Smectic A-C-A Liquid Crystal Reentrance: A Photon Transmission Study

Ultraviolet/visible photon transmission measurements were applied to study liquid crystal phase transitions in the binary BOPDOB-BOPOOB mixture. A sequence exhibiting a new reentrant, namely isotropic-nematic-smectic A-C-A as temperature is lowered, is identified. For the smectic A-C transition, the critical exponent g is seen to cross over from the mean-field 0.501 - 0.008 to the helium-like 0.336 - 0.012 as the transition is approached. The reentrant C-A transition is first-order, signalling a tricritical point in the phase diagram.     

Sorption and Desorption of PVA-Pyrene Chains in and out of Agarose Gel

In situ steady-state fluorescence (SSF) measurement technique was applied to investigation of pyrene labeled Poly(vinyl alcohol) (PVA-Py) molecules diffusion in and out of agarose gels. Gel samples with four different concentration of agarose were prepared. PVA-Py was synthesized by "click" chemistry method and dissolved in water to use in diffusion experiments. The results were analyzed by using Fickian type diffusion model, and it was found that sorption and desorption processes of PVA-Py molecules in and out of agarose gel have two distinct regions for short and long diffusion times. Sorption and desorption coefficients were measured and it was seen that the diffusion rates were much larger at short times and at lower agarose concentrations.     

The Role of Pyranine in Characterization of PAAm-κC Composites by Using Fluorescence Technique

Polyacrylamide (PAAm) doped by κ-carrageenan (κC) gels were prepared with various amounts of κC varying in the range between 0 wt.% and 3 wt.%. Steady-state fluorescence (SSF) technique was employed for studying sol-gel transition and swelling of PAAm-κC composite gels which were prepared by free-radical crosslinking copolymerization. Pyranine was introduced as a fluorescence probe. 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 allow one to monitor the sol-gel transition and to test the universality of the sol-gel transition as a function of some kinetic parameters like polymer concentration. Observations around the gel point, t _c for PAAm-κC composite gels showed that the gel fraction exponent β obeyed the percolation result for low κC (<2.0 wt. %) however classical results were produced at higher κC (>2.0 wt.%). On the other hand, fluorescence intensity of pyranine was measured during in situ swelling process at various amounts of κC and it was observed that fluorescence intensity values decreased as swelling is proceeded. Li-Tanaka equation was used to determine the swelling time constants, τ and cooperative diffusion coefficients, D.     

Drying of PAAm Hydrogels at Various Temperatures: A Fluorescence Study

The steady‐state fluorescence (SSF) technique was employed for studying the drying of polyacrylamide (PAAm) hydrogels. Disc‐shaped hydrogels were prepared by free‐radical crosslinking copolymerization of acrylamide (AAm) with N,N′‐methylene bisacrylamide (BIS) as crosslinker in the presence of ammonium persulfate (APS) as an initiator. Pyranine (P) was introduced as a fluorescence probe and the intensity of pyranine was monitored during in situ drying at various temperatures. It was observed that the fluorescence intensity of pyranine increased during the drying process. A supporting, gravimetrical experiment was also performed. A phenomenological equation was introduced to determine the desorption coefficient, D, of water molecules from the drying hydrogels at various temperatures. The desorption activation energy, ΔE _d, values were measured for the drying processes and found to be 91.08 and 36.82 kJ mol^–1 by fluorescence and gravimetrical methods, respectively. This difference most probably originates from the origin of the techniques; the fluorescence technique measures the parameters at a molecular level, whereas the gravimetrical technique measures a parameter in the bulk.     

Studying of the critical exponents around the glass transition in bulk polymerization of ethyl methacrylate by using fluorescence techniques

The glass transition during bulk polymerization was studied in free-radical crosslinking copolymerization (FCC) of ethyl methacrylate (EMA), using both the steady-state fluorescence (SSF) and the fast transient fluorescence (FTRF) techniques. Pyrene (Py) was used as a fluorescence probe. Changes in the viscosity of the pregel solutions due to gel formation dramatically enhance the fluorescent yield of Py molecules. The reaction time at which the Py intensity and lifetime exhibit a sudden increase corresponds to the reaction time at which the rate of polymerization becomes maximum resulting from the gel effect. This effect is used to study the gelation of EMA, as a function of time, at various crosslinker concentrations and different temperatures. The results were interpreted in the view of percolation theory. The gel fraction, β and weight average degree of polymerization, γ exponents β?=?0.37?±?0.01, γ?=?1.71?±?0.04 and β?=?0.36?±?0.002, γ?=?1.687?±?0.01 are found in agreement with percolation results for SSF and FTRF measurements, respectively.     

