@article{kim_carbonell_2010, title={Deposition of palladium catalyzed copper films by the displacement of two immiscible supercritical phases and subsequent reaction}, volume={20}, ISSN={["0959-9428"]}, DOI={10.1039/b925959g}, abstractNote={Palladium (Pd) catalyzed copper (Cu) films were produced by forming films of Cu(II) compound (Cu(hfac)2·H2O) and Pd(II) compound (Pd(hfac)2) on silicon oxide (SiOx) and titanium nitride (TiN) substrates using a Displacement from two Immiscible Supercritical Phases (DISPs) technique followed by reduction of the organometallic compounds films in hydrogen at 200 °C. The morphology of Cu films was observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). In the absence of Pd(hfac)2, Cu particles in the range of 60–95 nm formed on SiOx or TiN during the 5 min reduction period. As the Pd(hfac)2 concentration increased to 5 mol% (relative to the amount of Cu(hfac)2·H2O), a morphology transition from particle formation to film formation was observed. When the Cu(hfac)2·H2O concentration varied from 0.1 wt% to 3 wt% at a fixed Pd(hfac)2 concentration of 5 mol%, highly uniform, dense and adherent films with 10–40 nm in thickness were produced. Root mean square (rms) roughness of these films, estimated by AFM images, is in the range of 1.7–5.8 nm. Chemical composition analysis of 5 mol% Pd catalyzed Cu film by X-ray photoelectron spectroscopy (XPS) revealed that approximately the ratio of Pd to Cu incorporated into the film was two times larger than the initial Pd(hfac)2 to Cu(hfac)2·H2O ratio.}, number={19}, journal={JOURNAL OF MATERIALS CHEMISTRY}, author={Kim, Jaehoon and Carbonell, Ruben G.}, year={2010}, pages={3973–3978} }
 @article{kim_rolland_carbonell_desimone_2010, title={Ultrathin Cross-Linked Perfluoropolyether Film Coatings from Liquid CO2 and Subsequent UV Curing}, volume={22}, ISSN={["0897-4756"]}, DOI={10.1021/cm903598v}, abstractNote={Ultrathin fluorinated films with highly solvent-resistant and optically clear characteristics were produced using liquid carbon dioxide free-meniscus coating followed by UV curing. Unique film morphologies including mesh and droplets structures resulted due to autophobic dewetting behavior of hydrophilic terminated perfluoropolyether.}, number={8}, journal={CHEMISTRY OF MATERIALS}, author={Kim, Jaehoon and Rolland, Jason P. and Carbonell, Ruben G. and DeSimone, Joseph M.}, year={2010}, month={Apr}, pages={2411–2413} }
 @article{kim_dong_kiserow_roberts_2009, title={Complex Effects of the Sweep Fluid on Solid-State Polymerization: Poly(bisphenol A carbonate) in Supercritical Carbon Dioxide}, volume={42}, ISSN={["1520-5835"]}, DOI={10.1021/ma802193q}, abstractNote={The effects of the sweep fluid on solid-state polymerization (SSP) of poly(bisphenol A carbonate) (BPA-PC) were investigated. Prepolymers with two different number-average molecular weights, PCP6C (Mn = 3800 g/mol) and PCP9C (Mn = 2400 g/mol), were synthesized using melt transesterification. Solid-state polymerization of these prepolymers was carried out at temperatures in the range of 150−190 °C with supercritical carbon dioxide (scCO2) and N2 as the sweep fluids. It was found that scCO2 at 207 bar could either increase or decrease the rate of SSP relative to the rate in atmospheric N2, depending on the prepolymer molecular weight. At 190 °C, the molecular weights of the polymers synthesized from the higher-molecular-weight prepolymer (PCP6C) were higher with scCO2 as the sweep fluid compared to those of the polymers synthesized with N2. In contrast, at the same temperature of 190 °C, the molecular weights of the polymers synthesized from the lower-molecular-weight prepolymer (PCP9C) were lower with scCO...}, number={7}, journal={MACROMOLECULES}, author={Kim, Jaehoon and Dong, Laura Beth and Kiserow, Douglas J. and Roberts, George W.}, year={2009}, month={Apr}, pages={2472–2479} }
 @article{kelly_kim_roberts_lamb_2008, title={Characterization of Pd/gamma-Al2O3 Catalysts Prepared Using [Pd(hfac)(2)] in Liquid CO2}, volume={49}, ISSN={["1572-9028"]}, DOI={10.1007/s11244-008-9075-2}, number={3-4}, journal={TOPICS IN CATALYSIS}, author={Kelly, M. Jason and Kim, Jaehoon and Roberts, George W. and Lamb, H. Henry}, year={2008}, month={Aug}, pages={178–186} }
