Precipitation kinetics of W2B5 in (Ti0.4W0.5Cr0.1)B2 solid solutions

The isothermal precipitation kinetics of W₂B₅ secondary phase from supersaturated polycrystalline (Ti_0.4W_0.5Cr_0.1)B₂ solid solutions were investigated with X-ray diffractometry and scanning electron microscopy in the temperature range between 1500 and 1700°C. The precipitate formation is described by a modified Johnson–Mehl–Avrami–Kolmogorov (JMAK) model, where W₂B₅ particles nucleate preferentially at grain boundaries and subsequently grow into the volume by a two-dimensional process controlled by volume diffusion of the transition metals. Numerical calculations are used to describe quantitatively the time dependence of the precipitated fraction and to determine a differential JMAK exponent n _diff which gives information on the nucleation and growth modes. n _diff decreases during the precipitation process from 2 to about 0.8 for all temperatures investigated. The first limit corresponds to the classical JMAK model (two-dimensional diffusional growth and constant nucleation rate) and the decrease in n _diff is the consequence of an impingement of the nucleating and growing particles in the late stages of the process. Nucleation and growth rates are determined as functions of reciprocal temperature, where the first quantity shows a non-monotonic behaviour with a maximum at about 1650°C and the second quantity exhibits an Arrhenius behaviour with an activation enthalpy of 3.6?eV. From this it can be concluded that the overall precipitate formation is dominated by the kinetics of atomic motion at low temperatures and by the thermodynamics of nucleation at high temperatures.     

Double matrix membranes for potentiometric cation selective disposable sensors

The construction of double matrix membranes (DMM) for disposable NH ₄ ⁺ , Na⁺ and pH sensors is described. The usual polymer matrix membrane was incorporated in an inert micro fibre matrix (MFM). Capillary forces distribute the cocktail homogeneously in the MFM; this also determines the thickness. Sensors using the new DMM have shown selectivity, detection limits and slope comparable with polymer matrix membranes. The advantages of DMMs are their mechanical stability, the feasibility of low cost mass production with identical parameters and improved handling.     

A fast solver for the gyrokinetic field equation with adiabatic electrons

Describing turbulence and microinstabilities in fusion devices is often modelled with the gyrokinetic equation. During the time evolution of the distribution function a field equation for the electrostatic potential needs to be solved. In the case of adiabatic electrons it contains a flux-surface-average term resulting in an integro-differential equation. Its numerical solution is time and memory intensive for three-dimensional configurations. Here a new algorithm is presented which only requires the numerical inversion of a simpler differential operator and a subsequent addition of a correction term. This new procedure is as fast as solving the equation without the surface average.     

Silica gel assisted reductive cyclization of 2-nitro-β-piperidinostyrenes,derived from 2-nitrotoluenes,to indoles

An efficient modification of the Leimgruber-Batcho method of indole synthesis has been devised that facilitates the synthesis of a variety of 2,3-unsubstituted indoles containing halogen, methoxy and benzyloxy groups, from 2-nitrotoluenes, in high yields. The modified method involves the condensation of 2-nitrotoluenes with tripiperidinomethane followed by the reductive cyclization of the intermediate 2-nitro-β-piperidinostyrenes with iron and acetic acid in refluxing toluene in the presence of silica gel (column chromatography grade, 60–200 mesh).     

The effect of implanted yttrium on the oxidation behaviour at high temperatures of a Fe-Cr-Al alloy containing zirconium

Summary The influence of implanted yttrium on the oxidation behaviour of a ferritic Fe-23Cr-5Al+0.2Zr alloy was studied between 1473 K and 1600 K under isothermal and thermal cycling conditions in oxygen and in air, respectively. The microstructure and morphology of the starting material as well as of the scales were studied by means of optical and scanning electron microscopy. The composition of the alloy and of the scales was determined using various X-ray techniques. The oxidation mechanism was studied at 1473 K using the two-stage oxidation method in ¹⁸O/¹⁶O atmospheres. The implanted yttrium was found to affect the scale growth rate and the oxidation mechanism as well as the scale morphology. No spalling of the scale under thermal cycling conditions occurred. The observed growth mechanism of the scales was related to their complex morphology. On leave from: Institute of Materials Science, Academy of Mining and Metallurgy, Krakow, Poland     

“Trimethyl lock” facilitated spirocyclizations: A structural analysis

A trimethyl lock was shown earlier to significantly facilitate certain cyclization reactions. Our renewed interests in such facile cyclization systems stemmed from their potential applications in the preparation of redox-, esterase-, and phosphatase-sensitive prodrugs. Furthermore, such systems have also been used for the development of redox-sensitive protecting groups for amines and alcohols. However, there is an undesirable spirocyclization reaction associated with certain trimethyl lock facilitated cyclization systems. In an effort to probe factors important for the controlling of the undesirable spirocyclization reaction, we undertook the X-ray crystallographic studies of the such trimethyl lock facilitated spirocyclization systems. The spirocyclization product was crystallized from ethyl acetate/hexane mixture (space group: P2₁/c,a=13.467(1),b=13.297(2),c=13.626(8) Å, =92.120(6)°. It was found that spirocyclization results in release of steric congestion caused by the trimethyl lock to a larger degree than the desired lactonization. However, this release of steric congestion itself is not enough to bring about the cyclization. A kinetically reactive nucleophile is also essential for the initiation of the spirocyclization reaction. This is consistent with the fact that such spirocyclization reactions require specific base catalysis.