Chemical Engineering / Kimya Mühendisliği
Permanent URI for this collectionhttps://hdl.handle.net/11147/14
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Article Citation - WoS: 8Citation - Scopus: 7Cvd-Deposited Oxygen-Selective Fluorinated Siloxane Copolymers as Gas Diffusion Layers(American Chemical Society, 2022) Cihanoğlu, Gizem; Ebil, ÖzgençCopolymer thin films of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (V4D4), 2-(perfluorohexylethylacrylate) (PFHEA), and 2-(perfluoroalkylethylmethacrylate) (PFEMA) were synthesized via initiated chemical vapor deposition (iCVD) as potential candidates for gas diffusion layers (GDLs) in gas diffusion electrodes (GDEs) for aqueous metal–air batteries. Thin-film GDLs exhibited an average water vapor transmission rate of 7.5 g m–2 day–1 and enhanced oxygen diffusion with oxygen permeabilities as high as 3.53 × 10–15 mol m m–2 s–1 Pa–1 (10.5 Barrer). The electrochemical performance of GDEs fabricated using commercial catalysts, current collectors, and synthesized GDLs was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and potentiodynamic polarization measurements. The fabricated GDEs exhibited higher oxygen reduction current densities (228.2 mA cm–2) compared to commercial GDEs (132.7 mA cm–2). Copolymer GLDs exhibited an order of magnitude higher oxygen diffusion (39.5 × 10–8 cm2 s–1) in GDEs compared to commercial counterparts (1.84 × 10–8 cm2 s–1). Due to the high oxygen solubility of V4D4 and excellent hydrophobic behavior of PFHEA and PFEMA, their copolymers can effectively promote the diffusion of oxygen and restrict moisture intake, making them ideal materials for GDLs. Combining well-balanced properties of siloxane and fluorinated polymer chemistries, the iCVD process is an excellent low-cost method for the fabrication of GDLs for metal–air battery applications.Article Citation - WoS: 4Citation - Scopus: 4Adsorption Kinetics of Methane Reformer Off-Gases on Aluminum Based Metal-Organic Framework(Elsevier Ltd., 2020) Angı, Deniz; Çakıcıoğlu Özkan, Seher FehimeSolvothermal synthesis of aluminum based metal-organic frameworks (MIL-53(Al)s) were conducted by considering the effects of crystallization and activation temperatures, and the solvent at purification step. Adsorption kinetics of Steam Methane Reformer off gas components at 34, 70 and 100 °C temperatures was measured by using ZLC method. Henry constant decreases as diffusion coefficient of the gases increases with increasing temperature; It was determined that the CO gas has the highest activation energy. Adsorption kinetics of gases were controlled with electrostatic interaction. © 2020 Hydrogen Energy Publications LLCArticle Citation - WoS: 8Citation - Scopus: 8Phase Equilibrium and Diffusion of Solvents in Polybutadiene: a Capillary-Column Inverse Gas Chromatography Study(John Wiley and Sons Inc., 2002) Cai, W. D.; Ramesh, N.; Tıhmınlıoğlu, Funda; Danner, Ronald P.; Duda, John Larry; De Haan, A.The capillary-column inverse gas chromatography method was used to measure the diffusion and partition coefficients of ethylbenzene, styrene, and acrylonitrile in polybutadiene (PBD) at infinite dilution of the solvents. Experiments were performed over a temperature range of 50-125°C. At temperatures well above the glass-transition temperature of PBD, the diffusivities were correlated using an Arrhenius expression. The Arrhenius parameters in turn were intercorrelated and shown to be a function of the occupied volume, thus providing a method for predicting the diffusion of other solvents in the same polymer. Further, the activation energy was predicted using the Duda-Vrentas free-volume approach. The activation energy thus obtained was compared with the activation energy of the Arrhenius approach. The weight-fraction activity coefficient data were compared to the predictions of the group contribution, lattice-fluid equation-of-state, and the UNIquac Functional-group Activity Coefficient (UNIFAC) free-volume models.Article Citation - WoS: 3Citation - Scopus: 2Adsorption of No in Clinoptilolite-Rich Zeolitic Mineral by Concentration Pulse Chromatography Method(Elsevier Ltd., 2016) Narin, Güler; Ülkü, SemraThe equilibrium and kinetic parameters for NO adsorption in a clinoptilolite-rich natural zeolitic material from Turkey were determined using the concentration pulse chromatography method. Under the experimental conditions (carrier gas velocities and adsorption temperatures) the micropore diffusion resistance was found to be the mass transfer controlling step. Matching the first moment of the response peaks to the mathematical model the Henry's Law constants and heat of adsorption at zero loading were determined. The axial dispersion, external film, macropore and micropore diffusion coefficients, and activation energy for diffusion of NO in the micropores were calculated from the analysis of the second moments of the response peaks. For successive NO pulses without regeneration between the pulses, the retention times of the response peaks decreased and peak areas increased with the injection number indicating irreversible adsorption. The reversibly adsorbed NO could be desorbed by purging with an inert gas at the adsorption pressure and temperature. Temperature programmed desorption profile obtained by heating the NO saturated adsorbent to 400 °C under inert flow revealed presence of multiple irreversibly adsorbed species in NZ with different thermal stabilities. Desorption of these species was not achieved during the heating up to 400 °C which makes the natural zeolitic materıal suitable for NO storage rather than for cyclic adsorptive separation processes.Article Citation - WoS: 11Citation - Scopus: 13Sorption and Diffusion of Water Vapour on Edible Films(Springer Verlag, 2008) Berkün, Didem; Balköse, Devrim; Tıhmınlıoğlu, Funda; Alsoy Altınkaya, SacideTwo types of films consisting of sodium salt of carboxymethyl cellulose (NaCMC) and hydroxypropyl cellulose (HPC) as film forming materials and glycerin as plasticizer were prepared, characterized