Local variation of the dielectric properties of poly(vinylidene fluoride) during the α- to β-phase transformation

The phase transformation from the non-polar α-phase to the polar electroactive β-phase of polyvinylidene fluoride (PVDF) has been investigated using the fluorescence from Nile red. Films of α-PVDF doped with Nile red were stretched at controlled rates at a temperature of 80 °C to produce the α- to β-phase transition. The thermo/mechanical dependent changes in the crystalline structure are related to the physical rotation of the polar (CH₂-CF₂) group, which can be monitored by steady state fluorescence techniques. The degree of phase transformation is related to variation in the fluorescence, which in turn is linked to local dielectric constant of the polymer. The variation of the refractive index is more associated to the alignment of the polymeric chains than to the phase transformation. Thus, fluorescence is a suitable technique to monitor phase transitions coupled to a variation in the polarity of the dielectric medium.     

Synthesis in Water and Antimicrobial Activity of 5-Trichloromethyl-4,5-dihydroisoxazoles

Two series of 5-trichloromethylisoxazoles were synthesized from the cyclocondensation of 1,1,1-trichloro-4-methoxy-3-alken-2-ones [Cl₃CC(O)C(R²) = C(R¹)OMe, where R¹ = H, Me, Et, Pr, iso-Pr, cyclo-Pr, Bu, terc-Bu, CH₂Br, CHBr₂, CH(Me)SMe, (CH₂)₂Ph, and Ph, and R² = H; R¹ = H and R² = Me and Et; R¹ and R² = -(CH₂)₄- and -(CH₂)₅-; and R¹ = Et and Ph and R² = Me] with hydroxylamine hydrochloride through a rapid one-pot reaction in water. The 5-trichloromethyl-4,5-dihydroisoxazoles were aromatized by reaction with concentrated sulfuric acid to obtain the respective 5-trichloromethylisoxazoles. Their structures were confirmed by elemental analysis, ¹H/¹³C nuclear magnetic resonance, and electron impact mass spectroscopy. Crystal structure analysis for 5-triclhoromethyl-5-hydroxy-3-propyl-4,5-dihydroisoxazole (2d) and 5-trichloromethyl-5-hydroxy-3,4-hexamethylene-4,5-dihydroisoxazole (2o) is presented. The antimicrobial activities of the 5-trichloromethyl-4,5-dihydroisoxazole derivatives were examined using the standard twofold dilution method against Gram-positive bacteria (Staphylococcus aureus), Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa), and yeasts (Candida spp. and Cryptococcus neoformans). All of the tested 5-trichloromethyldihydroisoxazoles exhibited antibacterial and antifungal activities at the tested concentrations.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

On the Electromagnetic Origin of Inertia and Inertial Mass

We address the problem of inertial property of matter through analysis of the motion of an extended charged particle. Our approach is based on the continuity equation for momentum (Newton’s second law) taking due account of the vector potential and its convective derivative. We obtain a development in terms of retarded potentials allowing an intuitive physical interpretation of its main terms. The inertial property of matter is then discussed in terms of a kind of induction law related to the extended charged particle’s own vector potential. Moreover, it is obtained a force term that represents a drag force acting on the charged particle when in motion relatively to its own vector potential field lines. The time rate of variation of the particle’s vector potential leads to the acceleration inertia reaction force, equivalent to the Schott term responsible for the source of the radiation field. We also show that the velocity dependent term of the particle’s vector potential is connected with the relativistic increase of mass with velocity and generates a longitudinal stress force that is the source of electric field lines deformation. In the framework of classical electrodynamics, we have shown that the electron mass has possibly a complete electromagnetic origin and the obtained covariant equation solves the “4/3 mass paradox” for a spherical charge distribution.     

