Supercritical carbon dioxide extraction of Baizhu: Experiments and modeling

In this work, supercritical CO₂ extraction has been carried out on a traditional Chinese herb of Baizhu under pressure of 15-45 MPa, temperature of 40-60 °C, mean powder size of 0.167-0.675 mm, and extraction time of up to 180 min. The maximum extraction yield obtained in 5 h is about 6.76 × 10⁻² g per gram raw materials at 60 °C and 45 MPa. The extraction process is correlated by means of five different mathematical models. The evaluation of these models against experimental data shows that among these models the Sovová model performs the best with an overall average absolute relative deviation of 1.62%, followed by Crank and Naik models, finally the Barton and Martínez models. From the Sovová model, the mass transfer coefficient in solid or fluid are obtained and they are varying in the ranges of 4.02-6.14 × 10⁻⁸ m/s and 0.88-2.87 × 10⁻⁹ m/s, respectively. These results suggest that solute diffusion in solid matrices and solute mass transfer in fluid are both important in affecting the supercritical CO₂ extraction process of Baizhu.     

The Possibility of Reprocessing of Spent Nuclear Fuel Using Supercritical Fluids

For the first time, the possibility of dissolution of spent nuclear fuel from a nuclear power plant in liquid and supercritical carbon dioxide was demonstrated. As shown by the example of spent nuclear fuel, the dissolution and the extraction of actinides and fission products by solutions of tributyl phosphate and nitric acid adducts TBP(HNO₃)_1.8 in carbon dioxide can be used as one of the stages of spent nuclear fuel reprocessing.     

Supercritical CO2 as an efficient medium for layered silicate organomodification: Preparation of thermally stable organoclays and dispersion in polyamide 6

In this study, the preparation of organoclays via a new process using supercritical carbon dioxide is described. This method turns out to be very efficient with various surfactants, in particular nonwater-soluble alkylphosphonium salts. The influence of the surfactant as well as of the clay nature on the thermal stability of the organoclay is evaluated by thermogravimetric analysis. Phosphonium-based montmorillonites are up to 90 °C more stable than ammonium-based montmorillonites. Moreover, the use of hectorite adds another 40 °C of thermal stability to the phosphonium-modified clays. These organomodified clays have been melt-blended with polyamide 6 and morphology as well as fire properties of the nanocomposites are discussed, in terms of influence of the stability of organoclays. For the first time, comparison of nanocomposites based on clay organomodified by ammonium and phosphonium salts of the very same structure is reported.     

Supercritical CO2 extraction of essential oil from yarrow

Essential oil was extracted from yarrow flowers (Achillea millefolium) with supercritical CO₂ at pressure of 10 MPa and temperatures of 40–60 °C, and its composition and yield were compared with those of hydrodistillate. The yield of total extract, measured in dependence on extraction time, was affected by extraction temperature but not by particle size of ground flowers. CO₂-extraction of cuticular waxes was lowest at 60 °C. Major essential oil components were camphor (26.4% in extract, 38.4% in distillate), 1,8-cineole (9.6% in extract, 16.2% in distillate), bornyl acetate (16.7% in extract, 4.3% in distillate), γ-terpinene (9.0% in extract, 9.4% in distillate), and terpinolene (7.6% in extract, 3.9% in distillate). Compared to hydrodistillation, the yield of monoterpenes was lower due to their incomplete separation from gaseous CO₂ in trap but the yield of less volatile components like monoterpene acetates and sesquiterpenes was higher. Hydrolysis of γ-terpinene and terpinolene, occuring in hydrodistillation, was suppressed in supercritical extraction, particularly at extraction temperature of 40 °C.     

Supercritical CO2 sterilization of ultra-high molecular weight polyethylene

The aim of this study was to use a benign technique for the sterilization of ultra-high molecular weight polyethylene (UHMWPE), which is broadly used in artificial joints. The feasibility of using supercritical (SC) CO₂ modified with additives such as ethanol, water and hydrogen peroxide was assessed for the sterilization of UHMWPE. The operating conditions and the amount of modifiers were changed to achieve a complete inactivation of bacteria such as spores and fungi. Complete inactivation of all microorganisms including spores was achieved within 2 h at 37 °C and 170 bar CO₂, when at least 25 μL hydrogen peroxide was mixed with equal volume of other modifiers. The physio-chemical properties of the polymer were tested for untreated, as well as treated samples. Mechanical strength and elongation of the polymer were measured using an Instron and the oxidation of the polymer was measured using FTIR. Both the physical and chemical properties of the polymer were unchanged after the SC CO₂ sterilization technique.     

