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Yayın Vapor-induced film formation from low-T-g particles for different solvent compositions(Elsevier Inc, 2006-05-15) Arda, Ertan; Kara, Selim; Saraç, Ayfer; Pekcan, Mehmet ÖnderThe photon transmission method was used to study latex film formation from poly(vinyl acetate) (PVAc) particles induced by two different solvents. Films with the same latex content were prepared from PVAc particles and exposed to vapor of ethanol-water and acetone-water mixtures in various compositions. Transmitted photon intensities, I-tr, from these films increased with increasing vapor exposure time. The increase in I-tr is attributed to the increase in crossing density at the polymer-polymer junction. The Prager-Tirrell model was employed to obtain the back-and-forth frequency, v, of the reptating polymer chain during film formation induced by solvent vapor. It was observed that the produced v values increase as the solvent content is increased for both solvents. Abilities of both solvents to form films were interpreted with the solubility parameters of the solvents and the PVAc.Yayın Synthesis and liquid crystalline behavior of random copolymer of poly(ethylene oxide) macromonomer and liquid crystalline monomer by the photon transmission technique(Taylor & Francis Inc, 2005-12) Yıldız, Sevtap; Yılmaz, Faruk; Özbek, Haluk; Pekcan, Mehmet Önder; Ito, Koichi; Yağcı, YusufRandom copolymers of poly(ethylene oxide) macromonomer with p-vinylbenzyl end-functional group (PEOVB) and liquid crystalline monomer, namely 6-(4-cyanobiphenyl-4'-oxy)hexyl acrylate (COA), were prepared by conventional free radical polymerization. A living anionic polymerization technique was employed for the synthesis of PEO macromonomers bearing p-vinylbenzyl moiety at one end. The photon transmission method was also applied to study the phase transitions of COA monomer and its random copolymer with PEO. It was found that, for both samples, the nematic-smectic A transition is continuous, but the critical fluctuation regions do not allow to obtain 3D XY values. Instead, we have obtained the values close to mean field regime. Scaling of thermal hystersis for random copolymer sample near the nematic-isotropic transition was studied as well. Thermal hysteresis loops were produced under linearly varying temperature. It was shown that the areas of the hysteresis loops scale with the temperature scanning rate with an exponent being equal to 0.614 which is in good agreement with the field-theoretical value.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 Photon transmission study on conformational ordering of iota-carrageenan in CaCl2 solution(Taylor & Francis Inc, 2005-06) Kara, Selim; Pekcan, Mehmet ÖnderCoil-to-double helix (c-h) and double helix-to-dimer (h-d) phase transitions of iota-carrageenan in CaCl2 solution upon cooling were studied using photon transmission technique. Photon transmission intensity, I-iota r was monitored against temperature to determine the (c-h) and (h-d) transition temperatures (T-ch and T-hd) and activation energies (Delta E-ch and Delta E-hd). An extra dimer-to-dimer (d-d) transition was also observed during cooling at low temperature region. However, upon heating dimers disappear to double helices by making dimer-to-double helix (d-h) transition. Further heating resulted double helix-to-coil (h-c) transition at high temperature region. T-dh and T-ch temperatures and Delta E-dh and Delta E-hc activation energies were also determined. It was observed that T-hc and T-ch temperatures and Delta E-dh and Delta E-hd activation energies do not effected by carrageenan content. However, T-hd, T-dh and T-dd temperatures and Delta E-ch and Delta E-hc activation energies were found to be strongly correlated to the carrageenan content in the system.Yayın Small molecule sorption and desorption in and out of iota-carrageenan gels(Taylor & Francis Group, 2007-08) Ataman, Evren; Pekcan, Mehmet ÖnderSmall molecule sorption and desorption in and out of Iota-Carrageenan was studied by using steady-state fluorescence (SSF) technique. Pyranine dissolved in water used as fluorescence probe. Fluorescence emission intensity, I-p from pyranine was monitored for studying sorption and desorption processes at various temperatures. The Fickian model was applied to produce sorption, D-s, early desorption, D-ed, and desorption, D-d, coefficients. Corresponding activation energies were obtained and found to be 20.5 kJ mol(-1), 7.0 kJ mol(-1) and 34.9 kJ mol(-1), respectively. The observed D-ed value is an order of magnitude smaller than the D-s and D-d coefficients. On the other hand, sorption processes were shown to be twice as fast as desorption processes.Yayın A photon transmission study for film formation from poly(vinyl acetate) latex particles with different molecular weights(John Wiley & Sons Inc, 2007-10-15) Arda, Ertan; Kara, Selim; Pekcan, Mehmet ÖnderThe photon transmission technique was used to monitor the temperature evolution of film formation from poly(vinyl acetate) (PVAc) latex particles with two different molecular weights. Two sets of latex films were prepared below the glass transition temperature (T-g) of PVAc, which are named as low (LM) and high molecular weight (HM) films. These films were annealed at elevated temperatures above the Tg of PVAc for various time intervals. It is observed that transmitted photon intensity (I-tr) from these films increased as the annealing temperature was increased. Onset temperatures (T-H) at given times (tau H) for starting the optical clarity of LM and HM films were measured and used to calculate the healing activation energies (Delta H) for the PVAc minor chains, and found to be as 28.1 kcal/mol and 27.7 kcal/mol, respectively. The increase in the transmitted photon intensity, Itr above TH was attributed to the increase in the number of disappeared interfaces between the deformed latex particles. Prager-Tirrell (PT) model was employed to interpret the increase in the crossing density of chains at the junction surfaces. The interdiffusion (backbone) activation energies (Delta E) were measured and found to be 177.5 kcal/mol and 210.7 kcal/mol for a diffusing PVAc chains across the junction surface of LM and HM latex films, respectively.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 Monovalent and divalent cation effects on phase transitions of iota-carrageenan(Sage Publications Ltd, 2007-01) Kara, Selim; Arda, Ertan; Pekcan, Mehmet ÖnderPhase transitions Of L-carrageenan in a variety of monovalent (Li, Na, K) and divalent (Mg, Ca, Sr) cation solutions were studied during heating and cooling by using photon transmission technique. Photon transmission intensity (I-tr) was monitored against temperature to determine the transition temperatures and activation energies during the heating and cooling processes in the monovalent and divalent systems. Three distinct transition regions were observed during the heating and cooling cycles for the carrageenan-divalent salt system. At the first step of the heating process, dimer groups were transformed into dimers that presented (g-d) transitions, then these dimers were directly converted into a double helix by undergoing a (d-h) transition. In the higher temperature region, a double helix-to-coil (h-c) transition took place. During the cooling process, these transitions are arranged in the order of (c-h), (h-d), and (d-g). The carrageenan-monovalent salt system presented only coil-to-rod-like helix (c-r) and rod-like helix-to-coil (r-c) transitions during the cooling and heating processes, respectively. A hysteresis was observed between (r-c)-(c-r) and (g-d)-(d-g) transitions for the monovalent and divalent cations, respectively.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.