 @article{kim_gracz_roberts_kiserow_2008, title={Spectroscopic analysis of poly(bisphenol A carbonate) using high resolution C-13 and H-1 NMR}, volume={49}, ISSN={["0032-3861"]}, DOI={10.1016/j.polymer.2007.11.046}, abstractNote={Quantitative structural and end-group analysis of poly(bisphenol A carbonate) (BPA-PC) was carried out and number average molecular weights (Mn) were determined using 125.76 MHz 13C and 500.13 MHz 1H nuclear magnetic resonance (NMR) spectroscopy. BPA-PC with a wide range of end-group ratios (0.26–2.83) and number average molecular weights (1500–9000 g/mol) was synthesized using melt transesterification by changing the initial monomer (bisphenol A and diphenyl carbonate) ratios and reaction conditions. Results of the NMR analysis for the melt-polymerized samples were compared with those of a commercial BPA-PC with a Mn of 16,000 g/mol. It was demonstrated that NMR spectroscopy is a very selective and accurate method not only for quantification of both phenolic and phenyl chain end-groups but also in the structural analysis of main chain groups. Extremely small concentrations of end-groups (∼0.02 per repeating unit) were analyzed. In addition, NMR spectroscopy was found to be an excellent tool for detecting residual monomer and the presence of the reaction byproduct (phenol). The molecular weights that were determined using NMR end-group quantification agreed well with the molecular weights measured by gel-permeation chromatography (GPC).}, number={2}, journal={POLYMER}, author={Kim, Jaehoon and Gracz, Hanna S. and Roberts, George W. and Kiserow, Douglas J.}, year={2008}, month={Jan}, pages={394–404} }
 @article{kim_mcclain_carbonell_2007, title={Deposition of poly[2-(perfluorooctyl)ethyl acrylate] on silicon wafers by the displacement of two immiscible supercritical phases (DISP)}, volume={43}, ISSN={["1872-8162"]}, DOI={10.1016/j.supflu.2007.05.003}, abstractNote={Abstract Deposition from two immiscible supercritical phases (DISP), in which a solution of supercritical carbon dioxide (scCO2) with a desired solute is displaced by supercritical helium (scHe), has been applied to deposit poly[2-(perfluorooctyl)ethyl acrylate] (PFOEA) on silicon wafer substrate coupons. The polymer was precipitated at the interfacial boundary between the supercritical He phase and the supercritical CO2/PFOEA solution phase and deposited on the substrates. Depending on the deposition conditions, two different deposition regimes – a particle formation regime and a film formation regime – were found. At low solution concentration or high displacement velocity, particles in the range of 1–3 μm in diameter formed while at high solution concentration or low displacement velocity, films in the range of 30–500 nm in thickness formed. The solute concentration, displacement velocity, and pressure all had a strong effect on the particle size and film thickness. Optical microscopy and atomic force microscopy (AFM) were used to characterize film morphology including drying defects and film roughness. Highly uniform films with no drying defects and low root-mean-square (RMS) roughness (∼2–3 nm) were obtained at high solution concentration. Films formed at low-to-moderate solution concentration displayed ring-like drying defects. The thickness and morphology of films deposited from DISP were compared with films prepared from high-pressure free meniscus coating (hFMC) with liquid CO2 (l-CO2) as a solvent and from normal dip coating with an organic solvent (1,1,2-trifluorotrichloroethane, Freon113). The film deposited from DISP was much thicker and more uniform than the film formed using Freon113.}, number={1}, journal={JOURNAL OF SUPERCRITICAL FLUIDS}, author={Kim, Jaehoon and McClain, James B. and Carbonell, Ruben G.}, year={2007}, month={Nov}, pages={139–149} }
