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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 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 Theory of fluidity of liquids, glass transition, and melting(Elsevier B.V., 2006-03-01) Dimitrov, Ventzislav IvanovThis is a presentation of a rigorous theory of fluidity of liquids, glass transition and melting of solids in the frame of an asymmetric double well potential model. Potential wells are doubled time to time by the local density fluctuations caused by the thermal longitudinal waves. The average frequency of doubling of potential wells is equal to the frequency of the most energetic waves which obey a law similar to Wein's displacement law in black body radiation. Based on the equilibrium thermodynamic theory of fluctuations and the displacement law, a law of linear pre-diffusion mean-square displacement of particles in a solid is derived: the mean-square displacement of molecules within their potential wells increases linearly with temperature. It is shown that when this is broken-down (where the mean-square displacement at a certain temperature rapidly changes its slope as a function of temperature) glass devitrifies and crystal melts, and all possible solid-liquid transitions of a substance occur at the same critical mean-square displacement: any solid (not only crystals) transforms into liquid when the mean-square displacement, as a fraction of the average intermolecular distance, acquires a certain universal critical value - the same for different substances. It is proved that molecules in a liquid perform specific Brownian motion. The average jump distance is a function of temperature and it is much smaller than the nearest intermolecular distances. At a certain temperature, shown to be the Kauzmann temperature, the average jump distance of Brownian motion becomes equal to zero: the supercooled liquid undergoes glass transition. The transition was proven to be a phase transition of the fourth order: the free energy of the system and its first, second and third derivatives are all continuous functions, but its fourth derivative with respect to temperature is discontinuous. Molecular mobility, diffusion and viscosity are obtained as functions of temperature.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 Effects of annealing on morphology of polymer/polymer (PS/PMMA) blend; a fluorescence study(John Wiley& Sons Inc, 2006-05-05) Uğur, Şaziye; Pekcan, Mehmet ÖnderSteady state fluorescence (SSF) technique conjunction with optical microscopy were used to study the morphology of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend upon annealing above glass transition in elevated time intervals. The PS/PMMA blends were prepared from dissolution of pyrene (P) and naphthalene (N) labeled PS and PMMA particles, respectively. Monte Carlo Simulations were performed to model the N and P fluorescence intensities (I-N and I-P), Using photon diffusion theory. Number of N and P photons (N-N and N-P) emerging from the front surface of the blend are calculated when only N is excited, where N-P photons are combined of photons from radiative (N-PR) and nonradiative (N-PNR) energy transfer processes. Optical microscopy images were taken at each annealing step to Support Our findings from fluorescence measurements.Yayın Film formation from nano-sized polystyrene latex particles(John Wiley & Sons Ltd, 2005-05) Uğur, Şaziye; Elaissari, Abdelhamid; Pekcan, Mehmet ÖnderThis work reports on the steady state fluorescence (SSF) technique for studying film formation from surfactant-free, nano-sized polystyrene (PS) latex particles prepared via emulsion polymerization. The latex films were prepared from pyrene M-labeled PS particles at room temperature and annealed at elevated temperatures in 5, 10, 15, 20 and 30 min time intervals above the glass transition temperature (T-g) of PS. During the annealing processes, the transparency of the film was improved considerably. Monomer and excimer fluorescence intensities, I-p and I-E respectively, from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of the latex films was monitored by using photon transmission intensity, It,. Void closure and interdiffusion stages were modeled and related activation energies were determined and found to be 10.3 and 50.3 kJ mol(-1). Void closure temperatures, T-v, were determined from the minima of I-tr value. CopyrightYayın The liquid–glass transition – is it a fourth order phase transition?(Elsevier Science, 2005-09-01) Dimitrov, Ventzislav IvanovThe liquid-glass transition is analyzed using a theory of Brownian motion in liquids recently developed by the author. It is shown that if a liquid could be cooled in quasi-static process and still avoids crystallization it would transform into a stable non-crystalline solid, which would be a normal thermodynamic phase. This hypothetical phase transition is neither first nor second order. At equilibrium transition temperature the free energy of the system and its first, second and third derivatives are all continuous functions, but its fourth derivative with respect to temperature is discontinuous. Therefore, the equilibrium liquid to non-crystalline solid transition may be considered a fourth order phase transition. The temperature of this phase transition, T-K, which coincides approximately with the Kauzmann temperature, is below the standard glass transition temperature T, (When the temperature decreases below T-g, the viscosity increases above 10(13) dPa s.) When the temperature decreases below T-K, the system becomes an ideal solid because the molecular mobility becomes zero and the viscosity becomes infinite if we neglect vacancy-like mechanisms of mobility. This hypothetical quasi-static transition is physically unobservable because the real liquid-glass transition must be done at a cooling rate high enough to suppress the growth of nanocrystals, which makes the liquid-glass transformation a non-equilibrium complicated phenomenon. Understanding this ideal phase transition is a first step towards describing the real liquid-glass transition from first principles.Yayın Film formation stages for poly(vinyl acetate) latex particles: a photon transmission study(Springer-Verlag, 2006-07) Kara, Selim; Pekcan, Mehmet Önder; Saraç, Ayfer; Arda, ErtanPhoton transmission technique was used to monitor the evolution of transparency during film formation from poly(vinyl acetate) (PVAc) latex particles. The latex films were prepared below the glass transition temperature (T-g) of PVAc. These films were annealed at elevated temperatures in various time intervals above the T-g of PVAc. It is observed that transmitted photon intensity (I-tr) from these films increased as the annealing temperature is increased. It is seen from I (tr) curves that there are two film formation stages. These successive stages are named void closure (viscous flow) and interdiffusion. The activation energies for viscous flow (Delta H) and backbone motion (Delta E (b)) were obtained by using well-defined models. The averaged values of the backbone (Delta E (b)) and the viscous flow activation energies (Delta H) were found to be 188.6 and 5.6 kcal/mol, respectively. The minimum film formation (tau (M),T (M)) and healing points (tau (H),T (H)) were determined. Minimum film formation (Delta E (M)) and healing activation energies (Delta E (H)) were measured using these time-temperature pairs. Delta E (M) and Delta E (H) were found to be 32.5 and 28.3 kcal/mol, respectively.Yayın Reversible film formation from nano-sized PNIPAM particles below glass transition(Springer-Verlag, 2007-01) Uğur, Şaziye; Elaissari, Abdelhamid; Yargı, Önder; Pekcan, Mehmet ÖnderReversible film formation process from nano-sized Poly(N-isopropylacrylamide) (PNIPAM) microgel particles were studied during heating-cooling cycles at various rates. Photon transmission technique was used and transmitted photon intensity I (tr) was monitored during heating-cooling cycles. The increase and decrease in I (tr) during heating and cooling was explained with the void closure and void reconstruction processes, and the corresponding activation energies were measured. It was observed that PNIPAM microgels required less energy during reconstruction of voids than their closure.