Optical studies of ZnO nanocrystals doped with Eu3+ ions

Synthetic ZnO nanocrystals have been intentionally doped with Eu³⁺ ions. Structural analysis performed on the nanocrystals showed wurtzite-ZnO as the only phase present in the samples. Photoluminescence in emission and excitation modes allows the assignment of the intra-4f⁶ transitions for the Eu³⁺ ions. From the analysis of the optical data we are able to demonstrate that multiple Eu-related optical centres are present in the studied samples. Oxygen vacancies are likely candidates to be responsible for the ion accommodation in the ZnO lattice and from the photoluminescence excitation data we tentatively assign a trap level at ∼200 meV below the conduction band to this intrinsic defect. PACS 78.66.Hf; 78.67.-n; 82.80.Yc     

Automation of a Mass Flow Controller for Application in Time‐Multiplex SF6+CH4 Plasma Etching of Silicon

In this work is proposed the automation of a gas injection (mass flow) system in order to generate timemultiplex SF₆/CH₄ radiofrequency plasma applied for silicon (Si) etching process. The control of the gas injection system is important in order to better control the process anisotropy, i.e., the high‐aspect‐ratio of mask pattern transfer to substrate surface. In other words, this control allows the attainment of deep Si etching process. Here, the automation of the gas injection system was realized through the interface between a computer and a data acquisition board. The automation software developed allows controlling the gas flow rate switching it on and off during whole process through the use of a square waveform routine, intermittent flow, beyond the conventional condition of a fixed value for gas flow rate, continuous flow. In order to investigate the time‐multiplex SF₆/CH₄ plasma etching of Si, the residual gas analysis was performed. The investigations were made keeping the following process parameters: flow of SF₆: 10 sccm, flow of CH₄: 6 sccm, 100 W rf power, wave period: 20 sec. It were monitored the partial pressure of SF⁺ ₅ (parent neutral specie: SF₆), CH⁺₄ (CH4) and SiF+ ₃ (SiF4) species as a function of time for different gas flow switching and duty cycle. The results showed that with the generation of plasma occurs a drastic change in behavior of partial pressures of SF⁺ ₅ and CH⁺₄ species. Moreover, it is evidenced that the interactions between the SF₆ and CH₄ fragments promotes a high production rate of HF molecule and consequently a decrease of atomic fluorine, mainly when plasma is on. Finally, the behavior of partial pressure of SiF⁺ ₃ specie for alternatively intermittent SF₆ and CH₄ flow operation shows us that both the etching processes and the deposition of a polymer passivation layer are occurring alternatively, a desirable feature for multi‐step etching process (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis, antimicrobial and antiproliferative activity of novel silver(I) tris(pyrazolyl)methanesulfonate and 1,3,5-triaza-7-phosphadamantane complexes

Five new silver(I) complexes of formulas [Ag(Tpms)] (1), [Ag(Tpms)(PPh(3))] (2), [Ag(Tpms)(PCy(3))] (3), [Ag(PTA)][BF(4)] (4), and [Ag(Tpms)(PTA)] (5) {Tpms = tris(pyrazol-1-yl)methanesulfonate, PPh(3) = triphenylphosphane, PCy(3) = tricyclohexylphosphane, PTA = 1,3,5-triaza-7-phosphaadamantane} have been synthesized and fully characterized by elemental analyses, (1)H, (13)C, and (31)P NMR, electrospray ionization mass spectrometry (ESI-MS), and IR spectroscopic techniques. The single crystal X-ray diffraction study of 3 shows the Tpms ligand acting in the N(3)-facially coordinating mode, while in 2 and 5 a N(2)O-coordination is found, with the SO(3) group bonded to silver and a pendant free pyrazolyl ring. Features of the tilting in the coordinated pyrazolyl rings in these cases suggest that this inequivalence is related with the cone angles of the phosphanes. A detailed study of antimycobacterial and antiproliferative properties of all compounds has been carried out. They were screened for their in vitro antimicrobial activities against the standard strains Enterococcus faecalis (ATCC 29922), Staphylococcus aureus (ATCC 25923), Streptococcus pneumoniae (ATCC 49619), Streptococcus pyogenes (SF37), Streptococcus sanguinis (SK36), Streptococcus mutans (UA159), Escherichia coli (ATCC 25922), and the fungus Candida albicans (ATCC 24443). Complexes 1-5 have been found to display effective antimicrobial activity against the series of bacteria and fungi, and some of them are potential candidates for antiseptic or disinfectant drugs. Interaction of Ag complexes with deoxyribonucleic acid (DNA) has been studied by fluorescence spectroscopic techniques, using ethidium bromide (EB) as a fluorescence probe of DNA. The decrease in the fluorescence of DNA-EB system on addition of Ag complexes shows that the fluorescence quenching of DNA-EB complex occurs and compound 3 is particularly active. Complexes 1-5 exhibit pronounced antiproliferative activity against human malignant melanoma (A375) with an activity often higher than that of AgNO(3), which has been used as a control, following the same order of activity inhibition on DNA, i.e., 3 > 2 > 1 > 5 > AgNO(3)? 4.     

