Viscosity studies of poly(DL‐lactic acid) in supercritical CO2

The effect of supercritical CO₂ on the viscosity and activation energy to viscous flow of P_DLLA is investigated, using a high pressure parallel plate rheometer, over a range of temperatures (50–140 °C) and pressures (5–12 MPa). The Cross model is fitted to the data to enable calculation of the zero shear viscosity and critical shear rate. A significant decrease in the viscosity is observed on increasing both variables; however, at high temperatures, the pressure effect becomes negligible. An increase in the critical shear rate is also observed on raising the pressure, indicative of a reduction in the relaxation time of the polymer. Manipulation of the Arrhenius equation shows a reduction in the activation energy to viscous flow as the pressure is increased. Together, these results show that the melt processing temperature of P_DLLA can be reduced in the presence of supercritical and high pressure CO₂. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Solubilities of cinnamic acid,phenoxyacetic acid and 4-methoxyphenylacetic acid in supercritical carbon dioxide

The solid solubilities of cinnamic acid, phenoxyacetic acid and 4-methoxyphenylacetic acid in supercritical carbon dioxide were measured using a semi-flow apparatus. The experiments were taken at 308.2, 318.2 and 328.2 K. The pressure range was from 11 to 24 MPa. These data were confirmed as equilibrium solid solubilities based on a plug flow mass transfer model. The solid solubilities were further correlated using the equations of state or semi-empirical models. The correlation results are satisfactory with optimally fitted binary interaction parameters in the Peng–Robinson equation of state.     

Lanthanide extraction with 2,5-dimethyl-2-hydroxyhexanoic acid

The solvent extraction of lanthanides into chloroform solutions of 2,5-dimethyl-2-hydroxyhexanoic has been studied. The light lanthanides can be extracted by forming complexes with the acid anion. The extracted metal species is highly aggregated. This extraction has a solubility limit which increases with the addition of unionized acid. If the unionized acid-to-metal ratio becomes too great, extraction first occurs followed by slow precipitation of the metal salt. The heavy lanthanides do not extract from solutions of the acid and its potassium salt, but form aqueous emulsions and precipitates. In the presence of the organic soluble tetrabutylammonium ion, the heavy lanthanides can be extracted. At the tracer level, neodymium is extracted primarily as NdA₃(HA)₅ and (NdA₃)₂(HA)_q. The chloroform-water acid partition constant, te chloroform acid dimerization constant, and the stability constants of the light lanthanide carboxylates are also reported.     

Solubilities of caffeine and theophylline in supercritical ammonia

The solubilities of caffeine and theophylline in supercritical ammonia at 140°C have been determined. Both compounds exhibited substantial solubility in the ammonia, with caffeine showing the greatest increase in solubility near the critical pressure where density increases most rapidly. However, theophylline showed an appreciable solubility at pressures substantially below the critical pressure. Possible chemical reactions of supercritical ammonia with these solutes at this temperature were found to be unimportant in the present study. The role of supercritical ammonia as a solvent for polar organic molecules is discussed.     

Solubilities of benzoin,propyl 4-hydroxybenzoate and mandelic acid in supercritical carbon dioxide

A semi-flow type apparatus was used to measure the equilibrium solubilities of benzoin , propyl 4-hydroxybenzoate, and mandelic acid in supercritical carbon dioxide at 308.15, 318.15, and 328.15 K over the pressure range from 9 to 24 MPa. New equilibrium data of solid solubility in supercritical carbon dioxide are presented. The approach to solid–fluid phase equilibrium is examined based on a plug flow fluid–solid mass transfer model. The Soave–Redlich–Kwong and the Peng–Robinson equations of state (EOS), with the van der Waals and the Huron–Vidal type mixing rules were used to correlate the experimental data. The solid solubility data were also correlated with density based semi-empirical equations of Chrastil, and Santiago–Teja. It is shown that these solid solubility data are correlated with reasonably good accuracy using optimally fitted parameters.     

