Phase-resolved emission spectroscopy of a hydrogen rf discharge for the determination of quenching coefficients

Collisional effects can have strong influences on the population densities of excited states in gas discharges at elevated pressure. The knowledge of the pertinent collisional coefficient describing the depopulation of a specific level (quenching coefficient) is, therefore, important for plasma diagnostics and simulations. Phase resolved optical emission spectroscopy (PROES) applied to a capacitively coupled rf discharge excited with a frequency of 13.56 MHz in hydrogen allows the measurement of quenching coefficients for emitting states of various species, particularly of noble gases, with molecular hydrogen as a collision partner. Quenching coefficients can be determined subsequent to electron-impact excitation during the short field reversal phase within the sheath region from the time behavior of the fluorescence. The PROES technique based on electron-impact excitation is not limited â?? in contrast to laser techniques â?? by optical selection rules and the energy gap between the ground state and the upper level of the observed transition. Measurements of quenching coefficients and natural fluorescence lifetimes are presented for several helium (3 1S,4 1S,3 3S,3 3P,4 3S), neon (2p1 ,2p2 ,2p4 ,2p6), argon (3d2 ,3d4 ,3d18 and 3d3), and krypton (2p1 ,2p5) states as well as for some states of the triplet system of molecular hydrogen.

Determination of quenching coefficients in a hydrogen RF discharge by time-resolved optical emission spectroscopy

In gas discharges at elevated pressure, radiation-less collisional de-excitation (quenching) has a strong influence on the population of excited states. The knowledge of quenching coefficients is therefore important for plasma diagnostics and simulations. A novel time-resolved optical emission spectroscopic (OES) technique allows the measurement of quenching coefficients for emission lines of various species, particularly of noble gases, with molecular hydrogen as collision partner. The technique exploits the short electron impact excitation during the field reversal phase within the sheath region of a hydrogen capacitively coupled RF discharge at 13.56 MHz. Quenching coefficients can be determined subsequent to this excitation from the effective lifetime of the fluorescence decay at various hydrogen pressures. The measured quenching coefficients agree very well with results obtained by means of laser excitation. The time-resolved OES technique based on electron impact excitation is not limited - in contrast to laser techniques - by optical selection rules and the energy gap between the ground state and the observed excited level.

Nonisothermal moisture transport in hygroscopic building materials: modeling for the determination of moisture transport coefficients

A mathematical model for calculating the nonisothermal moisture transfer in building materials is presented in the article. The coupled heat and moisture transfer problem was modeled. Vapor content and temperature were chosen as principal driving potentials. The coupled equations were solved by an analytical method, which consists of applying the Laplace transform technique and the Transfer Function Method. A new experimental methodology for determining the temperature gradient coefficient for building materials was also proposed. Both the moisture diffusion coefficient and the temperature gradient coefficient for building material were experimentally evaluated. Using the measured moisture transport coefficients, the temperature and vapor content distribution inside building materials were predicted by the new model. The results were compared with experimental data. A good agreement was obtained.

High-performance liquid chromatographic determination of 17 beta-estradiol and 17 beta-estradiol-3-acetate solubilities and diffusion coefficients in silicone elastomeric intravaginal rings

A rapid, sensitive reversed-phase high-performance liquid chromatographic method has been developed for the determination of in vitro release of 17 beta-estradiol and its ester prodrug, 17 beta-estradiol-3-acetate, from silicone intravaginal rings. Partial hydrolysis of the acetate under the aqueous conditions provided by the 1% benzalkonium chloride release medium necessitates its conversion to 17 beta-estradiol prior to HPLC analysis. Both steroid peaks have been fully resolved from the benzalkonium chloride peaks by the reported chromatographic method,which employs a C-18 bonded reversed-phase column, an acetonitrile-water (50:50, v/v) mobile phase and a UV detection wavelength of 281 nm. The peak area versus 17 beta-estradiol concentration was found to be linear over the range of 0.0137-1347 mu g ml(-1) The HPLC method has also been used to determine the silicone solubilities and diffusion coefficients of the two related steroids. The almost 100-fold increase in 17 beta-estradiol-3-acetate release from the silicone core-type intravaginal rings compared to 17 beta-estradiol is shown to be due to a 60-fold increase in silicone solubility and a one and a half-fold increase in diffusitivity. The results demonstrate that an effective estrogen replacement therapy dose of 17 beta-estradiol may be administered from a silicone intravaginal reservoir device containing the labile 17 beta-estradiol-3-acetate prodrug. (C) 2000 Elsevier Science B.V. All rights reserved.

