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The pressure–volume–temperature (PVT) relationships for trimethoxymethylsilane (MTMS, CH3(CH3O)3Si) and tetramethyl orthosilicate (TMOS, (CH3O)4Si) were measured at temperatures ranging from 303.2 to 363.2 K and pressures up to 160 MPa. Density measurements were carried out with an experimental apparatus based on the variable volume method. The standard uncertainties u(T) = 0.17 K and u(P) = 0.14 MPa, and the relative combined expanded uncertainty Ur (0.95 level of confidence) were Ur(ρ) = (0.0016 and 0.0022) for MTMS and TMOS, respectively. The obtained PVT relationships were correlated using the Tait equation and the Sanchez–Lacombe equation of state to determine the characteristic parameters.

The solubility of sulfur dioxide (SO2) was measured in polyethelene glycol dimethyl ether (PEGDME) by use of a static type apparatus in the pressure range from 15.2 to 231.2 kPa at 308.18 K. The stated average molecular weight of PEGDME was Mw = 240 g·mol−1 and the molecular structure of the repeating unit is similar to that of dimethyl ether (DME). The bubble point pressure showed a negative deviation from Raoult law. The behavior was expected from consideration of the vapor–liquid equilibrium data of DME + SO2, reported by Noles and Zollweg (Fluid Phase Equilib 66:275–289, 1991). The ‘bridge-like structure’ will be microscopically formed between the DME unit and SO2, because the two unshared electron pairs of the oxygen atom in DME unit act as an electron donner for some molecules. The Peng–Robinson equation of state was used to correlate the experimental data. Two types of mixing rules were employed. One was a conventional model, and the other was of the excess Gibbs energy type. The latter, Wong–Sandler model combined with Flory–Huggins equation, showed a good reproducibility for the experimental data.

Supercritical drying is widely considered as the gold standard to produce aerogels that preserve the microstructure of the gels, but we have found this is not always the case. Chitosan aerogel, one of the emerging biopolymer aerogels, was prepared by chemical cross-linking gelation, followed by solvent exchange with methanol and supercritical drying using CO2. Small-angle X-ray scattering analysis shows that the structure of the wet gel, which consists of Gaussian chains of individual molecular strands, converts into a nanofibrous network during CO2 processing. In situ observation reveals a drastic shrinkage of the gel in CO2, demonstrating that physical coagulation caused by the low affinity between chitosan and CO2 is the main structure-forming step. These results challenge the common perception of supercritical drying: it is no longer an inactive drying method, but rather an active nanostructure forming a tool to produce porous biopolymer materials with tailored structure and properties.

Equations of state (EoS) can be used to estimate a wide variety of physical properties. However, there has been limited verification of the applicability of parameter sets derived from specific physical properties to correlate and estimate various other physical properties. The densities of homogeneous phase fluid mixtures of the carbon dioxide (CO2)/toluene (Tol) binary system were measured and correlated to three equations of state. The density measurements were performed using a high-pressure vibration-type density meter equipped with a circulation pump and variable-volume viewing cell, which guaranteed the homogeneity of the mixtures. The densities were measured at temperatures ranging from 313 to 353 K, pressures up to 20 MPa, and CO2 concentrations from 0 to 80 mol%. The experimental data obtained were correlated to the Tait density equation and three EoS, namely Peng–Robinson (PR), Sanchez–Lacombe (SL), and Perturbed Chain statistical associating fluid theory (PC-SAFT) EoS. Among them, SL and PC-SAFT EoS agree better with the experimental data compared to the PR EoS, presumably due to differences in the pure component parameters used in each EoS. Using parameter sets determined from the density measurements, the vapor liquid equilibrium (VLE) of the CO2/Tol mixtures was estimated. While we were unsuccessful in estimating VLE using the PR EoS, SL and PC-SAFT EoS were successfully used for the estimations. We also attempted to determine the densities from VLE correlations. It was found that SL and PC-SAFT EoS could be used to estimate the density well, whereas the PR was not predictive. From the results of the study, it is clear that for estimating density using EoS, the basic data used for determining the pure component parameters are important.

