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Yayın Molecular alignment during gel formation from methyl methacrylate: An excimer fluorescence study(Taylor & Francis Ltd, 2005-05) Kaya Aktaş, Demet; Erdoğan, Matem; Pekcan, Mehmet ÖnderGlass transition during bulk polymerization was studied in free-radical cross-linking copolymerization (FCC) of methyl methacrylate (MMA) using the steady-state fluorescence (SSF) technique. Naphthalene (N) was used as a monomer and excimer forming probe. Changes in the viscosity of the pregel solutions due to gel formation dramatically enhance both monomer and excimer fluorescent yield of N molecules. The reaction time at which the monomer and excimer intensities exhibit a sudden increase corresponds to the reaction time at which the rate of polymerization becomes maximum resulting from the gel effect. This effect was used to study the gelation of MMA, as a function of time, in various N concentrations. The results were interpreted in the view of percolation theory. The gel fraction, beta, and weight average degree of polymerization, gamma, exponents beta=0.40 +/- 0.02 and gamma=1.70 +/- 0.07 were found in agreement with percolation results for both monomer and excimer measurements, respectively.Yayın Study on critical behaviour in N-isopropyl acrylamide gels by using fluorescence technique(Taylor & Francis Group, 2006-11) Kaya Aktaş, Demet; Pekcan, Mehmet ÖnderThe steady state fluorescence (SSF) technique was used to study the sol-gel transition for the solution free radical crosslinking copolymerization of N-isopropyl acrylamide (NIPA), with N,N'-methylenebis (acrylamide) (BIS) as crosslinker in the presence of ammonium persulfate (APS) as an initiator. Pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, trisodium salt, HPTS) was used as a floroprobe for monitoring the polymerization. Pyranine molecules start to bind to NIPA polymer chains upon the initiation of the polymerization, thus the spectra of the bonded pyranines shift to the shorter wavelengths. The get fraction exponent beta and the weight average degree of polymerization exponent gamma' agree best with the mean-field (Flory-Stockmayer) results near the gel point for various crosslinker contents.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 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.