Supercritical CO2-assisted synthesis of poly(acrylic acid)/nylon6 and polystyrene/nylon6 blends

Poly(acrylic acid)/nylon6 and polystyrene/nylon6 blends were prepared using supercritical CO₂ as substrate-swelling agent and monomer/initiator carrier. Both supercritical CO₂/nylon6 binary system and SC CO₂/monomer/nylon6 ternary system were studied. Virgin nylon6 and synthesized blends were characterized through differential scanning calorimetry, infrared spectroscopy, and polarizing microscopy. Supercritical CO₂-induced crystallization was found in modified nylon6.     

Supercritical CO2 impregnation of lactulose on chitosan: A comparison between scaffolds and microspheres form

Nowadays, the application of green chemistry principles in the production of new polymeric materials is receiving an increasing attention. In the present work, we have investigated the impregnation of chitosan with lactulose using supercritical fluids under various operating conditions, in order to improve the solubility of this natural polymer at neutral or basic pH. A comparison between chitosan scaffolds and microspheres is also presented; both chitosans were characterized using scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP) and Fourier transform infrared spectroscopy (FTIR). The degree of impregnation was evaluated by quantitative gas chromatography (GC-FID) analysis and interactions chitosan-lactulose by ninhydrin method. The supercritical carbon dioxide impregnation proved to be feasible for both chitosan forms. The highest impregnation yield (8.6%) was obtained for chitosan scaffolds using the following impregnation parameters: continuous process, 60 min contact time, 14% (v/v) of co-solvent ethanol:water (95:5), depressurization rate equal to 3.3 bar/min, 100 bar of pressure and 100 °C. Under these conditions, Maillard reaction also occurred.     

Diffusion During the Supercritical Drying of Silica Gels

Drying is the most critical elaboration step of large monolithic and crack-free silica aerogel plates. In the present work, we are studying the supercritical CO₂ drying and more precisely the first step, here called the supercritical washing step. This phase consists of replacing the liquid phase contained in the nanopores with supercritical CO₂. Within this study, this step is governed by molecular diffusion through the gels. These phenomena were investigated experimentally in order to estimate the duration of the washing step. The experimental results were then fitted with an analytical mass transfer model to identify the effective diffusion coefficient.     

Synthesis of PCL/clay masterbatches in supercritical carbon dioxide

Pre-exfoliated nanoclays were prepared through a masterbatch process using supercritical carbon dioxide as solvent and poly(?-caprolactone) as organic matrix. In situ polymerization of ?-caprolactone in the presence of large amount of clay was conducted to obtain these easily dispersible nanoclays, collected as a dry and fine powder after reaction. Dispersion of these pre-exfoliated nanoclays in chlorinated polyethylene was also investigated. All the results confirm the specific advantages of supercritical CO₂ towards conventional solvents for filler modification.     

Grafting of polypropylene with N-cyclohexylmaleimide and styrene simultaneously using supercritical CO2

Monomer mixture of styrene (St) and N-cyclohexylmaleimide (ChMI) and initiator benzoyl peroxide (BPO) were first impregnated into isotactic polypropylene (iPP) films simultaneously using supercritical carbon dioxide (SC CO₂) as a solvent and swelling agent at 35.0 °C. The composites were obtained after the monomers were grafted onto the iPP matrix at 70 °C. The effects of various conditions, such as pressure, monomer concentration, and the molar ratio of the two monomers in the soaking process, on the composition of the composites were determined. The molar ratios of St to ChMI in the composites were estimated by Fourier transform infrared spectroscopy. The thermal properties, the morphology, and the mechanical properties of the composites were characterized by different techniques. The results demonstrated that the phase size of the grafted St-ChMI was very small and the phase boundary was very ambiguous. The composites had better thermal stability than the original iPP film. The Young's modulus and tensile strength of the film increased continuously with increasing grafting percentage. The two grafted monomers in the composites had good synergetic effect.     

Supercritical CO2 extraction of Plumula nelumbinis oil: Experiments and modeling

Supercritical CO₂ extraction of Plumula nelumbinis oil was investigated at temperatures of 308–338 K and pressures of 15–45 MPa. The yield of the extracted oil was 0.128 g/g material at optimal conditions, in which gamma-sitosterol, unsaturated fatty acids and gamma-tocopherol had higher relative concentrations as determined by GC–MS. The broken and intact cell (BIC) model, with reduced adjustable parameters, was utilized to simulate the SFE process. The values of average absolute relative deviation (AARD) were in the range 2.34–10.9%, indicating that the improved method had a similar effect to the BIC model when three parameters were adjusted. The parameters obtained during the modeling had clear physical meanings and were used to gain an in-depth understanding of the SFE process theoretically.     

