Synthesis of functional polymers—Vinylidene fluoride based fluorinated copolymers and terpolymers bearing bromoaromatic side‐group

The radical co‐ and terpolymerization of 4‐[(α,β,β‐trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF, or VF₂), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the co‐ and terpolymers were assessed by ¹⁹F and ¹H‐NMR spectroscopy. The thermal and physico chemical properties were also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5077–5097, 2004     

Study of the effect of swift heavy Ni ion irradiation on ruby single crystal by using the XANES and EXAFS techniques

We have made the XAFS measurements at the Cr–K-edge on natural Indian ruby single crystals (corundum) and its two irradiated samples with fluence 1×10¹² Ni⁶⁺ and 5×10¹² Ni⁶⁺ ions/cm². Irradiated samples show interesting changes in their physical appearance. XANES measurements show progressive decrease in Δ_oct value on increase of Ni fluence in irradiated samples. EXAFS measurements on these samples show decrease in Cr–O distance on increase of Ni fluence. Lowering of Δ_oct value is correlated with the increase of Cr–O distance.     

Near-field thermoelastic imaging coupled with infrared detection

Near-field thermoelastic imaging is a simple way to investigate the thermal and coupled thermoelastic properties of materials. A few microscopes, deriving from the atomic force microscope, have been used to observe and to quantify the samples observed. But the main problem is the absolute measurement of the temperature, because surface topography and thermal expansion contributions are not easily discernible. In the proposed SThEM (scanning thermoelastic microscope), the tip is excited at the resonance frequency of the cantilever and the sample is periodically heated by the Joule effect. Thus the static contributions (drift, topography) are reduced. Moreover, a radiometric sensor, operating in the far field, has been added in order to quantify the temperature. This multi-acquisition microscope enables one to investigate small objects at the nanoscale with complementary information at the micrometric scale.     

UV curing of a novel resin derived from poly(ethylene terephthalate)

The synthesis and characterization of photopolymerizable unsaturated polyester resins based on PET waste are described. The resins came from a depolymerization process based on the glycolysis of PET by diethylene glycol (DEG). Different molecular weights of glycolysates were synthesized. Then, the latter was functionalized by a methyl hemiester of maleic acid to obtain unsatured α,ω‐bismaleate PET oligomers. In the presence of an electron donor monomer, such as triethylene glycol divinyl ether, these electron acceptor oligomers were copolymerized by way of charge‐transfer complexes under UV irradiation. The reaction was monitored in situ by real‐time IR spectroscopy to study the kinetics of photopolymerization. This one was studied in relation with the physical and chemical characteristics of oligoesters and the composition of mixtures containing divinyl ethers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1324–1335, 2007     

Nonstatic perfect fluid sphere in higher-dimensional space-time

It is shown that in the case of a spherical nonstatic fluid distribution undergoing shear-free motion the field equations in higher dimensional space-time can be reduced to a single second-order differential equation involving an arbitrary function of the radial co-ordinate. This result extends to higher dimensions a similar one obtained by Wyman and Faulkes earlier for 4D space-time. Solving this differential equation a number of new solutions is found, and the dynamical behaviour of one of the models is briefly discussed. The ansatz is later generalised to include the electromagnetic field as well.     

ON SOME INTERPRETATIONS OF CLASSICAL LOGIC

In distinction from the well-known double-negation embeddings of the classical logic we consider some variants of single-negation embeddings and describe some classes of superintuitionistic first-order predicate logics in which the classical first-order calculus is interpretable in such a way. Also we find the minimal extensions of Heyting's logic in which the classical predicate logic can be embedded by means of these translations.     

Computational advances in organic chemistry: Molecular structure and reactivity. Edited by C. Ögretir and I. G. Csizmadia,NATO ASI Series C,Vol, 330.

We here report an AM 1 study for the reaction of different types of radicals with the acetone enolate ion 1 and other ambident nucleophiles. The theoretical reactivity order determined is phenyl > methyl > tert-butyl ? bicyclo-[2.2.1]hept-1-yl. The activation energy for the coupling of aliphatic radicals is ascribed mainly to nonbonded interactions. Considering possible solvent effects, we propose the same order of reactivity in solution. The coupling reaction of phenyl radical with 1 is an exothermic process with nonactivation energy in the gas phase. Any energy barrier in solution is here ascribed to desolvation of the anion. The regiochemistry of the coupling of radicals with ambident nucleophiles such as 1 , phenoxide, or phenylamide anions is also explained on a theoretical basis. © 1992 John Wiley & Sons, Inc.     

Continuous removal of radiolytic products from TBP extraction systems

In the actinide separation process using TBP as extractant, hydrolytic and radiolytic reactions cause a gradual decomposition of the extractant, resulting in the formation of degradation products which can affect process performance adversely. The TBP diluent has to be cleaned from these degradation products before it is reused. This paper deals with a procedure for solvent cleanup, using a fourstage continuous contactor for increasing the scrubbing efficiency.