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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 Cation effect on gel-sol transition of kappa carrageenan(Springer, 2008-04) Pekcan, Mehmet Önder; Tarı İlgin, ÖzlemThe steady state fluorescence (SSF) technique was employed to study gel - sol transitions of kappa carrageenan in NaCl, KCl and CaCl2 solutions. Pyranine was used as a fluorescence probe for monitoring these transitions. Scattered light, I-sc and fluorescence intensity, I was monitored against temperature to determine the gel - sol (T-gs) transition temperatures and exponents. It was observed that T-gs values are strongly correlated to the NaCl, KCl and CaCl2 contents. The weight average degree of polymerization, DPw and gel fraction G, exponents (gamma and beta) were measured and found to be in accord with the classical Flory-Stockmayer 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 Small molecule diffusion into swelling Iota-Carrageenan gels: A fluorescence study(Taylor & Francis Group, 2007-04) Ataman, Evren; Pekcan, Mehmet ÖnderSmall molecule diffusion into Iota-Carrageenan gel was studied by using steady-state fluorescence (SSF) technique. Pyranine, dissolved in water was used as fluorescence probe. Fluorescence emission intensity, I-p, and scattered light intensity, I-sc, were monitored to study diffusion and swelling processes at various temperatures respectively. Fickian and Li-Tanaka models were elaborated to produce diffusion, D, and collective diffusion, D-0, coefficients. Diffusion and swelling activation energies were also obtained and found to be 20.5 kj mol(-1) and 28.2 kj mol(-1). respectively.Yayın Swelling activation energy of kappa-carrageenan in its gel state: A fluorescence study(John Wiley & Sons Inc, 2007-12-15) Tarı İlgin, Özlem; Pekcan, Mehmet ÖnderA steady-state fluorescence technique was employed to study the swelling Of K-carrageenan gels at various temperatures. Pyranine was used as a fluorescence probe. The fluorescence intensity of pyranine was measured during the in situ swelling process of K-carrageenan gels. The fluorescence intensity increased exponentially as the swelling time increased. The increase in the fluorescence intensity was modeled with the Li-Tanaka equation, from which the swelling time constants and cooperative diffusion coefficients were determined. The swelling time constants decreased and the cooperative diffusion coefficients increased as the swelling temperature was increased. The swelling activation energies were measured to be 47.05 kJ/mol.Yayın Universal behaviour of gel formation from acrylamide-carrageenan mixture around the gel point: A fluorescence study(Taylor & Francis Group, 2006-08) Kaya Aktaş, Demet; Evingür, Gülşen Akın; Pekcan, Mehmet ÖnderThe steady state fluorescence (SSF) technique was used to study the sol-gel transition, for the solution free radical crosslinking copolymerization of acrylamide (AAm) with various carrageenan content. N, N'- methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) are used as crosslinker and an initiator, respectively. Pyranine (8-hydroxypyrene-1, 3,6-trisuffonic acid, trisodium salt, HPTS) was added as a floroprobe for monitoring the polymerization. Pyranine molecules start to bind to acrylamide polymer chains upon the initiation of the polymerization; thus, the spectra of the bonded pyranines shift to the shorter wavelengths. Fluorescence spectra from the bonded pyranines allows one to monitor the sol-gel transition, without disturbing the system mechanically, and to test the universality of the sol-gel transition as a function of some kinetic parameters like polymer concentration. Observations around the critical point show that the gel fraction exponent P obeyed the percolation result for low carrageenan concentrations (< 2.0%) however classical results were produced at higher carrageenan concentration (> 2.0%).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 Effects of annealing on morphology of polymer/polymer (PS/PMMA) blend; a fluorescence study(John Wiley& Sons Inc, 2006-05-05) Uğur, Şaziye; Pekcan, Mehmet ÖnderSteady state fluorescence (SSF) technique conjunction with optical microscopy were used to study the morphology of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend upon annealing above glass transition in elevated time intervals. The PS/PMMA blends were prepared from dissolution of pyrene (P) and naphthalene (N) labeled PS and PMMA particles, respectively. Monte Carlo Simulations were performed to model the N and P fluorescence intensities (I-N and I-P), Using photon diffusion theory. Number of N and P photons (N-N and N-P) emerging from the front surface of the blend are calculated when only N is excited, where N-P photons are combined of photons from radiative (N-PR) and nonradiative (N-PNR) energy transfer processes. Optical microscopy images were taken at each annealing step to Support Our findings from fluorescence measurements.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.
