivity exhibit a similar chain-length dependence: with increasing chain length, they start dropping steadily, and later, they saturate to constant values. These results are surprising because Li-cations are strongly correlated with the polymer chains, whereas TFSI-anions do not have such bonding. To understand this phenomenon, we perform molecular dynamics simulations of this system for four different polymer chain lengths. The diffusion results obtained from our simulations display excellent agreement with the experimental data. The cation transport model based on the Rouse dynamics can successfully quantify the Li-diffusion results, which correlates Li diffusion with the polymer center-of-mass motion and the polymer segmental motion. The ionic conductivity as a function of the chain length is then estimated based on the chain-length-dependent ion diffusion, which shows a temperature-dependent deviation for short chain lengths. We argue that in the first regime, counterion correlations modify the conductivity, whereas for the long chains, the system behaves as a strong electrolyte.

Methods for multi-material stereolithography

DOEpatents

Wicker, Ryan [El Paso, TX; Medina, Francisco [El Paso, TX; Elkins, Christopher [Redwood City, CA

2011-06-14

Methods and systems of stereolithography for building cost-efficient and time-saving multi-material, multi-functional and multi-colored prototypes, models and devices configured for intermediate washing and curing/drying is disclosed including: laser(s), liquid and/or platform level sensing system(s), controllable optical system(s), moveable platform(s), elevator platform(s), recoating system(s) and at least one polymer retaining receptacle. Multiple polymer retaining receptacles may be arranged in a moveable apparatus, wherein each receptacle is adapted to actively/passively maintain a uniform, desired level of polymer by including a recoating device and a material fill/remove system. The platform is movably accessible to the polymer retaining receptacle(s), elevator mechanism(s) and washing and curing/drying area(s) which may be housed in a shielded enclosure(s). The elevator mechanism is configured to vertically traverse and rotate the platform, thus providing angled building, washing and curing/drying capabilities. A horizontal traversing mechanism may be included to facilitate manufacturing between components of SL cabinet(s) and/or alternative manufacturing technologies.

Application of mass spectrometry to process control for polymer material in autoclave curing

NASA Technical Reports Server (NTRS)

Smith, A. C.

1983-01-01

Mass spectrometer analysis of gas samples collected during a cure cycle of polymer materials can be used as a process control technique. This technique is particularly helpful in studying the various types of solvents and resin systems used in the preparation of polymer materials and characterizing the chemical composition of different resin systems and their mechanism of polymerization.

Thermoresponsive Polymers for Nuclear Medicine: Which Polymer Is the Best?

PubMed

Sedláček, Ondřej; Černoch, Peter; Kučka, Jan; Konefal, Rafał; Štěpánek, Petr; Vetrík, Miroslav; Lodge, Timothy P; Hrubý, Martin

2016-06-21

Thermoresponsive polymers showing cloud point temperatures (CPT) in aqueous solutions are very promising for the construction of various systems in biomedical field. In many of these applications these polymers get in contact with ionizing radiation, e.g., if they are used as carriers for radiopharmaceuticals or during radiation sterilization. Despite this fact, radiosensitivity of these polymers is largely overlooked to date. In this work, we describe the effect of electron beam ionizing radiation on the physicochemical and phase separation properties of selected thermoresponsive polymers with CPT between room and body temperature. Stability of the polymers to radiation (doses 0-20 kGy) in aqueous solutions increased in the order poly(N-vinylcaprolactam) (PVCL, the least stable) ≪ poly[N-(2,2-difluoroethyl)acrylamide] (DFP) < poly(N-isopropylacrylamide) (PNIPAM) ≪ poly(2-isopropyl-2-oxazoline-co-2-n-butyl-2-oxazoline) (POX). Even low doses of β radiation (1 kGy), which are highly relevant to the storage of polymer radiotherapeutics and sterilization of biomedical systems, cause significant increase in molecular weight due to cross-linking (except for POX, where this effect is weak). In the case of PVCL irradiated with low doses, the increase in molecular weight induced an increase in the CPT of the polymer. For PNIPAM and DFP, there is strong chain hydrophilization leading to an increase in CPT. From this perspective, POX is the most suitable polymer for the construction of delivery systems that experience exposure to radiation, while PVCL is the least suitable and PNIPAM and DFP are suitable only for low radiation demands.

PAH Formation in O-rich Evolved Stars

NASA Astrophysics Data System (ADS)

Guzman-Ramirez, L.; Lagadec, E.; Jones, D.; Zijlstra, A. A.; Gesicki, K.

2015-08-01

Polycyclic aromatic hydrocarbons (PAHs) have been observed in O-rich planetary nebulae. This combination of oxygen-rich and carbon-rich material, known as dual-dust or mixed chemistry, is not expected to be seen around these objects. We recently proposed that PAHs could be formed from the photodissociation of CO in dense tori. Using VISIR/VLT, we spatially resolved the emission of the PAH bands and ionised emission from the [S IV] line, confirming the presence of dense central tori in all the observed O-rich objects. Furthermore, we show that for most of the objects, PAHs are located at the outer edge of these dense/compact tori, while the ionised material is mostly present in the inner parts, consistent with our hypothesis for the formation of PAHs in these systems. The presence of a dense torus has been strongly associated with the action of a central binary star and, as such, the rich chemistry seen in these regions may also be related to the formation of exoplanets in post-common-envelope binary systems.

Tools to Perform Local Dense 3D Reconstruction of Shallow Water Seabed ‡

PubMed Central

Avanthey, Loïca; Beaudoin, Laurent; Gademer, Antoine; Roux, Michel

2016-01-01

Tasks such as distinguishing or identifying individual objects of interest require the production of dense local clouds at the scale of these individual objects of interest. Due to the physical and dynamic properties of an underwater environment, the usual dense matching algorithms must be rethought in order to be adaptive. These properties also imply that the scene must be observed at close range. Classic robotized acquisition systems are oversized for local studies in shallow water while the systematic acquisition of data is not guaranteed with divers. We address these two major issues through a multidisciplinary approach. To efficiently acquire on-demand stereoscopic pairs using simple logistics in small areas of shallow water, we devised an agile light-weight dedicated system which is easy to reproduce. To densely match two views in a reliable way, we devised a reconstruction algorithm that automatically accounts for the dynamics, variability and light absorption of the underwater environment. Field experiments in the Mediterranean Sea were used to assess the results. PMID:27196913

Arbitrary electron acoustic waves in degenerate dense plasmas

NASA Astrophysics Data System (ADS)

Rahman, Ata-ur; Mushtaq, A.; Qamar, A.; Neelam, S.

2017-05-01

A theoretical investigation is carried out of the nonlinear dynamics of electron-acoustic waves in a collisionless and unmagnetized plasma whose constituents are non-degenerate cold electrons, ultra-relativistic degenerate electrons, and stationary ions. A dispersion relation is derived for linear EAWs. An energy integral equation involving the Sagdeev potential is derived, and basic properties of the large amplitude solitary structures are investigated in such a degenerate dense plasma. It is shown that only negative large amplitude EA solitary waves can exist in such a plasma system. The present analysis may be important to understand the collective interactions in degenerate dense plasmas, occurring in dense astrophysical environments as well as in laser-solid density plasma interaction experiments.

Liquid-liquid separation in solutions of normal and sickle cell hemoglobin

NASA Astrophysics Data System (ADS)

Galkin, Oleg; Chen, Kai; Nagel, Ronald L.; Elison Hirsch, Rhoda; Vekilov, Peter G.

2002-06-01

We show that in solutions of human hemoglobin (Hb)oxy- and deoxy-Hb A or Sof near-physiological pH, ionic strength, and Hb concentration, liquid-liquid phase separation occurs reversibly and reproducibly at temperatures between 35 and 40°C. In solutions of deoxy-HbS, we demonstrate that the dense liquid droplets facilitate the nucleation of HbS polymers, whose formation is the primary pathogenic event for sickle cell anemia. In view of recent results that shifts of the liquid-liquid separation phase boundary can be achieved by nontoxic additives at molar concentrations up to 30 times lower than the protein concentrations, these findings open new avenues for the inhibition of the HbS polymerization.

Structure and dynamics in low-dimensional guest host solids

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

Fischer, J.

