Direct fluorination—Useful tool to enhance commercial properties of polymer articles

Fundamental features and industrial applications of the direct fluorination of polymers are reviewed. Fundamental features of the direct fluorination of a set of polymers, such as polystyrene, polyethyleneterephthalate, poly(2,6-dimethyl-1,4-phenylene oxide), PMMA, LDPE (two types), HDPE (six types), polyvinyltrimethylsilane, poly(4-methyl-pentene-1), polyimide Matrimid 5216^®, polysulfones, polyetheretherketone, polycarbonatesiloxane, polysulphone-polybuthadiene block-copolymers, polypropylene, PVF, PVDF, etc. are described. Influence of composition of the fluorinating mixture (F₂-He-N₂-O₂-HF), fluorine partial pressure, temperature and fluorination duration, on the rate of formation of the fluorinated layer and the chemical composition, density, refraction index, surface energy, gas separation properties and friction coefficient of fluorinated layer have been investigated. Processes of formation and termination of long-living and short-living radicals and grafting of acrylonitrile to fluorinated polymers have been studied. Industrial applications of the direct fluorination to enhance the commercial properties of polymeric goods, such as separation factor of polymeric membranes for gas separation, barrier properties of polymer vessels, pipes and packagings, adhesion, printability, wetting and transparency in visible and IR are reviewed.     

Observation of zero creep in piezoelectric actuators

Piezoelectric actuators are frequently used nowadays in a wide variety of positioning devices. Although very suitable for small displacements in the range of nm to several hundreds of μm, the actuators always suffer from hysteresis and creep between the input voltage and resulting displacements. In scanning applications, the input voltage is often used as an indicator of the induced displacement. This procedure can result in a large position error depending on the amount of hysteresis and creep. In order to describe and control hysteretic systems various models for hysteresis have been published but little is known about relaxation and creep in piezo materials. In this paper we present detailed studies of the hysteretic behavior and piezo relaxation and creep. We have identified certain locations on the hysteresis loop that exhibit zero creep. From this observation, a more fundamental relation between the amount of creep and the local slope of the hysteresis loop and the virgin curve is presented. This observation could be useful in both open-loop and closed-loop position control, since it allows quantification of the creep. Futhermore, the experimentally observed relation between the creep and the hysteresis suggests a reduction of the creep for non-hysteretic transfers. First measurements on a system with reduced hysteresis support this hypothesis. Received: 15 February 1999 / Accepted: 16 February 1999 / Published online: 28 April 1999     

Improvement of selectivity and sensitivity by column switching in the determination of glycyrrhizin and glycyrrhetic acid in human plasma by high-performance liquid chromatography

A sensitive method is described for the simultaneous determination of glycyrrhizin and glycyrrhetic acid in human plasma. Quantitation is by high-performance liquid chromatography using ion-pair chromatography on a reversed-phase column. Variable-wavelength ultraviolet detection is employed. For the extraction of both compounds from plasma, a new solid-phase ion-pair extraction procedure using octadecylsilane columns was developed. Because of the strong forces involved in the protein binding of glycyrrhizin, quantitative extraction of this compound from plasma was possible only after an alkaline pH shift. A considerable improvement in selectivity and sensitivity was obtained by automated column switching involving on-line preseparation of the solid-phase extract on a short precolumn and chromatographic analysis of a heart-cut from the precolumn eluate. The limit of detection of both glycyrrhizin and glycyrrhetic acid was 0.1 mg/l in 0.5 ml of plasma. From a preliminary study in human volunteers, it was concluded that glycyrrhetic acid rather than glycyrrhizin is preferred in a study in human volunteers to assess the zero effect level of glycyrrhizin.     

The harmonic force field and absolute infrared intensities of butyne-2

The frequencies, harmonic force field and absolute IR intensities for butyne-2-d₀ and butyne-2-d₆ are reported. The final set of “harmonized” fundamental frequencies for butyne-2-d₀ and butyne-2-d₆ obeys the Teller—Redlich product rule very well. Starting values for the force constants were obtained from the harmonic force field of propyne, and diagonal force constants were adjusted in order to reproduce the experimental “harmonized” frequencies for the d₀ and d₆ compounds.The integrated IR intensities were measured according to the Wilson—Wells—Penner—Weber method, using nitrogen as a broadening gas. Thirteen sets of ?μ/?S values were obtained from the experimental intensities, using an iterative least-squares fitting procedure. This number could be reduced to one by use of several selection criteria. The signs of the remaining set appeared to be in complete agreement with the best set for propyne as reported both by Kondo and Koga and by Bode et al. The final ?μ/?S parameters were transformed into atomic polar tensors. Both kinds of intensity parameters are discussed and compared with corresponding parameters for related molecules.     

Resonant-Detector Mössbauer Spectroscopic Studies of Sn Doped SiO2 Analysed Using Quantum Mechanical Theory

It has already been established that, by using a resonant detector in Mössbauer spectroscopy, the minimum spectral linewidth is 1.46. Here is the linewidth of the Mössbauer excited-state nuclear level. It is well known that the minimum linewidth obtained in conventional Mössbauer experiments is 2. The quantum mechanical calculation using a nuclear-resonant detector, which predicts this result, is summarized. The fundamental equations describing the system are solved in the frequency domain and applied to the experimental results. The experimental results using the resonant-detector Mössbauer technique and an Sn-doped SiO₂ sample are presented. The best fit to the data is obtained using the resonant-detector quantum mechanical theory.