Search results for " transition"

Processing and adjusting the hydrophilicity of poly(oxymethylene) (co)polymers: nanoparticle preparation and film formation

2016

Handling the insoluble POM: the preparation of nanoparticles based on hyperbranched-linear-hyperbranched ABA triblock copolymers with variable hydrophilicity and composed of short hyperbranched polyglycerol (hbPG) as the A-blocks and linear poly(oxymethylene) (POM) as a B-block is described. The POM-hbPG-nanoparticles with diameters in the range of 190 to 250 nm were generated in a convenient process, combining the solvent evaporation process with the miniemulsion technique, a water borne handling for POM-copolymers. Furthermore, the film formation properties of the nanoparticles were investigated by deposition on silicon and subsequent sintering, which leads to films with a thickness in th…

Influence of the cross-linking density on the main dielectric relaxation of poly(methyl acrylate) networks.

2005

A series of polymer networks of varying cross-linking density was prepared by copolymerization of methyl acrylate and ethyleneglycol dimethacrylate. The aim of this work is to study the influence of cross-linking on the conformational mobility of the polymer chains using dielectric relaxation spectroscopy (DRS) in the temperature range of the main dielectric relaxation. As expected, the temperature range in which glass transition takes place became wider with increasing crosslinking density. DRS results were analyzed using the Havriliak-Negami equation. Master Cole-Cole arcs could be drawn for all the networks. The arcs become more symmetric as cross-linking density increases, as a conseque…

Isobornyl Methacrylate as a Reactive Solvent of Polyethylene

2004

Solutions containing 15 wt, -% of a low-molar-mass polyethylene (PE) in isobornyl methacrylate (IBoMA), containing 0, 5 or 10 wt.-% of 1,4 butanediol dimethacrylate (BDDMA) as crosslinker, were polymerized using either benzoyl peroxide (BPO), at 80°C, or dicumyl peroxide (DCPO), with a thermal cycle attaining 150°C, as initiators. Phase separation of an amorphous PE-rich phase took place when carrying out the reaction at temperatures higher than the PE melting temperature. Partial crystallization of PE was observed when cooling to room temperature. Depending on the initial amount of BDDMA, the fraction of PE that was phase separated varied between 57 and 66% of the initial amount, with crys…

Sorption of n-hexane in amorphous polystyrene

2014

Sorption properties of pure n-hexane vapor in amorphous polystyrene (PS) were studied at 298 K by thermogravimetry under controlled vapor pressure. Two sorption-desorption cycles were performed by varying the relative pressure between 0 and 0.91. Mixing of PS with n-hexane resulted in a strong plasticization, which was evidenced by quite significant depression in the glass transition temperature of the polymer as shown by differential scanning calorimetry. Maximum quantity of n-hexane sorbed in the PS at 298 K and at a pressure close to saturation was about 12.4 wt %. The thermogravimetry yielded an isotherm with a strong hysteresis loop, explanation of which was hypothesized with the help …

Dielectric properties of a filled epoxy resin: Effect of thermal treatments

1982

Dielectric measurements have been performed at several frequencies on samples of a cycloaliphatic epoxy resin filled with aluminum hydroxide. The samples were thermally treated at three different temperatures for times up to 2,000 hours. At low aging temperatures and times an improvement of the characteristics is observed due perhaps to an assessment of the bulk of the polymer and more precisely to a change in the free volume. At high temperatures and times a thermo-oxidation involving layers deeper and deeper becomes the predominant mechanism responsible of the decrease in the properties with respect to the virgin material.

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…

Relaxation processes and glass transition of confined polymer melts: A molecular dynamics simulation of 1,4-polybutadiene between graphite walls.

2017

Molecular dynamics simulations of a chemically realistic model for 1,4-polybutadiene in a thin film geometry confined by two graphite walls are presented. Previous work on melts in the bulk has shown that the model faithfully reproduces static and dynamic properties of the real material over a wide temperature range. The present work studies how these properties change due to nano-confinement. The focus is on orientational correlations observable in nuclear magnetic resonance experiments and on the local intermediate incoherent neutron scattering function, Fs(qz, z, t), for distances z from the graphite walls in the range of a few nanometers. Temperatures from about 2Tg down to about 1.15Tg…

Monte Carlo simulation of the glass transition in polymer melts: An application of MCT

1995

Abstract This paper reviews the results of a large scale Monte Carlo simulation for the dynamics of a supercooled polymer melt. The dynamics of the melt was studied by means of the time evolution of the incoherent intermediate scattering function φs q(t), which was monitored over seven decades in time. In an intermediate time window it is possible to describe the decay of φs q(t) quantitatively in the framework of mode-coupling theory, provided the extended version of the theory is used.

1982

The electro-optical properties of liquid crystalline polymers with polar mesogenic units in the side chain were investigated. It could be shown, that in an electric field, they show all effects known from low molecular weight liquid crystals, e.g. the Freedericksz-transition, the DAP-effect, the formation of William's domain, and the dynamic scattering. The optical response times are slightly longer than for low molecular weight liquid crystals, but in some cases at higher temperatures as short as 200 ms. By comparison of different polymers and some corresponding liquid crystalline monomers, it is found that: (1) the difference between the measuring temperature and the glass transition temp…

Calculation of low bandgap homopolymers: Comparison of TD-DFT methods with experimental oligomer series

2016

Made available in DSpace on 2018-12-11T17:26:45Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-02-01 The performance of different DFT functionals (B3LYP, BHLYP, CAM-B3LYP, M06HF) on the prediction of vertical transition energies Evert of low bandgap homopolymers is tested against the experimentally available oligomer series (thienopyrazines and thienothiophenes). This allows for a detailed and accurate comparison on the consistency of DFT methods for chainlength evolution and polymer limit prediction, and for an understanding of geometry and time-dependent contributions to Evert by combinatorial analysis. Together with former studies on wide/medium bandgap polymers and low bandgap c…