1991-04-01

This progress report presents results from work during the period of June 1, 1990 through May 31st, 1991. Topics discussed include instrumentation, publications, and personnel. Work areas discussed include: pressure-induced transitions in Li- and Ag-TiS{sub 2}, hyper-dense superconducting GIC's, temperature-dependent x-ray structure of (CH){sub x} and (CH){sub 2{sup x}}:analogies to rotator phases in short-chain alkanes, trans-(CH){sub x} at high'' pressure, broken symmetries'' in polymer intercalation channel lattices, high-resolution study of conductivity and cell potential vs. concentration in K-doped (CH){sub x}, new'' doped (CH){sub x} phases: ternary compounds and amorphous'' intercalation compounds, and vibrational density states from inelastic neutron scattering. (JF).

Controlled Release of Antimicrobial ClO2 Gas from a Two-Layer Polymeric Film System.

PubMed

Bai, Zhifeng; Cristancho, Diego E; Rachford, Aaron A; Reder, Amy L; Williamson, Alexander; Grzesiak, Adam L

2016-11-16

We report a two-component label system comprising a chlorite-containing polymer film and an acid-containing polymer film that can release antimicrobial ClO 2 gas upon adhering the two films together to enable a reaction of the chlorite and acid under moisture exposure. The chlorite-containing film comprises a commercial acrylate-based pressure-sensitive adhesive polymer impregnated with sodium chlorite. The acid-containing film comprises a commercial poly(vinyl alcohol) polymer loaded with tartaric acid. Both of the films were prepared on low ClO 2 -absorbing substrate films from stable aqueous systems of the polymers with high reagent loading. Rapid and sustained releases of significant amounts of ClO 2 gas from the label system were observed in an in situ quantification system using UV-vis spectroscopy. It was found that the ClO 2 release is slower at a lower temperature and can be accelerated by moisture in the atmosphere and the films. Controlled release of ClO 2 gas from the label system was demonstrated by tailoring film composition and thickness. A model was developed to extract release kinetics and revealed good conversions of the label system. This two-component system can potentially be applied as a two-part label without premature release for applications in food packaging.

Treatment System for Removing Halogenated Compounds from Contaminated Sources

NASA Technical Reports Server (NTRS)

Clausen, Christian A. (Inventor); Yestrebsky, Cherie L. (Inventor); Quinn, Jacqueline W. (Inventor)

2015-01-01

A treatment system and a method for removal of at least one halogenated compound, such as PCBs, found in contaminated systems are provided. The treatment system includes a polymer blanket for receiving at least one non-polar solvent. The halogenated compound permeates into or through a wall of the polymer blanket where it is solubilized with at least one non-polar solvent received by said polymer blanket forming a halogenated solvent mixture. This treatment system and method provides for the in situ removal of halogenated compounds from the contaminated system. In one embodiment, the halogenated solvent mixture is subjected to subsequent processes which destroy and/or degrade the halogenated compound.

Coupling nonlinear optical waves to photoreactive and phase-separating soft matter: Current status and perspectives

NASA Astrophysics Data System (ADS)

Biria, Saeid; Morim, Derek R.; An Tsao, Fu; Saravanamuttu, Kalaichelvi; Hosein, Ian D.

2017-10-01

Nonlinear optics and polymer systems are distinct fields that have been studied for decades. These two fields intersect with the observation of nonlinear wave propagation in photoreactive polymer systems. This has led to studies on the nonlinear dynamics of transmitted light in polymer media, particularly for optical self-trapping and optical modulation instability. The irreversibility of polymerization leads to permanent capture of nonlinear optical patterns in the polymer structure, which is a new synthetic route to complex structured soft materials. Over time more intricate polymer systems are employed, whereby nonlinear optical dynamics can couple to nonlinear chemical dynamics, opening opportunities for self-organization. This paper discusses the work to date on nonlinear optical pattern formation processes in polymers. A brief overview of nonlinear optical phenomenon is provided to set the stage for understanding their effects. We review the accomplishments of the field on studying nonlinear waveform propagation in photopolymerizable systems, then discuss our most recent progress in coupling nonlinear optical pattern formation to polymer blends and phase separation. To this end, perspectives on future directions and areas of sustained inquiry are provided. This review highlights the significant opportunity in exploiting nonlinear optical pattern formation in soft matter for the discovery of new light-directed and light-stimulated materials phenomenon, and in turn, soft matter provides a platform by which new nonlinear optical phenomenon may be discovered.

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer.

PubMed

Baker, Matthew B; Albertazzi, Lorenzo; Voets, Ilja K; Leenders, Christianus M A; Palmans, Anja R A; Pavan, Giovanni M; Meijer, E W

2015-02-20

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer

NASA Astrophysics Data System (ADS)

Baker, Matthew B.; Albertazzi, Lorenzo; Voets, Ilja K.; Leenders, Christianus M. A.; Palmans, Anja R. A.; Pavan, Giovanni M.; Meijer, E. W.

2015-02-01

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Structure and Entanglement Factors on Dynamics of Polymer-Grafted Nanoparticles

DOE PAGES

Liu, Siqi; Senses, Erkan; Jiao, Yang; ...

2016-04-15

Nanoparticles functionalized with long polymer chains at low graft density are interesting systems to study structure–dynamic relationships in polymer nanocomposites since they are shown to aggregate into strings in both solution and melts and also into spheres and branched aggregates in the presence of free polymer chains. Our work investigates structure and entanglement effects in composites of polystyrene-grafted iron oxide nanoparticles by measuring particle relaxations using X-ray photon correlation spectroscopy. And for particles within highly ordered strings and aggregated systems, they experience a dynamically heterogeneous environment displaying hyperdiffusive relaxation commonly observed in jammed soft glassy systems. Furthermore, particle dynamics ismore » diffusive for branched aggregated structures which could be caused by less penetration of long matrix chains into brushes. These results suggest that particle motion is dictated by the strong interactions of chains grafted at low density with the host matrix polymer.« less

Semi-2-interpenetrating polymer networks of high temperature systems

NASA Technical Reports Server (NTRS)

Hanky, A. O.; St. Clair, T. L.

1985-01-01

A semi-interpenetrating (semi-IPN) polymer system of the semi-2-IPN type is described in which a polymer of acetylene-terminated imidesulfone (ATPISO2) is cross linked in the presence of polyimidesulfone (PISO2). Six different formulations obtained by mixing of either ATPISO2-1n or ATPISO2-3n with PISO2 in three different proportions were characterized in terms of glass transition temperature, thermooxidative stability, inherent viscosity, and dynamic mechanical properties. Adhesive (lap shear) strength was tested at elevated temperatures on aged samples of adhesive scrim cloth prepared from each resin. Woven graphite (Celion 1000)/polyimide composites were tested for flexural strength, flexural modulus, and shear strength. The network polymers have properties intermediate between those of the component polymers alone, have greatly improved processability over either polyimide, and are able to form good adhesive bonds and composites, making the semi-2-IPN systems superior materials for aerospace structures.

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

NASA Astrophysics Data System (ADS)

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.

Preceramic Polymers for Use as Fiber Coatings

NASA Technical Reports Server (NTRS)

Heimann, P. J.; Hurwitz, F. I.; Wheeler, D.; Eldridge, J.; Baranwal, R.; Dickerson, R.

1996-01-01

Polymeric precursors to Si-C-O, SI-B-N and Si-C were evaluated for use as ceramic interfaces in ceramic matrix composites. Use of the preceramic polymers allows for easy dip coating of fibers from dilute solutions of a polymer, which are then pyrolyzed to obtain the ceramic. SCS-0 fibers (Textron Specialty Materials, Lowell, MA) were coated with polymers from three systems: polysilsesquioxanes, polyborosilazanes and polycarbosilanes. The polysilsesquioxane systems were shown to produce either silicon oxycarbide or silicon oxynitride, depending on the pyrolysis conditions, and demonstrated some promise in an RBSN (reaction-bonded silicon nitride) matrix model system. Polyborosilazanes were shown, in studies of bulk polymers, to give rise to oxidation resistant Si-B-N ceramics which remain amorphous to temperatures of 1600 C, and should therefore provide a low modulus interface. Polycarbosilanes produce amorphous carbon-rich Si-C materials which have demonstrated oxidation resistance.

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

Chew, K. W.; Tan, C. G.; Osman, Z.

