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Chemische Physik und Polymerphysik Dienstag CPP 14.3 Di 15:00 H 37 Biorelevant Reactions in Microchannel Mixing Devices Observed by Microbeam-SAXS — •Alexander Otten 1 , Sarah Köster 1 , Bernd Struth 2 , Anatoly Snigirev 2 , and Thomas Pfohl 1 — 1 Angewandte Physik, Universität Ulm, Albert Einstein Allee 11, D-89069 Ulm — 2 ESRF, 6 Rue Horowitz, 38043 Grenoble Cedex, France The application of microfluidic devices does not only allow to analyze small volume fractions of e.g. biomaterial solutions but also gives access to faster observations and improved sample characterization. We use a microchannel device consisting of two crossed channels to examine the behavior of biomacromolecules in elongational flow as well as for studies on biomaterial aggregation. In our microfluidic focussing device a microjet flow is achieved by hydrodynamically focussing a center stream by two symmetric side streams. The elongational flow and the biomaterial aggregation were studied by using the microbeam-SAXS (small angle X-ray scattering) technique. To achieve a spatial resolution of ≈20µm, the x-ray beam was focussed by compound refractive lenses. We present SAXS data on the elongation of DNA molecules in semi-dilute solutions and the increased orientation in the microjet flow. Furthermore, we studied DNA condensation by positively charged countermolecules, G4-Dendrimers. The mixing and the achieved aggregates in respect to different DNA/Dendrimer concentrations were examined and several structural phases were observed. CPP 14.4 Di 15:15 H 37 Structure and elastic properties of a block-copolymer bilayer doped with cationic surfactant — •Thomas Hellweg, Holger Egger, and Gerhard Findenegg — TU Berlin, Stranski Laboratorium f. Physikalische und Theoretische Chemie, Strasse des 17.Juni 112, 10623 Berlin In recent years much attention was paid to the commercially available triblock copolymers poly(ethylene oxide)-poly(propylene oxide)poly(ethylene oxide) (PEO-PPO-PEO). The phase behavior of these polymers, often called pluronics, is investigated intensively in binary systems with water, as well as in ternary systems containing water and oil or in polymer mixtures by a lot of different research groups. In the present work we study the influence of the cationic surfactant noctyltrimethyl-ammonium-bromide (C8TAB) on the triblock copolymer based system (EO37-PO58-EO37)/water/o-xylene. At sufficient high surfactant concentration the system shows an extended lamellar phase (Lα). This phase is characterized in terms of interlamellar spacing, thickness, and internal structure of the bilayers as a function of composition. The Caillé-model is used to correlate the profile of the first order Bragg peak with the elastic constants of the amphiphilic film. It is possible to obtain general trends for the dependence of the elastic constants κ and B of the block-copolymer-film on the surfactant concentration. CPP 14.5 Di 15:30 H 37 Nanophase separation in side chain polymers and the dynamics in self-assembled confinements — •Mario Beiner — FB Physik, Martin-Luther-Universität Halle-Wittenberg, 06099 Halle, Germany Structural and dynamic data for different series of amorphous side chain polymers with long alkyl groups show consistently that a nanophase separation of incompatible main and side chain parts on the one nanometer scale is a common feature of such materials [1]. Long alkyl groups – belonging to different monomeric units and chains – aggregate in the melt and form alkyl nanodomains with a typical size of 0.5-2 nm. The dynamics of the nanophase-separated side chain polymers is characterized by the presence of an additional polyethylene-like glass transition αPE within the alkyl nanodomains. Important features of this αPE process are main chain independent. With increasing size of the alkyl nanodomains a strong-to-fragile transition has been observed in the steepness index of the αPE process as obtained from relaxation spectroscopy measurements. This finding is discussed in the context of cooperative motions in self-assembled confinements and will be related to the long and controversial discussion about the size of dynamic heterogeneities in glasses. This is an interesting link between central questions in glass transition research and structural aspects in nanophase-separated materials. The general importance of nanophase separation effects for an understanding of the dynamics of complex materials in nanotechnology and nature is demonstrated. [1] M. Beiner and H. Huth, Nature Materials 2, 