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.     

DRIFTS study of surface reactivity to NO2 by zinc nanoparticle aggregates and zinc hollow nanofibers

Zinc nanostructures synthesized with different morphologies from the same evaporation/condensation technique are studied with concern to surface reactivity to NO₂ by Diffuse Reflectance Infrared Fourier Transformed Spectroscopy (DRIFTS). Synthesis of nanopowders is obtained, according to previous work, by gas flow thermal evaporation at 540 °C of bulk Zn grains. Two types of Zn powders are obtained and studied in experiments. The first one is collected on the cold walls of the reactor as a deposit produced by thermophoretic effect. It is constituted by grains (∼10 μm) originated by the stratification of smaller aggregates (∼200 nm) and isolated primary particles (∼50 nm) born in the gas flow. The second type of powder is grown from the condensation of Zn chemical vapors within the expansion orifice of the quartz reactor after relatively long time (∼1 h) deposition process. It is constituted mainly by hollow Zn nanofibers with external and internal diameter about 100 and 60 nm. Preliminary characterization of the two types of powders is made by SEM, TEM, XRD. Thereafter, the two types of samples are studied by DRIFTS at variable temperature (VT). Comparison is made between the home-synthesized nanopowders with respect to commercial Zn standard dust. The Zn hollow nanofibers when exposed to NO₂ are found to exhibit dramatic reactivity, which is not observed at all either in the case of clustered aggregate zinc or of commercial Zn dust powders. Results indicate that, at increasing temperature from RT to 300 °C, the hollow nanofibers surface reacts distinctively with adsorbant gas NO₂, with contemporary formation of a progressively growing narrow absorption band at 2500 cm⁻¹ and contemporary depression of a doublet (∼1600-1628 cm⁻¹) band. In order to justify this striking spectral feature, we propose the occurring of a possible polymerization process at nanofibers surface where most probably as a consequence of pre-treatment and exposure to gas NO₂ a very thin film of ZnO is formed. The possible role of huge specific surface of hollow nanofibers as inferred by preliminary SEM, TEM, XRD studies is discussed.     

An Introduction to Constant Curvature Spaces in the Commutative (Segre) Quaternion Geometry

It is known that complex numbers can be associated with plane Euclidean geometry and their functions are successfully used for studying extensions of Euclidean geometry, i.e., non-Euclidean geometries and surfaces differential geometry. In this paper we begin to study the constant curvature spaces associated with the geometry generated by commutative elliptic-quaternions and we show how the “mathematics” they generate allows us to introduce these spaces and obtain the geodesic equations without developing a complete mathematical apparatus as the one developed for Riemannian geometry.     

A remark on Serrin’s Theorem

An approximation theorem for families of weakly coercive convex functions by means of countably many smooth families of convex functions is proved. As a consequence, the classical “three-fold” lower semicontinuity theorem for integral functionals of the Calculus of Variations by James Serrin is unified in one single statement.     

The rotational-conformational distribution of 2,2'-bithienyl in liquid crystals

We have investigated the distribution of conformations and orientations for a simple internal rotor molecule, 2,2'-bithienyl dissolved in liquid crystal solvents, by re-analysing published proton dipolar coupling data with the maximum entropy internal order method (MEIO). We show that detailed, model independent, conformational information can be obtained when data of sufficiently high quality are available. We also propose a novel and convenient representation method for the orientational-conformational coupling.     

Analysis of the crystallization kinetics in poly(ethylene oxide) by calorimetric measurements

Summary Differential scanning calorimetric measurements in the early stage of isothermal crystal growth of polyethylene oxide are analysed in the light of irreversible thermodynamics. An accurate evaluation of the equilibrium melting temperature is done by fitting the thermograms obtained at different undercoolings and referring to the activation energy values already known from the literature. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

A kinetic Monte Carlo method on super-lattices for the study of the defect formation in the growth of close packed structures

A modified Kinetic Lattice Monte Carlo model has been developed to predict growth rate regimes and defect formation in the case of the homo-epitaxial growth of close packed crystalline structures. The model is an improvement over standard Monte Carlo algorithms, which usually retain fixed atom positions and bond partners indicative of perfect crystal lattices. Indeed, we extend the concepts of Monte Carlo growth simulations on super-lattices containing additional sites (defect sites) with respect to those of the reference material. This extension implies a reconsideration of the energetic mapping, which is extensively presented, and allows to describe a complex phenomenology that is out of accessibility of standard stochastic approaches. Results obtained using the Kawasaki and the Bond-Counting rules for the transition probability of the Monte Carlo event are discussed in details. These results demonstrate how the defect types (local or extended), the formation mechanisms and the defect generation regimes can be characterized using our approach.     

Lower Bounds for the Height and Size of the Ideal Class Group in CM-Fields

 We prove that, under the assumption of the Generalized Riemann Hypothesis, the exponent of the ideal class group of a CM-field goes to infinity with its absolute discriminant. This gives a positive answer to a question raised by Louboutin and Okazaki [4]. Received September 10, 2001; in revised form April 5, 2002