The effects of plasticizer and lithium salt on PMMA-based solid polymer electrolyte have been investigated. In current project, three system samples consisted of pure poly(methyl methacrylate (PMMA) system, plasticized poly(methyl methacrylate)(PMMA-EC) system and the LiCF{sub 3}SO{sub 3} salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF{sub 3}SO{sub 3}) system have been prepared using solution casting technique. The conductivities of the films from each system are characterized by impedance spectroscopy and infrared spectrum. With the addition of plasticizer, results show improvement on the ionic conductivity value where the value of 6.25x10{sup -10} Scm{sup -1} is obtained. This may be due tomore » the nature of plasticizer that softens the polymer and hence enhanced the ionic transportation across the polymer. The room temperature conductivity for the highest conducting sample in the ([PMMA-EC]-LiCF{sub 3}SO{sub 3}) system is 1.36x10{sup -5} Scm{sup -1}. Fourier Transform Infrared Spectroscopy (FTIR) indicates complexation between the polymer and the plasticizer and the polymer, the plasticizer and the salts, and the result of XRD further supports the observation.« less

The Role of Nanofillers in Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Xu, Di

Polymer nanocomposites have been widely used in many fields. By introducing nanoparticles as fillers, researchers are able to get reinforced materials and new materials with novel properties, such as stronger mechanics, enhanced optical properties and improved conductivity. Though experimental techniques have rapidly advanced to enable better control of materials at atomic level, there is still a lack of a fundamental understanding of the dynamics and structure-properties relations in polymer nanocomposites. In this thesis, we use computer simulations to study the molecular structure and connections between microstate to macro properties of a variety of nanocomposites. Our goal is to understand the role of nanofillers in complex nanocomposite systems and to assist nanocomposite design. Nanoplatelet fillers, such as clays, have shown superior effects on the properties of polymer gels. We used molecular dynamic simulation to study nanoplatelet-filled composite gel system, in which short-range attraction exists between the polymer and nanoplatelet fillers. We show that the polymers and nanoplatelet fillers formed organic-inorganic networks with nanoplatelets acting as crosslink junctions, and the network eventually percolates the system as fillers reached a critical concentration. Stress auto-correlation and step-strain test were applied to investigate the mechanical properties; the results show the simulated composites changed from fluid-like to solid-like. The mechanical changes were consistent with the percolation transition, and gelation mechanism was therefore believed to be similar to those pure polymer physical gels. It was observed platelets aggregated into a local intercalation structure, which significantly differs from typical spherical fillers. This unique intercalation structure was examined by radial distribution function and ordering parameters. We discussed how intercalation would affect the properties of the platelet composites by comparing them with spherical fillers. Nanofillers have been widely used in polymer blends to improve the interfacial compatibility of otherwise immiscible polymers. In the second system, we investigated the interfacial behavior of binary polymer blends with different types of fillers. The interfacial tension and shear resistance were studied as a function of filler-polymer interaction, filler concentration and species of fillers. We found filler-polymer interaction is the key factor to improve the interfacial compatibility. The results show that nanofillers reduce both interfacial tension and interfacial slip at strong filler-polymer interaction. The effects of nanofillers however differ significantly from each other by their shapes. We analyzed the structure of nanofillers at the interface and their effects on the interfacial behaviors. The self-assembly of polymers into a columnar structure, while subject to a thin film environment, provides an economic route to fabricate polymer solar cell (PSC) with high conversion efficiency. In our work, we showed that two immiscible polymer segregates into to a percolating columnar structure when confined to a thin film. By adding nanofillers, with specific functionality, we can template the segregation of nanofillers to the polymer-polymer interface. We prove this process is surface tension driven and is a result that is particular for thin film geometries, where the thickness is under critical value. The results provide a theoretical basis for the column structure forming in a self-assembled PSC system, and can help to select polymer candidates that optimize PSC efficiency. These studies serve as theoretical guideline for engineering novel nanocomposites, and could lead to the design of materials with new and improved properties.

Mechanism of the dielectric enhancement in polymer-alumina nano-particle composites

NASA Astrophysics Data System (ADS)

Jacob, Rebecca; Jacob, Anne Pavitra; Mainwaring, David E.

2009-09-01

Polymer-alumina nano-composites with enhanced dielectric properties as a possibility to enable the miniaturization of devices have been reported. The enhancement of dielectric properties was found to be unique to the polymer. In the present work, the mechanism of the dielectric enhancement is established by performing ab initio molecular orbital calculations in order to study the molecular interactions in the interfacial region between the alumina-nano-particle surface and the polymer medium. The calculations predict the existence of strong electrostatic attraction between the positive charge on the aluminium of the alumina clusters and the negative charge of the oxygens of the polymer at the polymer-nano-particle interface resulting in an increase in the dipole moment and the polarization of the system leading to enhanced dielectric properties. The oxygen thus plays a dual role by involving in covalent bonding with the polymer chain and electrostatic bonding interactions with the alumina nano-particles. The unique structure of the polymer provides the highly electronegative oxygens, as carbonyl groups or ether linkages in conjugation with aromatic rings in an extended polymer chain system, facilitating this type of bonding at the interface.

Long-term reduction in poly(dimethylsiloxane) surface hydrophobicity via cold-plasma treatments.

PubMed

Larson, B J; Gillmor, S D; Braun, J M; Cruz-Barba, L E; Savage, D E; Denes, F S; Lagally, M G

2013-10-22

Poly(dimethylsiloxane), PDMS, a versatile elastomer, is the polymer of choice for microfluidic systems. It is inexpensive, relatively easy to pattern, and permeable to oxygen. Unmodified PDMS is highly hydrophobic. It is typically exposed to an oxygen plasma to reduce this hydrophobicity. Unfortunately, the PDMS surface soon returns to its original hydrophobic state. We present two alternative plasma treatments that yield long-term modification of the wetting properties of a PDMS surface. An oxygen plasma pretreatment followed by exposure to a SiCl4 plasma and an oxygen-CCl4 mixture plasma both cause a permanent reduction in the hydrophobicity of the PDMS surface. We investigate the properties of the plasma-treated surfaces with X-ray photoelectron spectroscopy (XPS) and contact angle measurements. We propose that the plasma treated PDMS surface is a dynamic mosaic of high- and low-contact-angle functionalities. The SiCl4 and CCl4 plasmas attach polar groups that block coverage of the surface by low-molecular-weight groups that exist in PDMS. We describe an application that benefits from these new plasma treatments, the use of a PDMS stencil to form dense arrays of DNA on a surface.

Difference in EUV photoresist design towards reduction of LWR and LCDU

NASA Astrophysics Data System (ADS)

Jiang, Jing; De Simone, Danilo; Vandenberghe, Geert

2017-03-01

Pattern fidelity of EUV lithography is crucial for high resolution features, since small variation can affect device performance and even cause short or open circuit. For 1D features, dense lines and contact holes are the most common features for active, metal and contact layer, therefore line width roughness (LWR) and local critical dimension uniformity (LCDU) are important indexes to monitor. Both LWR and LCDU are greatly influenced by photon and acid shot noise. In addition, LWR is also affected by resist mechanical properties, like pattern collapse. In this study, we studied the influence of different chemically amplified resist components, such as polymer, PAG and quencher for both types and concentrations in order to understand the relative extent of influences of deprotection, acid diffusion, and base neutralization on pattern fidelity. However, conventional methods to approach higher resolution or low LWR/LCDU by sacrificing the dose are not sustainable. In order to continue to improve resist performance, a new component, metal salt sensitizer, is introduced into the resist system. This metal salt is able to achieve 30% dose reduction by increasing EUV absorption, maintaining LWR. We believe metal sensitizer might give us a new way to challenge the RLS trade-off.

Fabrication of chiroptically switchable films via co-gelation of a small chiral gelator with an achiral azobenzene-containing polymer.

PubMed

Yang, Dong; Zhang, Li; Yin, Lu; Zhao, Yin; Zhang, Wei; Liu, Minghua

2017-09-20

Helical polymers are widely found in nature and synthetic functional materials. Although a number of elaborate strategies have been developed to endow polymers with helicity through either covalent bonds or supramolecular techniques, it still remains a challenge to get the desired helical polymers with controlled handedness in an easy but effective manner. In this study, we report an easily accessible gelation-guided self-assembly system where the chirality of a gelator can be easily transferred to an achiral azobenzene-containing polymer during gelation. It is found that during the process of chiral induction, the induced chirality of the polymer was entirely dominated by the molecular chirality of the gelator. Experimentally, achiral azobenzene-containing polymers with different side-chain lengths were doped into a supramolecular gel system formed with amphiphilic N,N'-bis-(octadecyl)-l(d)-Boc-glutamic (LBG-18 or DBG-18 for short). CD spectra and SEM observation confirmed that the co-assembly of polymer/LBG-18 or polymer/DBG-18 in the xerogel state exhibited supramolecular chirality. More importantly, alternate UV and visible light irradiation on the xerogel film caused the induced CD signal to switch between on and off states. Thus a chiroptical switch was fabricated based on the isomerization of the azo-polymer in xerogel films.