595 (2003) 15 min. Pause CPP 14.6 Di 16:00 H 37 Structural Relaxation and Dynamic Heterogeneity in a Polymer Melt at Attractive Surfaces — •Grant Smith — Department of Materials Science and Engineering, University of Utah, Salt Lake City, Utah, USA Molecular dynamics simulation studies of polymer melts at attractive flat and structured surfaces reveals slowed dynamics and increased dynamic hetergeneity for polymer near the surface. For flat surfaces slow dynamics and increased dynamic heterogeneity of interfacial polymer relative to the bulk was found to be due to densification of the polymer in a surface layer, while for structured surfaces the energy topography of the surface played the dominant role in determining dynamics of interfacial polymer. Much of the dramatic increase in structural relaxation time for the interfacial polymer was found to be the result of dynamic heterogeneity induced by the surfaces. CPP 14.7 Di 16:15 H 37 Single Molecule Studies of Surface Melting in Free Standing Polymer Films — •Frank Cichos 1 and Jörg Schuster 2 — 1 Institut für Physik 123705, TU Chemnitz, 09107 Chemnitz — 2 Institut für Physik 121501, TU Chemnitz, 09107 Chemnitz Thin polymer films show a drastic decrease of the glass transition temperature with decreasing film thickness. While this effect depends on the chain length if the radius of gyration of the polymer chain is on the order of the film thickness, it is independent of it for small molecular weights and thus points to a very general effect involved in the glass transition. We present for the first time results of single molecule studies in free standing polymer films far below the bulk glass transition temperature. By tracking individual fluorescent molecules we are able to follow the local dynamics in the film as a function of temperature. We show that already at temperatures of about 40 K below the bulk glass transition temperature a small highly mobile fraction of dye molecules coexists with a large number of completely immobile molecules. The mobile fraction shows translational diffusion which only weakly depends on temperature. However, the number of molecules released from the film strongly increases with increasing temperature. This increase is explained by the desorption of dye molecules adsorbed at the polymer surface and by the release of molecules from a growing ”molten” layer. We interpret these findings in terms of an inhibition of the glass transition in the film by the dynamics of the surface. This inhibition becomes more effective for smaller film thicknesses and therefore effectively decreases the glass transition temperature of the film compared to the bulk value. CPP 14.8 Di 16:30 H 37 Monte Carlo Simulations of the phase behaviour of polymer brushes — •Ludger Wenning, Marcus Müller, and Kurt Binder — Johannes Gutenberg Universität Mainz A polymer brush in a poor solvent is investigated by Monte Carlo (MC) simulations of a bead-spring-model. A new MC-Move for the inner part of a polymer chain has been devised to efficiently equilibrate the chain conformations. This move is based on the Configurational Bias (CB) algorithm, but in contrast to the CB-move it needs no free end of the polymer chain. Therefore it works for grafted polymers or ring polymers. We observe the transition from a swollen, homogenous brush in a good solvent to a laterally structured cluster phase in a bad solvent. This transition depends on the solvent quality and the surface coverage. Unlike the prediction of self-consistent field theory, clusters do not form a hexagonal lattice, but rather arrange irregularly. Further the influence of the way of grafting is studied. Random grafting leads to slightly larger clusters, which are also more stable at better solvent quality. Moreover we demonstrate how the locations of the clusters correlate with density fluctuations in the grafting points. CPP 14.9 Di 16:45 H 37 Polymeric nanostructures created by destabilization of confined thin films — •P. Müller-Buschbaum 1 , R. Cubitt 2 , and W. Petry 1 — 1 TU München Physik Department LS E13, James-Franck- Str.1, 85747 Garching — 2 ILL, b.p. 156, 38042 Grenoble (France) the concept of self-assembly. Recently, it was shown that from a destabilization of confined ultra-thin films nano-structured polymeric surfaces result [1]. Following the scaling laws of dewetting, due to the reduced amount of polymeric material available, the size of the resulting struc-
