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Yayın Temperature effect on drying and swelling of kappa carrageenan gels: A steady state fluorescence study(Wiley-V C H Verlag GMBH, 2008) Tarı İlgin, Özlem; Pekcan, Mehmet ÖnderA novel technique based on in situ steady state fluorescence (SSF) measurements is introduced for studying drying and swelling Of kappa(-) carrageenan (kappa carrageenan) gels at various temperatures. kappa(-) carrageenan gels were completely dried and then swelled in water vapor. Pyranine was embedded in kappa(-) carrageenan and used as a fluorescence probe. Scattered light intensities, I-SC and fluorescence intensities, I were monitored during the drying and swelling Of kappa(-) carrageenan gels. it was observed that the fluorescence intensity decreased linearly as drying time was increased. A simple model consisting of Case II diffusion was used to quantify the drying processes of the kappa(-) carrageenan gels. This moving boundary model provided packing constant, kappa(o). During swelling, fluorescence intensity increased exponentially as time is increased. The increase in I, was modeled using Li-Tanaka equation from which swelling time constants, tau(c) and cooperative diffusion coefficients, D-c were determined. It was observed that swelling time constants, tau(c) decreased and diffusion coefficients, D-c increased as the swelling temperature was increased. Activation energies for drying and swelling were also obtained and found to be 53.9 and 47.2 kJ mol(-1), respectively.Yayın Time evolution of film formation from polystyrene particles: a percolation approach(Springer, 2005-12) Uğur, Şaziye; Pekcan, Mehmet ÖnderThis work reports the film formation process from surfactant-free polystyrene (PS) latex particles. Steady state fluorescence and photon transmission techniques were used to study the evolution of film formation. The films were prepared from fluorescein (F)-labeled PS latex particles at room temperature and annealed in 2.5-min-time intervals above the glass transition temperature (T-g) of PS. Fluorescence intensity (I-F) from F was measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films was monitored by using the photon transmission intensity, I-tr. Drastic increase in I-tr and I-F above the critical annealing times t(r) and t(c) respectively, were attributed to the percolation behavior of the PS material. Critical exponents, beta, of percolation clusters were measured and found to be around 0.31 and 0.37 for Itr and IF measurement, respectively, which were attributed to the site percolation model.Yayın Film formation from TiO2-polystyrene latex composite: a fluorescence study(Taylor & Francis Group, 2007-03-01) Uğur, Şaziye; Sunay Yapışkan, Münüre Selin; Tepehan, Fatma Zehra; Pekcan, Mehmet ÖnderThis work reports the use of the steady state fluorescence (SSF) technique for studying film formation from TiO2 covered polystyrene (PS) latex particles. The composite films were prepared from pyrene (P)-labeled PS particles by covering them with TiO2 at room temperature and then annealed at elevated temperatures in 10 min time interval above glass transition (T-g) temperature of polystyrene. Five different composite films were studied in various TiO2 layer contents. Fluorescence intensities Ip from P were measured after each annealing step to monitor the stages of film formation. Films showed considerable increase in Ip above the certain onset temperature called minimum film forming temperature, T-0. Void closure and interdiffusion stages were modeled and related activation energies were determined and found to be 23.12 and 92.80 kJ mol(-1), respectively.Yayın Molecular alignment during gel formation from methyl methacrylate: An excimer fluorescence study(Taylor & Francis Ltd, 2005-05) Kaya Aktaş, Demet; Erdoğan, Matem; Pekcan, Mehmet ÖnderGlass transition during bulk polymerization was studied in free-radical cross-linking copolymerization (FCC) of methyl methacrylate (MMA) using the steady-state fluorescence (SSF) technique. Naphthalene (N) was used as a monomer and excimer forming probe. Changes in the viscosity of the pregel solutions due to gel formation dramatically enhance both monomer and excimer fluorescent yield of N molecules. The reaction time at which the monomer and excimer intensities exhibit a sudden increase corresponds to the reaction time at which the rate of polymerization becomes maximum resulting from the gel effect. This effect was used to study the gelation of MMA, as a function of time, in various N concentrations. The results were interpreted in the view of percolation theory. The gel fraction, beta, and weight average degree of polymerization, gamma, exponents beta=0.40 +/- 0.02 and gamma=1.70 +/- 0.07 were found in agreement with percolation results for both monomer and excimer measurements, respectively.Yayın Percolation approach to film formation from surfactant-free polystyrene particles(Taylor & Francis, 2005-09) Uğur, Şaziye; Pekcan, Mehmet ÖnderIn this study, a film formation process from surfactant-free polystyrene (PS) latex particles is reported. Steady state fluorescence (SSF) and photon transmission (UVV) techniques were used to study the evolution of film formation. The latex films were prepared from pyrene (P)-labeled PS particles at room temperature and annealed at time intervals of 2.5 min above the glass transition temperature (T-g) of PS. During the annealing processes, the transparency of the film changed considerably. Fluorescence intensity (I-0P) from P was measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films were monitored by using photon