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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 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 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 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 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 Film formation from TiO2-polystyrene latex composite: a fluorescence study(Taylor & Francis Group, 2007-03-01) Uğur, Şaziye; Sunay Yapışkan, Münüre Selin; Tepehan, Fatma Zehra; Pekcan, Mehmet ÖnderThis work reports the use of the steady state fluorescence (SSF) technique for studying film formation from TiO2 covered polystyrene (PS) latex particles. The composite films were prepared from pyrene (P)-labeled PS particles by covering them with TiO2 at room temperature and then annealed at elevated temperatures in 10 min time interval above glass transition (T-g) temperature of polystyrene. Five different composite films were studied in various TiO2 layer contents. Fluorescence intensities Ip from P were measured after each annealing step to monitor the stages of film formation. Films showed considerable increase in Ip above the certain onset temperature called minimum film forming temperature, T-0. Void closure and interdiffusion stages were modeled and related activation energies were determined and found to be 23.12 and 92.80 kJ mol(-1), respectively.Yayın Small molecule diffusion into swelling Iota-Carrageenan gels: A fluorescence study(Taylor & Francis Group, 2007-04) Ataman, Evren; Pekcan, Mehmet ÖnderSmall molecule diffusion into Iota-Carrageenan gel was studied by using steady-state fluorescence (SSF) technique. Pyranine, dissolved in water was used as fluorescence probe. Fluorescence emission intensity, I-p, and scattered light intensity, I-sc, were monitored to study diffusion and swelling processes at various temperatures respectively. Fickian and Li-Tanaka models were elaborated to produce diffusion, D, and collective diffusion, D-0, coefficients. Diffusion and swelling activation energies were also obtained and found to be 20.5 kj mol(-1) and 28.2 kj mol(-1). 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 Universal behaviour of gel formation from acrylamide-carrageenan mixture around the gel point: A fluorescence study(Taylor & Francis Group, 2006-08) Kaya Aktaş, Demet; Evingür, Gülşen Akın; Pekcan, Mehmet ÖnderThe steady state fluorescence (SSF) technique was used to study the sol-gel transition, for the solution free radical crosslinking copolymerization of acrylamide (AAm) with various carrageenan content. N, N'- methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) are used as crosslinker and an initiator, respectively. Pyranine (8-hydroxypyrene-1, 3,6-trisuffonic acid, trisodium salt, HPTS) was added as a floroprobe for monitoring the polymerization. Pyranine molecules start to bind to acrylamide polymer chains upon the initiation of the polymerization; thus, the spectra of the bonded pyranines shift to the shorter wavelengths. Fluorescence spectra from the bonded pyranines allows one to monitor the sol-gel transition, without disturbing the system mechanically, and to test the universality of the sol-gel transition as a function of some kinetic parameters like polymer concentration. Observations around the critical point show that the gel fraction exponent P obeyed the percolation result for low carrageenan concentrations (< 2.0%) however classical results were produced at higher carrageenan concentration (> 2.0%).
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