Determination of Non-linear Damping Coefficients of bottom-hinged Oscillating Wave Surge Converters Using Numerical Free Decay Tests

Linear wave theory models are commonly applied to predict the performance of bottom-hinged oscillating wave surge converters (OWSC) in operational sea states. To account for non-linear effects, the additional input of coefficients not included in the model itself becomes necessary. In ocean engineering it is
common practice to obtain damping coefficients of floating structures from free decay tests. This paper presents results obtained from experimental tank tests and numerical computational fluid dynamics simulations of OWSC’s. Agreement between numerical and experimental methods is found to be very good, with CFD providing more data points at small amplitude rotations.
Analysis of the obtained data reveals that linear quadratic-damping, as commonly used in time domain models, is not able to accurately model the occurring damping over the whole regime of rotation amplitudes. The authors
conclude that a hyperbolic function is most suitable to express the instantaneous damping ratio over the rotation amplitude and would be the best choice to be used in coefficient based time domain models.

Measurement of Quenching Coefficients and Developement of Calibration Methods for Quantitative Spectroscopy of Plasma at Elevated Pressures

Measurements of collisional de-excitation (quenching) coefficients required for the interpretation of emission and fluorescence spectroscopic measurements are reported. Particular attention is turned on argon transitions which are of interest for actinometric determinations of atomic ground state populations and on fluorescence lines originating from excited atoms and noble gases in connection with two-photon excitation (TALIF) of atomic radicals. A novel method is described which allows to infer quenching coefficients for collisions with molecular hydrogen of noble gas states in the energy range up to 24 eV. The excitation is performed in these experiments by collisions of energetic electrons in the sheath of an RF excited hydrogen plasma during the field reversal phase which lasts about 10 ns. We describe in addition a calibration method - including quenching effects - for the determination by TALIF of absolute atomic radical densities of hydrogen, nitrogen and oxygen using two-photon resonances in noble gases close by the resonances of the species mentioned. The paper closes with first ideas on a novel technique to bypass quenching effects in TALIF by introducing an additional, controllable loss by photoionization that will allow quenching-free determination of absolute atomic densities with prevalent nanosecond laser systems in situations where collisional de-excitation dominates over spontaneous emission.

Validation and application of reporter gene assays for the determination of estrogenic and androgenic endocrine disruptor activity in sport supplements.

Previously developed estrogen and androgen mammalian reporter gene assays (RGAs) were assessed for their potential use as a quantitative screening method in the detection of estrogenic and androgenic endocrine disruptors (EDs) in sport supplements. The validation of both RGAs coupled with dispersive solid phase extraction (dSPE) was performed in accordance with European Commission Decision EC/2002/6579 for biological screening methods. Decision limits (CCa) and detection capabilities (CCß) were established for both the estrogen and androgen RGAs. All samples were compliant with CCa and CCß in both bioassays. Recovery rates were 96 % for 17ß-estradiol and 115 % for dihydrotestosterone as obtained in their corresponding RGA. Both estrogens and androgens were stable in samples for more than 3 weeks, when stored at -20 °C. Specificity, good repeatability (coefficients of variation (CV), 12–25 %), reproducibility and robustness of both bioassays were also observed. Four different ED modes of action were determined for estrogens and androgens in 53 sport supplements, using the validated RGAs. This study revealed that 89 % of the investigated sport supplements contained estrogenic EDs and 51 % contained androgenic compounds. In conclusion, both bioassays are suitable for sport supplement screening of estrogenic and androgenic EDs.

Electron-impact excitation and ionization of W 3+ for the determination of tungsten influx in a fusion plasma

Tungsten will be employed as a plasma facing material in the ITER fusion reactor under construction in Cadarache, France; therefore, there is a significant need for accurate electron-impact excitation and ionization data for the ions of tungsten. We report on the results of extensive calculations of ionization and excitation for W 3+ that are intended to provide the atomic data needed for the determination of impurity influx diagnostics of tungsten in several existing tokamak reactors. The electron-impact excitation rate coefficients for this study were determined using the relativistic R -matrix method. The contribution to direct electron-impact ionization was determined using the distorted-wave approximation, the accuracy of which was verified by an R -matrix with pseudo states calculation. Contributions to total ionization from excitation autoionization were also generated from the relativistic R -matrix method. These results were then employed to calculate values of ionization per emitted photon, or SXB ratios, for four carefully selected spectral lines; these data will allow the determination of impurity influx from tungsten facing surfaces. For the range of densities of importance in the edge region of a tokamak reactor, these SXB ratios are found to be nearly independent of electron density but vary significantly with electron temperature.