NREL, Giner Evaluated Polymer Electrolyte Membrane for Maximizing Renewable

Science.gov Websites

Energy on Grid | Energy Systems Integration Facility | NREL Giner NREL, Giner Evaluated Polymer -scale polymer electrolyte membrane (PEM) stack designed to maximize renewable energy on the grid by converting it to hydrogen when supply exceeds demand. Photo of a polymer electrolyte membrane stack in a

TOPICAL REVIEW: Monitoring of polymer melt processing

NASA Astrophysics Data System (ADS)

Alig, Ingo; Steinhoff, Bernd; Lellinger, Dirk

2010-06-01

The paper reviews the state-of-the-art of in-line and on-line monitoring during polymer melt processing by compounding, extrusion and injection moulding. Different spectroscopic and scattering techniques as well as conductivity and viscosity measurements are reviewed and compared concerning their potential for different process applications. In addition to information on chemical composition and state of the process, the in situ detection of morphology, which is of specific interest for multiphase polymer systems such as polymer composites and polymer blends, is described in detail. For these systems, the product properties strongly depend on the phase or filler morphology created during processing. Examples for optical (UV/vis, NIR) and ultrasonic attenuation spectra recorded during extrusion are given, which were found to be sensitive to the chemical composition as well as to size and degree of dispersion of micro or nanofillers in the polymer matrix. By small-angle light scattering experiments, process-induced structures were detected in blends of incompatible polymers during compounding. Using conductivity measurements during extrusion, the influence of processing conditions on the electrical conductivity of polymer melts with conductive fillers (carbon black or carbon nanotubes) was monitored.

Fast equilibration protocol for million atom systems of highly entangled linear polyethylene chains

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

Sliozberg, Yelena R.; TKC Global, Inc., Aberdeen Proving Ground, Maryland 21005; Kröger, Martin

Equilibrated systems of entangled polymer melts cannot be produced using direct brute force equilibration due to the slow reptation dynamics exhibited by high molecular weight chains. Instead, these dense systems are produced using computational techniques such as Monte Carlo-Molecular Dynamics hybrid algorithms, though the use of soft potentials has also shown promise mainly for coarse-grained polymeric systems. Through the use of soft-potentials, the melt can be equilibrated via molecular dynamics at intermediate and long length scales prior to switching to a Lennard-Jones potential. We will outline two different equilibration protocols, which use various degrees of information to produce the startingmore » configurations. In one protocol, we use only the equilibrium bond angle, bond length, and target density during the construction of the simulation cell, where the information is obtained from available experimental data and extracted from the force field without performing any prior simulation. In the second protocol, we moreover utilize the equilibrium radial distribution function and dihedral angle distribution. This information can be obtained from experimental data or from a simulation of short unentangled chains. Both methods can be used to prepare equilibrated and highly entangled systems, but the second protocol is much more computationally efficient. These systems can be strictly monodisperse or optionally polydisperse depending on the starting chain distribution. Our protocols, which utilize a soft-core harmonic potential, will be applied for the first time to equilibrate a million particle system of polyethylene chains consisting of 1000 united atoms at various temperatures. Calculations of structural and entanglement properties demonstrate that this method can be used as an alternative towards the generation of entangled equilibrium structures.« less

Tuning the Protein Corona of Hydrogel Nanoparticles: The Synthesis of Abiotic Protein and Peptide Affinity Reagents.

PubMed

O'Brien, Jeffrey; Shea, Kenneth J

2016-06-21

Nanomaterials, when introduced into a complex, protein-rich environment, rapidly acquire a protein corona. The type and amount of proteins that constitute the corona depend significantly on the synthetic identity of the nanomaterial. For example, hydrogel nanoparticles (NPs) such as poly(N-isopropylacrylamide) (NIPAm) have little affinity for plasma proteins; in contrast, carboxylated poly(styrene) NPs acquire a dense protein corona. This range of protein adsorption suggests that the protein corona might be "tuned" by controlling the chemical composition of the NP. In this Account, we demonstrate that small libraries of synthetic polymer NPs incorporating a diverse pool of functional monomers can be screened for candidates with high affinity and selectivity to targeted biomacromolecules. Through directed synthetic evolution of NP compositions, one can tailor the protein corona to create synthetic organic hydrogel polymer NPs with high affinity and specificity to peptide toxins, enzymes, and other functional proteins, as well as to specific domains of large proteins. In addition, many NIPAm NPs undergo a change in morphology as a function of temperature. This transformation often correlates with a significant change in NP-biomacromolecule affinity, resulting in a temperature-dependent protein corona. This temperature dependence has been used to develop NP hydrogels with autonomous affinity switching for the protection of proteins from thermal stress and as a method of biomacromolecule purification through a selective thermally induced catch and release. In addition to temperature, changes in pH or buffer can also alter a NP protein corona composition, a property that has been exploited for protein purification. Finally, synthetic polymer nanoparticles with low nanomolar affinity for a peptide toxin were shown to capture and neutralize the toxin in the bloodstream of living mice. While the development of synthetic polymer alternatives to protein affinity reagents is in its early stages, these recent successes using only small libraries of functional monomers are most encouraging. It is likely that by expanding the chemical diversity of functional hydrogels and other polymers, a much broader range of NP-biomacromolecule affinity pairs will result. Since these robust, nontoxic polymers are readily synthesized in the chemistry laboratory, we believe the results presented in this Account offer a promising future for the development of low cost alternatives to more traditional protein affinity reagents such as antibodies.

DEVELOPMENT OF LOW-DIFFUSION FLUX-SPLITTING METHODS FOR DENSE GAS-SOLID FLOWS

EPA Science Inventory

The development of a class of low-diffusion upwinding methods for computing dense gas-solid flows is presented in this work. An artificial compressibility/low-Mach preconditioning strategy is developed for a hyperbolic two-phase flow equation system consisting of separate solids ...

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

PubMed

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

2015-01-01

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

Amylose-Based Cationic Star Polymers for siRNA Delivery

PubMed Central

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

2015-01-01

A new siRNA delivery system using a cationic glyco-star polymer is described. Spermine-modified 8-arm amylose star polymer (with a degree of polymerization of approximately 60 per arm) was synthesized by chemoenzymatic methods. The cationic star polymer effectively bound to siRNA and formed spherical complexes with an average hydrodynamic diameter of 230 nm. The cationic 8-arm star polymer complexes showed superior cellular uptake characteristics and higher gene silencing effects than a cationic 1-arm polymer. These results suggest that amylose-based star polymers are a promising nanoplatform for glycobiomaterials. PMID:26539548

Nanostructural self-organization and dynamic adaptation of metal-polymer tribosystems

NASA Astrophysics Data System (ADS)

Mashkov, Yu. K.

2017-02-01

The results of investigating the effect of nanosize modifiers of a polymer matrix on the nanostructural self-organization of polymer composites and dynamic adaptation of metal-polymer tribosystems, which considerably affect the wear resistance of polymer composite materials, have been analyzed. It has been shown that the physicochemical nanostructural self-organization processes are developed in metal-polymer tribosystems with the formation of thermotropic liquid-crystal structures of the polymer matrix, followed by the transition of the system to the stationary state with a negative feedback that ensures dynamic adaptation of the tribosystem to given operating conditions.

