Search results for "Supercritical"
showing 10 items of 236 documents
Preparation of pH sensitive poly(vinilydenefluoride) porous membranes by grafting of acrylic acid assisted by supercritical carbon dioxide
2012
Free radical grafting of acrylic acid (AA) on poly(vinilydenefluoride) (PVDF) porous membranes was studied at 65°C using supercritical carbon dioxide (scCO 2) as a solvent and delivery agent. The process was initiated by the thermal decomposition of benzoylperoxide (BPO). Spectroscopic analyses confirmed the presence of poly(AA) chains linked to treated membranes. The mass fraction of grafted AA increased with grafting time and BPO concentration while it decreased when the density of the fluid phase was enhanced. A not-monotonic trend was obtained when the effect of the initial AA concentration was studied. The grafting process was accompanied by a reduction of the crystallinity of the PVDF…
Efficient parallel tempering for first-order phase transitions
2007
We present a Monte Carlo algorithm that facilitates efficient parallel tempering simulations of the density of states g(E) . We show that the algorithm eliminates the supercritical slowing down in the case of the Q=20 and Q=256 Potts models in two dimensions, typical examples for systems with extreme first-order phase transitions. As recently predicted, and shown here, the microcanonical heat capacity along the calorimetric curve has negative values for finite systems.
Order-Order Phase Transitions Induced by Supercritical Carbon Dioxide in Triblock Copolymer Thin Films
2019
We study the influence of supercritical carbon dioxide (scCO2) on the phase behavior of a cylinder-forming polystyrene-block-polybutadiene-b-polystyrenetriblock copolymer thin film. Solvent annealing with scCO2 can produce patterns with long-range order but these structures become unstable for thin films with small thicknesses. These results are in good agreement with self-consistent mean field calculations, which indicate that a drying transition occurs for thicknesses below the radius of gyration of the molecule.After decompression and solvent extraction, the initially swollen polymer nanostructure suffers a strong reduction in the average domain spacing, which has a deleterious effect on…
Highly robust and selective system for water pollutants removal: How to transform a traditional photocatalyst into a highly robust and selective syst…
2019
Highly porous monolithic aerogels based on ZnO photocatalyst and syndiotactic polystyrene (s-PS) were obtained by supercritical CO2 treatment of ZnO/s-PS gels. The prepared aerogels were characterized and their photocatalytic activity was evaluated using phenol and toluene as water pollutant models. The s-PS nanoporous crystalline phase, able to absorb pollutant molecules, was proven to be necessary to ensure high photocatalytic efficiency as the aerogel acts not only as a support, but also as pollutant pre-concentrator. The reusability of ZnO/s-PS aerogels is also strong showing no decrease in photocatalytic activity after six consecutive degradation trials. Finally, the aerogel matrix pre…
Antioxidant phenolic compounds recovery from Mangifera indica L. by-products by supercritical antisolvent extraction
2015
Abstract Supercritical Antisolvent Extraction (SAE) was used in the recovery of antioxidant compounds from mango by-products. The antioxidant extract was obtained by solid–liquid extraction using aqueous acetone (80% v/v) and subsequent adsorption/desorption in C18 cartridge. Recovery of antioxidants was performed by SAE using SC-CO 2 as antisolvent. The temperature and pressure parameters were varied in the range 35–45 °C and 8–15 MPa. The SAE process allowed the recovery of about 90% of the initial phenolic compounds, the best recovery was obtained at 40 °C and 10 MPa and the main compounds were mangiferin, isomangiferin, quercetin 3-O-galactoside, quercetin 3-O-glucoside, quercetin 3-O-x…
SAXS investigation on aggregation phenomena in supercritical CO2.
2004
Synchrotron Small-Angle X-Ray scattering (SAXS) measurements on aggregate formation of a Polyvinyl acetate- b-Perfluoro octyl acrylate (PVAc- b-PFOA) block copolymer in supercritical CO(2) are here reported. Experiments were carried out for a series of different thermodynamic conditions, changing the solvent density by profiling both the pressure at constant temperature and the temperature at constant pressure. This block copolymer and in general fluorocarbon-hydrocarbon di-blocks form aggregates depending on the value of CO(2) density. A sharp transition between monomers dissolved as random coils and micelles characterized by a solvophilic shell and a solvophobic core occurs when the CO(2)…
Hydrothermal Synthesis of ZnO Crystals from Zn(OH)2 Metastable Phases at Room to Supercritical Conditions
2014
The originality of this work is to highlight the effect of temperature and pressure on the size and morphology of hydrothermal ZnO particles from ambient to supercritical conditions (T > 374 °C and P > 221 bar) using a unique continuous one-step process. Experiments were carried out from zinc nitrate (Zn(NO3)2) and potassium hydroxide (KOH) solutions in the ranges of 1–300 bar and 30–400 °C. The as-prepared particles of ZnO (flower, ellipsoid, and sphere) and e-Zn(OH)2 (polyhedral) sized from nano to micrometers were characterized by X-ray diffraction and electronic microscopy. The wulfingite phase (e-Zn(OH)2) was detected inside some powders especially at room temperature for higher pressu…
Gamma radiation induced polymerization of vinyl monomers in dense CO2
2002
Abstract The dispersion polymerization of methyl methacrylate in dense carbon dioxide, initiated by γ-rays, utilizing different polysiloxanes as polymeric stabilizers, was investigated. The progress of the reaction, as a function of the irradiation dose, was also studied and the occurrence of a gel effect has been detected. For comparison, the dispersion polymerization has been carried out in supercritical conditions ( T =65°C and 38 MPa) in the presence of 2,2′-azobis(isobutyronitrile) (AIBN) as initiator. High molecular weight polymer (M w > 1000 kg/mol) with narrow molecular weight distribution has been obtained both with γ-rays and AIBN. The electron scanning micrographs show that regul…
Direct synthesis of dimethyl carbonate with supercritical carbon dioxide: characterization of a key organotin oxide intermediate
2006
The direct synthesis of dimethyl carbonate (DMC) using carbon dioxide as solvent and reagent for its fixation to methanol was explored with din-butyldimethoxystannane in order to get insight into the reaction mechanism for activity improvement. Catalytic runs including recycling experiments allowed isolation and characterization by NMR, IR, and single-crystal X-ray diffraction of a new tin complex containing 10 tin atoms. This compound could be prepared independently and is considered as a resting species. The yield of DMC is highest under 20 MPa pressure that fits with a monophasic supercritical medium in agreement with fluid phase equilibria calculations. In line, preliminary kinetics and…
Supercritical water gasification of waste oils as a source of syngas
2021
A huge amount of waste oil is produced worldwide. Also substantial amount of virgin oils is available that are interesting candidates for upgrading into syngas. Supercritical water gasification (SCWG) can be considered as an aqueous phase reforming process to produce syngas from oils. In this work, a variety of waste and virgin oils were gasified in a continuous down-flow autoclave reactor at supercritical conditions. Experiments were carried out at 430 °C and 660 °C, 25 MPa, with a residence time in the range 103-170 s, in order to investigate gasification and carbon efficiency, hydrogen yield and composition of the produced gas. All the analysed feedstocks were suspended in water at vario…