Search results for "Amorphous solid"
showing 10 items of 622 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…
Homogeneous mixtures of polybetaines with low molecular weight salts
1996
The prepaparation of amorphous, homogeneous blends of zwitterionic polymers with various low molecular weight salts, and in particular with ionic dyes was studied. Homogeneous miscibility was achieved in many cases up to equimolar amounts of salt, even for bulky compounds. Whether miscibility is achieved, or not, depends in a subtle way on the chemical structure of the salt, but no obvious correlation between structure and miscibility could yet be revealed. Spectral shifts of the dye UV/Vis spectra in solution as well as in bulk suggest strong interactions between the polybetaines and the admired salts.
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.
PEO/CHCl3. Crystallinity of the Polymer and Vapor Pressure of the Solvent. Equilibrium and Nonequilibrium Phenomena
2003
Vapor pressures were measured for the system CHCl3/PEO 1000 (PEO stands for poly(ethylene oxide) and 1000 for Mw in kg/mol) at 25 °C as a function of the weight fraction w of the polymer by means of a combination of headspace sampling and gas chromatography. The establishment of thermodynamic equilibria was assisted by employing thin polymer films. The degrees of crystallinity α of the pure PEO and of the solid polymer contained in the mixtures were determined via DSC. An analogous degree of polymer insolubility β was calculated from the vapor pressures measured in this composition range. The experiments demonstrate that both quantities and their concentration dependence are markedly affect…
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…
Residual order in amorphous dry films of polymer latices: indications of an influence of particle interaction
2002
Abstract We report small angle X-ray scattering and atomic force microscopy measurements on macroscopically thick, dry films of polymer latex particles. While the surface of dried droplets has long range order due to layering effects, the overall bulk structure is amorphous. This holds for both low charge polymethylmetacrylate particles and for highly charged polystyrene particles with additional stabilisation with sodiumdodecylsurfate. In the latter case, however, considerable amounts of residual crystal-like order is observed.
Self-Diffusion of Small Molecules into Rubbery Polymers: A Lattice Free-Volume Theory
2010
In the framework of the Free Volume Theory, a new equation was derived for the evaluation of self-diffusion coefficients of small molecules in polymers above the mixture glass transition temperature. The derivation of the equation turned out to be straightforward once the equivalence between the free-volume and the unoccupied volume given by Thermodynamic Lattice Theories is assumed. A parameter evaluation scheme is proposed, which is substantially simpler compared to the conventional Vrentas-Duda approach, even without losing generality. The key assumption is discussed and its consistency is verified from a numerical viewpoint. A comparison with experimental solvent self-diffusion coeffici…
No-Flow Temperature in Injection Molding Simulation
2010
Most injection molding simulation packages use the no-flow temperature (NFT) as a means of determining whether the polymer flows or is solid. The NFT is not well defined, and a standard method for measuring it does not exist. A sensitivity analysis of the filling stage has been carried out with two different packages [VISI Flow (Vero Software Limited, Gloucestershire, UK) and Moldflow (Autodesk, Inc., San Rafael, CA)] to estimate the influence of the NFT on the main processing parameters. The NFT has a large influence on the thickness of the frozen layer, but it does not appreciably affect the filling pressure. Because the NFT affects the frozen layer, an effect on the estimation of shrinka…
Small angle scattering study of the structure of isotactic polypropylene-hydrogenated oligo(cyclopentadiene) blends
1996
Abstract Blends of isotactic polypropylene ( i PP) and hydrogenated oligo cyclopentadiene (HOCP) have been studied by means of small angle X-ray scattering in the temperature range 70–160°C. The structure of blends containing less than 25% HOCP is very similar to the one of plain i PP, i.e. lamellae whose thickness increases by increasing the temperature. Blends containing more than 25% HOCP are characterized by two kinds of lamellae formed by layers of i PP and amorphous material rich in i PP and in HOCP, respectively. The crystallizable i PP present in both phases crystallizes from the melt, in analogy to what happens in HDPE/HOCP blends and in agreement with the values of the crystallini…
Amorphous Complexes MM (EDTA) (H2O)4 · 2H2O . LAXS and XPS Investigation of the Local Structure
1988
Abstract The amorphous MM (EDTA)(H2O)4·2 H2O (M = Ni,Co) substances are made up of infinite chains of alternating "hydrated" and "chelated" octahedra bridged by carboxylate groups: M(H2O)4 - M(EDTA)-M(H2O)4-... . XPS enables to ascertain that the coordination of the EDTA ligand in the amorphous phase is identical to that in the crystalline phase, i.e., hexacoordination toward the M atom and two bridging groups in the Ni -Ni, Co - Co compounds.