The phase behaviors of carbon dioxide (CO2)/tetramethyl orthosilicate (TMOS)/poly(methyl methacrylate) (PMMA) and CO2/TMOS/poly(styrene) (PS) ternary systems were measured. The measurements were performed using a synthetic method involving observations of the bubble point and cloud point. The phase boundaries were measured at temperatures ranging from 313.2 K to 393.2 K and CO2 weight fractions ranging from 0.01 to 0.40. At a constant TMOS:polymer weight ratio of 9:1, both systems showed similar CO2 mass fraction dependence of their phase behaviors. When the vapor-liquid (VL) and vapor-liquid-liquid (VLL) phase boundaries of the ternary systems were compared with those of the binary CO2/TMOS system using polymer-free bases, they were found to be nearly identical. On the other hand, the two systems showed completely opposite polymer mass fraction dependence of their phase behaviors at a constant CO2 ratio.

Ultrasound is used in various chemical reaction processes, and these reactions are influenced by ultrasonic frequency. A threshold power is required for the ultrasonic degradation reaction and oxidation reaction caused by hydroxyl radicals, and the cavitation threshold power is also influenced by frequency generally. In this study, the effects of frequency on the threshold power of methylene blue degradation and KI oxidation were investigated in the range between 22.8 kHz and 1640 kHz. The threshold power of KI oxidation reaction increased with increasing frequency. This phenomenon well agrees with previous study, and it is revealed that the generation of I- 3 ion is caused by oxidation reaction of Iˉ ions with hydroxyl radicals. On the other hand, the threshold power of methylene blue degradation reaction was not affected by frequency. The ultrasonic degradation of methylene blue is considered to be caused by hydroxyl radicals, and there is a linear relationship between degradation rate constant and sonochemical efficiency value. However, it is guessed that the degradation of methylene blue is occurred inside cavitation bubble by pyrolysis at high frequency regions.

The phase behaviors of carbon dioxide (CO2)/trimethoxy(methyl)silane (MTMS) and CO2/Methylsilicate 51 (MS-51: methylsilicate tetramer) binary systems were determined. The experiments were performed using a synthetic method by observing the bubble point. The phase boundaries were determined at temperatures of 313.2 K–393.2 K and CO2 molar fractions of 0.2–0.9. The experimentally obtained bubble points of the CO2/MTMS binary system were correlated using the Peng-Robinson equation of state (PR EoS), and the molecular interaction parameters kij and lij were determined. The results of the CO2/MS-51 binary system were correlated using the PR EoS and the Sanchez-Lacombe equation of state (SL EoS). In the SL EoS, two types of mixing rules, originally proposed by Sanchez et al. which uses kij as a fitting parameter and modified by McHugh et al. which uses two fitting parameters kij and lij, were used. For this system, the experimental results were correlated better using the SL EoS than using the PR EoS, and the latter mixing rule was more suitable than the former.

The pressure-volume-temperature (PVT) relationships of pure diisononyl phthalate (DINP) were measured at temperatures of 303.15–363.15 K and pressures up to 160 MPa by a variable-volume method. Using a synthetic method that involved observing the bubble point, the phase behavior of the CO2/DINP binary system was also measured. The phase boundaries were determined at temperatures of 313.15–393.15 K and CO2 molar fractions of 0.3–0.9. The characteristic parameters of DINP were obtained by correlating the measured PVT data using the Sanchez-Lacombe equation of state (SL EoS), and the bubble points of the system were correlated using the SL EoS with the determined characteristic parameters. The interaction parameter exhibited temperature dependence, and the introduction of the temperature dependence improved the correlation.

