• Polymer(Korea)
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• v.28 no.6
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• pp.445-454
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• 2004

The requirement for a much finer line width circuits on semiconductors needs new developers such as supercritical fluid to prevent the collapse of the photoresist micro-patterns. The copolymers contain t-butyl methacrylate having an acid-cleavable t-butyl group and supercritical fluid $CO_2$ soluble perfluorinated decyl methacrylate segments. The supercritical fluid $CO_2$-philic properties of the photoresist changed to supercritical fluid $CO_2$-phobic properties after the deprotection reaction by exposure, which made the exposed resist insoluble in the supercritical fluid $CO_2$ developer. The synthesized copolymers containing more than 30% of perfluorinated decyl methacrylate were found to be soluble in supercritical fluid $CO_2$. The variation of film thickness before and after exposure was largest when the mole ratio of perfluorinated decyl methacrylate in the copolymer was 30%.

• Clean Technology
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• v.10 no.3
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• pp.149-158
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• 2004

Supercritical carbon dioxide is often promoted as an environmentally friendly solvent having useful properties for a wide range of technical and chemical processes. But the limited ability of $CO_2$ to dissolve polar or non-volatile compounds represents a major drawback in many processes, because the key components will often fail to form homogeneous solution under practical conditions. The design of $CO_2$ soluble ($CO_2$-philic) surfactant to aid this process is therefore paramount in these areas, which has advanced the "greening" of demanding yet important applications in dyeing, cleaning of fibers and texiles, polymerization and polymer processing, photoresist removal, electroplating, and chemical synthesis.

• Clean Technology
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• v.12 no.2
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• pp.53-61
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• 2006

A PGSS (Particles from Gas Saturated Solutions) process designed to generate nano-particles using supercritical fluids has been conducted for the fabrication of Poly(lactide-co-glycolide) (PLGA) microparticles that encapsulate a protein drug. It is demonstrated that the polymer and the dry powder of a protein can be mixed under supercritical carbon dioxide conditions and that the protein component retains its biological activity. In this experiment, the mixture of polymer which is plasticized and dry powder protein was sprayed to form solid polymer that encapsulate the protein. It is found that supercritical fluid process give fine tuning of particle size and particle size distribution by simple manipulations of the process parameters. Porous particles were formed with irregular shape. Protein encapsulated in the polymer was found to have enzymatic activity without significant loss of its initial value.

• Clean Technology
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• v.11 no.3
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• pp.147-152
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• 2005

For estblishing the best technique for the micronization of Ibuprofen using supercritical fluids, the solubility should be known. The solubility of Ibuprofen in supercritical carbon dioxide was measured by observing the cloud point. The cloud point was observed using high pressure equipment equipped a variable volume view cell between temperature of 35, 40 and $45^{\circ}C$. The solubility data was correlated by the Peng-Robinson equation of state Solute physical properties, such as critical temperature (Tc), critical pressure (Pc) and acentric factor (${\omega}$) were estimated by the some group contribution method. As pressure was increased, the solubility increased at constant temperature. The retrograde phenomenon by a solute vapor pressure and a density of solvent was observed at the pressure of around 150bar. It was found that $CO_2$ can be used as a supercritical solvent in micronization of ibuprofen by RESS.

• Clean Technology
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• v.11 no.3
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• pp.141-146
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• 2005

The composite membranes were made by grafting using supercritical carbon dioxide (scCO2) impregnation and polymerization procedures. The membranes were synthesized by changing amount of monomer. The polypropylene grafted polystyrene sulfonic acid (PP-g-pssa) membranes were characterized with various methods. The morphology and structure of PP-g-pssa membranes were analyzed with scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). As amount of monomer was increased, ion conductivity, cell performance was increased and methanol permeability was decreased. However PP-g-pssa membranes with 1.5g monomer and over had similar values of methanol permeability, ion conductivity and cell performance.

• Journal of the Semiconductor & Display Technology
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• v.16 no.2
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• pp.55-60
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• 2017

The supercritical $CO_2$ (sc-$CO_2$) mixture and the sc-$CO_2$-based Photoresist(PR) stripping(SCPS) process were applied to the removal of the post etch/ash PR residue on aluminum patterned wafers and the results were observed by scanning of electron microscope(SEM). In the case of MDII wafers, the carbonized PR was able to be effectively removed without pre-stripping by oxygen plasma ashing by using sc-$CO_2$ mixture containing the optimum formulated additives at the proper pressure and temperature, and the same result was also able to be obtained in the case of HDII wafer. It was found that the efficiency of SCPS of ion implanted wafer improved as the temperature of SCPS was high, so a very large amount of MEA in the sc-$CO_2$ mixture could be reduced if the temperature could be increased at condition that a process permits, and the ion implanted photoresist(IIP) on the wafer was able to be removed completely without pre-treatment of plasma ashing by using the only 1 step SCPS process. By using SCPS process, PR polymers formed on sidewalls of metal conductive layers such as aluminum films, titanium and titanium nitride films by dry etching and ashing processes were removed effectively with the minimization of the corrosion of the metal conductive layers.

