Search results for "Glass"
showing 10 items of 1153 documents
Molecular dynamics of solid polymers as revealed by deuteron NMR
1983
Pulsed deuteron NMR spectroscopy is described, which has recently been developed to become a powerful tool for studying molecular dynamics in solid polymers. It is shown that by analyzing the line shapes of2H absorption spectra and spectra obtained via solid echo and spin alignment, respectively, both type and timescale of rotational motions can be determined over an extraordinary wide range of characteristic frequencies, approximately 10 MHz to 1 Hz. By applying these techniques to selectively deuterated polymers, motional mechanisms involving different segments of the monomer unit can be monitored. In addition, motional heterogeneities in glassy polymers can be detected. The information a…
Glass transition of polymer melts: Test of theoretical concepts by computer simulation.
2003
Abstract Polymers are good glass formers and allow for the study of melts near the glass transition in (meta-)stable equilibrium. Theories of the glass transition imply such an equilibrium and can, hence, be tested by the study of polymer melts. After a brief summary of the basic experimental facts about the glass transition in polymers, the main theoretical concepts are reviewed: mode coupling theory (MCT), entropy theory, free-volume theory, the idea of a growing length describing the size of cooperative regions, etc. Then, two basic coarse-grained models of polymers are described, which have been developed aiming at a test of these concepts. The first model is the bond-fluctuation model …
Molecular dynamics simulations of the glass transition in polymer melts
2004
Computer simulations of polymer models have contributed strongly to our understanding of the glass transition in polymer melts. The ability of the simulation to provide information on experimentally not directly accessible quantities like the detailed spatial arrangement of the particles allows for stringent tests of theoretical concepts about the glass transition and provides additional insight for the interpretation of experimental data. Comparing coarse-grained simulations of a bead-spring model and chemically realistic simulations of 1,4-polybutadiene the importance of dihedral barriers for the glass transition phenomenon can be elucidated.
Deuteron n.m.r. in relation to the glass transition in polymers
1985
Abstract 2H n.m.r. is introduced as a tool for investigating slow molecular motion in the glass transition region of amorphous polymers. In particular, we compare 2H spin alignment echo spectra of chain deuterated polystyrene with models for restricted rotational Brownian motion. Molecular motion in the polystyrene-toluene system has been investigated by analysing 2H n.m.r. of partially deuterated polystyrene and toluene, respectively. The diluent mobility in the mixed glass has been decomposed into ‘solid’ and ‘liquid’ components where the respective average correlation times differ by more than 5 decades.
Polymer and Dye Probe Diffusion in Poly(methyl methacrylate) below the Glass Transition Studied by Forced Rayleigh Scattering
1999
By dissolving tracer quantities of 9,10-phenanthrenequinone (PQ) in poly(methyl methacrylate) (PMMA) it was possible to study by forced Rayleigh scattering (FRS) the tracer diffusion of the unbleached PQ as well as the photoproduct which is covalently bound to the PMMA molecules. The PMMA samples with molecular weights, Mw, of 103−105 were intermittently annealed at 80 °C for diffusion times of up to one year. From the results we conclude that polymer chain diffusion may be possible at temperatures more than 20 K below the glass transition temperature Tg, but further experiments are necessary, in particular, since we cannot exclude that our results are due to yet unexplained long time aging…
Synthesis and properties of aromatic ionenes
1993
Cationic polyelectrolytes with aromatic segments can be synthesized by a repetitive alkylation reaction. The structure of the products, their synthesis and their solubility are described. All ionenes are not, or only in small amounts, water soluble. The best solubility can be achieved by mixtures of polar protic and aprotic solvents. Variations of the counterion produces sufficient solubility in THF. All ionenes show a typical polyelectrolyte effect. The thermal stability of aromatic ionenes and the glass transition temperature is dominated by the nature of the counterion. The molecular weight of oligomers can be described by using a combination of a conductive titration method and an ion s…
4-Vinylphthalic anhydride
1994
4-Vinylphthalic anhydride can be prepared from phthalic acid via bromination and subsequent olefination (Heck-reaction). Homo- and copolymerization with styrene was accomplished using AIBN as initiator. The copolymer compositions were determined by infrared-spectroscopy. The copolymerization parameters are rs=0,15 and rVPA=3,09, the corresponding Q, e values of 4-vinylphthalic anhydride are estimated as Q=3,34 and e=0.09.
On the handedness of helical aggregates of C3 tricarboxamides: a multichiroptical characterization
2015
A complete chiroptical characterization of the supramolecular polymers formed by tricarboxamides (S)-1 and (R)-1 is performed using ECD, VCD and CPL dichroic techniques. The helical aggregates show an intense CPL signal and their absolute P- or M-configuration is assigned with the help of theoretical calculations.
Monte carlo simulation of the glass transition of polymer melts
2007
The bond fluctuation model of polymer melts is presented as a reasonable compromise between simulation efficiency and realistic chemical detail. It is shown that inclusion of a potential energy that depends on the length of the effective bonds connecting the effective monomers easily creates a conflict between configurational entropy of dense packing and the energetic tendency of the bonds to stretch. This competition leads to a glass transition of the model, which very well describes many features of real systems.
Monte Carlo simulation studies of the interfaces between polymeric and other solids as models for fiber-matrix interactions in advanced composite mat…
1996
As a coarse-grained model for dense amorphous polymer systems interacting with solid walls (i.e., the fiber surface in a composite), the bond fluctuation model of flexible polymer chains confined between two repulsive surfaces is studied by extensive Monte Carlo simulations. Choosing a potential for the length of an effective bond that favors rather long bonds, the full temperature region from ordinary polymer melts down to the glass transition is accessible. It is shown that in the supercooled state near the glass transition an “interphase” forms near the walls, where the structure of the melt is influenced by the surface. This “interphase” already shows up in static properties, but also h…