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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 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 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 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 Sorption and slow release kinetics of PAAM gels at various temperatures(Freund Publishing House Ltd, 2007-11) Akın Evingür, Gülşen; Pekcan, Mehmet ÖnderSmall molecule sorption and slow release in and out of polyacrylamide (PAAm) gels were studied by using steady state fluorescence (SSF) technique. Pyranine (P-y) dissolved in water used as a probe. Fluorescence emission intensity, I-p from P-y was used to monitor for studying sorption and slow release processes at various temperatures. Sorption and slow release processes were analyzed by using Fickian diffusion model and coefficients were obtained. Related activation energies were also calculated for the corresponding physical processes.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 Investigation of OSL signals from very deep traps in unfired and fired quartz samples(Elsevier Science BV, 2010-03-15) Kitis, George; Güneç Kıyak, Nafiye; Polymeris, George S.; Pagonis, VasilisThis paper presents an attempt to isolate experimentally optically stimulated luminescence (OSL) signals which may originate from very deep traps (VDT) in quartz samples. As VDT we consider those traps which are responsible for TL glow peaks with a peak maximum temperature above a TL readout temperature of 500 C. The basic experimental procedure used to isolate OSL signals from VDT is heating the quartz samples to 500 C immediately before measuring the OSL signal. The study was carried out on eight quartz samples of very different origins; it is found that all eight samples exhibit OSL signals from VDT, and for a wide region of OSL stimulation temperatures. The OSL signal from VDT depends strongly on the type of quartz sample studied and on whether the sample was fired at high temperatures or not. The behavior of the OSL signal from VDT as a function of the stimulation temperature is found to be very different in fired and unfired samples. The thermal activation energy E for the OSL signals from VDT is obtained in both fired and unfired samples. The OSL signal from VDT in quartz samples fired at 800 C for 1 h is very high, and the OSL curves consist of three well-defined components and a fourth slow component which is rather poorly resolved. The dose response of these components is obtained using a computerized deconvolution procedure for the dose region 0.5-300 Gy. The results are of importance for dating of ancient fired ceramics, since OSL signals from VDT could potentially extend appreciably the equivalent dose region toward both lower and higher values.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.
