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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 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.
