Search results for "Critical"
showing 10 items of 3024 documents
Polymeric alloys: Model materials for the understanding of the statistical thermodynamics of mixtures
1997
Polymeric materials find industrial applications that are comparable to those of metals and ceramics.1 In addition to the great variability via the synthesis of various monomers and the choice of the degree of polymerization (N), alloying of polymers finds increasing attention for combining favorable materials properties.1,2 But polymeric (binary) alloys (A,B) of flexible polymers with chain lengths NA, NB are also most interesting for testing theoretical concepts: changing NA, NB one controls the entropy of mixing, keeping intermolecular forces invariant. Variation of these control parameters thus allows stringent tests of the theories on miscibility, unmixing etc. Furthermore, the large s…
Growing range of correlated motion in a polymer melt on cooling towards the glass transition
1999
Many liquids cooled to low temperatures form glasses (amorphous solids) instead of crystals. As the glass transition is approached, molecules become localized and relaxation times increase by many orders of magnitude1. Many features of this ‘slowing down’ are reasonably well described2 by the mode-coupling theory of supercooled liquids3. The ideal form of this theory predicts a dynamical critical temperature T c at which the molecules become permanently trapped in the ‘cage’ formed by their neighbours, and vitrification occurs. Although there is no sharp transition, because molecules do eventually escape their cage, its signature can still be observed in real and simulated liquids. Unlike c…
High Pressure Solubility Data of the System Limonene + Linalool + CO2
2001
The feasibility of deterpenating orange peel oil with supercritical CO2 depends on relevant vapor−liquid equilibrium data because the selectivity of this solvent for limonene and linalool (the two key components of the oil) is of crucial importance. In this work the solubility data for the CO2 + limonene + linalool ternary system were measured at (318.2 and 328.2) K. The range of pressures covered was from (70 to 110) bar. Two different mixtures of limonene + linalool were used: a 40 mass % limonene + 60 mass % linalool mixture and a 60 mass % limonene + 40 mass % linalool mixture. To correlate the obtained results, two equations of state were successfully used (Peng−Robinson (PR) and Soav…
Fast and continuous synthesis of nanostructured iron spinel in supercritical water: influence of cations and citrates
2014
International audience; Spinel iron oxide nanoparticles were obtained under supercritical water conditions in a continuous and fast (less than 10s) way by modifying the initial stoichiometric Fe II /Fe III molar ratio from (1/2) to (3/0), without base solution, and using citrates directly with iron precursors. This result opens the way of an economical and environmentally benign approach to synthesize superparamagnetic iron oxide nanoparticles (SPIONs) in important yields.
Macroscopic persistent currents in YBa2Cu3O7
1988
Persistent currents in polycrystalline YBa2Cu3O7 rings have been investigated by measuring the spatial distribution of the magnetic flux trapped in field-cooled samples. The results unambiguously show that macroscopic persistent ring currents exist. The critical current density depends very sensitively on the sample quality, reachingj c ≈250 A/cm2 at 77 K for our best samples.
Expanded micro-particles by supercritical antisolvent precipitation: Interpretation of results
2008
Abstract Supercritical antisolvent (SAS) micronization has been used to obtain nanoparticles and micro-particles of several kinds of materials. Sometimes hollow expanded micro-particles have also been obtained. This work is focused on the analysis of this last morphology. We organized literature data and our previous experiments and we added new experiments on previously tested compounds and on compounds never tested before. As a result, expanded micro-particles using several compounds belonging to different categories and precipitated from different solvents in laboratory and pilot scale plants were obtained with diameters between about 10 and 180 μm. They also showed different sub-structu…
Temperature-Responsive Surface Coatings Based on Poly(methylsilsesquioxane)-hybrid Polymers
2007
The present paper presents a new method to build up temperature-responsive surfaces. First a poly(silsesquioxane)-block-poly(N-isopropyl-acrylamide) (PMSSQ-b-PNIPAM) was successfully synthesized using RAFT polymerization. Spin-coating or dip-coating of PMSSQ-b-PNIPAM onto glass surfaces resulted in temperature-responsive surfaces. Surface ATR FT-IR measurements proofed the successful surface modification using PMSSQ-b-PNIPAM. IR fine structures of PNIPAM and PMSSQ could be assigned, respectively. In capillary rise experiments a change of the meniscus height measured at temperatures below or above LCST was observed, indicating a different wetting behavior. Thus, a simple spin- or dip-coating…
Dynamics of phase separation and critical phenomena in polymer mixtures
1987
The phenomenological mean-field theory for statics and dynamics of polymer mixtures is described, generalizing the approaches of Flory-Huggins, Cahn-Hilliard and de Gennes. Predictions are made for critical behavior, spinodal decomposition and homogeneous nucleation. The validity of the mean-field approximations is discussed with Ginzburg criteria. The results of the theory are compared to computer simulations and recent experiments.
Pressure-induced formation of diblock copolymer "micelles" in supercritical fluids. A combined study by small angle scattering experiments and mean-f…
2004
We developed a simple time-dependent mean-field theory to describe the phase separation kinetics of either homopolymers or AB-diblock copolymers in supercritical (SC) fluids. The model, previously used to describe the phase behavior of AB-block copolymers under the assumption of strong solvent selectivity for just one copolymer chain, has been extended to study the kinetics of the phase separation process. Time resolved small angle x-ray scattering (TR-SAXS) measurements have been performed on different AB-diblock copolymers containing a perfluorinated chain and dissolved in SC-CO2. The data obtained over a wide range of pressure and temperature confirm our theoretical predictions. Particul…
QENS from polymer aggregates in supercritical CO2
2000
Abstract We report QENS measurements from PS-b-PFOA aggregates in supercritical CO2. Line shapes are dominated by localized diffusive modes and segmental dynamics of the anchored, finite-length PFOA chains. For Q⩽0.6 A−1, we obtain effective diffusion coefficients of ≅0.8 10−6 cm2/s. At higher Q, a single component is not sufficient as shown by excess intensity on the flanks. For Q⩾1.5 A−1, the wings reflect contributions due to a distribution of faster, more localized chain modes.