transmission intensity, I-tr. A drastic increase in I-tr and I-0P above the critical annealing times, t(r) and t(c) were attributed, respectively to percolation behavior of PS material from one side to the other side of the latex film. Critical exponents, beta of percolation clusters were measured and found to be around 0.35 and 0.25 for I-tr and I-0P measurements, respectively.Yayın In situ fluorescence study of swelling, sorption and desorption processes in and out of PAAm gels(Wiley-V C H Verlag GMBH, 2008-05) Evingür, Gülşen Akın; Karslı, Kadir; Pekcan, Mehmet ÖnderSmall molecule sorption and desorption in and out of polyacrylamide (PAAm) gels were studied at various temperatures. Pyranine (P(y)) dissolved in water used as a probe. Fluorescence emission intensity, I(p) from P(y) was monitored for studying sorption and desorption processes. Scattered light intensities, I(SC) from PAAm gel was also monitored to observed structural variations during sorption and desorption process. Li-Tanaka model was applied to produce the swelling time constants, tau(C) and sorption coefficients, D(C) for the swelling processes. on the other hand, sorption and desorption processes were studied and coefficients were produced by using Fickian model. Related activation energies were also calculated from the corresponding physical processes.Yayın Study on critical behaviour in N-isopropyl acrylamide gels by using fluorescence technique(Taylor & Francis Group, 2006-11) Kaya Aktaş, Demet; Pekcan, Mehmet ÖnderThe steady state fluorescence (SSF) technique was used to study the sol-gel transition for the solution free radical crosslinking copolymerization of N-isopropyl acrylamide (NIPA), with N,N'-methylenebis (acrylamide) (BIS) as crosslinker in the presence of ammonium persulfate (APS) as an initiator. Pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, trisodium salt, HPTS) was used as a floroprobe for monitoring the polymerization. Pyranine molecules start to bind to NIPA polymer chains upon the initiation of the polymerization, thus the spectra of the bonded pyranines shift to the shorter wavelengths. The get fraction exponent beta and the weight average degree of polymerization exponent gamma' agree best with the mean-field (Flory-Stockmayer) results near the gel point for various crosslinker contents.Yayın Universal behaviour of glass transition exponents in various polymeric systems(VSP BV, Brill Academic Publishers, 2005) Pekcan, Mehmet Önder; Kaya Aktaş, DemetThe fast transient fluorescence (FTRF) technique was used to study the critical exponents during glass transition in free-radical cross-linking copolymerization (FCC). Methyl methacrylate (MMA), ethyl methacrylate (EMA) and various combinations of MMA with EMA were used during FCC experiments. Pyrene (Py) was used as a fluorescence probe and its fluorescence lifetimes from its decay traces were measured during glass transition. Changes in the viscosity of the pre-gel solutions due to glass formation dramatically increased the Py fluorescent lifetimes, which were used to study the glass transition of MMA, EMA and their mixtures as a function of time, at various temperatures and monomer concentrations. The results were interpreted in the view of percolation theory. The critical exponents, beta and gamma, were measured near the glass transition point and found to be around 0.37 +/- 0.015 and 1.69 +/- 0.05, respectively, in all systems studied, which are in good agreement with the static percolation results.Yayın Dissolution of Al2O3-polystyrene latex composites: A fluorescence study(Taylor & Francis Ltd, 2005) Uǧur, Şaziye; Tepehan, Fatma Zehra; Pekcan, Mehmet ÖnderThis work reports the use of the steady state fluorescence (SSF) technique to study dissolution of a composite film formed from a mixture of Al 2O3 and polystyrene (PS) latex particles. The composite films were cast from dispersion of pyrene (P)-labeled PS particles in Al 2 O3 solution at room temperature and annealed at 280°C temperature for 10 min. Eight different composite films were studied in various latex contents. Toluene was used as dissolution agent. Fluorescence intensities Ip from P were monitored during dissolution. Fickian diffusion was employed to model the dissolution processes. Dissolution coefficients, D d, were measured and found to be increased at high PS content in the composite films.Yayın Films formed from polystyrene latex/clay composites: A fluorescence study(Springer New York, 2005-07) Uğur, Şaziye; Alemdar, Ayşe; Pekcan, Mehmet ÖnderThis study reports a steady-state fluorescence (SSF) technique for studying film formation from surractant-free polystyrene (PS) latex and Na-montmorillonite (SNaM) composites. The composite films were prepared from pyrene (P)-labeled PS particles and SNaM clay at room temperature and annealed at elevated temperatures in 10-min intervals above glass transition temperature (T-g) of polystyrene. During the annealing processes, the transparency of the fllm improved considerably. Scattered light (I-s) and fluorescence intensity (I-s) from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of composite films was monitored by using photon transmission intensity, I-tr Scanning electron microscopy (SEM) was used to detect the variation in physical structure of annealed composite-films. Minimum flIm formation temperature, T-o, and healing temperatures, T-h, were determined. Void closure and interdiff-usion stages were modeled and related activation energies were determined. It was observed that both activation energies increased as the percent of SNaM was increased in composite films.