and their water vapour sorption properties were determined. The water sorption isotherms of the films were measured using a magnetic suspension balance. Results show that diffusion of water vapour in NaCMC based film is faster than that in HPC based films, due to the heterogeneous structure and larger pore dimensions of the NaCMC films.Article Citation - WoS: 18Citation - Scopus: 21Predicting Emission Characteristics of Volatile Organic Compounds From Wet Surface Coatings(Elsevier Ltd., 2009) Alsoy Altınkaya, SacideA mathematical model is developed to describe the emission characteristics of VOCs from homogeneous wet coating materials deposited on impermeable substrates. The model considers mass transfer in the material and in air, boundary layer resistance and the change in the coating thickness with time due to emission of VOC. Key features of the model are incorporation of concentration dependent VOC diffusion coefficients predicted from a physical model and nonlinear equilibrium isotherm at the coating/air interface. The model is applied to predict emission characteristics of MMA from acrylic based surface coatings. In an attempt to investigate the influences of equilibrium isotherm type and diffusion formalism on the predictions, simulations are performed with either constant or concentration dependent diffusivities and linear or nonlinear equilibrium isotherms. The lowest MMA concentration in air is predicted by incorporating the concentration dependent diffusivity and nonlinear equilibrium isotherm. The results suggest that assuming the diffusivity of MMA constant or equilibrium isotherm linear may lead to wrong conclusions about the emission rates from wet coatings. The model is general, fully predictive and can be used to predict emission rates of different VOCs from different coating materials if diffusion and thermodynamic parameters are available.Article Citation - WoS: 12Citation - Scopus: 17Diffusion Mechanism of Water Vapour in a Zeolitic Tuff Rich in Clinoptilolite(Springer Verlag, 2008) Çakıcıoğlu Özkan, Seher Fehime; Ülkü, SemraThe adsorption kinetics of H2O in a clinoptilolite rich zeolitic tuff was experimentally investigated at 18°C. In the identification of the diffusion mechanism the isothermal adsorption model equation was used. It was found out that the intraparticle mass transfer becomes more dominant over the heat transfer with increase in particle size and the adsorptive dose pressure. Although initially intraparticle mass transfer was the controlling resistance later external heat transfer also contributes to the transfer mechanism.Article Citation - WoS: 5Citation - Scopus: 5Solvent Sorption in a Polymer-Solvent System - Importance of Swelling and Heat Effects(Elsevier Ltd., 2006) Alsoy Altınkaya, Sacide; Ramesh, Narayan; Duda, John LarrySorption experiments are often conducted in gravimetric sorption columns where several deviations from ideal conditions could potentially occur. For example, heat effects due to solvent sorption, errors introduced due to concentration dependent diffusion coefficients and swelling are unavoidable. In this study, we develop a model to study the importance of the combination of these effects in obtaining diffusion coefficients from sorption experiments. The model is used to explore a wide range of operating conditions and physical parameters.Article Citation - WoS: 6Citation - Scopus: 7Solubility and Diffusivity of Methylmethacrylate and Butylacrylate Monomers in a Mma-Ba Copolymer(John Wiley and Sons Inc., 2007) Yürekli, Yılmaz; Alsoy Altınkaya, Sacide; Zielinski, John M.Mutual diffusion coefficients and sorption isotherms of methyl methacrylate (MMA) and butyl acrylate (BA) monomers in methyl methacrylate-butyl acrylate copolymer (MMA-BA) have been measured by gravimetric sorption. MMA is found to have higher solubility and diffusion rates in the copolymer than BA. Sorption data for MMA were interpreted using classical Flory-Huggins thermodynamic theory with a constant interaction parameter (χ). A modified version of this theory has been applied to correlate the sorption data of BA, which exhibit a temperature and concentration-dependent χ parameter. For MMA, the isotherm data reveal enhanced polymer-solvent interactions with increasing temperature, while for BA the data indicate a drive toward phase separation with increasing temperature. Despite the difference in thermodynamic behavior, both monomers are found to exhibit Fickian diffusion and the diffusivity data are correlated reasonably well with the Vrentas-Duda free volume theory. Some deviation between the free-volume correlation and the experimental data is observed at the lowest temperature and BA concentration examined.Article Citation - WoS: 2Citation - Scopus: 1Errors Associated With Swelling in the Analysis of Polymer-Solvent Diffusion Measurements(Elsevier Ltd., 2005) Alsoy Altınkaya, SacideSorption curves are generated from a mathematical model which includes the influence of the polymer swelling for unsteady-state sorption of a vapor or liquid by a polymer. To investigate the simultaneous effects of the specific volumes of the polymer-penetrant pair and the difference between the final and initial equilibrium concentrations on the sorption curves, statistical experimental design approach is used. Simulation results obtained from the numerical solution of model equations are utilized to estimate the error that would occur if one simply evaluates the diffusion coefficient using the traditional formulas derived from the analytical solution of the sorption equation. An empirical expression is developed that describes the effects of the difference between the final and initial equilibrium concentrations and the specific volumes of the polymer and the penetrant on the magnitude of error in diffusivity associated with the use of one of these traditional formulas so called the initial slope method. The predictive ability of the regression model is tested by performing additional simulations not used in the regression analysis.