Physical aging of syndiotactic polypropylene

Syndiotactic polypropylene (sPP) was quenched from the melt in an ice‐water bath, and changes in the structural organization, during the aging time, were followed by X‐rays, differential scanning calorimetry, and transport properties of dichloromethane at low activities. After 1 month, an increase of crystallinity from 19 to 26% was observed. In addition, the results of sorption and diffusion indicated a consistent increase of an intermediate phase not crystalline, yet impermeable to the vapors. The study of the mechanical properties showed that there is a remarkable increase of all the mechanical parameters with the aging time, and this effect was associated to the increase of the intermediate phase. The elastic modulus increased three times in the first hours of aging. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 173–180, 1999     

Effect of TiO<Subscript>2</Subscript> surface modification in Rhodamine B photodegradation

Commercial TiO₂ nanoparticles were superficially modified through polymeric resins obtained from polymerization of citrate complexes of Y³⁺ and Al³⁺ with ethylenglycol. The materials were treated at 450 °C for 4 h to obtain modified nanoparticles, which were characterized by HR-TEM, Zeta potential and surface area through N₂ fisisorption. Rhodamine B photodegradation by visible light irradiation and in presence of those modified nanoparticles was compared with the same process in presence of unmodified commercial TiO₂ nanoparticles. It was observed, by UV–visible spectroscopy, that the catalytic photoactivity in presence of modified nanoparticles was smaller than that observed with commercial TiO₂ nanoparticles. However, the surface modifier played an important role in the photodegradation kinetic process, showing a non-linear relation between modifier amount and photodegradation rate, presenting a maximum value at 0.8% (w/w).     

Spectral Triples and the Super-Virasoro Algebra

We construct infinite dimensional spectral triples associated with representations of the super-Virasoro algebra. In particular the irreducible, unitary positive energy representation of the Ramond algebra with central charge c and minimal lowest weight h = c/24 is graded and gives rise to a net of even θ-summable spectral triples with non-zero Fredholm index. The irreducible unitary positive energy representations of the Neveu-Schwarz algebra give rise to nets of even θ-summable generalised spectral triples where there is no Dirac operator but only a superderivation.     

Experimental study on oscillating grid turbulence and free surface fluctuation

This paper analyses the interaction between the turbulence and free surface. The phenomenon takes place in many natural flows and industrial processes. In the present experiments, turbulence is generated by a vertically oscillating grid moving beneath the free surface. Fluid velocity has been measured through a hot-film anemometer, and the free surface elevation has been measured by an ultrasonic sensor. Integral length scales and several turbulence estimators have been computed. In order to detect the generation of turbulence near the free surface, the correlation between free surface elevation and the underneath flow velocity has been studied, as well as the time lag between turbulence and free surface. The free surface dynamics has been characterized by a velocity scale and a length scale. The kinetic energy associated with the free surface fluctuations increases with the Reynolds number at a rate depending on the frequency of the grid movement. For Reynolds number larger than ≈1000, however, the relationships collapse to a single curve characterized by a lower rate. The present experiments do not achieve the inertial sub-range in the vertical velocity fluctuations, and the estimated spectrum decays with an exponent smaller than ?3, which is the typical value for the two-dimensional turbulence in the inertial sub-range. The macro length scale, estimated by using the Taylor’s frozen turbulence hypothesis, experiences a decay away from the grid, which follows reasonably well the profile of Thompson and Turner (J Fluid Mechanics 67: 349–368, 1975). The micro length scale reduces immediately beneath the free surface, which can be interpreted by the increase of dissipation rate in the subsurface layer. The classification diagram by Brocchini and Peregrine (J Fluid Mech 449: 225–254, 2001) indicates that most tests fall in the weak turbulence domain, but some tests fall in the wavy domain. The vertical velocity fluctuations and the free surface level show a significant correlation with a negative phase lag, that is, the free surface fluctuations are ahead of the vertical velocity fluctuations.     