The origins of microstructure in phase inversion coatings or membranes: Snapshots of the transient from time-sectioning cryo-SEM

NASA Astrophysics Data System (ADS)

Prakash, Sai Sivasankaran

2001-11-01

Time-sectioning cryogenic scanning electron microscopy (cryo-SEM) is a unique method of visualizing how the microstructure of liquid coatings evolves during processing. Time-sectioning means rapidly freezing (nearly) identical specimens at successively later stages of the process; doing this requires that coating and drying be well controlled in the dry phase inversion process, and solvents exchange likewise in the wet phase inversion process. With control, frozen specimens are fractured, etched by limited sublimation, sputter-coated, and imaged at temperatures of ca -175°C. The coatings examined were of cellulose acetate, of high and low molecular weights, and polysulfone in mixed solvents and nonsolvents: acetone and water with cellulose acetate undergoing dry phase inversion; and tetrahydrofuran, dimethylacetamide, ethanol with polysulfone undergoing dry-wet phase inversion. All coatings, cast on silicon substrates, were initially homogeneous. The initial compositions of the high and low molecular weight cellulose acetate ternary solutions were "off-critical" and "near-critical", respectively, connoting their proximities to the critical or plait point of the phase diagram. The initial composition of the polysulfone quaternary solution was located near the binodal of the pseudo-ternary phase diagram. It appeared that as the higher molecular weight cellulose acetate coating dries, it nucleates and grows polymer-poor droplets that coalesce into a bicontinuous structure underlying a thin, dense skin. Bicontinuity of structure was verified by stereomicroscopy of the dry sample. The lower molecular weight cellulose acetate coating phase-separates, seemingly spinodally, directly into a bicontinuous structure whose polymer-rich network, stressed by frustrated in-plane shrinkage, ruptures far beneath the skin in some locales to form macrovoids. When, after partial drying, the polysulfone coating was immersed in a bath of water, a nonsolvent, it appeared to swell in thickness as it phase-separates. A dense skin, thinner than a micron, appeared to overlie a two-phase substructure that is punctuated with pear-shaped macrovoids. At early immersion times, this substructure is visibly bicontinuous or open-celled near the bath-side, and dispersion-like (droplets dispersed in a polymeric matrix) or closed-celled near the substrate-side. Moreover, in the bicontinuous regions, length-scales of the individual phases seem to increase across the coating thickness from the bath-side to the substrate-side. After prolonged immersion, the substructure, excluding the macrovoids, is entirely bicontinuous. The bicontinuity presumably results from a combination of spinodal decomposition and nucleation and growth plus coalescence. Quite strikingly, macrovoids are present exclusively in regions where phases are bicontinuous, and are absent where droplets are dispersed in the polymeric matrix. Evidence suggests that macrovoids result from an instability caused by a progressive rupture of polymer-rich links deeper and deeper beneath the skin, aggravated by stress localization in the rupturing network and a buildup of pressure in the polymer-poor phase (the pore space), as suspected by Grobe and Meyer in 1959.

Holographic Recording Materials Development

NASA Technical Reports Server (NTRS)

Verber, C. M.; Schwerzel, R. E.; Perry, P. J.; Craig, R. A.

1976-01-01

Organic photorefractive materials were evaluated for application in a reversible holographic memory system. Representative indigo and thioindigo derivatives and several stilbene derivatives were studied as well as 15, 16-dialkyldihydropyrene derivatives the following goals were achieved: (1) the successful writing of phase holograms in a thioindigo/polymer gel system, (2) the successful writing and erasing of phase holograms in a variety of indigo/polymer gel and indigo/solid polymer systems, and (3) the identification of indigoid dyes and 15, 16-dialkyldihydropyrene derivatives as materials potentially suitable for utilization in an operational system. Photochemical studies of the stilbene, indigo, thioindigo, and dialkyldihydropyrene derivatives in solution and in a variety of polymer matrix materials were conducted with the goal of optimizing the photorefractive behavior of the chemical system as a whole. The spectroscopic properties required of optimal photorefractive materials were identified, and it was shown that both the indigoid dyes and the dialkyldihydropyrenes closely match the required properties.

Hybrid protein-synthetic polymer nanoparticles for drug delivery.

PubMed

Koseva, Neli S; Rydz, Joanna; Stoyanova, Ekaterina V; Mitova, Violeta A

2015-01-01

Among the most common nanoparticulate systems, the polymeric nanocarriers have a number of key benefits, which give a great choice of delivery platforms. Nevertheless, polymeric nanoparticles possess some limitations that include use of toxic solvents in the production process, polymer degradation, drug leakage outside the diseased tissue, and polymer cytotoxicity. The combination of polymers of biological and synthetic origin is an appealing modern strategy for the production of novel nanocarriers with unprecedented properties. Proteins' interface can play an important role in determining bioactivity and toxicity and gives perspective for future development of the polymer-based nanoparticles. The design of hybrid constructs composed of synthetic polymer and biological molecules such as proteins can be considered as a straightforward tool to integrate a broad spectrum of properties and biofunctions into a single device. This review discusses hybrid protein-synthetic polymer nanoparticles with different structures and levels in complexity and functionality, in view of their applications as drug delivery systems. © 2015 Elsevier Inc. All rights reserved.

Environmental Catastrophes in the Earth's History Due to Solar Systems Encounters with Giant Molecular Clouds

NASA Technical Reports Server (NTRS)

Pavlov, Alexander A.

2011-01-01

In its motion through the Milky Way galaxy, the solar system encounters an average density (>=330 H atoms/cubic cm) giant molecular cloud (GMC) approximately every 108 years, a dense (approx 2 x 103 H atoms/cubic cm) GMC every approx 109 years and will inevitably encounter them in the future. However, there have been no studies linking such events with severe (snowball) glaciations in Earth history. Here we show that dramatic climate change can be caused by interstellar dust accumulating in Earth's atmosphere during the solar system's immersion into a dense (approx ,2 x 103 H atoms/cubic cm) GMC. The stratospheric dust layer from such interstellar particles could provide enough radiative forcing to trigger the runaway ice-albedo feedback that results in global snowball glaciations. We also demonstrate that more frequent collisions with less dense GMCs could cause moderate ice ages.

Elasticity-induced force reversal between active spinning particles in dense passive media

PubMed Central

Aragones, J. L.; Steimel, J. P.; Alexander-Katz, A.

2016-01-01

The self-organization of active particles is governed by their dynamic effective interactions. Such interactions are controlled by the medium in which such active agents reside. Here we study the interactions between active agents in a dense non-active medium. Our system consists of actuated, spinning, active particles embedded in a dense monolayer of passive, or non-active, particles. We demonstrate that the presence of the passive monolayer alters markedly the properties of the system and results in a reversal of the forces between active spinning particles from repulsive to attractive. The origin of such reversal is due to the coupling between the active stresses and elasticity of the system. This discovery provides a mechanism for the interaction between active agents in complex and structured media, opening up opportunities to tune the interaction range and directionality via the mechanical properties of the medium. PMID:27112961

Leachability of boron from wood treated with natural and semi-synthetic polymers and calcium precipitating agent

Treesearch

S. N. Kartal; F. Green

2003-01-01

Several fixation systems to limit or decrease boron leachability from treated wood have been developed. Some attempts have relied on limiting of water penetration of treated wood using water repellents, monomer and polymer systems. On the other hand, non-toxic polymers such as proteins were tried to reduce amount of boron leached from wood (Thevenon et al. 1997, 1998...

Molecular simulation of dispersion and mechanical stability of organically modified layered silicates in polymer matrices

NASA Astrophysics Data System (ADS)

Fu, Yao-Tsung

The experimental analysis of nanometer-scale separation processes and mechanical properties at buried interfaces in nanocomposites has remained difficult. We have employed molecular dynamics simulation in relation to available experimental data to alleviate such limitations and gain insight into the dispersion and mechanical stability of organically modified layered silicates in hydrophobic polymer matrices. We analyzed cleavage energies of various organically modified silicates as a function of the cation exchange capacity, surfactant head group chemistry, and chain length using MD simulations with the PCFF-PHYLLOSILICATE force field. The range of the cleavage energy is between 25 and 210 mJ/m2 upon the molecular structures and packing of surfactants. As a function of chain length, the cleavage energy indicates local minima for interlayer structures comprised of loosely packed layers of alkyl chains and local maxima for interlayer structures comprised of densely packed layers of alkyl chains between the layers. In addition, the distribution of cationic head groups between the layers in the equilibrium state determines whether large increases in cleavage energy due to Coulomb attraction. We have also examined mechanical bending and failure mechanisms of layered silicates on the nanometer scale using molecular dynamics simulation in comparison to a library of TEM data of polymer nanocomposites. We investigated the energy of single clay lamellae as a function of bending radius and different cation density. The layer energy increases particularly for bending radii below 20 nm and is largely independent of cation exchange capacity. The analysis of TEM images of agglomerated and exfoliated aluminosilicates of different CEC in polymer matrices at small volume fractions showed bending radii in excess of 100 nm due to free volumes in the polymer matrix. At a volume fraction >5%, however, bent clay layers were found with bending radii <20 nm and kinks as a failure mechanism in good agreement with simulation results. We have examined thermal conductivity of organically modified layered silicates using molecular dynamics simulation in comparison to experimental results by laser measurement. The thermal conductivity slightly increased from 0.08 to 0.14 Wm-1K-1 with increasing chain length, related to the gallery spacing and interlayer density of the organic material.