Static electric dipole polarizability of small sodium aggregates

We present pseudopotential local-spin-density calculations of the static electric polarizability of sodium dimers and trimers and their respective cations. The electronic polarizabilities are obtained from self-consistent calculations in the presence of an external electric field, which is kept sufficiently small to avoid non-linear effects. The calculated polarizability tensor has a strong anisotropy directly related to the geometric and electronic structures of the molecules, the anisotropy being larger for the neutral clusters. The polarizabilities are averaged over the vibrational motion and rotations of the aggregates in order to be compared with the experimental measurements. The obtained values show an improvement in the agreement with experiment with respect to the values calculated in the spherical approximation.     

Dynamics on certain sets of stochastic matrices

We study iteration of polynomials on symmetric stochastic matrices. In particular, we focus on a certain one-parameter family of quadratic maps which exhibits chaotic behavior for a wide range of the parameters. The well-known dynamical behavior of the quadratic family on the interval, and its dependence on the parameter, is reproduced on the spectrum of the stochastic matrices. For certain subclasses of stochastic matrices the referred dynamical behavior is also obtained in the matrix entries. Since a stochastic matrix characterizes a Markov chain, we obtain a discrete dynamical system on the space of reversible Markov chains. Therefore, depending on the parameter, there are initial conditions for which the corresponding reversible Markov chains will lead under iteration to a fixed point, to a periodic point, or to an aperiodic point. Moreover, there are sensitivity to initial conditions and the coexistence of infinite repulsive periodic orbits, both features of chaos.     

Application of X-ray diffraction, micromagnetic and hole drilling methods for residual stress determination in a ball bearing steel ring

A basic understanding of distortion problems requires the analysis of a complete manufacturing process including an almost complete overview of residual stress states in the component during each production step. To reduce the measurement time in the future, three measurements methods (X-ray diffraction, micromagnetic and blind hole drilling methods) have been used to analyze residual stress states in machined AISI 52100 ball bearing rings. X-ray diffraction was used as a state-of-the-art method for machining induced residual stresses with pronounced gradients. The ring exhibited a complex residual stress state with high tensile residual stresses at the surface, a strong gradient in depth, and also showed some variation along the outer circumference due to a superimposition of machining induced residual stresses and effects from the clamping device process. Due to this surface state, micromagnetic signals depend on the analyzing frequency. A calibration of the signals was only possible with the X-ray diffraction data. The results of the three different measurement methods correlate reasonably well.     

Residual stress field and reduction of stress intensity factors in cold-worked holes

Closed-form and semi-analytical solutions are obtained for the residual stress distributions in a plate caused by pressure acting on a central circular hole, representing the cold-work process. The material is elastic–perfectly plastic. Both Tresca and von Mises yield criteria are used and the corresponding residual stress distributions are compared. The relation between the dimension of the plastic zone and the value of internal pressure is presented. The relation between the magnitude of the residual stresses and the remote uniform tensile stress required to open symmetrical radial cracks is also presented. The reduction of the stress intensity factors of cracked open and riveted holes as a function of the internal pressure applied (or mandrel radial displacement) is investigated using numerical models for both an elastic–perfectly plastic material and for an Al 2024-T3 Alclad aluminum alloy.