Resonance ionization spectroscopy for trace analysis and fundamental research

Resonance ionization spectroscopy (RIS) and its combination with mass spectrometry (RIMS) have grown to become powerful techniques, which offer high sensitivity as well as elemental and isotopic selectivity. The principles of RIS and RIMS are introduced; they primarily concern the analysis of the optical spectra for the choice of efficient excitation schemes and the suitable design of the experimental apparatus. Recent applications span from studies of short-lived isotopes at on-line mass separators to a wide variety of trace analysis applications for radioactive isotopes, which can range from measurements of solar neutrino flux to environmental assessment.On leave from Pacific Northwest Laboratory, Richland, USA     

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.     

Comparison of short range interactions in nematic liquid crystals A 2H-NMR study of 5CB-d19 as a solute

Previous studies using dideuterium as a solute have demonstrated the importance for orientation of the interaction between the solute molecular quadrupole moment and the average electric field gradient present in liquid crystals. With the aim of learning about additional orientational mechanisms, we have studied the temperature dependence of the ²H-NMR spectra of the liquid crystal 5CB-d₁₉ as the solute in three liquid crystal mixtures: 55 wt % 1132/EBBA, 56·5 wt % 1132/EBBA and 70 wt % 5CB/EBBA. In these mixtures, the contribution from the environment to the average electric field gradient at the ²H nucleus of dideuterium is zero. The spectra of 5CB-d₁₉ in the mixtures 55 wt % 1132/EBBA and 56·5 wt % 1132/EBBA are equivalent, but are different from those in 70 wt % 5CB/EBBA. The spectra of 5CB in 55 wt % 1132/EBBA and 70 wt % 5CB/EBBA are analysed using two different models for the short range potential, and param eters of the models are used to compare the potentials in the different mixtures. For a given spectral splitting of the chain C₁ deuteron, the reduced short range potential is the same in all three mixtures studied. The spectral differences observed are a consequence of different nematic-isotropic phase transition temperatures combined with the effect of trans/gauche-isomerization in the hydrocarbon chain.     

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.     

Octahedral metallo-mesogens of chromium, molybdenum and tungsten with 1,4,7-trisubstituted 1,4,7-triazacyclononane and three carbonyl groups as ligands

Liquid crystalline complexes with chromium, molybdenum and with tungsten as metallic centres are reported. 1,4,7-Trisubstituted 1,4,7-triazacyclononane and three carbonyl groups are coordinated in an octahedral geometry. The observed mesophases are characterized as disordered rectangular columnar of a pyramidic type.     

Manifestation of biquadratic coupling in the smectic C* phase soft mode dielectric response

The soft mode dielectric response of three ferroelectric chiral smectic C* substances is studied in the vicinity of the smectic C*-smectic A* phase transition. For some substances the soft mode dielectric strength exhibits a pronounced anomaly in the C* phase just below the phase transition. We show how this anomaly can be systematically correlated with a corresponding anomaly in the experimentally determined ratio of spontaneous polarization over tilt. By comparing the experimental results with the theoretical predictions of an extended Landau model, we demonstrate how the crossover behaviour of the system can be interpreted as being the consequence of the presence of a biquadratic coupling between tilt and polarization in the Landau free-energy of the system.     

Kinetic model for hydrocarbon-assisted particulate boron combustion

A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc.     

Determination of Structure Corrections using Geodetic VLBI Observations of Fiducial Extragalactic Radio Sources

We present the further development of the mathematical technique for calculating the structure corrections using VLBI images of fiducial extragalactic radio sources entering the celestial reference frame. In contrast to techniques described in the literature, the proposed approach can be applied to arbitrary images rather than to images which can be represented by a few Gaussian or delta functions. This is especially topical in view of the appearance of new sophisticated and high-precision image-reconstruction techniques different from the conventional CLEAN procedure or model fitting. The calculation efficiency of the structure corrections is ensured by using the algorithm of fast Fourier transform. We apply the proposed method to analyze a sufficiently representative sample of 36 fiducial extragalactic sources entering the celestial reference frame and illustrate its use for four sources, 1357+769, 0229+131, 2201+315, and 2200+420, each of them belonging to one of the four structure-index classes.