The impact of ultra-low amounts of amino-modified MMT on dynamics and properties of densely cross-linked cyanate ester resins

NASA Astrophysics Data System (ADS)

Bershtein, Vladimir; Fainleib, Alexander; Egorova, Larisa; Gusakova, Kristina; Grigoryeva, Olga; Kirilenko, Demid; Konnikov, Semen; Ryzhov, Valery; Yakushev, Pavel; Lavrenyuk, Natalia

2015-04-01

Thermostable nanocomposites based on densely cross-linked cyanate ester resins (CER), derived from bisphenol E and doped by 0.01 to 5 wt. % amino-functionalized 2D montmorillonite (MMT) nanoparticles, were synthesized and characterized using Fourier transform infrared (FTIR), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDXS), wide-angle X-ray diffraction (WAXD), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), far-infrared (Far-IR), and creep rate spectroscopy (CRS) techniques. It was revealed that ultra-low additives, e.g., 0.025 to 0.1 wt. %, of amino-MMT nanolayers covalently embedded into CER network exerted an anomalously large impact on its dynamics and properties resulting, in particular, in some suppression of dynamics, increasing the onset of glass transition temperature by 30° to 40° and twofold rise of modulus in temperature range from 20°C to 200°C. Contrarily, the effects became negligibly small or even negative at increased amino-MMT contents, especially at 2 and 5 wt. %. That could be explained by TEM/EDXS data displaying predominance of individual amino-MMT nanolayers and their thin (2 to 3 nanolayers) stacks over more thick tactoids (5 to 10 nanolayers) and the large amino-MMT aggregates (100 to 500 nm in thickness) reversing the composite structure produced with increasing of amino-MMT content within CER matrix. The revealed effect of ultra-low amino-MMT content testifies in favor of the idea about the extraordinarily enhanced long-range action of the `constrained dynamics' effect in the case of densely cross-linked polymer networks.

Quantum Linear System Algorithm for Dense Matrices.

PubMed

Wossnig, Leonard; Zhao, Zhikuan; Prakash, Anupam

2018-02-02

Solving linear systems of equations is a frequently encountered problem in machine learning and optimization. Given a matrix A and a vector b the task is to find the vector x such that Ax=b. We describe a quantum algorithm that achieves a sparsity-independent runtime scaling of O(κ^{2}sqrt[n]polylog(n)/ε) for an n×n dimensional A with bounded spectral norm, where κ denotes the condition number of A, and ε is the desired precision parameter. This amounts to a polynomial improvement over known quantum linear system algorithms when applied to dense matrices, and poses a new state of the art for solving dense linear systems on a quantum computer. Furthermore, an exponential improvement is achievable if the rank of A is polylogarithmic in the matrix dimension. Our algorithm is built upon a singular value estimation subroutine, which makes use of a memory architecture that allows for efficient preparation of quantum states that correspond to the rows of A and the vector of Euclidean norms of the rows of A.

An investigative study of polymer adsorption onto montmorillonite clay

NASA Astrophysics Data System (ADS)

McConnell Boykin, Cheri Lynn

For colloidal systems with adsorbed polymer, the mechanisms governing stabilization and flocculation are defined by the critical overlap concentration, c*. Below c*, steric stabilization or bridging flocculation are viable mechanisms of adsorption, while above c* associative thickening stabilization, depletion stabilization or depletion flocculation may occur. While these types of systems have been described by their mechanism of interaction, few studies have been geared towards evaluating and actually defining these interactions. This research focuses on elucidating the mechanisms of interaction for a series of polyacrylamide copolymers adsorbed onto montmorillonite clay. The well-defined copolymers synthesized and characterized for these studies include: nonionic polyacrylamide, (PAm); cationic poly(acrylamide-co-[3-(methacryloylamino) propyl] trimethylammonium chloride), (PAmMaap Quat); nonionic/anionic poly(acrylamide-co-acrylic acid), (PAmAA); and anionic poly(acrylamide-co-[2-acrylamido-2-methylpropane sulfonic acid]), (PAmAmps). By combining the results from the following experiments it was possible to determine the mechanisms of interaction for each of the clay/polymer systems at pH 3, 7 and 10. The adsorption capacity of each of the copolymers was determined from constructing adsorption isotherms while the polymer conformation was determined from 13C NMR line-broadening experiments. FTIR spectroscopy verified which surface of the clay was involved in adsorption along with the polymer moiety bound to the surface. Finally, the stabilization behavior was evaluated from statistically designed phase diagrams as a function of polymer and clay concentrations. By evaluating the phase behavior as well as c* for the polymer/solvent systems, it was determined that there was no direct correlation between c* for a polymer/solvent system and the mechanism of interaction for colloid/polymer/solvent systems previously defined by Vincent, Sato and Napper. In general, the nonionic polymers act as H-bond acceptors (amide and acid moieties) and donators (acid groups) which result in associatively stabilized homogeneous montmorillonite clay dispersions. The cationic copolymers exhibit strong, irreversible interactions with the clay resulting in heterogeneous bridging flocculation, which was shown to be dependent on the charge density of the copolymer. Furthermore, the anionic copolymers show no signs of adsorption, but create a network of repulsive forces with the montmorillonite clay, which ultimately results in depletion stabilization with some degree of depletion flocculation.

TiO2 as conductivity enhancer in PVdF-HFP polymer electrolyte system

NASA Astrophysics Data System (ADS)

Bhattacharya, Shreya; Manojkumar Ubarhande, Radha; Usha Rani, M.; Shanker Babu, Ravi; Arunkumar, R.

2017-11-01

Composite polymer electrolytes were prepared by incorporating inorganic filler TiO2 into PVdF-HFP-PMMA-EC-LiClO4 system. The electrolyte films were prepared by solvent casting technique. The effect of inorganic filler on the conductivity of the blended polymer electrolyte was studied and it is found that there is a considerable increase in ionic conductivity 1.296 × 10-3 S/cm-1 on the addition of TiO2. X-ray diffraction (XRD) study elucidate the increase in amorphous nature of the polymer electrolyte. This tendency of the polymer electrolyte could be the reason behind the increase in ionic conductivity. Fourier transform infrared spectroscopy (FTIR) spectra show the occurrence of complexation and interaction among the components.

Synthesis of organosilicon compounds

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

Zhao, G.

1996-01-01

Silicon-containing polymers have been a focus of synthesis and study in Dr. Barton`s group because of their chemistry and properties which are not offered by other systems or materials. For example, the polymer -[-SiMe 2C≡C-] n-can be easily processed to films or fibers from melt or solution, and thermally converted to a SiC-containing ceramic in high yield at high temperature. In recent years, carbosilane dendritic polymers have been of great interests in many research groups. However, no synthesis of carbosilane dendrimers with functionalties both inside and outside the dendrimer has been reported. Functionality is very important in the synthesis ofmore » preceramic polymers. This thesis will be devoted to exploring several new organosilicon polymer systems.« less

Piezoelectric Polymers

NASA Technical Reports Server (NTRS)

Harrison, J. S.; Ounaies, Z.; Bushnell, Dennis M. (Technical Monitor)

2001-01-01

The purpose of this review is to detail the current theoretical understanding of the origin of piezoelectric and ferroelectric phenomena in polymers; to present the state-of-the-art in piezoelectric polymers and emerging material systems that exhibit promising properties; and to discuss key characterization methods, fundamental modeling approaches, and applications of piezoelectric polymers. Piezoelectric polymers have been known to exist for more than forty years, but in recent years they have gained notoriety as a valuable class of smart materials.

Optical Pumping of High Power Lasers with an Array of Plasma Pinches.

