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     

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.     

Influence of concentration on the activation energy for diffusion in polymer-solvent systems

The self-diffusion of benzene, toluene, and ethylbenzene in polystyrene have been analyzed using the Vrentas/Duda free-volume diffusion model. Diffusion coefficient predictions suggest an exponential concentration dependence of the activation energy required to overcome attractive forces, E. Without the use of any diffusion data approximating E as zero over the entire concentration range yields self-diffusion coefficient predictions which are in good agreement with experimental data. © 1992 John Wiley & Sons, Inc.     

Morphology of Nylon-6 blends with styrenic polymers

The morphology of blends of styrenic polymers in a matrix of 75% Nylon-6 prepared in a Brabender Plasti-Corder was examined by scanning electron microscopy. Styrene/acrylonitrile copolymers (SAN) form smaller particles as the AN level increases owing to the corresponding decrease in the SAN–polyamide interfacial tension. Various styrenic polymers containing functional groups, maleic anhydride or oxazoline type, that can react with Nylon-6 during melt processing were added to the SAN phase which also led to a decrease in the particle size owing to the graft copolymer formed in situ. The effects of functional group type, amount of functional groups per chain, amount of functional polymer added, and the miscibility of the styrene/maleic anhydride (SMA) and SAN copolymers on the morphology of the styrenic phase in the Nylon-6 matrix are described. © 1992 John Wiley & Sons, Inc.     

TERNARY OPERATIONS AS PRIMITIVE NOTIONS FOR PLANE GEOMETRY II

We proved in the first part [1] that plane geometry over Pythagorean fields is axiomatizable by quantifier-free axioms in a language with three individual constants, one binary and three ternary operation symbols. In this paper we prove that two of these operation symbols are superfluous.     

Ultraviolet photoemission spectroscopy of hydrogen complex deactivation on InP:Zn(1 0 0) surfaces

Ultraviolet photoemission spectroscopy is used to study the kinetics of the H-Zn complex deactivation in Zn doped InP(1 0 0). Hydrogen injected into the material electronically passivates the local carrier concentration. Reverse-biased anneals of the InP under ultra-high vacuum show a dramatic change in the work function of the material with increasing temperature. Spectral features are also shown to be sensitive to sample temperature. To our knowledge, we show the first view of hydrogen retrapping at the surface using photoemission spectroscopy. A simple photoelectron threshold energy analysis shows the state of charge compensation of the material.     

Adsorption of dicarboxylates on nano-sized gibbsite particles: effects of ligand structure on bonding mechanisms

The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition ⁻O₂C---C_n---CO₂⁻; n=0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n=2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n=1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) at the surface. This showed the importance of chelate ring structure for the formation of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n=2 only small variations in surface speciation were observed as a function of steric factors; irrespective of the relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption mode. Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles.     

Apparatus for High-Resolution Solid Hydrogen Matrix Isolation Spectroscopy and Its Application

Apparatus integrating a Fourier transform-infrared (FT-IR) spectrometer and a mid-infrared difference frequency generation (DFG) laser spectrometer was built for the study of the matrix isolation spectrum in solid molecular hydrogen. A 3-cm-long molecular hydrogen crystal was grown in a liquid-helium Dewar, and its infrared absorption spectrum in the 1-5 μm region was recorded to test the system. The W₀(0) (ν=0←0, J=6←0) line around 2410 cm⁻¹ of solid hydrogen was investigated with the DFG laser spectroscopy. High-resolution matrix isolation spectrum of CO² co-deposited with hydrogen on a BaF₂ cold plate at liquid-helium temperature was studied.     

Modification of multiwalled carbon nanotubes by carboxy groups and determination of the degree of functionalization

Multiwalled carbon nanotubes were modified by carboxy groups. Four independent methods for the determination of the degree of functionalization of the surface were proposed: ¹³C NMR spectroscopy, thermogravimetry, titrimetry, and fluorimetry. The first two methods show the total content of carboxy groups in the sample, and the latter two methods give information about the content of the surface groups only. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 291–295, February, 2008.