Extraction of ferulic acid from Angelica sinensis with supercritical CO2

Extraction of pharmacologically active ingredient of ferulic acid from the root of Angelica sinensis with supercritical CO2 was investigated. The experimental results show that the extract yields were 0.87-4.06% at temperatures from 45 to 65 degrees Celsius and pressures from 30 to 50 MPa, and the maximum content of ferulic aicd in the extracts was about 0.35-0.37%, which is lower than that of 0.61-0.85% by conventional percolation methods. Ethanol was used as co-solvent in different ratios to raw materials in order to increase the content of ferulic acid in the extracts. The experimental results show that both the extract yields and the content of ferulic acid in the extracts increase greatly compared with pure CO2 extraction. When the ratio of ethanol to the raw material was 1.6, the content of ferulic acid in the extracts was 0.91-1.27%, indicating that supercritical fluid extraction (SFE) with CO2 in the presence of suitable co-solvent is superior to percolation in extracting polar ferulic acid from Angelica sinensis.     

Fluorinated surfactants in supercritical CO2

Liquid or supercritical carbon dioxide has important environmental and economic advantages over petrochemical solvents currently used for industrial processes. However, low solubility in CO₂, particularly of polar compounds, is a hurdle to its implementation as an acceptable alternative. These solubility problems have been overcome by employing specialised fluorinated surfactants to stabilise water nano-droplets as water-in-supercritical/liquid CO₂ microemulsions. Such novel microemulsions can now facilitate innovative ‘green-and-clean’ applications of carbon dioxide technology.     

Solubilities of palmitic and stearic fatty acids in supercritical carbon dioxide

The solubilities of two fatty acids, namely hexadecanoic acid (palmitic acid) and octadecanoic acid (stearic acid) in supercritical carbon dioxide (SCCO₂), were determined at T = (328 and 338) K from 12.8 MPa to 22.6 MPa. Three models, namely a thermodynamic model based on the Peng–Robinson equation of state with Kwak and Mansoori mixing rules, a model based on dilute solution theory proposed by Mendez-Santiago and Teja and a new reformulated Chrastil equation model, were used to correlate the solubilities. In all the models, the correlation constants are temperature independent. All the models successfully correlated the experimental results for the solubilities of hexadecanoic acid within 3%.     

Sorption and swelling of semicrystalline polymers in supercritical CO2

The equilibrium sorption and swelling behavior of four different polymers—poly(methyl methacrylate), poly(tetrafluoroethylene), poly(vinylidene fluoride), and the random copolymer tetrafluoroethylene–perfluoromethylvinylether–in supercritical CO₂—are studied at different temperatures (from 40 to 80 °C) and pressures (up to 200 bar). Swelling is measured by visualization, and sorption through a gravimetric technique. From these data, the behavior of amorphous and semicrystalline polymers can be compared, particularly in terms of partial molar volume of CO₂ in the polymer matrix. Both poly(methyl methacrylate) and the copolymer of tetrafluoroethylene exhibit a behavior typical of rubbery systems. On the contrary, polymers with a considerable degree of crystallinity, such as poly(tetrafluoroethylene) and poly (vinylidene fluoride), show larger values of partial molar volume. These can be related to the limited mobility of the polymer chains in a semicrystalline matrix, which causes the structure to “freeze” during the sorption process into a nonequilibrium state that can differ significantly from the actual thermodynamic equilibrium. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1531–1546, 2006     

AKD-Modification of bacterial cellulose aerogels in supercritical CO2

Different approaches towards hydrophobic modification of bacterial cellulose aerogels with the alkyl ketene dimer (AKD) reagent are presented. If AKD modification was performed in supercritical CO₂, an unexpectedly high degree of loading was observed. About 15 % of the AKD was bound covalently to the cellulose matrix, while the other part consisted of re-extractable AKD-carbonate oligomers, which are novel chemical structures described for the first time. These oligomers contain up to six AKD and CO₂ moieties linked by enolcarbonate structures. The humidity uptake from environments with different relative humidity by samples equipped with up to 30 % AKD is strongly reduced, as expected due to the hydrophobization effect. Samples above 30 % AKD, and especially at very high loading between 100 and 250 %, showed the peculiar effect of increased humidity uptake which even exceeded the value of unmodified bacterial cellulose aerogels.     