DTIC Science & Technology

1986-04-01

Two dense plasma focus systems, the hypocycloidal pinch and the Mather type were investigated as the potential excitation light sources for high...was also performed for the first time using the Mather type dense plasma focus (MDPF) sucsessfully. Results thus fare indicate that both HCP and MDPF

In situ creation of reactive polymer nanoparticles and resulting polymer layers formed at the interfaces of liquid crystals (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kang, Shin-Woong; Kundu, Sudarshan; Park, Heung-Shik; Oh, Keun Chan; Lyu, Jae Jin

2017-02-01

We report the in situ creation of reactive polymer nanoparticles and resulting polymer networks formed at the interfaces of liquid crystals. It is known that polymerization-induced phase separation proceeds in two distinct regimes depending on the concentration of monomer. For a high monomer concentration, phase separation occurs mainly through the spinodal decomposition process, consequently resulting in interpenetrating polymer networks. For a dilute system, however, the phase separation mainly proceeds and completes in the binodal decomposition regime. The system resembles the aggregation process of colloidal particle. In this case, the reaction kinetics is limited by the reaction between in situ created polymer aggregates and hence the network morphologies are greatly influenced by the diffusion of reactive polymer particles. The thin polymer layers localized at the surface of substrate are inevitably observed and can be comprehended by the interfacial adsorption and further cross-linking reaction of reactive polymer aggregates at the interface. This process provides a direct perception on understanding polymer stabilized liquid crystals accomplished by the interfacial polymer layer. The detailed study has been performed for an extremely dilute condition (below 0.5 wt%) by employing systematic experimental approaches. Creation and growth of polymer nanoparticles have been measured by particle size analyzer. The interfacial localization of polymer aggregates and resulting interfacial layer formation with a tens of nanometer scale have been exploited at various interfaces such as liquid-solid, liquid-liquid, and liquid-gas interfaces. The resulting interfacial layers have been characterized by using fuorescent confocal microscope and field emission scanning electron microscope. The detailed processes of the polymer stabilized vertically aligned liquid crystals will be discussed in support of the reported study.

A high-speed tracking algorithm for dense granular media

NASA Astrophysics Data System (ADS)

Cerda, Mauricio; Navarro, Cristóbal A.; Silva, Juan; Waitukaitis, Scott R.; Mujica, Nicolás; Hitschfeld, Nancy

2018-06-01

Many fields of study, including medical imaging, granular physics, colloidal physics, and active matter, require the precise identification and tracking of particle-like objects in images. While many algorithms exist to track particles in diffuse conditions, these often perform poorly when particles are densely packed together-as in, for example, solid-like systems of granular materials. Incorrect particle identification can have significant effects on the calculation of physical quantities, which makes the development of more precise and faster tracking algorithms a worthwhile endeavor. In this work, we present a new tracking algorithm to identify particles in dense systems that is both highly accurate and fast. We demonstrate the efficacy of our approach by analyzing images of dense, solid-state granular media, where we achieve an identification error of 5% in the worst evaluated cases. Going further, we propose a parallelization strategy for our algorithm using a GPU, which results in a speedup of up to 10 × when compared to a sequential CPU implementation in C and up to 40 × when compared to the reference MATLAB library widely used for particle tracking. Our results extend the capabilities of state-of-the-art particle tracking methods by allowing fast, high-fidelity detection in dense media at high resolutions.

Dense power-law networks and simplicial complexes

NASA Astrophysics Data System (ADS)

Courtney, Owen T.; Bianconi, Ginestra

2018-05-01

There is increasing evidence that dense networks occur in on-line social networks, recommendation networks and in the brain. In addition to being dense, these networks are often also scale-free, i.e., their degree distributions follow P (k ) ∝k-γ with γ ∈(1 ,2 ] . Models of growing networks have been successfully employed to produce scale-free networks using preferential attachment, however these models can only produce sparse networks as the numbers of links and nodes being added at each time step is constant. Here we present a modeling framework which produces networks that are both dense and scale-free. The mechanism by which the networks grow in this model is based on the Pitman-Yor process. Variations on the model are able to produce undirected scale-free networks with exponent γ =2 or directed networks with power-law out-degree distribution with tunable exponent γ ∈(1 ,2 ) . We also extend the model to that of directed two-dimensional simplicial complexes. Simplicial complexes are generalization of networks that can encode the many body interactions between the parts of a complex system and as such are becoming increasingly popular to characterize different data sets ranging from social interacting systems to the brain. Our model produces dense directed simplicial complexes with power-law distribution of the generalized out-degrees of the nodes.

Modeling semiflexible polymer networks

NASA Astrophysics Data System (ADS)

Broedersz, C. P.; MacKintosh, F. C.

2014-07-01

This is an overview of theoretical approaches to semiflexible polymers and their networks. Such semiflexible polymers have large bending rigidities that can compete with the entropic tendency of a chain to crumple up into a random coil. Many studies on semiflexible polymers and their assemblies have been motivated by their importance in biology. Indeed, cross-linked networks of semiflexible polymers form a major structural component of tissue and living cells. Reconstituted networks of such biopolymers have emerged as a new class of biological soft matter systems with remarkable material properties, which have spurred many of the theoretical developments discussed here. Starting from the mechanics and dynamics of individual semiflexible polymers, the physics of semiflexible bundles, entangled solutions, and disordered cross-linked networks are reviewed. Finally, recent developments on marginally stable fibrous networks, which exhibit critical behavior similar to other marginal systems such as jammed soft matter, are discussed.

An in-situ infection detection sensor coating for urinary catheters.

PubMed

Milo, Scarlet; Thet, Naing Tun; Liu, Dan; Nzakizwanayo, Jonathan; Jones, Brian V; Jenkins, A Toby A

2016-07-15

We describe a novel infection-responsive coating for urinary catheters that provides a clear visual early warning of Proteus mirabilis infection and subsequent blockage. The crystalline biofilms of P. mirabilis can cause serious complications for patients undergoing long-term bladder catheterisation. Healthy urine is around pH 6, bacterial urease increases urine pH leading to the precipitation of calcium and magnesium deposits from the urine, resulting in dense crystalline biofilms on the catheter surface that blocks urine flow. The coating is a dual layered system in which the lower poly(vinyl alcohol) layer contains the self-quenching dye carboxyfluorescein. This is capped by an upper layer of the pH responsive polymer poly(methyl methacrylate-co-methacrylic acid) (Eudragit S100®). Elevation of urinary pH (>pH 7) dissolves the Eudragit layer, releasing the dye to provide a clear visual warning of impending blockage. Evaluation of prototype coatings using a clinically relevant in vitro bladder model system demonstrated that coatings provide up to 12h advanced warning of blockage, and are stable both in the absence of infection, and in the presence of species that do not cause catheter blockage. At the present time, there are no effective methods to control these infections or provide warning of impending catheter blockage. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Effect of fabric structure and polymer matrix on flexural strength, interlaminar shear stress, and energy dissipation of glass fiber-reinforced polymer composites

USDA-ARS?s Scientific Manuscript database

We report the effect of glass fiber structure and the epoxy polymer system on the flexural strength, interlaminar shear stress (ILSS), and energy absorption properties of glass fiber-reinforced polymer (GFRP) composites. Four different GFRP composites were fabricated from two glass fiber textiles of...

[The action of high-molecular linear polymers on the circulatory system].

PubMed

Grigorian, S S; Sokolova, I A; Shakhnazarov, A A

1995-01-01

An analysis of the hemodynamic consequences of the injections of long linear polymers with high molecular weight is introduced. These injections lead to an increase of the cardiac output, to a decrease of the blood pressure, and hence cause a reduction of the resistance to blood flow. It follows that such kind of polymers is able to normalize hemodynamics under some pathophysiological conditions, e.g., during experimental atherosclerosis, ischemic state, hemorrhagic shock. An addition of drag-reducing polymers into the blood system is associated with a modification of the blood flow microstructure itself.

Tellurium-containing polymer micelles: competitive-ligand-regulated coordination responsive systems.

PubMed

Cao, Wei; Gu, Yuwei; Meineck, Myriam; Li, Tianyu; Xu, Huaping

2014-04-02

Nanomaterials capable of achieving tunable cargo release kinetics are of significance in a fundamental sense and various biological or medical applications. We report a competitive coordination system based on a novel tellurium-containing polymer and its ligand-regulated release manners. Tellurium was introduced to water-soluble polymers for the first time as drug delivery vehicles. The coordination chemistry between platinum and tellurium was designed to enable the load of platinum-based drugs. Through the competitive coordination of biomolecules, the drugs could be released in a controlled manner. Furthermore, the release kinetics could be modulated by the competitive ligands involved due to their different coordination ability. This tellurium-containing polymer may enrich the family of delivery systems and provide a new platform for future biomedical nanotechnologies.

