Rate constants for the decarboxylation of the t-butoxicarbonyl radical and concurring radical terminations directly obtained by kinetic ESR

Rate constants of various simultaneous reactions of t-butoxicarbonyl and t-butyl radicals generated by photolysis of t-butylpivalate in n-heptane are directly determined by kinetic electron spin resonance. The temperature dependence of the decarboxylation reaction t-BuO?O → t-Bu^. + CO₂ obeys log )K/S^?1( = 13.8?49.0/θ where θ = 2.303 RT/kJ ^. mol^?1. The self- and cross-termination of the radicals are diffusion limited.     

Dynamical studies of highly deuterated betaine phosphate near the antiferroelectric phase transition

The dielectric response and the Raman spectra of single crystals of deuterated betaine phosphate are studied around the antiferroelectric phase transition. The dielectric data between 10 MHz and 11 GHz can be explained on the basis of a simple Debye-relaxation with a critical slowing-down of the relaxation rate on approachingT _C . Using the Cole-Davidson form of the dielectric function we succeeded in fitting the data in the whole frequency range from 10 MHz to 11 GHz and from 64–400 GHz over a temperature range from 145–280 K. Raman spectra clearly indicate that the doubling of the unit cell does not take place at the antiferroelectric transition temperature, but some degrees below.     

Cross relaxation studied by β NMR

The dipole-dipole interaction between polarized β active probes implanted into a metal and the surrounding host nuclei may lead to a transfer of polarization from the probe to the host. As energy must be conserved in this cross-relaxation (CR) process, resonance-like dips show up at certainB values, if the polarization of the probes is measured as a function of magnetic inductionB. The probe isotope¹²B has been studied in several metallic stoppers. For¹²B in the fec crystals Al, Cu the three possible cubic implantation sites could easily be discriminated by means of the CR technique. The temperature dependence of the dips yielded information on the diffusion of the probes. In the case of¹²B, in Cu above 400 K a further CR structure was found due to trapping of the probe at another site. In the bcc metal VCR spectra belonging to two different¹²B trapping sites could be separately registered using a special radiofrequency technique. Both, static and dynamical properties of the CR could be quantitatively explained by theory.     

Managing polymer surface structure using surface active block copolymers in block copolymer mixtures

Surface coatings were prepared from semifluorinated monodendron surface‐active block copolymers (SABC) and a thermoplastic elastomer (TPE) [poly(styrene‐b‐ethylene butylene‐b‐styrene)] by either spin‐casting a bilayer structure or by blending. The surface of these coatings was characterized by contact angle measurements, scanning force microscopy (SFM) and near‐edge X‐ray absorption fine structure (NEXAFS) methods. Both bilayers and blends resulted in very low energy surfaces under the right processing conditions and the liquid crystallinity of the semifluorinated monodendrons gave rise to temporally stable, non‐reconstructing surfaces in water. However for small thicknesses of the SABC top layer or for low SABC content blends, SFM shows islands of the fluorinated block of the SABC and incomplete surface coverage of the TPE, an observation confirmed by NEXAFS analysis. Very high water contact angles were produced by even modest amounts of SABC in either case but to achieve low contact angle hysteresis, it was necessary to produce uniform surface coverage by the SABC. Such uniform coverage can be accomplished by spin casting a top layer of SABC as thin as 60 nm in the bilayer case but at least 10 wt% SABC in TPE combined with drop casting of a hot solutions is needed for the blends to achieve equivalent surface structure and properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 411–420, 2004     

Velocity analysis of mechanisms with ball joints

A procedure is developed for analyzing velocities in spatial mechanisms with ball joints has been designed for practical computerization. The correspondence between the calculated velocities in a ball joint and the time changes of the physical displacements is clarified. The methodology is demonstrated using the RSPC mechanism which has seen commercial application as a washing-machine agitator mechanism.     

In Process Citation

Analyses for the metals Cd, Pd and Cu in the estuary and bay of the Scine have been made. The site was chosen because of the very high tides, which produce considerable water displacement. For the purpose of analysis the metals have been divided into three categories: free metals, metals forming complexes that are unstable at low pH, and metals forming stable complexes that are destroyed in an acidic medium by ultraviolet radiation. The special properties of copper have been used to establish a “complexing capacity” of the different water samples studied. By making the simple hypothesis of the existence of an equilibrium of the type Cu + L CuL, where L represents the ligand, the total ligand concentration, as well as the stability constants of the CuL complexes, has been determined. These results are presented and discussed.