In this study, we introduced an artificial neural network (ANN), which can represent objects that are difficult to formulate, rather than the integrated model of the group contribution method (GCM), because the integrated model in the existing GCM is no longer able to manage enormous diversification of substances. Hence, a model to estimate the pure component parameters m, σ, and e of the perturbed chain statistical associating fluid theory (PC-SAFT) equation of state (EoS) was developed. We optimized the structure of the ANN by changing the number of neurons and layers in the hidden layer. In this study, the optimized ANN structure was two hidden layers and 40 neurons. The results confirm that the model can determine the pure component parameters of PC-SAFT EoS, which can estimate the liquid density, saturated vapor pressure, and critical properties. In terms of the critical properties, the estimated results were almost as good or better than those obtained using the GCMs, which are specified for the critical properties. We were able to calculate properties for substances whose parameters were not reported in the literature by using this ANN. The results would be useful for chemical process design, for example, to be incorporated into process simulators.

Alkyl groups of tetraalkoxysilane have different chain lengths, which results in different reactivity of the sol–gel reaction. Hence, it is essential to understand the phase behavior for designing chemical processes using the sol–gel reaction. The phase behavior of CO2/tetrapropyl orthosilicate (TPOS) and CO2/tetrabutyl orthosilicate (TBOS) binary systems was measured. The experiments were performed using a synthetic method combined with a laser displacement measurement wherein the movement of the piston inside the high-pressure vessel was measured. The phase boundaries were determined at 313–373 K and CO2 molar fractions of 0.1–0.9. No significant difference was observed in the phase behavior of tetraalkoxysilanes, which have alkyl groups of different chain lengths. The experimentally obtained vapor–liquid equilibria of the two binary systems were correlated by the Sanchez–Lacombe equation of state using the original mixing rule reported by Sanchez et al. The results showed that molecular interaction parameter kij exhibits a clear temperature dependence.

The thermal decomposition of copper (II) acetylacetonate (Cu(II)(acac)2) in supercritical carbon dioxide (scCO2) was investigated via in situ UV–vis spectroscopy. Release of acetylacetone ligands from the central metal atom was observed as the initial step in the decomposition. The kinetics of the decomposition at 423–453 K and 15–25 MPa in scCO2 were studied. The decomposition reaction generally followed the first-order kinetics. The reaction rate was slightly increased with an increase in the pressure, due to changes in the scCO2 density. The activation energy of the decomposition was calculated as 60.3 kJmol−1 at 15 MPa, 56.3 kJmol−1 at 20 MPa and 52.4 kJmol−1 at 25 MPa, which are lower values than those observed in air and in vacuum. The pressure dependence of the activation energy of the decomposition reaction was clarified quantitatively for the first time, and revealed the energy conservation benefit of using scCO2 as a process solvent for a variety of metal/metal oxide deposition process of nanomaterials.

Supercritical drying is widely considered as the gold standard to produce aerogels that preserve the microstructure of the gels, but we have found this is not always the case. Chitosan aerogel, one of the emerging biopolymer aerogels, was prepared by chemical cross-linking gelation, followed by solvent exchange with methanol and supercritical drying using CO

For the design of spray propellants, bubble point pressures were measured for binary mixtures of ethanol with propane, dimethyl ether (DME) or trans-1,3,3,3-tetrafluoropropene (R1234ze(E)), with a static type apparatus at (293.15–313.15) K. Experimental data were correlated with the Peng-Robinson (PR) and Stryjek-Vera (PRSV) equations of state using the Wong-Sandler (WS) mixing rules. The NRTL activity coefficient model in the WS mixing rules was effective for correlation of systems that exhibited large non-idealities (ethanol - propane, ethanol - R1234ze(E)). Correlation of the bubble point pressures with the PRSV equation of state and WS mixing rules was to within an average of 2.391% absolute deviation in pressure for all systems, which is considered to be sufficient for design of spray devices with propellants that have low global warming potential.

The phase behavior of a carbon dioxide (CO2)/toluene (Tol)/polystyrene (PS) ternary system was measured. The measurements were performed using a synthetic method combined with a reflected light intensity measurement. The bubble points were determined by visual observation, and the cloud points were determined from the change in the reflected light intensity. The phase boundaries were measured at temperatures ranging from 313.2 K to 373.2 K and CO2 weight fractions ranging from 0.10 to 0.41. The homogeneous phase area decreased when the molecular weight of PS and/or the ratio of PS to Tol increased. It was found that the phase behavior of ternary systems, especially the liquid-liquid phase separation behavior, was altered by a change in the mutual solubility between the three components.