Supercritical CO2 processing and annealing of polytetrafluoroethylene (PTFE) and modified PTFE for enhancement of crystallinity and creep resistance

A method is reported to improve creep resistance in tension for polytetrafluoroethylene (PTFE) and modified PTFE (M-PTFE). PTFE and M-PTFE from different sources were annealed in air, N₂ or supercritical CO₂ (scCO₂) at a range of temperatures, pressures and time intervals. Annealing PTFE in scCO₂ increases crystallinity from 9 to 53%, depending on the material and annealing conditions. No corresponding increase occurs for samples annealed in air or N₂. In comparison to as-received PTFE, significant improvements in tensile creep resistance (18-60%) are observed also dependent upon the material and annealing conditions. For a given temperature and duration, the increase in PTFE tensile creep resistance after annealing in air or N₂ is greater than after annealing in scCO₂ despite the higher crystallinity for post-scCO₂ processed PTFE. Density measurements indicate that the effect of increased crystallinity is counterbalanced by scCO₂-generated microvoids, particularly at higher pressures, leading to smaller creep resistance. In contrast, thermal annealing in air or N₂, which does not significantly change the density or enhance the crystallinity of PTFE or M-PTFE, yields better tensile creep resistance. The detailed morphological origin of improved resistance to tensile creep is unknown, but stress relief by thermal annealing is evident.     

Polymer melt rheology with high-pressure CO2 using a novel magnetically levitated sphere rheometer

A magnetically levitated sphere rheometer (MLSR) designed to measure viscosity of fluids exposed to high-pressure carbon dioxide has been developed. This device consists of a magnetic sphere submerged inside a test fluid within a high-pressure housing and levitated at a fixed point. The housing is constructed from an optically transparent sapphire tube. The cylindrical tube can be moved vertically to generate a shear flow around the levitated sphere. The difference in magnetic force required to levitate the sphere at rest and under fluid motion can be directly related to fluid viscosity. Rheological properties, specifically zero shear viscosities, of transparent high-pressure materials can be measured to a precision of about 5% and over a wide range of viscosities. In addition, operation at constant pressure, in concentration regimes from a pure polymer to an equilibrated polymer/supercritical fluid solution, and at shear rates over several orders of magnitude is possible, eliminating many of the disadvantages associated with other high-pressure rheometers. Experiments performed at different temperatures with a poly(dimethylsiloxane) melt at atmospheric pressure are compared with data from a commercial Couette rheometer to demonstrate device sensitivity and viability. Measurements of a PDMS melt plasticized by high-pressure CO₂ are performed to illustrate the utility of the new rheometer under high-pressure conditions. Experimental data are obtained at 30 °C, for pressures up to 20.7 MPa and CO₂ concentrations reaching 30 wt%. Viscosity reductions of nearly two orders of magnitude compared with the pure polymer viscosity at atmospheric pressure are observed. Additionally, the effects of pressure on a polymer/CO₂ system are directly investigated taking advantage of the constant pressure operation mode of the MLSR. This allows us, for the first time in experiments of polymers with supercritical fluids, to decouple the effects of CO₂ concentration and pressure in a single device.     

Glass Transition Temperature in Microcellular Foaming Process with Supercritical Carbon Dioxide: A Review

In microcellular foaming process, the glass transition temperature (T_g) of polymer determines foaming temperature and has an effect on the other physical properties of polymer. In thisstudy, an evaluation of the current state of understanding for T_g was reviewed. Inaddition, we focused on the establishment and advancement of three main widely-used models that predict T_g (i.e. Chow model, Cha-Yoon model and Condo - Sanchez model). The comparisons of the three T_g-prediction models, with attention being given to their ownadvantages, disadvantages and scopes of application provide a reference for the further study.     

Cetirizine solubility in supercritical CO2 at different pressures and temperatures

A simple static technique was used to obtain the solubility of cetirizine in supercritical carbon dioxide. The solubility measurements were performed at temperatures and pressures ranging from 308.15 to 338.15 K and 160 to 400 bar, respectively; resulting in mole fractions in the 1.05 × 10⁻⁵ to 4.92 × 10⁻³ range. The Chrastil, Bartle, Kumar & Johnston and the Mendez-Santiago and Teja (MST) models were used to correlate the experimental data. The calculated solubilities showed good agreement with the experimental data in the temperature and pressure ranges studied.     

Supercritical CO2 Spray Drying of Ethyl Cellulose (EC) for Preparing Microparticles

Even though common spray drying has been widely used for drying food and related products, the effect of drying conditions of supercritical CO₂ spray drying on the particle sizes of dried products has not been well studied. The objective of this study was to study the effect of drying conditions and design parameters on the particle sizes of biomaterials dried with supercritical CO₂ spray drying. The ethyl cellulose (EC) microparticles were prepared with supercritical CO₂ as the dry medium using an experimental spray-drying apparatus. This research studied the influences of spray nozzle diameter, mass ratio of gas to liquid, solution concentration, temperature, and pressure on the physical characteristics of ethyl cellulose microparticles. The results indicated that the average size of the dried particles ranged from 1.07 to 9.84 µm. The spray nozzle with 8-mm diameter produced smaller microparticles with narrower distribution than the 4-mm spray nozzle. The average particle size increased with the increase of the ratio of gas to liquid. Also, the average size and distribution of the microparticles increased with the rise of temperature and solution concentration but decreased with the increase of pressure.     

