Synthesis of poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) by the competitive single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization in water

The synthesis of a block copolymer poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) is reported. This new material was synthesized by single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization (SET‐DTLRP) in two steps. First, a bifunctional macroinitiator of α,ω‐di(iodo)poly (butyl acrylate) [α,ω‐di(iodo)PBA] was synthesized by SET‐DTLRP in water at 25 °C. The macroinitiator was further reinitiated by SET‐DTLRP, leading to the formation of the desired product. This ABA block copolymer was synthesized with high initiator efficiency. The kinetics of the copolymerization reaction was studied for two PBA macroinitiators with number–average molecular weight of 10 k and 20 k. The relationship between the conversion and the number–average molecular weight was found to be linear. The dynamic mechanical thermal analysis suggests just one phase, indicating that copolymer behaves as a single material with no phase separation. This methodology provides the access to several block copolymers and other complex architectures that result from combinations of thermoplastics (PVC) and elastomers (PBA). From industrial standpoint, this process is attractive, because of easy experimental setup and the environmental friendly reaction medium. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3001–3008, 2006     

Single electron transfer–degenerative chain transfer living radical polymerization of N‐butyl acrylate catalyzed by Na2S2O4 in water media

Living radical polymerization of n‐butyl acrylate was achieved by single electron transfer/degenerative‐chain transfer mediated living radical polymerization in water catalyzed by sodium dithionate. The plots of number–average molecular weight versus conversion and ln[M]₀/[M] versus time are linear, indicating a controlled polymerization. This methodology leads to the preparation of α,ω‐di(iodo) poly (butyl acrylate) (α,ω‐di(iodo)PBA) macroinitiators. The influence of polymerization degree ([monomer]/[initiator]), amount of catalyst, concentration of suspending agents and temperature were studied. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right‐angle light scattering (RALLS), a differential viscometer (DV), and refractive index (RI). The methodology studied in this work represents a possible route to prepare well‐tailored macromolecules made of butyl acrylate in an environmental friendly reaction medium. Moreover, such materials can be subsequently functionalized leading to the formation of different block copolymers of composition ABA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2809–2825, 2006     

Gold ultra-microelectrode arrays: application to the steady-state voltammetry of hydroxide ion in aqueous solution.

Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array.     

Phase equilibria in the Tl-TlBr-S system

The polythermal sections TlBr-Tl₂S, TlBr-Tl₄S₃, TlBr-TlS, and Tl₆SBr₄-Tl; the isothermal section at 300 K of the phase diagram; and the projection of the liquidus surface of the Tl-S-Br system have been investigated in the composition region Tl-TlBr-S by DTA, X-ray powder diffraction analysis, and microhardness measurements. The primary crystallization regions, including that of the only ternary compound (Tl₆SBr₄), have been determined, and the types and coordinates of the invariant and univariant equilibria in the phase diagram are determined.     

Ferromagnetic material CdGeP2:Mn for spintronics

Solid solutions Cd_1?x Mn_xGeP₂ (x=0?0.19) have been synthesized and identified. In these solutions, the unit cell parameters decrease with an increase in the manganese content. The solid solution Cd_0.81Mn_0.19GeP₂ is a ferromagnet with the Curie temperature T _C ≈ 311 K. The paramagnetic moment of Mn²⁺ ions equal to 5.8 μ_B, as well as the spontaneous magnetization constituting 76% of the total magnetization of a crystal, has been determined with the use of the Langevin function. The origin of ferromagnetism in CdGeP₂:Mn is exchange mediated by charge carriers (holes). These holes are caused by cationic defects in the structure of chalcopyrite.     

Narrow linewidth 2 μm optical parametric oscillation in periodically poled LiNbO<Subscript>3</Subscript> with volume Bragg grating outcoupler

An optical parametric oscillator using a periodically poled LiNbO₃ crystal and a volume Bragg grating output coupler is presented. Signal and idler wavelengths of 2008 and 2264 nm were generated from the 1064 nm Nd:YVO₄ pump laser. The Bragg grating was reflecting in a narrow band around 2008 nm, creating a purely singly resonant cavity. Signal and idler linewidths of approximately 0.44 and 0.72 nm, respectively, were measured. This is a reduction of 80 and 60 times compared to when using a mirror as output coupler. A total output energy of 156 μJ was measured with 47% slope efficiency. PACS 42.65.Yj; 42.72.Ai; 42.40.Eq     

Chaotic buffering and its mathematical models

We propose a general idea of obtaining different chains of coupled oscillators with chaotic buffering. As examples, we consider chains of diffusively coupled generalized cubic Schrödinger equations and nonlinear telegraph equations. We also give examples of systems that have an infinite-dimensional chaotic attractor.     

Generation of H− ions in a low-pressure xenon-hydrogen discharge. I

A theory of a low-pressure discharge in a xenon-molecular hydrogen mixture is developed. It is shown that, in such a discharge, at an interelectrode distance of L = 1 cm and a total plasma pressure of p ₀ ～ 1 Torr, the density of negative hydrogen ions produced via the dissociative attachment of thermal electrons to vibrationally excited molecules H₂ can reach a value as high as N_H ^? ≥ 10¹² cm^?3. According to calculations, the electron temperature in discharge operating regimes under study attains T _e ≈ 1?2 eV, which corresponds to the maximum of the e-v exchange rate constant of H₂ molecules. This ensures a relatively high rate of vibrational pumping of H₂ molecules in the discharge.