ABSTRACT
Small molecule diffusion into Iota-Carrageenan gel was studied by using steady-state fluorescence (SSF) technique. Pyranine, dissolved in water was used as fluorescence probe. Fluorescence emission intensity, I(p), and scattered light intensity, I(sc), were monitored to study diffusion and swelling processes at various temperatures respectively. Fickian and Li-Tanaka models were elaborated to produce diffusion, D, and collective diffusion, D(0), coefficients. Diffusion and swelling activation energies were also obtained and found to be 20.5 kj mol(-1) and 28.2 kj mol(-1), respectively.
Subject(s)
Carrageenan/chemistry , Hydrogels/chemistry , Water/chemistry , Diffusion , Fluorescence , Particle SizeABSTRACT
This work reports the encapsulation of latex particles in Al2O3-polystyrene (PS) composite films. These films were prepared from PS particles in Al2O3 dispersion at room temperature in various latex contents. Composite films were annealed at elevated temperatures in 10 min time interval above the glass transition temperature (Tg) of polystyrene. Transmitted photon intensities, I(tr) were monitored after each annealing step. AFM micrographs were also used to observe the physical changes of the composite films during annealing. It was observed that latex particles are encapsulated above a critical Al2O3 content of 33 wt% which corresponds to the critical occupation probability of p(c) = 0.33 at which the film obey the site-percolation model with a critical exponent of 0.45. Below p(c), it was seen that complete latex film formation process took place, where transparency of the film was increased by annealing.
ABSTRACT
The fluorescence technique was employed to study gel-to-sol transitions in kappa-carrageenan systems with various carrageenan contents. Pyranine was used as a fluorescence probe for monitoring these transitions. Fluorescence, Ip and scattered light, Isc intensities were measured against temperature to determine critical phase transition temperatures and exponents. It was observed that gel-to-sol transition temperatures, Tgs are found to be dependent to the carrageenan content. The measured critical exponents gamma' and beta' were found to be very close to the weight average degree of polymerization, DPw and gel fraction G, exponents (gamma and beta) of the classical Percolation Model.
Subject(s)
Carrageenan/chemistry , Phase Transition , Hydrogen-Ion Concentration , Light , Microscopy, Fluorescence , Models, Molecular , Models, Statistical , Protein Conformation , Scattering, Radiation , TemperatureABSTRACT
A nanosecond scale in situ probe reveals that a bulk linear polymer undergoes a sharp phase transition as a function of the degree of conversion, as it nears the glass transition. The scaling behaviour is in the same universality class as percolation. The exponents gamma and beta are found to be 1.7 +/- 0.1 and 0.41 +/- 0.01 in agreement with the best percolation results in three dimensions.
ABSTRACT
Two different sets of powder latex film were prepared from high- and low-molecular-weight (HM and LM) poly(methyl methacrylate) (PMMA). The optical transmission method was used to the study film formation induced by organic vapor. Various HM and LM films with the same latex content were prepared separately from the PMMA particles and exposed to vapor of a chloroform-heptane mixture in various volume percents of chloroform. Transmitted light intensities, I(tr), from these films increased in time under vapor exposure, which was attributed to the increase in "crossing density" at the junction surface. The Prager-Tirrell model was employed to obtain the back-and-forth frequency, nu, of the reptating polymer chain during film formation induced by solvent vapor. nu values were obtained and found to be strongly correlated with the percent of chloroform in the solvent mixture and the molecular weight of the polymer chain. It is observed that high-molecular-weight chains reptate much more slowerly than low-molecular-weight chains.
ABSTRACT
A fast transient fluorescence (FTRF) technique was used to study latex film formation induced by organic solvent vapor. Seven different films with the same latex content were prepared separately from poly(methyl methacrylate) (PMMA) particles and exposed to vapor of various chloroform-heptane mixtures in seven different experiments. Latex films were prepared from pyrene (Py)-labeled latex particles and fluorescence lifetimes of Py were monitored during vapor-induced film formation. It was observed that pyrene lifetimes decreased as vapor exposure time increased. A Stern-Volmer kinetic analysis was used for low quenching efficiencies to interpret the decrease in pyrene lifetimes. A Prager-Tirrel model was employed to obtain back-and-forth frequencies, nu, of the reptating PMMA chains during latex film formation induced by solvent vapor. nu values were found to be correlated with chloroform content in vapor mixture. It was observed that polymer interdiffusion obeyed a t(1/2) law during film formation. The results of optical transmission experiments were found to support these findings.
