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Yayın Reversible film formation from PS doped PNIPAM particles in various compositions(John Wiley & Sons Inc, 2008-02) Uğur, Şaziye; Yargı, Önder; Pekcan, Mehmet ÖnderFilm formation from polystyrene (PS) doped poly(N-isopropylacrylamide) (PNIPAM) particles was studied using photon transmission technique. The transmitted light intensity, Itr, was monitored during film formation process. Films were prepared by mixing PS and PNIPAM particles in various compositions ranging from 5 to 50 %. Samples were separately heated and cooled in constant rate at temperatures ranging from 10 to 100 C. The increase and decrease in Itr during heating-cooling cycles were explained by void closure and void reconstruction processes. The corresponding activation energies were measured during the reversible film formation process. Percolation model was used to interpret the distribution of PS particles in PNIPAM lattice.Yayın Theoretical calculation of the kinetic coefficient of normal crystal growth(Trans Tech Publications Ltd, 2004) Dimitrov, Ventzislav IvanovAn expression for the velocity u of migration of a diffuse simple crystal-melt interface has been derived on the basis of the theory of atomic mobility in supercooled liquids: u = K-0 (T / T-m) DeltaT, where DeltaT = T-m - T the undercooling below the melting point T-m; K-0 is the kinetic coefficient of atomic attachment, which is used in models of crystal growth. It has been calculated for a number of metals. u(max) = K0Tm / 4 is the theoretical limit of the velocity of crystal growth. For a number of FCC metals the theoretical limit of crystal growth has been found to be of order of 200 m/s. The crystal growth kinetics has been shown to be limited by the atomic self-diffusion in the interface, for which the strong dependence on the orientation of the crystal/melt interface has been explained.Yayın Breakdown of the Stokes-Einstein relation in supercooled liquids(Trans Tech Publications Ltd, 2004) Dimitrov, Ventzislav IvanovBreakdown of the Einstein-Stokes relation in undercooled liquids is one of the unsolved problems in the theory of liquids. The self-diffusion coefficient follows the temperature dependence of the Einstein-Stokes equation D = kT / 6pietar at high temperatures but only down to approximately 1.2T(g) (T-g - glass-temperature). Below 1.2T(g) the temperature behavior of the diffusion coefficient is weaker than 1/eta. In the present study we show that this is a consequence of increasing correlations in the Brownian motion of the constituting particles of the liquid. We derive a relation, which includes the Einstein-Stokes equation as a limiting case for high temperatures.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 Films formed from polystyrene latex/clay composites: A fluorescence study(Springer New York, 2005-07) Uğur, Şaziye; Alemdar, Ayşe; Pekcan, Mehmet ÖnderThis study reports a steady-state fluorescence (SSF) technique for studying film formation from surractant-free polystyrene (PS) latex and Na-montmorillonite (SNaM) composites. The composite films were prepared from pyrene (P)-labeled PS particles and SNaM clay at room temperature and annealed at elevated temperatures in 10-min intervals above glass transition temperature (T-g) of polystyrene. During the annealing processes, the transparency of the fllm improved considerably. Scattered light (I-s) and fluorescence intensity (I-s) from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of composite films was monitored by using photon transmission intensity, I-tr Scanning electron microscopy (SEM) was used to detect the variation in physical structure of annealed composite-films. Minimum flIm formation temperature, T-o, and healing temperatures, T-h, were determined. Void closure and interdiff-usion stages were modeled and related activation energies were determined. It was observed that both activation energies increased as the percent of SNaM was increased in composite films.Yayın Fluorescence study on Al2O3-polystyrene latex composite film formation(John Wiley & Sons Inc, 2005-06) Uğur, Şaziye; Salman, Oğuz Umut; Tepehan, Galip Gültekin; Tepehan, Fatma Zehra; Pekcan, Mehmet ÖnderThis work reports a steady state fluorescence (SSF) technique for studying film formation from mixture of Al2O3 and polystyrene (PS) latex particles. The composite films were prepared from dispersion of pyrene (P)labeled PS particles in Al2O3 solution at room temperature and annealed at elevated temperatures in 10-min time interval above glass transition (T-g) temperature of polystyrene. Nine different composites film were studied in various latex contents. Fluorescence intensities (I-P) from P were measured after each annealing step to monitor the stages of film formation. No variations in I-p were detected for the films prepared with higher than 33 wt% Al2O3 content. However films prepared below 33 wt% Al2O3 content show considerable increase in I-P above the certain onset temperature called minimum film forming temperature, To. Healing temperatures T., were determined from the maxima of I-P. Void closure and interdiffusion stages were modeled and related activation energies were determined and found to be 20 and 97 kJ.mol(-1), respectively.Yayın 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 Fluctuation theory of the liquid-glass transition(Trans Tech Publications Ltd, 2004) Dimitrov, Ventzislav IvanovThe glassy state and the character of the liquid-glass transition from undercooled liquid to amorphous solid is one of the biggest challenges of our time. In spite of significant progress we still cannot explain accurately the sudden solidification of undercooled liquids on the atomic scale. In the present paper we present an analytical theory of the dependence of the glass transition temperature on the rate of cooling: the glass transition temperature increases with increasing cooling rate but does not exceed some upper limit. At almost zero cooling rates (hypothetical reversible transformation of the liquid into glass) the glass transition temperature reduces to a critical temperature, similar to a phase transition temperature.
