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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 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%).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.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 Comparision of critical parameters of polymerization and gelation processes: A fast transient fluorescence study(World Scientific Publ Co Pte Ltd, 2005-03-10) Kaya Aktaş, Demet; Pekcan, Mehmet ÖnderThe fast transient fluorescence technique was used to study free-radical polymerization and crosslinking copolymerization of styrene. Ethylene glycol dimethacrylate and Pyrene were used as crosslinking agent and fluorescence probe, respectively. The fluorescence lifetimes of Pyrene from its decay traces were measured and used to monitor the vitrification processes at various temperatures. Changes in the viscosity due to polymer formation dramatically enhanced the fluorescent yield of pyrene molecules. This effect is used to monitor the polymerization and crosslinking copolymerization of Styrene as a function of time, at various temperatures. The results are interpreted in the view of static percolation theory. The critical exponents ß and ? for vitrified fraction and average degree of polymerization were found to be 0.39 ± 0.012; 1.62 ± 0.036 and 0.39 ± 0.004; 1.69 ± 0.064 in agreement with percolation results for polymerization and gelation processes, respectively. Activation energies for polymerization and gelation (?EP and ?EG) were measured and found to be 112.0 ± 4 and 86.9 ± 4 kJ mol-1, respectively.
