Correction procedure for the electron microprobe analysis of porous materials

A correction method is proposed for the quantitative determination of stoichiometric ratios in porous materials by electron microprobe analysis. Analysis of this kind of material is complicated by an imperfect surface that can only be improved to some extent. The correction is based on a linear dependence (different for each element) of the analyses on a sum of weight concentrations of oxides. With this correction it is possible to use analyses affected by the imperfection of the surface with much better confidence compared to common normalisation. An example is presented for a series of ceramic superconductors Bi_2.1(SrCa)_2.9Cu₂O₈₊.     

The inhomogeneity of plastic deformation

Considerable local strain differences occur in single crystals as a consequence of slip bands. A significant contribution to this phenomenon is the effect of the deformation rate on the inhomogeneity of its distribution. In polycrystalline materials the plastic deformation is affected by grain boundaries and their vicinity as well as by various orientations of single grains in onephase metals and alloys, and by various component properties in multiphase materials. In some cases it has been possible to describe these phenomena by means of micromechanics. Valuable information has also been acquired by means of three-dimensional stereology.     

The influence of tensile stress on grain and cell boundary precipitation in supersaturated Al-Zn alloys during creep

The results are presented of the optical microscopic and X-ray diffraction study of the stress-induced nucleation and growth of (Zn) precipitates at grain and cell boundaries (GB's and CB's) during uniaxial creep at 200 °C of supersaturated AlZn20 and AlZn30 alloys. The rate of precipitation is increased mainly owing to the modifying effect of tensile stress on diffusion processes in alloy samples during their anneal. The diffusion of Zn atoms toward GB's and CB's from adjacent regions of grains is accompanied during creep by diffusive flux of Zn along boundaries parallel or nearly parallel to the tensile creep axis toward boundaries with near to normal orientation to that axis. Enhanced precipitation of results then preferentially at the latter and is supressed at the former boundaries where even the dissolution of preexisting has been found during a later application of tensile stress. The stress-induced precipitation of at GB's gradually ceases with prolonged creep exposures due to the lengthening of duffusion paths of Zn atoms from grain interior to GB's.Dissolution of lamellae by their regress toward GB's and CB's is assisted with the stress-induced diffusion of Zn along epitaxial / lamellar interfaces. Copious precipitation of at the parts of GB's and/or CB's with near to normal orientation to the creep axis is then observed on account of Zn from dissolved lamellae. Creep strain also leads to the fragmentation of lamellae and thus also to breaking down of the paths for diffusion of Zn along / interfaces. Spheroidization of fragmented parts of lamellae is then observed. Spheroids of remain embedded within the former lamellar regions.Large creep strains and high strain rates observed on fine-grained alloy samples may be associated with an enhanced viscous GB sliding due to the stress-dependent flow of Zn along GB's and/or CB's.     

On kinetics of the photodissociation iodine laser

The kinetics of iodine laser amplifiers is examined by solving the time evolution equations of chemical kinetics during optical pumping. The pumping radiation intensity is modelled by a black body of the temperature varying in time (corresponding to the flash lamp pulse). A brief comparison is made of pumping effects by long and short light pulses. Pumping by the long pulse is studied in more detail and it is found that there exists an optimum pulse strength beyond which the inversion in the laser mixture no longer grows appreciably, only its lifetime is shortened. In this connection the effect of pyrolysis of the alkyliodide molecule is also discussed. The pyrolysis is found to occur under very strong illumination, but it does not interfere with the photolytic decomposition and the optimum laser action. Finally, the influence of the reaction rate constants is studied in a systematic way and only few of them are found to carry real weight.The authors are obliged to Drs. S. V. Kuznetsova and A. I. Maslov who were consulted on the values of the reaction constants and who also drew our attention to some of the references.     

Analytical Detectors Based on Microplasma Spectrometry

Miniaturizing all dimensions of apparatus, such as electronics and computers, is the current trend followed by scientists in various fields. The idea of Lab-on-a-Chip has significantly expanded and found its broad applications in analytical chemistry. Microplasmas can act as a sample excitation source and are the miniaturized versions of full-sized plasmas. These can be created in various forms, such as direct current, microwave induced, capacitively coupled and inductively coupled plasmas. Scaling down the size would reduce the amount of gases, liquids and consumables required, as well as the sample analysis time, which in turn would decrease the operating costs. Therefore, several research groups are involved in the development of microplasmas for utilisation in analytical instruments.     

Volumetric properties of ethanol–water mixtures under high temperatures and pressures

The densities of ethanol and ethanol–water mixtures were measured with a vibrating tube densimeter at 25.0, 50.0 and 75.0 °C in the pressure range from 0.10 to 40.00 MPa. Densities were correlated using an empirical model. Partial molar volumes, excess molar volumes, isothermal compressibilities, cubic expansion coefficients and internal pressures were calculated from obtained densities. This study reports the dependence of densities, partial molar volumes, excess molar volumes, isothermal compressibilities, cubic expansion coefficients and internal pressures on composition, temperature and pressure.     

Stereospecific total synthesis of (±)-strempeliopine

The 18-methylene-1,2-dehydroaspidospermidine (III) was stereospecifically transformed into the schizozygane alkaloid strempeliopine (II) in 16,6 % overall yield.     

Comparison of quantitative methods for analysis of polyphasic pharmaceuticals

Adequate very sensitive quantification methods are needed for the development and are also now required for the monitoring of undesirable solid form(s) as routine tests. The pre-requisite for quantitation are selectivity, sensitivity and most important the purity of standards and their proper storage, what is a challenge for metastable forms. Several analytical techniques are available such as X-ray diffraction, spectroscopy, thermal analysis and microcalorimetry. The different steps of the validation of the analytical methods and problems to be solved are discussed. Examples illustrate the different techniques and compare their possible advantages and limits. The relative standard deviation of measurements should allow for checking the homogenization procedure of mixtures for calibration. The validation should be carried out following ICH guidelines for validation of analytical methods. Comparison of different techniques in adequate concentration range add confidence in the analytical results.