A new microwave dielectric method for studying photoinitiated chain radical polymerization processes

Measurements of both real and imaginary parts of the dielectric constant at a fixed microwave frequency have been performed on n-butyl acrylate/poly(n-butyl acrylate) mixtures. The dielectric constant of the mixtures has been compared with that of neat n-butyl acrylate during UV photoinitiated polymerization. The values of the imaginary part of the dielectric constant thus obtained have allowed determination of the instantaneous monomer concentration and verified the kinetic equation for the photoinitiated polymerization process. The limits of validity of the method as well as its capability of providing detailed kinetic information are also discussed.     

Poly(butylene terephthalate)/poly(ε-caprolactone) blends: Influence of PCL molecular mass on PBT melting and crystallization behavior

The isothermal crystallization kinetics and melting behavior of poly(butylene terephthalate) (PBT) in binary blends with poly(ε-caprolactone) (PCL) was investigated as a function of PCL molecular mass by differential scanning calorimetry and optical microscopy. The components are miscible in the melt when oligomeric PCL (M_w = 1250) is blended with PBT, whereas only partial miscibility was found in mixtures with higher molecular mass (M_w = 10,000 and 50,000). The equilibrium melting point of PBT in the homopolymer and in blends with PCL was determined through a non-linear extrapolation of the T_m = f(T_c) curve. The PBT spherulitic growth rate and bulk crystallization rate were found to increase with respect to plain PBT in blends with PCL1250 and PCL10000, whereas addition of PCL50000 causes a reduction of PBT solidification rate. The crystallization induction times were determined by differential scanning calorimetry for all the mixtures through a blank subtraction procedure that allows precise estimation of the crystallization kinetics of fast crystallizing polymers. The results have been discussed on the basis of the Hoffman-Lauritzen crystallization theory and considerations on both the transport of chains towards the crystalline growth front and the energy barrier for the formation of critical nuclei in miscible and partially miscible PBT/PCL mixtures are widely debated.     

Analysis of Concentration as Sampled in

The aim of this paper is to analyze the statistical properties of solute concentration in natural aquifers as sampled in observation wells, having a small diameter in comparison with the characteristic size of the heterogeneity in hydraulic properties. The analysis, in Langragian framework, takes advantage of the reverse formulation, where, instead of considering the destination of the injected particles, the origin of the particle being sampled is sought. In the case of small values of the log-conductivity variance _Y², it allows the derivation of an analytical expression for concentration mean, variance and pdf, while for aquifer characterized by high value in _Y², a numerical analysis based on a Monte Carlo approach using a reverse scheme is developed and applied for values of _Y² up to 2. In this case, the use of a Beta function to fit the concentration pdf proves valid for practical applications. The comparison between the numerical and the analytical results defines the range of validity of the analytical ones. The relative role of large-scale dispersion processes and pore-scale effects is analyzed in terms of global variance in order to point out limits and accuracy of the Eulerian scheme in comparison with the Lagrangian one.     

Solute Concentration Statistics in Heterogeneous Aquifers for Finite Péclet Values

A Lagrangian framework is used for analysing the concentration fields associated with transport of nonreactive solutes in heterogeneous aquifers. This is related to two components: advection by the random velocity field v(x) and pore-scale dispersion, characterized by the dispersion tensor D _d; the relative effect of the two components is quantified by the Péclet number. The principal aim of this paper is to define the probability density function (pdf) of a nonreactive solute concentration and its relevant moments >C< and ² _c as sampled on finite detection volumes. This problem could be relevant in technical applications such as risk analysis, field monitoring and pollution control. A method to compute the concentration statistical moments and pdf is developed in the paper on the basis of the reverse formulation widely adopted to study solute dispersion in turbulent flows. The main advantages of this approach are: (i) a closed form solution for concentration mean and variance is attained, in case of small size of the sampling volume; (ii) a numerically efficient estimate of the concentration pdf can be derived. The relative effects of injection and sampling volume size and Péclet number on concentration statistics are assessed. The analysis points out that the concentration pdf can be reasonably fitted by the beta function. These results are suitable to be employed in practical applications, when the estimate of probability related to concentration thresholds is required.     

The low-temperature endotherm in poly(ethylene terephthalate): partial melting and rigid amorphous fraction mobilization

A detailed investigation of the low-temperature endotherm of poly(ethylene terephthalate) (PET) performed by temperature-modulated differential scanning calorimetry is presented. The origin of the small endotherm, generally observed a few degrees above the crystallization temperature in PET and in many other polymers, is a widely discussed matter. The most frequent interpretation considers it the result of partial fusion with superposition of a recrystallization process even if it has also been proposed that it can originate from enthalpic recovery connected to mobilization of the rigid amorphous fraction. In an attempt to resolve the question, a new method for the interpretation of the modulated heat-flow-rate curve resulting from a temperature modulation program is proposed. The procedure consists of the analysis of the initial points of the steady-state heat-flow-rate signals in the heating and cooling semiperiods with the temperature modulation being performed with a sawtooth profile. The study conducted in parallel on the reversing specific heat capacity and the heat-flow-rate curves, observed on heating after isothermal crystallization at various temperatures, showed that multiple processes, involving both the crystalline and the rigid amorphous fraction, overlap in the temperature range in which the low-temperature endotherm is observed. The origin of the endotherm under investigation is therefore connected with both partial fusion of the crystalline portions and enthalpy recovery subsequent to structural relaxation of the rigid amorphous fraction. An estimation of the relative percentages of the two different processes is presented and discussed.