Efficient cooling in supersonic jet expansions of supercritical fluids: CO and CO2

Pulsed, supersonic beams of pure carbon monoxide and carbon dioxide at stagnation conditions above their critical point have been investigated by time-of-flight measurements as a function of pressure and temperature. Although both molecules form clusters readily in adiabatic expansions, surprisingly large speed ratios (above 100) indicative of very low translational temperatures (below 0.1 K) have been achieved. In particular, the supersonic expansion of CO(2) at stagnation temperatures slightly above the phase transition to the supercritical state results in unprecedented cold beams. This efficient cooling is attributed to the large values of the heat capacity ratio of supercritical fluids in close vicinity of their critical point.     

Sorption and swelling of poly(DL‐lactic acid) and poly(lactic‐co‐glycolic acid) in supercritical CO2: An experimental and modeling study

Tissue engineering scaffolds require a controlled pore size and structure to host tissue formation from cell populations. Supercritical carbon dioxide (scCO₂) processing can be used to form porous scaffolds in which the escape of CO₂ from a plasticized polymer melt generates gas bubbles that shape the pores. The process is difficult to control with respect to changes in final pore size, porosity, and interconnectivity, while the solubility of CO₂ in the polymers strongly affects the foaming process. An in‐depth understanding of polymer CO₂ interaction will enable a successful scaffold processing. Amorphous poly(DL ‐lactic acid) (P_DL LA) and poly(lactic acid‐co‐glycolic acid) (PLGA) polymers are attractive candidates for fabricating scaffolds. In this study, CO₂ sorption and swelling isotherms at 35 °C and up to 200 bar on a variety of homo‐ and copolymers of lactic acid and glycolic acids are presented. Sorption is measured through a gravimetric technique using a suspension microbalance and swelling by visualization. The obtained results are modeled using the Sanchez‐Lacombe equation of state. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 483–496, 2008     

Interaction of pharmaceutical hydrates with supercritical CO2

The aim of this work was to study the solubility in supercritical CO₂ of the hydrated phase of three model drugs, namely theophylline, carbamazepine, and diclofenac sodium, in comparison with the respective anhydrous form. Possible solid-state modifications, stemming from the interaction with supercritical CO₂, were investigated by differential scanning calorimetry, thermogravimetric analysis, hot stage microscopy, Fourier Transform infrared spectroscopy and Karl-Fischer titrimetry. It was found that all three pharmaceutical hydrates exhibited higher solubility in supercritical CO₂ than the relevant anhydrous phases. In the case of theophylline monohydrate, the instability of the crystal phase at the experimental temperature adopted has been evidenced. Diclofenac sodium tetrahydrate represents a peculiar case of chemical interaction with the acid supercritical fluid, mediated by crystal water. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sequestration of supercritical CO2 by mercury oxide

HgCO₃·2HgO (mercury oxide carbonate), along with partly unreacted reactants, was obtained by exploring the behaviour of the Hg₂Cl₂/HgO binary system in supercritical CO₂ (scCO₂) at 200°C, 22000 kPa in the presence and absence of water, using a self-made laboratory-scale system. The reaction of pure HgO with scCO₂ aimed at the synthesis of HgCO₃ (mercury carbonate), also yielded the same product. Meanwhile, with a small amount of water present in the Hg₂Cl₂/HgO-scCO₂ system, at 200°C, 22000 kPa, the mineral terlinguaite (Hg₄O₂Cl₂) was obtained instead of mercury oxide carbonate. Repeating this reaction under the same conditions, but in the absence of CO₂, again resulted in the synthesis of terlinguaite, leading to the assumption that the scCO₂ had no influence on the synthesis of terlinguaite. This study reveals a new moisture-free laboratory method and conditions for the permanent fixation of CO₂ by HgO. This method bears two benefits: 1) it can be introduced to reduce the Hg content in flue gas and fly ash emitted from coal-burning power plants and municipal waste incinerators; 2) it can contribute to CO₂ mineralisation in montroydite (HgO) geological formations as mercury oxide carbonate.     