Chemische Physik und Polymerphysik Dienstag tures decreases with decreasing film thickness. Destabilizing confined ultra-thin diblock copolymer films thus offers the opportunity to introduce two intrinsic lateral length scales, the characteristic periodicity of the micro phase separation structure Lo and the most prominent in-plane length of the dewetting structure Λ. While on a local scale the surface structure is nicely pictured by atomic force microscopy (AFM) to obtain CPP 15 POSTER: Polymers and Biomaterials a statistically significant information scattering is helpful. With grazing incidence small-angle scattering a length regime from molecular to micrometer-sized and thus comparable to AFM is addressed [2]. [1] P.Müller-Buschbaum, R.Cubitt, W.Petry, Langmuir 19, 7778 (2003) [2] P. Müller-Buschbaum, Anal.Bioanal.Chem. 376, 3 (2003) Zeit: Dienstag 17:00–19:00 Raum: B CPP 15.1 Di 17:00 B Phase-behavior of bidisperse ferrocolloids — •Gabriel M. Range and Sabine H.L. Klapp — Stranski-Laboratorium für Physikalische und Theoretische Chemie, Sekr. TC7, Fakultät II, Technische Universität Berlin, Straße des 17. Juni 124, 10623 Berlin, Germany Using density functional theory in the modified mean-field (MMF) approximation we study the phase behavior of bidisperse ferrocolloids, consisting of a binary mixture of dipolar hard spheres (DHS). We focus on the fluid phase regime, where we consider both isotropic and anisotropic phases. In a recent MMF study of binary mixtures of equisized DHS, differing only in their dipole moments, we found a rich phase behavior resulting from the interplay of isotropic-to-ferroelectric and demixing transitions. In systems with strongly asymmetric dipole moments the isotropic-toferroelectric transition is shifted towards significantly lower temperatures compared to the one-component case, while the demixing transition becomes more and more dominating. We also found, that demixing is always accompanied by spontaneous ferroelectricity in the MMF approach. Based on these findings we analyze the relative importance of differing sizes versus differing dipole moments on the phase-behavior of ferrocolloids. We also investigate the influence of external fields, particularly on demixing and size separation. CPP 15.2 Di 17:00 B Properties and Crystallization of PNIPAM-co-PS core-shell microgels — •Thomas Hellweg — TU Berlin, Stranski Laboratorium, Strasse des 17.Juni 112, 10623 Berlin During the last decade thermosensitive hydrogels have received increasing attention due to their potential with respect to applications in drug delivery or as sensors. However, macroscopic gels have rather long equilibration times with respect to swelling and deswelling. In some cases it might take days until the equilibrium state is reached. Therefore, with respect to applications as sensors or drug delivery systems so called microgels have preferable properties compared to their macroscopic homologues. Recently, these particles were also investigated with respect to their crystallization behaviour. Due to their low polydispersity they form colloidal crystals in solution as usual hard-sphere colloids. Additionally, their response to temperature allows to vary the volume fraction over a wide range. Here, we are going to discuss the properties of poly((N-isopropyl acrylamide)-co-polystyrene (PNIPAM-co-PS) coreshell microgel particles with extended PNIPAM shells. The particles are characterized by dynamic light scattering (DLS), electron microscopy and SANS. CPP 15.3 Di 17:00 B Elastic and Thermal Properties of Nano-Particle Composites within Polymer Matrices — •Andrä le Coutre 1,2 , Bernd Wetzel 3 , Jörg Baller 1,2 , Ravi Bactavatchalou 1,2 , Ulrich Müller 1,2 , and Jan K. Krüger 1,2 — 1 Laboratoire Européen de Recherche Universitaire Saarland-Lorraine (LERUSL) — 2 Universität des Saarlandes, Fakultät für Physik und Elektrotechnik 7.2, Geb. 38, Saarbrücken, Germany — 3 Universität Kaiserslautern, Institut für Verbundwerkstoffe GmbH, Germany Composite systems gain importance in material science as well as in industrial applications. One aim is the improvement of the mechanical properties by reinforcement of polymer matrices with particles or fibers. By means of Brillouin spectroscopy we investigated the effective elastic modulus (compressional and shear modulus) of DGEBA/DETA-epoxies filled with Al2O3 and SiO2 nanoparticles with sizes below 50 nm. In addition to the stiffening as expected by averaging models of elastic properties, an enhanced stiffness for particle concentrations below 6% volume fraction is observed. The reason for this is assumed either to be an effect of a special chemical affinity of the hardening component (DETA) to the nanoparticle