Film formation from pure and mixed latices; transient fluorescence study

A fast transient fluorescence technique was used to study latex film formation induced by organic solvent vapor. Mixtures of pyrene (P)- and naphthalene (N)-labeled and/or pure naphthalene-labeled latex films were prepared separately from poly(methyl methacrylate) (PMMA) particles. Then these pure and mixed latex films were exposed to vapor of various chloroform-heptane mixtures in seven different experiments. In both films, fluorescence lifetimes from N were monitored during vapor-induced film formation. It was observed that N lifetimes decreased as the vapor exposure time is increased. A Stern-Volmer kinetic analysis was used for low quenching efficiencies to interpret the decrease in N lifetimes. A Prager-Tirrell model was employed to obtain back-and-forth frequencies, nu, of reptating PMMA chains during latex film formation induced by solvent vapor. In both pure and mixed latex films, nu values were found to be correlated with the chloroform content in the vapor mixture. It was observed that polymer interdiffusion obeyed a t1/2 law during film formation.     

Film Formation from Nanosized Copolymeric Latex Particles: A Photon Transmission Study

The photon transmission technique was used to monitor the evolution of transparency during film formation from nanosized copolymeric latex particles. The latex films were prepared from poly(methyl methacrylate-co-butyl methacrylate) (P(MMA-co-BMA)) particles which were produced by microemulsion polymerization. These films were annealed at elevated temperatures in various time intervals above the glass transition temperature (T(g)) of P(MMA-co-BMA). It is observed that the transmitted photon intensity (I(tr)) from these films increased as the annealing temperature increased. There are three different film formation stages. These stages are explained by the void closure, healing, and interdiffusion processes, respectively. The activation energies for viscous flow (DeltaH approximately 16 kcal/mol), minor chains (DeltaE(H) approximately 27 kcal/mol), and backbone motion (Delta E(b) approximately 132 kcal/mol) were obtained using various models. Void closure (tau(v), T(v)) and healing points (tau(H), T(H)) were determined. Using the time-temperature pairs, void closure and healing activation energies were measured and found to be 21 and 30 kcal/mol, respectively. Copyright 2001 Academic Press.     

Interdiffusion of polymer chains during latex coating

The fluorescence method was used to study the interdiffusion of polymer chains during annealing of latex above its glass transition temperature (T_g). The latex film was prepared from mixture of naphthalene (N) (donor) and pyrene (P) (acceptor)-labeled poly(methyl methacrylate) (PMMA) latex particles. Heptane was used as the coalescent agent. A steady-state fluorescence technique was employed to measure the amount of direct nonradiative energy transfer from N to P during the interdiffusion of polymer chains across the particle–particle junction. Various latex films with different latex contents were used to measure the percentage critical occupation for the reliable steady-state fluorescence measurements. Diffusions activation energies in these latex films were measured and found to be around 30 kcal/mol, which was attributed to the backbone motion of PMMA chains.     

Ffast Transient Fluorescence Technique to Study Critical Exponents at the Glass Transition

The fast transient fluorescence (FTRF) technique was used to study critical exponents at the glass transition in free-radical crosslinking copolymerization (FCC) for two different monomeric systems, methyl methacrylate (MMA) and styrene (S). Pyrene (P_y ) was used as a fluorescence probe. The fluorescence lifetimes of P_y from its decay traces were measured and used to monitor the gelation process. Changes in the viscosity of the pregel solutions due to glass formation dramatically enhance the fluorescent yield of aromatic molecules. This effect is used to study the glass transition upon gelation of MMA and S monomeric systems as a function of time, at various temperatures and crosslinker concentrations. The results are interpreted in the view of percolation theory. The gel fraction and weight average degree of polymerization exponents β and γ are found to be 0.37 ± 0.02 and 1.66 ± 0.07 in agreement with percolation results.     

Superelastic percolation network of polyacrylamide (PAAm)–kappa carrageenan (κC) composite

The elasticity of the polyacrylamide (PAAm)-kappa carrageenan (κC) composite was determined as a function of (w/v-%) κC content at 40 °C. The gel composites studied contained various percentages (w/v-%) of κC. The elasticity of the swollen PAAm-κC composite was characterized by using the tensile testing technique. This study investigated the elasticity and the percolation threshold of PAAm-κC composite as a function of κC content. It is understood that the compressive elastic modulus decreases up to 1 (w/v-%) of κC and then increases at contents above 1(w/v-%) of κC. The critical exponent of elasticity y was determined between 1 and 1.6 (w/v-%) of κC and found to be 0.68. The observed elastic percolation threshold is consistent with the suggested values of the superelastic percolation network.     

