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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 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 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 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 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 Reordering of polystyrene gel due to multiple swelling in organic vapor fast transient fluorescence technique study(Elsevier Science SA, 2006-07-31) Erdoğan, Matem; Pekcan, Mehmet ÖnderReordering of disc-shaped polystyrene (PS) gels due to multiple swelling, under organic vapor was studied by using Fast Transient Fluorescence (FTRF) technique. Disc-sbaped polystyrene gels were prepared by free radical copolymerization (FRC) of styrene (S) with ethylene glycol dimethacrylate (EGDM) as a crosslinker. Pyrene (P) was introduced as a fluorescence probe during polymerization. Swelling experiments were performed by using P doped PS gels under chloroform vapor. After each swelling step, gels were left to dry in an oven at 30 degrees C for consecutive reswelling experiments. Decay curves of P were measured and pyrene lifetimes, tau, were determined. It was observed that tau values decreased as swelling recycles were repeated. It was observed that after the fifth swelling step, two different regimes appeared in the swelling processes in PS gels. Swelling time constant, tau(c), and cooperative diffusion coefficients, D-c were determined by using Li-Tanaka equation for each swelling step in both regimes. It was observed that D-c values decreased up to tenth swelling step and then remained unchanged in both regimes.Yayın Critical behavior of thermal phase transitions of iota-carrageenan in CaCl2 solution(Elsevier B.V., 2006-07-15) Özbek, Haluk; Pekcan, Mehmet ÖnderIn situ photon transmission method was applied to study thermal phase transitions of ?-carrageenan in CaCl2 solution. Coil-to-helix (c-h) and helix-to-dimer (h-d) transitions were detected upon cooling. An extra dimer-to-dimer (d-d) transition was observed as well during cooling at low-temperature region. Upon heating only dimer-to-helix (d-h) and helix-to-coil (h-c) transitions were detected. Photon transmission intensity, Itr was monitored against temperature to determine several phase transitions and transition temperatures. It was observed that the c-h transition in ?-carrageenan-CaCl2 system performs a crossover between 3D percolation to classical theory. Upon heating, the specific heat exponent over the d-h transition was extracted from the transmitted intensity data and was found to be 0.045.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 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 Study on swelling of hydrogels (PAAm) at various temperatures by using fluorescence technique(Springer US, 2007-10) Kaya Aktaş, Demet; Akın Evingür, Gülşen; Pekcan, Mehmet ÖnderSteady-state fluorescence (SSF) technique was employed for studying swelling of polyacrylamide (PAAm) hydrogels. Disc-shaped gels were prepared by free-radical crosslinking copolymerization of acrylamide (AAm) with N, N'- methylenebis (acrylamide) (BIS) as crosslinker in the presence of ammonium persulfate (APS) as an initiator. Pyranine was introduced as a fluorescence probe. Fluorescence intensity of pyranine was measured during in situ swelling process at various temperatures and it was observed that fluorescence intensity values decreased as swelling is proceeded. Li-Tanaka equation was used to determine the swelling time constants, tau(c) and cooperative diffusion coefficients, D-c from intensity, weight and volume variations during the swelling processes. It is observed that swelling time constants, tau(c) decreased and diffusion coefficients, D-c increased as the swelling temperature is increased. The swelling activation energies, Delta E were measured from the intensity, weight and volume variations and found to be 10.7, 32.2 and 64.1 kJ mol(-1), respectively.