Concentration Dependence of the Electric Field Gradient in PbZr1−x Ti x O3 Ceramics

The concentration dependence of the electric field gradient (EFG) in PZT ceramics was studied by Time Differential Perturbed Angular Correlations (PAC) using the ¹⁸¹Ta radioactive probe in samples with x=0.3, 0.5 and 0.8 at room temperature. This phase presents two sites, probably related to defects close to probes, caused by oxygen and lead vacancies. We can also state that both the paraelectric and ferroelectric phases of these systems have two sites with different characteristics and that the high-frequency quadrupolar frequency site presents the highest fraction. The concentration dependence revealed by our results is discussed by comparing the latter with previous PAC studies. This revised version was published online in September 2006 with corrections to the Cover Date.     

Preparation and characterisation of Na2S and ZnSO4 nanoparticles in water/sodium bis(2-ethylhexyl)sulphosuccinate/n-heptane microemulsions

The preparation procedure for nanoparticles of the water-soluble salts Na₂S and ZnSO₄, two commonly used reagents to synthesise ZnS nanoparticles, by evaporation of volatile components of salt-containing water-in-oil microemulsions is described. In suitable conditions, the evaporation leads to the formation of dry salt–surfactant composites and to the formation of Na₂S or ZnSO₄ nanoparticles. It was found that the salt–surfactant composites can be totally redissolved in a dry apolar organic solvent allowing the formation of virtually water-free solutions containing a considerable amount of the water-soluble salts. The presence of nanoparticles in these solutions and in the composites has been proved by small-angle X-ray scattering and transmission electron microscopy, respectively. By mixing these solutions, the solid–solid reaction between Na₂S and ZnSO₄ nanoparticles leading to the formation of very small-sized ZnS nanoparticles has been ascertained by UV spectrophotometry. Received: 09 February 2001 Accepted: 19 March 2001     

Double implantation in silica glass for metal cluster composite formation: a study by synchrotron radiation techniques

Silica glass containing metal clusters is studied for both basic and applied aspects, related to the physics of cluster formation and to the optical properties of these materials. To obtain such composite structure, Cu + Ni, Au + Cu, Au + Ag, Cu + Co, and Cu + Ag sequential implantations in fused silica were realized. The resulting systems, after possible annealing in various atmospheres, were studied by synchrotron radiation-based techniques, namely, extended X-ray absorption fine structure (EXAFS) spectroscopy, grazing incidence X-ray diffraction (GIXRD), and grazing incidence small angle X-ray scattering (GISAXS). The unique potential of these techniques is the capability to investigate dilute (volume fraction of clusters0.01) and very thin (50 nm) systems. In the presented experiment, both pure and alloy clusters in the nanometer range of size were observed to form, pointing out the complexity of the cluster formation process in terms of physical and chemical driving forces.     

Microwave Induced Reaction of H-Dimethylphosphonate with Styrene Oxide

Microwave catalyzed reaction of a neat mixture of styrene oxide and H-dimethylphosphonate furnished dimethyl methylphosphonate, trimethylphosphate, phenylacetaldehyde, 1-methoxy-2-phenylethanol, 1-phenylethleneglycol, cis- and trans-1,3-diphenylcyclobutanes, hydrogen 1-(2-phenylethyl)methylphosphinate, (1-phenylethyl)dimethylphosphonate, and (1-phenylethyl)dimethylphosphonate via free radical processes.     

An Analogue of the Kac—Wakimoto Formula¶and Black Hole Conditional Entropy

A local formula for the dimension of a superselection sector in Quantum Field Theory is obtained as vacuum expectation value of the exponential of the proper Hamiltonian. In the particular case of a chiral conformal theory, this provides a local analogue of a global formula obtained by Kac and Wakimoto within the context of representations of certain affine Lie algebras. Our formula is model independent and its version in general Quantum Field Theory applies to black hole thermodynamics. The relative free energy between two thermal equilibrium states associated with a black hole turns out to be proportional to the variation of the conditional entropy in different superselection sectors, where the conditional entropy is defined as the Connes—St?rmer entropy associated with the DHR localized endomorphism representing the sector. The constant of proportionality is half of the Hawking temperature. As a consequence the relative free energy is quantized proportionally to the logarithm of a rational number, in particular it is equal to a linear function of the logarithm of an integer once the initial state or the final state is taken fixed. Received: 31 May 1996 / Accepted: 8 November 1996