ABSTRACT
A UV-visible technique is used to study the evolution of transparency during film formation from latex particles. Latex particles with high and low molecular weight (HM and LM) polymethyl methacrylate (PMMA) are used to prepare films. Two sets of films with different latex content were prepared from HM and LM particles separately, by annealing PMMA particles above the glass transition temperature. Transmitted photon intensity, I(tr), from HM and LM films increased as the annealing temperature was increased. The increase in the transmitted photon intensity is attributed to the latex content (film thickness) for the annealed film samples. It is suggested that as the latex particles are packed (film thickness is increased) fewer voids or cracks are formed in the films. Positive and negative absorption coefficients are measured below and above 210 and 180 degrees C annealing temperatures for the HM and LM films. Packing coefficients are obtained for films in various latex contents. It is observed that LM particles are packed much easier than HM particles. Copyright 2001 Academic Press.
ABSTRACT
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.
ABSTRACT
Latex films have been prepared by annealing pyrene (Py)-labeled poly(methyl methacrylate)-polyisobutylene particles at the glass transition temperature (100 degrees C). These films were then irradiated by gamma rays from (60)Co in a gamma cell at room temperature at various dose rates (rad/h). Before dissolution the films were annealed at 200 degrees C for a 30 min time interval to complete the film formation process. Steady-state fluorescence techniques were used to monitor the dissolution of irradiated latex films. Dissolution of films in a chloroform-heptane (80%-20%) mixture was monitored in real time by the Py fluorescence intensity change. Relaxation constants, k(0), and dissolution coefficients, D(d), of polymer chains were measured. Two different regimes of D(d) values were observed during dissolution, which are related to two different molecular weight distributions caused by scission and branching of polymer chains when they were irradiated and annealed. Copyright 2001 Academic Press.
ABSTRACT
Latex films with various thicknesses are formed from pyrene (P) labeled poly (methyl methacrylate) (PMMA) latex particles sterically stabilized by poly isobutylene (PIB). Annealings of latex films were performed above T(g) at elevated temperatures up to 270 degrees C for 30 min time intervals. The UV-Visible (UVV) technique was used for monitoring latex film formation and dissolution. It was observed that thicker films formed more transparent films than thinner films. Absorption of solvent molecules (chloroform) into the annealed latex film was followed by diffusion of PMMA chains into a solvent reservoir. Diffusion of pyrene-labeled PMMA chains was monitored in real time by the absorbance change of pyrene in the polymer-solvent mixture. A diffusion model with a moving boundary was employed to quantify real-time UVV data. Diffusion coefficients of PMMA chains were measured and found to be between 2.6 x 10(-9) and 9.7 x 10(-13) cm(2) s(-1) for the latex films in various thicknesses. It is observed that thicker and more transparent films dissolved much faster than the thinner and turbid films; i.e., highly packed films dissolve more easily. Copyright 1999 Academic Press.
ABSTRACT
A simple fluorescence technique is proposed for the measurement of the diffusion coefficient of oxygen into latex films. These latex films were prepared by annealing pyrene (P) labeled polymethyl methacrylate (PMMA) particles above the glass transition temperature. Transparency of these films were measured by monitoring the transmitted photon intensity, I(tr), which increased as the annealing temperature was increased. Steady state fluorescence was used to monitor oxygen diffusion into latex films. Diffusion coefficients, D, of oxygen were determined using fluorescence quenching method and are found to be around 5.6 x 10(-11) cm(2)s(-1). Copyright 1999 Academic Press.
ABSTRACT
The photon transmission method was used to probe the time evolution of film formation from latex particles. Two different latex films were prepared from high molecular weight (HM) and low molecular weight (LM) polystyrene particles at room temperature and were annealed at various temperatures in 2.5-min time intervals above the glass transition. The increase in the transmitted photon intensity (Itr) is attributed to the increase in "crossing density" at the junction surface. The Prager-Tirrell model was employed to interpret the increase in crossing density at the junction surface. The back and forth activation energies were measured for HM and LM films and found to be around 59 and 87 kcal/mol for a reptating polymer chain across the junction surface. Monte Carlo simulations were performed for photon transmission through a rectangular lattice. The number of transmitted photons (Ntr) was calculated as a function of the mean free path of photons. It was observed that Ntr, similar to Itr, increases as the square of the mean free path of photons is increased. Copyright 1999 Academic Press.
ABSTRACT
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.
