Simple, expedient methods for the determination of water and electrolyte contents of cellulose solvent systems

The concentrations of water, W, and electrolytes present in solutions of LiCl in N,N-dimethylacetamide, LiCl/DMAc, and of tetrabutylammonium fluoride. x-hydrate in DMSO, TBAF.xW/DMSO can be accurately and expediently determined by three independent methods, UV–vis, FTIR and EMF measurement. The first relies on the use of solvatochromic probes whose spectra are sensitive to solution composition. It is applicable to W/LiCl/DMAc solutions but not to TBAF.xW/DMSO, because the charge-transfer complex bands of the probes are suppressed by strong interactions with the latter electrolyte. Integration of ν_OH band of water may be employed in order to determine [W], hence [electrolyte] by weight difference. EMF measurement uses ion-selective electrodes in order to determine [electrolyte], hence [W] by weight difference. Results of the latter method were in excellent agreement with those of FTIR. The reason for the failure of Karl Fischer titration is addressed, and the relevance of the results obtained to functionalization of cellulose under homogenous solution conditions is briefly commented on.     

A thermodynamic description of the distribution of water in H2O-tributyl phosphate and H2O-tributyl phosphate-solvent systems

Various methods for describing the distribution of water in the H₂O-tributyl phosphate (TBP) system were considered. An equation for describing the deviations from the Henry law was proposed. A three-parameter equation for calculating the distribution of water in H₂O-TBP-solvent systems was derived. It is based on the additive solubility model and allows for the dependence of the activity coefficients on the TBP concentration. Based on the published data, the parameters of the equation for a number of systems were calculated.     

Global fit analysis including the ν9 + ν4 − ν4 hot band of ethane: Evidence of an interaction with the ν12 fundamental

The ν₉ fundamental band of ethane occurs in the 12 μm region. It is the strongest band of ethane in a terrestrial window and is commonly used for the identification of ethane in the Jovian planets. The ν₉ + ν₄ − ν₄ band occurs in the same region; neither can be analysed as an isolated band, since both are embedded in the torsional bath of the ground vibrational state. We report here two global fit models including data from both of these bands as well as the ν₃ fundamental and the ν₄, 2ν₄ − ν₄, and 3ν₄ torsional transitions. The first is restricted to −5 ? KΔK ? 15 in the hot band and gives an excellent fit to the included data. Three resonant interactions are identified in this fit—a Coriolis interaction with two resonant cases between the ν₉ torsional stack and that of the ground vibrational state (gs) and a resonant Fermi interaction between the ν₃ fundamental and the gs. Hot band lines with KΔK < −5 are influenced by a fourth perturbation, with a crossing at −11 < KΔK < −10, which has been attributed to an interaction with the ν₁₂ fundamental. A second fit, demonstrating a promising treatment of this interaction, is also presented.     

Highly accurate calculation of radial spheroidal functions

A new method for calculating the radial spheroidal functions of the first kind is proposed for the arguments that are greater than unity in modulus. A well-known representation of these functions is refined and used for this purpose. The constructs and the software implementation proposed in the paper provide an efficient tool for the calculation of the functions with a desired accuracy in a wide range of parameters.     

3D-TOFSIMS characterization of black spots in polymer light emitting diodes

The occurrence and formation of black spots areas in PolyLED devices has been studied by time-of-flight SIMS (TOFSIMS). The composition, shape and position of the black spots is visualised by three-dimensional (3D)-TOFSIMS depth-profiling. It has been established that the formation of non-emissive spots is due to the growth of aluminium oxide clusters at the AlBa/polymer interface. Electron injection in the black spots is lost by the resulting local increase of the resistivity of the cathode.     

Towards a general solution of the Hamiltonian constraints of General Relativity

The present work has a double aim. On the one hand, we call attention on the relationship existing between the Ashtekar formalism and other gauge-theoretical approaches to gravity, in particular the Poincaré Gauge Theory. On the other hand, we study two kinds of solutions for the constraints of General Relativity, consisting of two mutually independent parts, namely a general three-metric-dependent contribution to the extrinsic curvature K _ab in terms of the Cotton–York tensor, and besides it further metric independent contributions, which we analyze in particular in the presence of isotropic three-metrics.     

Specific features of photoisomerization of provitamin D 3 in a nematic liquid crystal

Photoisomerization of provitamin D ₃ (7-dehydrocholesterol) in a nematic liquid crystal (ZLI-1695, Merck) is investigated in detail by UV absorption spectroscopy. It is found that dissolution of chiral molecules of provitamin D ₃ induces the cholesteric phase in a nematic. The spectral kinetics of photoisomerization in this phase changes significantly from that in an ethanol solution. A sharp nonmonotonic dependence of the increase in accumulation of trans isomer tachysterol in a liquid crystal matrix with a decrease in the induced cholesteric pitch from 2200 to 25 μm is revealed.     

INFLUENCE OF A LEVELNESS DEFECT IN A THRUST BEARING ON THE DYNAMIC BEHAVIOUR OF AN ELASTIC SHAFT

This paper examines the non-linear dynamic behaviour of a flexible shaft. The shaft is mounted on two journal bearings and the axial load is supported by a defective hydrodynamic thrust bearing at one end. The defect is a levelness defect of the rotor. The thrust bearing behaviour must be considered to be non-linear because of the effects of the defect. The shaft is modelled with typical beam finite elements including effects such as the gyroscopic effects. A modal technique is used to reduce the number of degrees of freedom. Results show that the thrust bearing defects introduce supplementary critical speeds. The linear approach is unable to show the supplementary critical speeds which are obtained only by using non-linear analysis.