Search results for "GLASS"
showing 10 items of 1153 documents
Cure monitoring of catalysed cyanate ester resins
2000
The cure behaviour of two bisphenol A-based cyanate ester resins, AroCy B10 and B30, catalysed by copper acetylacetonate and nonylphenol was studied. For this purpose, differential scanning calorimetric (DSC) and rheological measurements were carried out at temperatures between 130 and 170 °C. The cyanate conversion profiles are fitted with a second-order rate law in the kinetically controlled regime where a good time–temperature superposition is attained. However, it is necessary to add an empirical kinetic term to give a good description of the entire range of curing. Simultaneously, times to gelation and vitrification have been determined by dynamic rheological measurements over the same…
Influence of water, temperature and sucrose on dynamics in glassy starch-based products studied by low field 1H NMR
2009
Abstract In this study, the influence of both water content and temperature on the mobility of glassy starch-based matrices (starch alone or mixed with sucrose at the ratio 0% to 20% db) were studied using time domain 1 H NMR. The 2nd moment M 2 , and transversal relaxation time T 2 ∗ were used to study the molecular mobility of the rigid and mobile fraction of the NMR signal, respectively. The molecular mobility of the protons constituting the samples increased with water content (up to 13% wb) at all temperatures. For a given water content, both rigid and mobile protons exhibited a lower mobility in the presence of sucrose. When mobility characteristic parameters, M 2 second moment values…
Synthesis of linear polyglycerols with tailored degree of methylation by copolymerization and the effect on thermorheological behavior
2017
Abstract We introduce a two-step strategy for the synthesis of linear polyglycerols (linPG-OHx/OMey) with an adjustable degree of methylation ( y = D M 100 ). Ethoxy ethyl glycidyl ether (EEGE) and glycidyl methyl ether (GME) were copolymerized via the “activated monomer” polymerization technique, using tetraoctylammonium bromide (NOct4Br) as an initiator and triisobutylaluminum (i-Bu3Al) as a catalyst under mild conditions. Subsequent acidic cleavage of the acetal protective groups generates linear polyglycerols with different degree of methylation (DM) by varying the GME comonomer content between 10 and 91%. Size exclusion chromatography (SEC) evidenced good control over molecular weight …
Towards bio-based tapered block copolymers: the behaviour of myrcene in the statistical anionic copolymerisation
2019
To explore the potential of myrcene (Myr) as a bio-based monoterpene comonomer for styrenic copolymers and to establish its general applicability for the carbanionic copolymerisation, several statistical copolymerisations of myrcene and common monomers like isoprene (I), styrene (S) and 4-methylstyrene (4MS) were carried out in cyclohexane and monitored by in situ1H NMR spectroscopy. Real-time NMR kinetic studies permitted the determination of the reactivity ratios and the composition profile for each monomer combination. While the copolymerisation of Myr/I yielded a gradient copolymer and reactivity ratios of moderate disparity (rMyr = 4.4; rI = 0.23), the statistical copolymerisation of M…
Spatial heterogeneity in glassy polystyrene detected by deuteron NMR relaxation
1999
Using deuteron NMR, the dynamics of supercooled polystyrene-d 3 was investigated near the calorimetric glass transition. At these temperatures non-exponential spin lattice relaxation is found, indicating the presence of spatial heterogeneity. With increasing temperature, structural relaxation becomes fast enough to average efficiently over different spatial environments, leading to exponential magnetization decays. A qualitative comparison with toluene as a representative of a low molecular weight glass former is carried out. Indications are found that in polystyrene the observed averaging process is more effective at T g than it is in toluene.
Infrared linear dichroism spectroscopy by a double modulation technique
1990
A linear IR dichroism experiment has been devised using a FTIR instrument in combination with a photoelastic modulator. Based on the Mueller-Stokes calculus, a method to directly obtain the absorbance spectra Av parallel and Av perpendicular from the modulated interferogram is developped, which allows the sensitive evaluation of the dichroic ratio. The photoelastic modulator, in combination with a FTIR instrument, offers high sensitivity, high speed, excellent signal to noise ratio and a broad spectral range from 3300 to 850 cm-1. First experimental results obstained from SBS block copolymer are reported.
Linear infrared dichroism by a double modulation technique
1991
In the first part of this paper an experimental setup using Fourier-transform infrared spectroscopy (FTIR) in combination with a photoelastic modulator (PEM) for linear dichroism measurements is described. The second part shows the influence of PEM-amplitude and scan-velocity on the sensitivity of the instrument. The third part deals with the fringe-problem in the baselines of absorbance spectra and its influence on the determination of the linear dichroic ratio.
Single Molecules Probing the Freezing of Polymer Melts: A Molecular Dynamics Study for Various Molecule-Chain Linkages
2010
8 pages; International audience; We present molecular dynamics simulations of coarse-grained model systems of a glassforming polymer matrix containing fluorescent probe molecules. These probe molecules are either dispersed in the matrix or covalently attached to the center or the end of a dilute fraction of the polymer chains. We show that in all cases the translational and rotational relaxation of the probe molecules is a faithful sensor for the glass transition of the matrix as determined from a mode-coupling analysis or Vogel-Fulcher analysis of their R-relaxation behavior. Matrix and dumbbell related relaxation processes show a clear violation of the Stokes-Einstein-Debye laws. In accor…
Diffusion in concentrated colloidal suspensions and glasses
1998
The well established analogy between colloidal suspensions and atomic fluids has been extended to the glass transition problem in the past few years. Colloids have become the ideal test case for checking glass transition theories; this was due to the possibility of modeling hard spheres with colloidal dispersions. Significant progress has also been made in instrumentation, especially in the development of light-scattering techniques allowing moderately turbid and nonergodic samples to be analyzed. Mode coupling theory has become a paradigm not only for the glass transition, but also for the understanding of dynamics in highly concentrated colloidal dispersions where crystallization is suppr…
Novel hydrogels based on a polyasparthydrazide. Synthesis and characterization
2000
α,β-polyasparthydrazide (PAHy), a synthetic water-soluble biocompatible polymer, was chemically crosslinked with ethyleneglycol diglycidylether (EGDGE), in order to obtain water swellable microparticies. These were characterized by means of FT-IR spectrophotometry and by means of particle size distribution analysis. The mean pore size of the prepared gels as various crosslinking ratios and the fractal dimensions were determined by light scattering measurements. Swelling measurements gave evidence of the high affinity of PAHy-EGDGE microparticles towards aqueous media at different pH values. The physical state of the prepared networks was evaluated by means of X-rays diffractometry and therm…