Synthesis and Liquid Crystalline Behavior of Random Copolymer of Poly(ethylene oxide) Macromonomer and Liquid Crystalline Monomer by the Photon Transmission Technique

Random copolymers of poly(ethylene oxide) macromonomer with p‐vinylbenzyl end‐functional group (PEOVB) and liquid crystalline monomer, namely 6‐(4‐cyanobiphenyl‐4′‐oxy)hexyl acrylate (COA), were prepared by conventional free radical polymerization. A living anionic polymerization technique was employed for the synthesis of PEO macromonomers bearing p‐vinylbenzyl moiety at one end. The photon transmission method was also applied to study the phase transitions of COA monomer and its random copolymer with PEO. It was found that, for both samples, the nematic‐smectic A transition is continuous, but the critical fluctuation regions do not allow to obtain 3D XY values. Instead, we have obtained the values close to mean field regime. Scaling of thermal hystersis for random copolymer sample near the nematic‐isotropic transition was studied as well. Thermal hysteresis loops were produced under linearly varying temperature. It was shown that the areas of the hysteresis loops scale with the temperature scanning rate with an exponent being equal to 0.614 which is in good agreement with the field‐theoretical value.     

Pure uterine lipoma

Lipomatous tumors of the uterus are unusual, benign neoplasms seen in postmenopausal women. Although many of the mixed-type cases such as lipoleiomyoma and fibrolipoma have been reported, pure uterine lipomas are extremely rare. In the literature, a few cases with pure uterine lipoma have been reported. We first present the advanced magnetic resonance findings of pure uterine lipoma, followed by those of ultrasonography (US) and computed tomography (CT). We markedly detected lipid peaks on the magnetic resonance spectroscopy (MRS) and the apparent diffusion coefficient value to be 0.00 due to chemical-shift effects with diffusion-weighted imaging (DWI). Although pelvic lipomatous tumors can be diagnosed with US and CT, in some cases, further workup may be required to localize the lesion. MRI may yield more valuable data for differential diagnosis. MRS and DWI findings provide additional clues on the nature of the lesion.     

Sonolytic degradation of halogenated organic compounds in groundwater: mass transfer effects

Organic pollutants in liquid exposed to acoustic waves behave differently according to their physical and chemical properties. Laboratory batch experiments of sonication for the degradation of trichloroethylene (TCE) and ethylene dibromide (EDB) were carried out in groundwater at 20 kHz, and 12.5 and 35 W/cm(2). A theoretical model for the batch sonication system was derived to examine the mass transfer dependency of the ultrasonic degradation. Experimental results were supported with model predictions suggesting that both liquid phase diffusion coefficient and Henry's law constant are important parameters for the sonolytic degradation of the halogenated organic compounds in groundwater. When compared with the effect of the diffusion coefficient, Henry's constant exerts a greater influence on sonolytic degradation. When Henry's constant exceeds a value of 1 (volume/volume ratio), however, it no longer has much influence on the degradation process. The results also suggest that degradation is enhanced with an increase in ultrasonic power probably due to a greater bubble residence time and the formation of larger bubble at high-energy intensities.     

Swelling Kinetics of PAAm–κ-Carrageenan Composites: A Fluorescence Technique

The steady-state fluorescence (SSF) technique was introduced for studying swelling of disc-shaped polyacrylamide (PAAm) gels containing various amount of κ?carrageenan (κC). They were prepared by free-radical cross-linking copolymerization. N,N^′-methylenebisacrylamide (BIS) and ammonium persulfate (APS) were added as a cross-linker and an initiator, respectively. Composite gels were prepared at 80°C with pyranine as a fluorescence probe. After drying of these gels, swelling kinetics were performed in water at 60°C by real-time monitoring of the pyranine fluorescence intensity, I, which decreased as swelling proceeded. The Li–Tanaka equation was used to determine the swelling time constants, τ ₁, and cooperative diffusion coefficients, D ₀, from fluorescence intensity, weight, and volume variations of the gels during the swelling processes in all cases. It was observed that τ ₁ decreased and D ₀ increased as the κC concentrations in the composites were increased indicating that high κC gels swell faster than low κC gels.     

A fluorescence study on critical exponents during sol-gel phase transition in complex monomeric systems

Methyl methacrylate (MMA), ethyl methacrylate (EMA) and various combinations of MMA with EMA were used during FCC experiments. Pyrene (P_y) was introduced as a fluorescence probe and fluorescence lifetimes from its decay traces were measured during sol-gel phase transitions. The fast transient fluorescence (FTRF) technique was used to study the critical exponents during sol-gel phase transition in free-radical crosslinking copolymerization (FCC). The results were interpreted in the view of percolation theory. The critical exponents of gel fraction, β and weight average degree of polymerization, γ were measured near the point of gel effect and found to be around 0.37 ± 0.015 and 1.69 ± 0.05 in all systems studied respectively.