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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 Swelling of iota-carrageenan gels prepared with various CaCl2 content: A fluorescence study(European Polymer Federation, 2008-01-05) Tarı İlgin, Özlem; Pekcan, Mehmet ÖnderIota carrageenan gels prepared with various CaCl2 content were completely dried and then swelled in water vapor. Steady-state fluorescence ( SSF) technique was used to monitor the swelling process of each iota carrageenan gels at various temperatures. Pyranine was used as a fluorescence probe. Apparent fluorescence intensity, I increased as swelling time increased for all gel samples. The increase in I was modelled using Li-Tanaka equation from which the swelling time constants, tau(1) and cooperative diffusion coefficients, D-c were determined. It was observed that D-c increased as the swelling temperature was increased. On the other hand at each temperature, it was seen that D-c decreased as CaCl2 content was increased. Activation energies for swelling were obtained and found to be 60.5, 61.0, 61.5 and 62.8 kJmol(-1) for the gels prepared with increasing amount of CaCl2 content.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 Phase transitions of kappa-carrageenan gels in various types of salts(John Wiley & Sons Inc, 2006-11-05) Kara, Selim; Arda, Ertan; Kavzak, Burhan; Pekcan, Mehmet ÖnderSol-gel and gel-sol phase transitions of K-carrageenan in various types of salts were studied using photon transmission technique. Here, LiCl, NaCl, KCl, MgCl2, CaCl2, and SrCl2 were chosen as the proper salts for the K-carrageenan-water system. Photon transmission intensity, I-tr was monitored against temperature to determine the sol-gel and gel-sol temperatures (T-sg and T-gs) and activation energies (Delta E-sg and Delta E-gs). It was observed that T-gs temperatures were notably higher than T-sg due to the hysteresis on the phase transition loops. It was observed that stronger carrageenan gels are formed in the presence of KCl compared to the others.Yayın Cation effects on phase transition of kappa-iota-carrageenan hybrids: a photon transmission study(Taylor & Francis Group, 2007) Pekcan, Mehmet Önder; Kara, Selim; Arda, ErtanPhase transitions of kappa-iota-carrageenan hybrid in various types of salts were studied using photon transmission technique: NaCl, KCI, MgCl2, CaCl2 and KCl+CaCl2 were chosen as the salt solutions for the carrageenan hybrid. Coil-to-helix (c-h), helix-to-dimer (h-d) and back to helix-to-coil (h-c), dimer-to-helix (d-h) phase transitions of carrageenan hybrid in these mono- and bivalent cation solutions were studied upon cooling and heating, respectively. Photon transmission intensity, It, was monitored against temperature to determine the (c-h), (h-d) and (h-c), (d-h) transition temperatures (T-ch, T-hd and T-hc, T-dh) and activation energies (Delta E-ch, Delta E-hd and Delta E-hc, Delta E-dh) of carrageenan hybrids. Two distinct transition regions were observed both during heating and cooling of the carrageenan-bivalent salt systems. During the heating process, at first dimers decompose into helices by making a (d-h) transition. Then at the high temperature region, a (h-c) transition takes place. During cooling, back transitions repeat themselves. However, the carrageenan-monovalent salt system presented only (c-h) and (h-c) transitions during the cooling and heating processes, respectively. A hysteresis was observed between (h-c)-(c-h) and (d-h)-(h-d) transitions for the monovalent and bivalent cation systems respectively.Yayın Determination of pre-gelation and post-gelation activation energies during free radical crosslinking copolymerization(Taylor & Francis Ltd, 2005) Kaya Aktaş, Demet; Pekcan, Mehmet ÖnderSteady-state fluorescence (SSF) and dilatoraetric techniques were used to study the free-radical crosslinking copolymerization (FCC) of styrene (S) and divinylbenzene (DVB) in bulk. The gel points (t g) were recorded by dilatometry at various DVB contents and temperatures in pre-gelation regime during FCC process. Pyrene (Py) was used as a fluorescence probe for the in situ polymerization experiments. The time required for a sudden increase in the fluorescence intensity of Py was recorded for the samples at various DVB contents and temperatures. Py fluorescence intensity during FCC exhibits a sudden increase corresponding to the reaction time at which the rate of polymerization becomes maximum due to the gel effect in post-gelation regime. The onset of gel effect point (t ge) was determined for various DVB contents and temperatures. The results show that alhough the dilatometric technique recorded the gel point, the fluorescence technique can be used to monitor the onset of the gel effect during S–DVB copolymerization. Pre-gelation and post-gelation actuation energies. ?E pre and ?E post were measured and it is observed that pre-gelation regime needs smaller energies than post-gelation regime during FCC.Yayın Film formation stages for poly(vinyl acetate) latex particles: a photon transmission study(Springer-Verlag, 2006-07) Kara, Selim; Pekcan, Mehmet Önder; Saraç, Ayfer; Arda, ErtanPhoton transmission technique was used to monitor the evolution of transparency during film formation from poly(vinyl acetate) (PVAc) latex particles. The latex films were prepared below the glass transition temperature (T-g) of PVAc. These films were annealed at elevated temperatures in various time intervals above the T-g of PVAc. It is observed that transmitted photon intensity (I-tr) from these films increased as the annealing temperature is increased. It is seen from I (tr) curves that there are two film formation stages. These successive stages are named void closure (viscous flow) and interdiffusion. The activation energies for viscous flow (Delta H) and backbone motion (Delta E (b)) were obtained by using well-defined models. The averaged values of the backbone (Delta E (b)) and the viscous flow activation energies (Delta H) were found to be 188.6 and 5.6 kcal/mol, respectively. The minimum film formation (tau (M),T (M)) and healing points (tau (H),T (H)) were determined. Minimum film formation (Delta E (M)) and healing activation energies (Delta E (H)) were measured using these time-temperature pairs. Delta E (M) and Delta E (H) were found to be 32.5 and 28.3 kcal/mol, respectively.Yayın Reversible film formation from nano-sized PNIPAM particles below glass transition(Springer-Verlag, 2007-01) Uğur, Şaziye; Elaissari, Abdelhamid; Yargı, Önder; Pekcan, Mehmet ÖnderReversible film formation process from nano-sized Poly(N-isopropylacrylamide) (PNIPAM) microgel particles were studied during heating-cooling cycles at various rates. Photon transmission technique was used and transmitted photon intensity I (tr) was monitored during heating-cooling cycles. The increase and decrease in I (tr) during heating and cooling was explained with the void closure and void reconstruction processes, and the corresponding activation energies were measured. It was observed that PNIPAM microgels required less energy during reconstruction of voids than their closure.