 @article{marias_mancini_cansell_mercadier_2007, title={Hydrothermal oxidation treatment of solid particles between 250 and 350 degrees C: Modelling and experiments}, volume={41}, ISSN={["1872-8162"]}, DOI={10.1016/j.supflu.2007.01.002}, abstractNote={Abstract Hydrothermal oxidation is an efficient and clean way for the treatment of wastewater containing organic matter. The purpose of this work is to develop a mathematical model of a reactor for hydrothermal oxidation. This reactor is of the tank type and it is designed for the oxidation of solid particles of waste or biomass. According to some previous work, the experimental device developed by the Institut de Chimie et de la Matiere condensee de Bordeaux is known to behave as a battery of three completely stirred tank reactors (CSTR). To reach our goal, governing equations are written within each of the three CSTR. This set of equations is composed of the mass, species and energy balances for the fluid phase as well as equations allowing for the evaluation of the rate of shrinkage of a particle (shrinking core model) and a population balance. Thanks to this model, the particle size distribution (PSD) of the output of the reactor is computed as a function of the incoming one and of the operating parameters (temperature, residence time, pressure, …). The numerical predictions of the model are compared to experimental profiles obtained in the case of hydrothermal oxidation treatment of black carbon. These comparisons show very good agreement.}, number={3}, journal={JOURNAL OF SUPERCRITICAL FLUIDS}, author={Marias, F. and Mancini, F. and Cansell, F. and Mercadier, J.}, year={2007}, month={Jul}, pages={352–360} }
 @article{kim_efimenko_genzer_carbonell_2007, title={Surface properties of poly[2-(perfluorooctyl)ethyl acrylate] deposited from liquid CO2 high-pressure free meniscus coating}, volume={40}, ISSN={["1520-5835"]}, DOI={10.1021/ma0623791}, abstractNote={The surface characteristics of poly[2-(perfluorooctyl)ethyl acrylate] (PFOEA) films deposited using a high-pressure free meniscus coating (hFMC) process with liquid CO{sub 2} (l-CO{sub 2}) as the coating solvent on 12.5 cm diameter silicon wafer substrates were investigated using contact angle measurements, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy. The results were compared with surface property measurements of PFOEA films deposited from 1,1,2-trichlorotrifluoroethane (Freon 113) under normal dip coating conditions at atmospheric pressure. NEXAFS measurements showed that perfluoroalkyl groups in the films from l-CO{sub 2} and Freon 113 were well-organized and oriented normal to the substrate at the air/polymer interface. AFM images and XPS measurements revealed that a terrace-like structure of the PFOEA film from l-CO{sub 2} resulted in carbonyl group exposure at the air/polymer interface. This leads to smaller contact angles on the films cast from l-CO{sub 2} relative to the specimens deposited from Freon 113. Annealing the films deposited from the solvents resulted in droplet formation on the surface due to dewetting. The critical surface tension ({gamma}{sub c}) after annealing the film prepared from Freon 113 increased from 6.5 to 8.5 mJ/m{sup 2}, whereas {gamma}{sub c} of the film deposited frommore » l-CO{sub 2} decreased slightly from 9.7 to 8.9 mJ/m{sup 2}. We discuss how surface morphology changes before and after annealing play a role in the variation of {gamma}{sub c}.« less}, number={3}, journal={MACROMOLECULES}, author={Kim, Jaehoon and Efimenko, Kirill and Genzer, Jan and Carbonell, Ruben G.}, year={2007}, month={Feb}, pages={588–597} }
 @article{kwark_kim_novak_2007, title={Titanium complexes: A possible catalyst for controlled radical polymerization}, volume={15}, DOI={10.1007/BF03218749}, number={1}, journal={Macromolecular Research}, author={Kwark, Y. J. and Kim, J. and Novak, B. M.}, year={2007}, pages={31–38} }