surface or a structurizing effect of the surface on the surrounding epoxy matrix. As a kind of inverse situation DGEBA-filled nanoporous glass matrices were investigated giving hints for a structurizing effect of the inner surfaces to the DGEBA molecules. CPP 15.4 Di 17:00 B Micro-Nanopattern by Block Copolymer Micelle Nanolithography — •Roman Glass 1 , Martin Moeller 2 , and Joachim Spatz 1 — 1 Institute for Physical Chemistry, Biophysical Chemistry, University of Heidelberg, Germany — 2 Deutsches Wollforschungsinstitut at the RWTH Aachen, Germany A key issue in the fabrication of functional nanostructures is the defined placement and connection of nanometre sized objects in periodic or aperiodic arrangements on surfaces with different chemical composition and electrical properties. The basis of our approach is the self-assembly of polystyrene-b-poly[2-vinylpyridine (HAuCl4)] diblock copolymer micelles into uniform monomicellar films on solid supports such as Si-wafers or glass cover slips. Subsequent hydrogen plasma treatment of micellar film causes deposition of Au-nanoparticles (between 2 and 8 nm) onto the substrate by entire removal of the polymer. The limitation of the separation distance between individual dots or the pattern geometry is overcome by combining self-assembly of diblock copolymer micelles with pre-structures formed by photo or e-beam lithography. Capillary forces of a retracting liquid film due to solvent evaporation on the pre-structured substrate push micelles in the corners of these defined topographies. A more direct process is demonstrated by applying monomicellar films as negative e-beam resist. This process is also feasible on electrical isolating substrates if the monomicellar film is coated in addition with a 5 nm thick conductive layer of carbon before e-beam treatment. CPP 15.5 Di 17:00 B Chemical Modification of microphase-separated Triblock Terpolymer Films — •Kristin Schmidt, Sabine Ludwigs, Andrej Voronv, Robert Magerle, and Georg Krausch — Physikalische Chemie II, Universität Bayreuth, Bayreuth, Germany In this presentation we discuss a polystyrene-b-poly(2vinylpyridine)-b-poly(tertbutylme thacrylate) triblock terpolymer (SVT) exhibiting a core-shell cylinder structure in bulk (φPS = 0.16, φP2V P = 0.21, φPtBMA = 0.63, Mw = 140k, Mw/Mn = 1.02) which was synthesized via sequential living anionic polymerization 1 . After annealing in controlled solvent vapour atmosphere thin films of these triblock terpolymer self-assemble into a highly ordered perforated lamellae structure with PS-core and a P2VP-shell in the PtBMA matrix phase. A chemical modification of the poly(tertbutylmethacrylate) matrix phase to poly(methacrylic acid) via acid-catalyzed saponification leads to a pH-responsive nanostructure which was investigated with scanning force microscopy in aqueous environment. Furthermore, we show that the perforated lamella might serve as a lithographic mask by selective UV-depolymerization of the poly(tertbutylmethacrylate) matrix phase 2 . 1 Ludwigs, S.; Böker, A.; Abetz, V.; Müller, A.H.E.; Krausch, G. Polymer 2003, 44, 6815 2 Ludwigs, S.; Böker, A.; Voronov, A.; Rehse, N.; Magerle, R.; Krausch, G. Nature Materials 2003, 2, 744 CPP 15.6 Di 17:00 B Response of polyelectrolyte multilayers to external stimuli — •Regine v. Klitzing 1 , John Wong 1 , and Roland Steitz 2 — 1 Stranski-Laboratorium, TU Berlin, Strasse d. 17. Juni 112, 10623 Berlin — 2 Hahn-Meitner-Institut, Glienicker Strasse 100, 14109 Berlin The polymer films presented in this study were made by alternate adsorption of polyanions and polycations from aqueous solution onto solid
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Symposium Physics of Foams Mittwoch
Page 511 and 512:
Symposium Quantum Shot Noise in Nan
Page 513 and 514:
Symposium X-RAY Magneto-Optics Tage
Page 515 and 516:
Symposium X-RAY Magneto-Optics Dien
Page 517 and 518:
Lehrertage Regensburg Hauptvorträg
Page 519 and 520:
A. D., Mirlin .................HL 1
Page 521 and 522:
Breidenbach, Boris ........ AKB 50.
Page 523 and 524:
Elli, Alexandra .............SYLS 3
Page 525 and 526:
Greer, Lindsay ......... M 9.1, M 1
Page 527 and 528:
Horn-von Hoegen, M. O 13.2, O 14.40
Page 529 and 530:
Korn, Tobias ...............MA 13.6
Page 531 and 532:
Martin, Tobias ............. MA 13.
Page 533 and 534:
Partyka, Ewa ................ M 18.
Page 535 and 536:
Rugeramigabo, Eddy Patrick O 14.38,
Page 537 and 538:
Sihler, J. .................... DS
Page 539 and 540:
Volz, K. .................... HL 44
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