• Resources Recycling
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• v.20 no.6
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• pp.78-82
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• 2011

Supercritical $CO_2$($scCO_2$) extraction has a great possibility to be a new process to recover metal and to replace the existing leaching/solvent extraction processes. The cobalt extraction was carried out using $scCO_2$ from cobalt sulphate solution. The bis (2,4,4-trimethylpentyl) phosphinic acid and diethylamine ligands were used to extract cobalt ion in $scCO_2$. The recommended method consists of $scCO_2$/extractants complexation process and metal extraction process at 60, 200bar. Experimental results showed that the extraction efficiency of Co was increased by 16-99% with increasing the ligand amount.

• Macromolecular Research
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• v.16 no.1
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• pp.6-14
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• 2008

Polypropylene (PP)-layered silicate nanocomposites were developed using a new processing method involving a supercritical carbon dioxide ($scCO_2$)-assisted co-rotating twin-screw extrusion process. The nanocomposites were prepared through two step extrusion processes. In the first step, the PP/clay mixture was extruded with $CO_2$ injected into the barrel of the extruder and the resulting foamed extrudate was cooled and pelletized. In the second step, the foamed extrudate was extruded with venting to produce the final PP/clay nanocomposites without $CO_2$. In this study, organophilic-clay and polypropylene matrix were used. Maleic anhydride grafted polypropylene (PP-g-MA) was used as a compatibilizer. This study focused on the effect of $scCO_2$ on the dispersion characteristics of the clays into a PP matrix and the rheological properties of the layered silicate based PP nanocomposites. The dispersion properties of clays in the nanocomposites as well as the rheological properties of the nanocomposites were examined as a function of the PP-g-MA concentration. The degree of dispersion of the clays in the nanocomposites was analyzed by X-ray diffraction and transmission electron microscope. Various rheological properties of the nanocomposites were measured using a rotational rheometer. In the experimental results, the $scCO_2$ assisted continuous manufacturing extrusion system was used to successfully produce the organophilic-clay filled PP nanocomposites. It was found that $scCO_2$ had a measurable effect on the clay dispersion in the polymer matrix and the melt intercalation of a polymer into clay layers.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2178-2182
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• 2011

Recently, the synthesis of ordered macroporous materials has received much attention due to its potential use as photonic band gap materials.$^1$ In this study, we have used the three-dimensional (3D) latex array template impregnated with benzenesulfonic acid (BSA), which is capable of catalyzing the reaction using tetraethyl orthosilicate (TEOS) as a precursor and distilled water. The polystyrene (PS) templates were reacted with TEOS in $scCO_2$ at 40 $^{\circ}C$ and at 80 bar. In the reactor, TEOS was filtrated into the PS particle lattice. After the reaction, porous silica materials were obtained by calcinations of the template. The stability test of the PS template in pure $CO_2$ was conducted before the main experiment. Scanning electron microscopy (SEM) images showed that the reaction in $scCO_2$ takes place only on the particle surface. This new method using $scCO_2$ has advantages over conventional sol-gel processes in its capability to control the fluid properties such as viscosity and interfacial tension. It has been found that the reaction in $scCO_2$ occurs only on the particle surface, making the proposed technique as more rapid and sustainable method of synthesizing inverse opal materials than conventional coating processes in the liquid phase and in the vapor phase.

• Elastomers and Composites
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• v.45 no.4
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• pp.256-262
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• 2010

Dispersion polymerization of methyl acrylate, ethyl acrylate, butyl acrylate, and glycidyl methacrylate were performed in supercritical $CO_2$ at $80\;^{\circ}C$ and 346 bar. Glycidyl methacrylate linked poly(dimethylsiloxane) (GMS-PDMS) surfactant, which was prepared by linking glycidyl methacrylate to monoglycidyl ether terminated PDMS with amino-propyltriethoxysilane, was used as surfactant for the dispersion polymerization in $CO_2$. The yield of the poly(alkyl acrylate) polymers, synthesized in $CO_2$ medium, decreased as the alkyl tail of the acrylate monomers increased. Poly(glycidyl methacrylate) and poly(methyl acrylate) were produced in bead form whereas poly(ethyl acrylate) and poly(butyl acrylate) were viscous liquid. The poly(glycidyl methacrylate) particles had a number average diameter of 2.45 ${\mu}m$ and monodisperse distribution. The poly(methyl acrylate) had a number average diameter of 0.52 ${\mu}m$ and the particle size distribution was bimodal. The glass transition temperatures ($T_g$) of the poly(glycidyl methacrylate) and the poly(alkyl acrylate) products were 4~9 K higher than the $T_g$ of the corresponding acrylate polymers synthesized in conventional processes.