Solubility of semi-fluorinated and nonfluorinated alkyl dichlorobenzoates in supercritical CO2

Isopleths and solution densities, from ∼25 to 100 °C, are reported for mixtures of CO₂ with semi-fluorinated and nonfluorinated propyl, butyl, octyl, and decyl 2,5-dichlorobenzoates. The maxima in the pressure–composition (P–x) isotherms for the alkyl 2,5-dichlorobenzoates range from 70 to 600 bar and the maxima increase with increasing alkyl chain length at each temperature. When the alkyl side chains are semi-fluorinated, the P–x maxima range from 60 to 175 bar over the same temperature range as with the nonfluorinated analogs. The P–x maxima of the semi-fluorinated 2,5-dichlorobenzoates in CO₂, first decrease as the benzoate alkyl chain is increased from propyl to butyl, but then increase as the alkyl chain length is further increased from butyl to octyl to decyl, although the differences in the maxima at a given temperature between these four semi-fluorinated benzoates are not as great as that observed with the nonfluorinated analogs. Also, the alkyl 2,5-dichlorobenzoate–CO₂ mixtures exhibit three-phase, liquid–liquid–vapor (LLV), equilibria near the vapor pressure curve and critical point of CO₂ whereas three phases are not observed for the semi-fluorinated analogs.     

Catalysis in supercritical CO2 using dendrimer-encapsulated palladium nanoparticles

Dendrimer-encapsulated nanoparticles are shown to be versatile catalysts for both the hydrogenation of styrene and Heck heterocoupling of iodobenzene and methacrylate in supercritical CO2 (scCO2).     

Soft fluctuating surfactant membranes in supercritical CO2-microemulsions

The bending rigidity of surfactant membranes in novel bicontinuous CO(2)-microemulsions of the type H(2)O/NaCl-scCO(2)-Zonyl FSH/Zonyl FSN 100 was determined using both high pressure small angle neutron scattering and neutron-spin echo spectroscopy. As an important result it was found, that the stiffness of the membrane increases solely by an increase of the pressure.     

Solubilities and partial molar volumes of three bis(2-ethoxyethyl) ethanedioate derivatives in supercritical carbon dioxide

Three new CO₂-philic bis(2-ethoxyethyl) ethanedioate derivatives, bis(2-(2-methoxyethoxy)ethyl) ethanedioate (compound 1), bis(2-(2-ethoxyethoxy)ethyl) ethanedioate (compound 2), and bis(2-(2-butoxyethoxy)ethyl) ethanedioate (compound 3), were designed and synthesized and their solubilities in supercritical carbon dioxide (scCO₂) were then measured at different temperatures (313, 323, 333) K over the pressure range (8.9 to 13.9) MPa. The measured solubility data were correlated with five different theoretical semi-empirical models (Chrastil, kJ, SS, MST, JCF) and satisfactory agreements were obtained. The JCF model provided the best fit and the lowest average absolute relative deviation (AARD) varied from (3.58 to 6.80)%. Furthermore, the partial molar volumes of three compounds in the supercritical phase were also calculated according to the Kumar and Johnston theory, and the values were between −(19105 and 3510) cm³ · mol⁻¹.     

Homogeneous photochemical oxidation via singlet O2 in supercritical CO2

This communication describes the reaction chemistry of singlet oxygen in supercritical carbon dioxide, demonstrating rapid and quantitative conversion of alpha-terpinene to ascaridole.