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Yayın Reversible film formation from PS doped PNIPAM particles in various compositions(John Wiley & Sons Inc, 2008-02) Uğur, Şaziye; Yargı, Önder; Pekcan, Mehmet ÖnderFilm formation from polystyrene (PS) doped poly(N-isopropylacrylamide) (PNIPAM) particles was studied using photon transmission technique. The transmitted light intensity, Itr, was monitored during film formation process. Films were prepared by mixing PS and PNIPAM particles in various compositions ranging from 5 to 50 %. Samples were separately heated and cooled in constant rate at temperatures ranging from 10 to 100 C. The increase and decrease in Itr during heating-cooling cycles were explained by void closure and void reconstruction processes. The corresponding activation energies were measured during the reversible film formation process. Percolation model was used to interpret the distribution of PS particles in PNIPAM lattice.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 Small molecule desorption from a swelling polymeric glass in polymer solution: Energy transfer method(Elsevier Science Sa, 2005-07-15) Uğur, Şaziye; Pekcan, Mehmet ÖnderDirect energy transfer (DET) method conjunction with fast transient fluorescence (FTRF) technique were used to study small molecule desorption from a swelling poly(methyl methacrylate) (PMMA) glass in polymer solution, which is consist of naphthalene (N)-labeled PMMA chains in chlorofrom-heptane mixture. Desorption coefficients, D-d of pyrene (P) desorbing from the swelling PMMA glass prior to dissolution were measured and found to be 8.3 x 10(-8) and 1.3 x 10(-5) cm(2) s(-1) in short and long time regions, 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 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 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.Yayın Size-dependent self-organization of colloidal particles on chemically patterned surfaces(SP Zhejiang University Press, 2006-04-14) Karakurt, İsmail; Leiderer, Paul; Boneberg, JohannesA study of the self-organization of colloidal particles during the evaporation of particle solutions on chemically patterned surfaces is presented. On a surface with hydrophilic and hydrophobic regions, colloidal particles form compact structures on the hydrophilic sites. When a colloidal solution containing a mixture of particles with a variation in size is used, the number density of each type of particle deposited on the hydrophilic islands after evaporation decreases with increasing particle size. This makes it possible to produce a concentration gradient of the particles on islands of different sizes. It is shown that this technique could allow for particle separation.Yayın Film formation from pure and mixed latices; transient fluorescence study(Academic Press Inc Elsevier Science, 2005-11-15) Uğur, Şaziye; Pekcan, Mehmet ÖnderA fast transient fluorescence technique was used to study latex film formation induced by organic solvent vapor. Mixtures of pyrene (P)- and naphthalene (N)-labeled and/or pure naphthalene-labeled latex films were prepared separately from poly(methyl methacrylate) (PMMA) particles. Then these pure and mixed latex films were exposed to vapor of various chloroform-heptane mixtures in seven different experiments. In both films, fluorescence lifetimes from N were monitored during vapor-induced film formation. It was observed that N lifetimes decreased as the vapor exposure time is increased. A Stern-Volmer kinetic analysis was used for low quenching efficiencies to interpret the decrease in N lifetimes. A Prager-Tirrell model was employed to obtain back-and-forth frequencies, v, of reptating PMMA chains during latex film formation induced by solvent vapor. In both pure and mixed latex films, v values were found to be correlated with the chloroform content in the vapor mixture. It was observed that polymer interdiffusion obeyed a t(1/2) law during film formation.
