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Yayın Universal behaviour of glass transition exponents in various polymeric systems(VSP BV, Brill Academic Publishers, 2005) Pekcan, Mehmet Önder; Kaya Aktaş, DemetThe fast transient fluorescence (FTRF) technique was used to study the critical exponents during glass transition in free-radical cross-linking copolymerization (FCC). Methyl methacrylate (MMA), ethyl methacrylate (EMA) and various combinations of MMA with EMA were used during FCC experiments. Pyrene (Py) was used as a fluorescence probe and its fluorescence lifetimes from its decay traces were measured during glass transition. Changes in the viscosity of the pre-gel solutions due to glass formation dramatically increased the Py fluorescent lifetimes, which were used to study the glass transition of MMA, EMA and their mixtures as a function of time, at various temperatures and monomer concentrations. The results were interpreted in the view of percolation theory. The critical exponents, beta and gamma, were measured near the glass transition point and found to be around 0.37 +/- 0.015 and 1.69 +/- 0.05, respectively, in all systems studied, which are in good agreement with the static percolation results.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 Universality of sol-gel phase transition of kappa-carrageenan in various salts: a steady state fluorescence study(Taylor & Francis Ltd, 2007-08) Pekcan, Mehmet Önder; Tarı İlgin, ÖzlemThermal phase transitions of kappa-carrageenan in NaCl, KCl and CaCl2 solutions were studied using steady state fluorescence (SSF) technique. Pyranine was introduced as a fluorescence probe for studying sol-gel phase transitions. Scattered light, I-sc and fluorescence intensity, I was monitored against temperature to determine the sol-gel (T-sg) phase transition temperatures. It was observed that T-sg values are strongly correlated to 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, i.e., gamma and beta were found to be close to 1.0, independent of salt content.
