Search results for "Gyration"
showing 10 items of 118 documents
Effects of isotopic substitution on the conformational properties of polymeric aqueous solutions
2000
Abstract This work deals with a side-by-side comparison between the PEO conformational properties in H 2 O and D 2 O. The gyration radius, evaluated by SANS, the hydrodynamic radius, evaluated by PCS, and the Raman D-LAM band analysis furnish valuable information on the structural arrangement of the molecules. The findings clearly show different behavioural properties of the polymer in H 2 O and D 2 O.
Complex Formation of DNA with Oppositely Charged Polyelectrolytes of Different Chain Topology: Cylindrical Brushes and Dendrimers
2007
The complex formation between DNA (pUC19-supercoiled DNA, 2686 base pairs) and some polycations of different chain topologies in aqueous solution was studied by light scattering, gel electrophoresis, and AFM. The investigated polycations comprised cylindrical brush polymers with quaternized poly(vinylpyridine) and polyethylene imine side chains as well as a fifth generation dendrimer thus covering a broad molar mass regime of 3 × 104 g mol-1 < Mw < 1 × 107 g mol-1 and very different chemical charges/molecule, Z+, of 127 < Z+ < 5500. Irrespective of the polycation, the complexes formed in dilute solution exhibited a similar size in terms of the mean square radius of gyration, 〈Rg2〉, i.e., 30…
Collapse of Linear Polyelectrolyte Chains in a Poor Solvent: When Does a Collapsing Polyelectrolyte Collect its Counterions?
2008
To better understand the collapse of polyions in poor solvent conditions the effective charge and the solvent quality of the hypothetically uncharged polymer backbone need to be known. In the present work this is achieved by utilizing poly-2-vinylpyridine quaternized to 4.3% with ethylbromide. Conductivity and light scattering measurements were utilized to study the polyion collapse in isorefractive solvent/nonsolvent mixtures consisting of 1-propanol and 2-pentanone, respectively, at nearly constant dielectric constant. The solvent quality of the uncharged polyion could be quantified which, for the first time, allowed the experimental investigation of the effect of the electrostatic intera…
Polymer Films in the Normal-Liquid and Supercooled State: A Review of Recent Monte Carlo Simulation Results
2000
This paper reviews recent Monte Carlo simulation studies of the glassy behavior in thin polymer films. The simulations employ a version of the bond-fluctuation lattice model, in which the glass transition is driven by the competition between a stiffening of the polymers and their dense packing in the melt. The melt is geometrically confined between two impenetrable walls separated by distances ranging from once to about fifteen times the bulk radius of gyration. The confinement influences static and dynamic properties of the films: Chains close to the wall preferentially orient parallel to it. This orientation tendency propagates through the film and leads to a layer structure at low temper…
Dynamics of Glassy Polymer Melts in Confined Geometry: A Monte Carlo Simulation
1996
Dynamic properties of a dense polymer melt confined between two hard walls are investigated over a wide range of temperatures by dynamic Monte Carlo simulation. The temperature interval ranges from the ordinary liquid to the strongly supercooled melt. The influence of temperature, density and confinement on the polymer dynamics is studied by various mean-square displacements, structural relaxation functions and quantities derived from them (relaxation times, apparent diffusion coefficients, monomer relaxation rates), yielding the following results: The motion of the monomers and polymers close to the walls is enhanced in parallel, but reduced in perpendicular direction. This dynamic anisotr…
Unmixing of Polymer Blends Confined in Ultrathin Films: Crossover between Two-Dimensional and Three-Dimensional Behavior
2006
The interplay between chain conformations and phase separation in binary symmetric polymer mixtures confined into thin films by "neutral" hard walls (i.e., walls that do not preferentially attract or repel one of the two components of the mixture) is studied by Monte Carlo simulations. Using the bond fluctuation model on a simple cubic lattice in the semi grand canonical ensemble, we locate the critical temperature of demixing via finite size scaling methods for a wide range of chain lengths (16/= N/= 256 effective monomers per chain) and film thicknesses (2/= D/= 19 lattice spacings). Simultaneously, we investigate the geometrical structure of the chains, showing that despite using melt de…
Statistical properties of linear-hyperbranched graft copolymers prepared via "hypergrafting" of AB(m) monomers from linear B-functional core chains: …
2015
The reaction of ABm monomers (m = 2, 3) with a multifunctional Bf-type polymer chain ("hypergrafting") is studied by coarse-grained molecular dynamics simulations. The ABm monomers are hypergrafted using the slow monomer addition strategy. Fully dendronized, i.e., perfectly branched polymers are also simulated for comparison. The degree of branching of the molecules obtained with the "hypergrafting" process critically depends on the rate with which monomers attach to inner monomers compared to terminal monomers. This ratio is more favorable if the ABm monomers have lower reactivity, since the free monomers then have time to diffuse inside the chain. Configurational chain properties are also…
Determination of the conformation of polymers in the amorphous solid state and in concentrated solution by neutron diffraction
1975
Abstract From the coherent neutron scattering on dilute solid solutions of the ordinary polymer within the deuterated polymer, conformation parameters of polymer chains in amorphous solid states can be determined. In this way vitreous poly(methyl methacrylate) (PMMA) has been investigated. The chains form unperturbed coils and the radius of gyration is very near to the corresponding value in dilute solutions of the same polymer in the low molecular θ-solvent butyl chloride. The same principle of measurement has been applied to concentrated solutions of PMMA in D-acetone. The solutions contained 50% polymer, the main part of which (98% and more) was deuterated so that the system was opticall…
Preparation and determination of the structure of high-performance polymer blends by small-angle neutron scattering
1995
Amorphous blends from a deuterated polyaryletherketone and a polyetherimide have been prepared and investigated by neutron scattering. The used components differ remarkably in their structure antheir solution properties. The blends on the other hand are combinatorial mixtures : the scattering quantity Φ 1 Φ 2 /S(q) is independent of the composition of the blends if the polymer chains have the same length
Reduction of the glass transition temperature in polymer films: A molecular-dynamics study
2001
We present results of molecular dynamics (MD) simulations for a non-entangled polymer melt confined between two completely smooth and repulsive walls, interacting with inner particles via the potential $U_{\rm wall}\myeq (\sigma/z)^9$, where $z \myeq |z_{\rm particle}-z_{\rm wall}|$ and $\sigma$ is (roughly) the monomer diameter. The influence of this confinement on the dynamic behavior of the melt is studied for various film thicknesses (wall-to-wall separations) $D$, ranging from about 3 to about 14 times the bulk radius of gyration. A comparison of the mean-square displacements in the film and in the bulk shows an acceleration of the dynamics due to the presence of the walls. %Consistent…