Polymer-Polymer Förster Resonance Energy Transfer Significantly Boosts the Power Conversion Efficiency of Bulk-Heterojunction Solar Cells.

PubMed

Gupta, Vinay; Bharti, Vishal; Kumar, Mahesh; Chand, Suresh; Heeger, Alan J

2015-08-01

Optically resonant donor polymers can exploit a wider range of the solar spectrum effectively without a complicated tandem design in an organic solar cell. Ultrafast Förster resonance energy transfer (FRET) in a polymer-polymer system that significantly improves the power conversion efficiency in bulk heterojunction polymer solar cells from 6.8% to 8.9% is demonstrated, thus paving the way to achieving 15% efficient solar cells. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The relationships between breast volume, breast dense volume and volumetric breast density with body mass index, body fat mass and ethnicity

NASA Astrophysics Data System (ADS)

Zakariyah, N.; Pathy, N. B.; Taib, N. A. M.; Rahmat, K.; Judy, C. W.; Fadzil, F.; Lau, S.; Ng, K. H.

2016-03-01

It has been shown that breast density and obesity are related to breast cancer risk. The aim of this study is to investigate the relationships of breast volume, breast dense volume and volumetric breast density (VBD) with body mass index (BMI) and body fat mass (BFM) for the three ethnic groups (Chinese, Malay and Indian) in Malaysia. We collected raw digital mammograms from 2450 women acquired on three digital mammography systems. The mammograms were analysed using Volpara software to obtain breast volume, breast dense volume and VBD. Body weight, BMI and BFM of the women were measured using a body composition analyser. Multivariable logistic regression was used to determine the independent predictors of increased overall breast volume, breast dense volume and VBD. Indians have highest breast volume and breast dense volume followed by Malays and Chinese. While Chinese are highest in VBD, followed by Malay and Indian. Multivariable analysis showed that increasing BMI and BFM were independent predictors of increased overall breast volume and dense volume. Moreover, BMI and BFM were independently and inversely related to VBD.

Effect of cold drawing on mechanical properties of biodegradable fibers.

PubMed

La Mantia, Francesco Paolo; Ceraulo, Manuela; Mistretta, Maria Chiara; Morreale, Marco

2017-01-26

Biodegradable polymers are currently gaining importance in several fields, because they allow mitigation of the impact on the environment related to disposal of traditional, nonbiodegradable polymers, as well as reducing the utilization of oil-based sources (when they also come from renewable resources). Fibers made of biodegradable polymers are of particular interest, though, it is not easy to obtain polymer fibers with suitable mechanical properties and to tailor these to the specific application. The main ways to tailor the mechanical properties of a given biodegradable polymer fiber are based on crystallinity and orientation control. However, crystallinity can only marginally be modified during processing, while orientation can be controlled, either during hot drawing or cold stretching. In this paper, a systematic investigation of the influence of cold stretching on the mechanical and thermomechanical properties of fibers prepared from different biodegradable polymer systems was carried out. Rheological and thermal characterization helped in interpreting the orientation mechanisms, also on the basis of the molecular structure of the polymer systems. It was found that cold drawing strongly improved the elastic modulus, tensile strength and thermomechanical resistance of the fibers, in comparison with hot-spun fibers. The elastic modulus showed higher increment rates in the biodegradable systems upon increasing the draw ratio.

Development of Simulation Methods in the Gibbs Ensemble to Predict Polymer-Solvent Phase Equilibria

NASA Astrophysics Data System (ADS)

Gartner, Thomas; Epps, Thomas; Jayaraman, Arthi

Solvent vapor annealing (SVA) of polymer thin films is a promising method for post-deposition polymer film morphology control. The large number of important parameters relevant to SVA (polymer, solvent, and substrate chemistries, incoming film condition, annealing and solvent evaporation conditions) makes systematic experimental study of SVA a time-consuming endeavor, motivating the application of simulation and theory to the SVA system to provide both mechanistic insight and scans of this wide parameter space. However, to rigorously treat the phase equilibrium between polymer film and solvent vapor while still probing the dynamics of SVA, new simulation methods must be developed. In this presentation, we compare two methods to study polymer-solvent phase equilibrium-Gibbs Ensemble Molecular Dynamics (GEMD) and Hybrid Monte Carlo/Molecular Dynamics (Hybrid MC/MD). Liquid-vapor equilibrium results are presented for the Lennard Jones fluid and for coarse-grained polymer-solvent systems relevant to SVA. We found that the Hybrid MC/MD method is more stable and consistent than GEMD, but GEMD has significant advantages in computational efficiency. We propose that Hybrid MC/MD simulations be used for unfamiliar systems in certain choice conditions, followed by much faster GEMD simulations to map out the remainder of the phase window.

Advances in polymeric systems for tissue engineering and biomedical applications.

PubMed

Ravichandran, Rajeswari; Sundarrajan, Subramanian; Venugopal, Jayarama Reddy; Mukherjee, Shayanti; Ramakrishna, Seeram

2012-03-01

The characteristics of tissue engineered scaffolds are major concerns in the quest to fabricate ideal scaffolds for tissue engineering applications. The polymer scaffolds employed for tissue engineering applications should possess multifunctional properties such as biocompatibility, biodegradability and favorable mechanical properties as it comes in direct contact with the body fluids in vivo. Additionally, the polymer system should also possess biomimetic architecture and should support stem cell adhesion, proliferation and differentiation. As the progress in polymer technology continues, polymeric biomaterials have taken characteristics more closely related to that desired for tissue engineering and clinical needs. Stimuli responsive polymers also termed as smart biomaterials respond to stimuli such as pH, temperature, enzyme, antigen, glucose and electrical stimuli that are inherently present in living systems. This review highlights the exciting advancements in these polymeric systems that relate to biological and tissue engineering applications. Additionally, several aspects of technology namely scaffold fabrication methods and surface modifications to confer biological functionality to the polymers have also been discussed. The ultimate objective is to emphasize on these underutilized adaptive behaviors of the polymers so that novel applications and new generations of smart polymeric materials can be realized for biomedical and tissue engineering applications. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal and energetic processing of astrophysical ice analogues rich in SO2

NASA Astrophysics Data System (ADS)

Kaňuchová, Z.; Boduch, Ph.; Domaracka, A.; Palumbo, M. E.; Rothard, H.; Strazzulla, G.

2017-08-01

Context. Sulfur is an abundant element in the cosmos and it is thus an important contributor to astrochemistry in the interstellar medium and in the solar system. Astronomical observations of the gas and of the solid phases in the dense interstellar/circumstellar regions have evidenced that sulfur is underabundant. The hypothesis to explain such a circumstance is that it is incorporated in some species in the solid phase (I.e. as frozen gases and/or refractory solids) and/or in the gas phase, which for different reasons have not been observed so far. Aims: Here we wish to give a contribution to the field by studying the chemistry induced by thermal and energetic processing of frozen mixtures of sulfur dioxide (one of the most abundant sulfur-bearing molecules observed so far) and water. Methods: We present the results of a series of laboratory experiments concerning thermal processing of different H2O:SO2 mixtures and ion bombardment (30 keV He+) of the same mixtures. We used in situ Fourier transform infrared (FTIR) spectroscopy to investigate the induced effects. Results: The results indicate that ionic species such as HSO, HSO, and S2O are easily produced. Energetic processing also produces SO3 polymers and a sulfurous refractory residue. Conclusions: The produced ionic species exhibit spectral features in a region that, in astronomical spectra of dense molecular clouds, is dominated by strong silicate absorption. However, such a dominant feature is associated with some spectral features, some of which have not yet been identified. We suggest adding the sulfur-bearing ionic species to the list of candidates to help explain some of those features. In addition, we suggest that once expelled in the gas phase by sublimation, due to the temperature increase, and/or by non-thermal erosion those species would constitute a class of molecular ions not detected so far. We also suggest that molecular sulfur-bearing ions could be present on the surfaces and/or in the atmospheres of several objects in the solar system, for example icy satellites of the giant planets and comets.