The density of homogeneous phase fluid mixtures for various carbon dioxide (CO2)/organic solvent systems was measured in homogeneous phase. Solvents included cyclohexane (C6H12), methylcyclohexane (C6H11CH3), and ethylbenzene (C6H5C2H5). Density measurements were performed using a high-pressure vibration type density meter equipped with a circulation pump and variable volume viewing cell which guarantee the homogeneity of mixtures. The density was measured at temperatures ranging from 313 K to 353 K and pressures up to 20 MPa, and the CO2 composition varied from (0 to 80) mol%. The obtained experimental data were correlated according to a density equation. The resulting correlation agrees well with the experimental data.

It is well known that high-pressure carbon dioxide (CO2) lowers the glass transition temperature (Tg) of polymers. We therefore investigated whether Tg depression of high-pressure CO2 results in interparticle bridging of a polymer and the tablet characteristics that makes the manufacture of an orally disintegrating tablet (ODT) possible. Copolyvidone (Kollidon®) and polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer (Soluplus®) were examined and found to exhibit a large Tg depression. Placebo ODTs were prepared and hardness, disintegration rate, porosity, and change in thickness and appearance were evaluated before and after the high-pressure CO2 treatment. This enabled the establishment of the optimal conditions for pressure, temperature, and treatment time under pressure. Experimental results showed that it was possible to manufacture ODTs comprising Kollidon® as a water-soluble polymer with CO2 treatment under the suitable conditions such as temperature at 45°C, pressure lower than 8 MPa, and a treatment time shorter than 30 min, which is a new ODT manufacturing process called "Carbon Dioxide Assisted Tablet Formation Scheme" (CATS). In comparison to the conventional processes, which require high temperatures or humidity, CATS is expected to be applicable to drugs that are unstable at high temperature and humidity, and to functional drug particles used for bitter taste masking, sustained release, and other uses.

The ultrasonic degradation of methylene blue at a frequency of 490 kHz was carried out in the absence and presence of TiO2 or Al2O3 particle, and the effects of amounts of particle on the enhancement of degradation rate constant estimated by assuming first-order-kinetics were investigated. The degradation reaction was enhanced by particle addition, and the apparent degradation rate constant is proportional to the increase in amount of particle. In addition, the constant of proportionality is not influenced by degraded material and ultrasonic frequency. However, particle type influences the constant of proportionality, and the value of TiO2 particle is about 6 times as large as that of Al2O3 particle.

Biobased nanofiber aerogels are ones of the attractive emerging materials in the fields of biochemistry and materials chemistry, but their poor humidity stability due to high hydrophilicity has limited their practical uses. In this paper, a new series of hydrophobic nanofibrous aerogels made from regenerated chitosan and alkyl aldehydes were prepared via a simple one-pot reaction followed by supercritical drying. Hexanal-modified chitosan aerogel shows excellent hydrophobicity with a water contact angle of ∼136°, a low density of 0.04–0.07 g cm–3, and structurally homogeneous three-dimensional nanofiber network at the nanoscale. Systematic investigations using various alkyl aldehydes revealed that pentanal-modified aerogel has similar high hydrophobicity and low density compared to the hexanal-modified material, while heptanal- and octanal-modified aerogels show drastic shrinkage during gelation. The aldehyde modification also suppresses permeation of water droplets into aerogel monoliths as well as reduc...

The ultrasonic degradation of methylene blue was carried out in the absence and presence of dimethyl sulfoxide (DMSO) as a radical scavenger for various frequencies, and the effects of DMSO addition on the degradation rate constant estimated by assuming first-order kinetics were investigated. The degradation reaction rate decreased with DMSO addition, and hydroxyl radicals were observed to play important roles in the degradation of methylene blue. However, the degradation reaction did not stop with DMSO addition, and the degradation rate constant in the presence of DMSO was not affected by ultrasonic frequency.