Comparison of four quantification methods for the determination of PCB in transformer oils

The analysis of PCB in transformer oils has been achieved with three HRGC/ECD based methods, proposed by the International Electrotechnical Commission (IEC/TC 10), by the Comité Européen de Normalisation (CEN/TC 19/WG 22) and by the Deutsches Institut für Normung (DIN 51 527). The same clean-up, described in the CEN/TC 19/WG 22, has been used for all the samples, allowing a comparison of the quantification procedure only. The total chlorine content has also been determined with X-ray fluorescence. These different methods of quantification are compared and their application for legislative purposes is discussed.Dedicated to Professor Dr Dieter Klockow on the occasion of his 60th birthday     

Stressed states in domain switching of ferroelectric liquid crystal devices

In this paper we show that the director profile of a low pre-tilt surface stabilized ferroelectric liquid crystal passes through quasi-static stressed states during domain switching under direct drive conditions. Using polarized stroboscopic microscopy, we have observed two quasi-static transmission levels during a domain switching transition from dark to light. This is a result of the directors reorienting into stressed profiles both before and after the chevron interface has switched. By modelling the interaction between the elastic forces and the torque from the applied field, we have determined these voltage dependent director profiles and, by calculating their corresponding transmissivities, have shown very good agreement with the experimentally observed values.     

Raman spectroscopic investigations of the structure and phase transitions of liquid crystalline lead(II) alkanoates

Lead(II) alkanoates with even chain lengths from octanoate to octadecanoate have been investigated by Raman spectroscopy. In the low frequency region, transverse and longitudinal acoustical modes (TAM, LAM) have been assigned. It was shown that LAM-1 is the vibration of the double chain with the node of the vibration in the Pb²⁺ layer. A fully extended conformation of the chains in the low temperature phase was confirmed. The frequencies and intensities of the LAMs as compared with those of the alkanes and the fatty acids led to an estimate of the force constant and polarizability of the Pb²⁺ -COO^- bond relative to the C-C bond. The defects at the chain ends were investigated in the ρ(CH₃) and v(CC) region. For the intermediate (CM) phase, both the Pb²⁺ layer distance reduction and the chain length independent enthalpy contributions can be attributed mainly to defects at the chain ends.     

Interpretation of inorganic arsenic metabolism in humans in the light of observations made in vitro and in vivo in the rat

The toxicity of inorganic trivalent arsenic for living organisms is reduced by in vivo methylation of the element. In man, this biotransformation leads to the synthesis of monomethylarsonic (MMA) and dimethylarsinic (DMA) acids, which are efficiently eliminated in urine along with the unchanged form (As_i). In order to document the methylation process in humans, the kinetics of As_i, MMA and DMA elimination were studied in volunteers given a single dose of one of these three arsenicals or repeated doses of As_i. The arsenic methylation efficiency was also assessed in subjects acutely intoxicated with arsenic trioxide (As₂O₃) and in patients with liver diseases. Several observations in humans can be explained by the properties of the enzymic systems involved in the methylation process which we have characterized in vitro and in vivo in rats as follows: (1) production of As_i metabolites is catalyzed by an enzymic system whose activity is highest in liver cytosol; (2) different enzymic activities, using the same methyl group donor (S-adenosylmethionine), lead to the production of mono- and di-methylated derivatives which are excreted in urine as MMA and DMA; (3) dimethylating activity is highly sensitive to inhibition by excess of inorganic arsenic; (4) reduced glutathione concentration in liver moderates the arsenic methylation process through several mechanisms, e.g. stimulation of the first methylation reaction leading to MMA, facilitation of As_i uptake by hepatocytes, stimulation of the biliary excretion of the element, reduction of pentavalent forms before methylation, and protection of a reducing environment in the cells necessary to maintain the activity of the enzymic systems.     

Surface heating and energy transfer in pulsed microwave catalytic systems: A microwave-induced acoustic study

Since the early demonstrations of our concept of pulsed microwave catalysis in chemistry, we have witnessed the coming of age of the technique as an enabling technology in the industrial world, despite the inadequate understanding of the basic mechanisms of how microwaves interact with metallic surface sites and the subsequent energy transfer. We shall present here some very recent developments of the microwave-induced acoustic technique and its applications to a better understanding of the basic surface heating and energy transfer phenomena in pulsed microwave catalytic systems.     