 @article{kim_carbonell_2006, title={Deposition of small organic molecules by the displacement of two immiscible supercritical phases}, volume={22}, ISSN={["0743-7463"]}, DOI={10.1021/la052625m}, abstractNote={A new coating process is described (deposition from two immiscible supercritical phases, or DISP) in which a solution of supercritical carbon dioxide (scCO2) with a desired solute is displaced by supercritical helium (scHe). After depressurization, the solute is deposited on substrates initially submerged in the coating solvent. Micron-sized particles and thin films of sucrose octaacetate (SOA) were formed on silicon wafer substrate coupons from DISP at relatively low temperatures and pressures (< or = 6500 psi and < or = 60 degrees C). The particle size, film thickness, and morphology of SOA were characterized as a function of coating conditions-solution concentrations, withdrawal velocities, and pressures. Particles in the range of 1-14 microm in diameter were deposited at low solute concentrations (< or = 0.2 wt % at 4500 psi), whereas films in the range of 0.1-0.5 microm in thickness were deposited at higher solute concentrations (> or = 1.5 wt % at 4500 psi). Particle sizes decreased with increasing displacement velocity and increasing pressure. Estimates of characteristic times for diffusion and nucleation indicate that DISP is a diffusion-limited process. Optical microscopy and atomic force microscopy (AFM) were used to characterize film morphology, including defect formations and film roughness. Highly uniform films with low root-mean-square (RMS) roughness (approximately 10 angstroms) were obtained at a low displacement velocity of 0.0035 cm/s, while ring-like defect structures were observed in films deposited at a higher displacement velocity of 0.035 cm/s. The film thickness and morphology of the films deposited from DISP were compared with films from normal dip coating with typical organic solvents (acetone and toluene). Films deposited from scCO2 by DISP were much thicker, more uniform, and exhibited much fewer drying defects and lower RMS roughness compared with films from the organic solvents.}, number={5}, journal={LANGMUIR}, author={Kim, J and Carbonell, RG}, year={2006}, month={Feb}, pages={2117–2129} }
 @article{kim_novick_desimone_carbonell_2006, title={Ultrathin film deposition by liquid CO2 free meniscus coating-uniformity and morphology}, volume={22}, ISSN={["0743-7463"]}, DOI={10.1021/la0521600}, abstractNote={Ultrathin organic films of sucrose octaacetate (SOA) were deposited on 12.5 cm diameter silicon wafer substrates using high-pressure free meniscus coating (hFMC) with liquid CO2 (l-CO2) as a coating solvent. The dry film thickness across the wafer and the morphology of deposited films were characterized as a function of coating conditions-withdrawal velocity, solution concentration, and evaporation driving force (deltaP). When no evaporation driving force was applied (deltaP = 0), highly uniform films were deposited with thickness in the range of 8-105 angstroms over the entire concentration range (3-11 wt%). Uniform films were also obtained at low concentrations (3-5 wt%) with a low evaporation driving force (deltaP = 0.0138 MPa). However, films deposited at medium to high concentrations (7-11 wt%) were thicker (110-570 angstroms) and less uniform, with larger nonuniformities at higher applied evaporation driving forces. Optical microscopy and atomic force microscopy (AFM) were used to characterize film morphology including drying defects and film roughness. Films deposited without evaporation had no apparent drying defects and very low root-mean-square (RMS) roughness (1.4-3.8 angstroms). Spinodal-like dewetting morphologies including holes with diameters in the range of 100-300 nm, and surface undulations were observed in films deposited at medium concentration (7 wt%) and low deltaP (0.0138-0.0276 MPa). At higher concentrations and higher evaporative driving forces, spinodal-like dewetting morphologies disappeared but concentric ring defect structures were observed with diameters in the range 20-125 microm. The film thickness and morphology of SOA films deposited from 1-CO2 hFMC were compared to those deposited from toluene and acetone under normal dip coating. Films deposited from l-CO2 hFMC were much thinner, more uniform, and exhibited much fewer drying defects and lower RMS roughness.}, number={2}, journal={LANGMUIR}, author={Kim, J and Novick, BJ and DeSimone, JM and Carbonell, RG}, year={2006}, month={Jan}, pages={642–657} }