In situ study of ionic conductivity for polyether-LiCF3SO3 electrolytes with subcritical and supercritical CO2

In situ measurements of the ionic conductivity were performed on polyethers, poly(ethylene oxide) (PEO) and poly(oligo oxyethylene methacrylate) (PMEO), with lithium triflate (LiCF₃SO₃) as crystalline and amorphous electrolytes, and at CO₂ pressures up to 20 MPa. Both PEO and PMEO systems in subcritical and supercritical CO₂ increased more than five fold in ionic conductivity at 40 °C composed to atmospheric pressure. The pressure dependence of the ionic conductivity for PEO electrolytes was positive under CO₂, and increased by two orders of magnitude under pressurization from 0 to 20 MPa, whereas it decreases with increasing pressure of N₂. The enhancement is caused by the plasticizing effect of CO₂ molecules that penetrate into the electrolytes.     

Real time intracellular pH dynamics in Listeria innocua under CO2 and N2O pressure

This article investigates the inactivation mechanism of high-pressure food treatment, considered as alternative to conventional biocidal processes. We aimed to determine intracellular pH decrease under CO₂ and N₂O pressure, so far postulated as one of the main causes of inactivation. Working with a lab-scale bioreactor in mild conditions – 25 °C and pressures up to 8 MPa – we monitored – for the first time during pressurization – cytoplasmic pH variations of Listeria innocua labeled with pH-sensitive fluorophores based on fluorescein.We show that carbonic acid, due to solubilization of CO₂ into the aqueous phase, causes a rapid pH drop in the cytosol, reaching pH 4.8 at 1 MPa and falls below the detection limit of the indicator fluorophore of pH 4.0. This correlates with a reduced viability (below 90%) in all the pressure ranges investigated. Contrarily, treatment under N₂O pressure reduces cell viability without significant pH-drop neither of intra- nor extra-cellular liquid at any pressure investigated. The pH value remains between 7 and 6 while an inactivation of more than 80% is achieved at 8 MPa.Our data clearly demonstrate that, as a critical pressure is achieved, microbial inactivation is mainly due to pressure-induced membrane permeation – stimulated by non-acidifying fluids as well, rather then cytoplasmic acidification, as widely argued so far. A definitive understanding of the microbial inactivation mechanism due to CO₂/N₂O under pressure has been advanced significantly.     

Supercritical CO2 conditioning promotes γ-crystal formation in amorphous syndiotactic polystyrene during further heating

The conditioning history of amorphous syndiotactic polystyrene (sPS) in mild supercritical CO₂ (scCO₂) changes significantly the thermal behavior and crystal phase transformation of sPS in further thermal treatment by inducing the formation of helical segments. The results of differential scanning calorimetry and temperature-dependent Fourier transform infrared spectroscopy show that polymer chains are preferred to arrange into crystalline γ-form with helical conformation in the conditioned sPS by heating under ambient pressure. Thus, mixed γ-form and α-form with all-trans conformation are formed in the amorphous sPS after conditioning instead of α-form in the amorphous sPS without conditioning, and the formation of α-form is totally suppressed in the conditioned sPS having only γ-form of small degree of crystallinity.     

Impact of SO2 concentration on the corrosion rate of X70 steel and iron in water-saturated supercritical CO2 mixed with SO2

The corrosion behavior of X70 steel and iron in water-saturated supercritical CO₂ mixed with SO₂ was investigated using weight-loss measurements. As a comparison, the instantaneous corrosion rate in the early stages for iron in the same corrosion environment was measured by resistance relaxation method. Surface analyzes using SEM/EDS, XRD and XPS were applied to study the morphology and chemical composition of the corroded sample surface. Weight-loss method results showed that the corrosion rate of X70 steel samples increased with SO₂ concentration, while the corrosion rate increased before decreasing with SO₂ concentration for iron sample. Comparing resistance relaxation method results with weight-loss method results, it is found that the instantaneous corrosion rate of iron is much higher than the uniform corrosion rate of the iron tablet specimens which are covered with thick corrosion product films after a long period of corrosion. The corrosion product films were mainly composed of FeSO₄ and FeSO₃ hydrates. The possible reaction mechanism under such environment was also analyzed, and the electrochemical reaction between the dissolved SO₂ in the condensed water film with iron is the critical reaction step.