Comparative study of liquid-crystalline ordering in a monomer,linear polymer,and graft copolymer by the photon transmission technique

The photon transmission technique was used to study the phase transitions of a liquid crystalline acrylate monomer, 6-(4-cyanobiphenyl-4′oxy)hexyl acrylate (LC6), its homopolymer (PLC6) and its graft copolymer (GLC6) with polytetrahydrofuran grafts. The phase transitions were also confirmed by DSC and polarizing microscopy. We observed the phase transition sequence isotropic–nematic–smectic A–smectic C in the LC6 monomer. In PLC6 and GLC6 polymers, the nematic and smectic A phases appear dominant. The apparent nematic–smectic A transition is of first order in PLC6 and of second order in GLC6, with the transition temperature remaining the same. The effects of quenched random constraints introduced in GLC6 are consistent with the theory of quenched random interactions. The critical exponents were also evaluated.     

Critical Exponents of Kappa Carrageenan in the Coil-Helix and Helix-Coil Hysteresis Loops

The steady-state fluorescence technique was used to study coil-helix (sol-gel) and helix-coil (gel-sol) transitions of the kappa carrageenan-water system with various carrageenan contents. Fluorescence (I) and scattered light (I_sc ) intensities were measured against temperature to determine critical phase transition temperatures and exponents. It was observed that the coil-helix transition temperatures, T_ch were much lower than the helix-coil (T_hc ) transition temperatures due to the hysteresis of the phase transition loops. The gel fraction exponent (β) was measured and found to be in accord with the classical Flory-Stockmayer model.     

Photon transmission technique for studying multiple phase transitions in a liquid crystal

A photon transmission technique was used to monitor the multiple phase transitions in a 4-butoxyphenyl4(')-declyoxybenzoate (BOPDOB) liquid crystal. Drastic decreases in the transmitted photon intensity (I) were attributed to the sequential phase transitions in BOPDOB upon cooling. In this paper, it is assumed that the order parameter rho is proportional to the transmitted photon intensity. The isotropic-nematic and nematic-smectic-A transitions were observed and found to be of first order. It was observed that the smectic-A-smectic-C and smectic-C-smectic-G transitions are second order. It was found that for the smectic-A-smectic-C transition, critical exponent crosses over from beta=0.513+/-0.006, which is consistent with mean-field theory, to beta=0.35+/-0.009, which is consistent with heliumlike behavior, as the Ginzburg criterion predicts. The critical exponent for the smectic-C-smectic-G transition was found to be beta=0.703+/-0.001. Transition temperatures were established at each phase transitions and found to be 84.92 degrees C, 74.85 degrees C, 52.96 degrees C, and 33.03 degrees C for isotropic-nematic, nematic-smectic-A, smectic-A-smectic-C and, smectic-C-smectic-G transitions, respectively.     

Magnetic resonance absorption of host-guest triplet paired centers in a mixed organic crystal system

Electron paramagnetic resonance absorptions of the host-guest paired centers has been observed at room temperature in pyrene-d₁₀ doped fluorene single crystal, when irradiated with ultraviolet light. The spin hamiltonian of the model paired center was denied, in terms of the probabilities of finding the excitation on the equivalent positions of the two different kinds of molecules. From comparison of theory and experiment, the fine structure parameters of the spin hamiltonian were calculated and the probabilities of finding the excitation on fluorene and pyrene-d₁₀ molecules were found to be equal.     

Can the glass transition in bulk polymers be modeled by percolation picture?

Recent observations (Eur. Phys. J. E 9, 135 (2002)) showed that the vitrification process, which sets in during the linear bulk methyl methacrylate (MMA) polymerization carried out below glass transition temperatures, can be modelled by static percolation picture. To generalize this observation for different kind of bulk linear or crosslinked polymers not enough data are present in the literature. To cover partly this deficit we studied the glass transition of MMA and styrene (Sty) crosslinking copolymerization in varying ratios of MMA and Sty. Both the fluorescence intensity I and the lifetime of pyrene (Py) used as a nanosecond in situ fluoroprobe were monitored during the gelation time. Both I and increase dramatically as a result of the reduced mobility of the probes trapped in the glassy regions, appearing near the glass transition point. The average size of the glassy regions just below, and the strength of the infinite network formed upon the connection of the glassy regions above the glass transition point obey power law relations. The data around were interpreted on the basis of the percolation theory and we observed that the corresponding exponents and give static percolation values independent of the polymer composition.Received: 9 July 2004, Published online: 1 October 2004PACS: 64.60.Ak Renormalization-group, fractal, and percolation studies of phase transitions - 64.70.Pf Glass transitions - 82.35.Jk Copolymers, phase transitions, structure