Calibration of depth profiles of microparticles measured with plasma-based secondary neutral mass spectrometry

A gravimetric method is presented for the easy determination of sputter erosion rates for powders, applicable also to non-conducting materials. Measurements of the erosion rates of 22 powders gave an average value of 0.4 nm/s ±50% for bombardment with 400 eV Ar⁺ at 1 mA/cm². The validity of the data has been demonstrated with technical pigments and outdoor aerosol particles.     

ARXPS-analysis and morphology of sputtered nanocrystalline TiC/SiC coatings

ARXPS (angle resolved X-ray photoelectron spectroscopy) measurements are used to obtain informations about surfaces and grain boundaries. Data acquired from nanocrystalline carbidic hard coatings have been employed to establish structural models. Magnetron-sputtered coatings of TiC, SiC and TiC/SiC were examined. In such coatings, partly defective TiC nanocrystallites are surrounded by interfacial carbide. This excess carbon shows a binding state similar to that of doped graphite or fullerenes. X-ray amorphous SiC is found in the residue. On top of sputtered SiC coatings, less oxide and graphite is found as compared to TiC/SiC or TiC coatings.     

Liquid crystalline hexa-amides and side chain polysiloxanes of azacrown [18]-N6

The hexa-4-dodecyloxybenzoyl derivative 1 of azacrown [18]-N₆ was originally reported to have a 'tubular' mesophase on the basis of its large central ring and 6-fold symmetry. Starting in the mesophase, annealing of 1 under a cover slip results in formation of a new crystalline phase that melts directly to an isotropic liquid at the temperature previously observed for the mesophase to isotropic transition. Thus the phase behaviour of 1 is kinetically controlled. The analogous hexa-3,4-bisdodecyloxybenzoyl derivative 2 of azacrown [18]-N₆ has no kinetic limitations to its phase changes and has an enantiotropic columnar liquid crystalline phase. We have synthesized side chain copolysiloxanes with a (CH₂)₁₁ spacer and 75-84 per cent by weight of the same 4-dodecyloxybenzoyl-[18]-N₆ mesogen. The polysiloxanes also display a liquid crystalline phase.     

The influence of the liquid crystalline core geometry on the mesogenicity of novel chiral 2-(4-substituted-phenoxy)propanonitriles

The synthesis and characterization of seven novel (R)-2-(4-substituted-phenoxy)propanonitriles are described. The propanonitriles were prepared to evaluate their potential use as thermochromics and ferroelectric dopants, as well as to determine their twist sense properties. The materials exhibit smectic and chiral nematic phases of high thermal stability; the mesogenic behaviour of the nitriles is directly related to the type of two-ring core unit employed. The effects of the different molecular geometries and polarizabilities of the liquid crystalline cores on mesophase stability are discussed, particularly in relation to other members of this series. The chiral nematic phase of the propanonitriles is assigned as having a left-handed twist sense from contact preparation studies, and this is in agreement with rules relating absolute configuration and molecular structure to helical twist sense.     

Pretransitional electro-optic response of 6CB liquid crystal in the isotropic phase

In this work, the electro-optic response of a 6CB liquid crystal layer is studied using a sensitive differential technique. The layer is held at a temperature just above the nematic to isotropic phase transition. Transverse magnetic (p) polarized light incident on the cell is coupled to guided modes in the liquid crystal layer using prism coupling. The modes manifest themselves as sharp dips in the reflectivity as the angle of incidence is scanned. When a low frequency sinusoidal voltage is applied to the cell, the resonant mode shapes and excitation angles are altered at a frequency which is twice that of the applied field, resulting in a modulation of the reflectivity for a given angle of incidence. By synchronous observation of the modulated signal, a differential signal is recorded. Comparing the data with modelling generated from multilayer optics theory, two effects are then quantified. The first of these is an induced birefringence, varying quadratically with applied voltage, which is well understood and can be expressed in terms of Landau-de Gennes theory. The second is a field induced perturbation in the imaginary part of the optical permittivity, δε_i, which implies a modification of the light scattering properties of the liquid crystal. The measurement of the latter effect is, as far as we know, a novel one, being only made possible by the remarkable sensitivity of the synchronous differential technique.