Mechanism of the addition of alcohols to substituted phenylisothiocyanates : Electrical effects of the substituents on the reaction

The addition reaction of alcohols to substituted phenylisothiocyanates is found to be a second-order reaction. The reaction is catalysed by triethylamine. First-order rate constants of the addition reaction have been determined in excess of ethanol, for a number of substituted phenylisothiocyanates and the rate data give a satisfactory linear correlation with Hammett σ constants of groups. While the energies of activation vary randomly with substitution, the entropies of activation bear a linear relationship to the energies of activation. Infra-red spectra indicate that the thiourethanes which are the products of the addition reaction exist in the thioamide form. The most prominent resonance form which can satisfactorily explain both the kinetic and infrared data, has been suggested.

Low-temperature deformation behaviour of polycrystalline copper

Low-temperature plastic flow in copper was investigated by studying its tensile and creep deformation characteristics. The dependence of the flow stress on temperature and strain rate was used to evaluate the thermal activation energy while the activation area was derived from the change-in-stress creep experiments. A value of 0.6 eV was obtained for the total obstacle energy both in electrolytic and commerical copper. The activation areas in copper of three selected purities fell in the range 1200 to 100 b2. A forest intersection mechanism seems to control the temperature dependent part of the flow stress. The increase in the athermal component of the flow stress with impurity content in copper is attributed to a change in the dislocation density. The investigation also revealed that thermal activation of some attractive junctions also takes place during low-temperature creep. The model of attractive junction formation on a stress decrement during creep, yields a value of 45±10 ergs cm-2 for the stacking fault energy in copper.

Elastic behaviour of matter under very high pressures - Uniform compression

In order to study the elastic behaviour of matter when subjected to very large pressures, such as occur for example in the interior of the earth, and to provide an explanation for phenomena like earthquakes, it is essential to be able to calculate the values of the elastic constants of a substance under a state of large initial stress in terms of the elastic constants of a natural or stress-free state. An attempt has been made in this paper to derive expressions for these quantities for a substance of cubic symmetry on the basis of non-linear theory of elasticity and including up to cubic powers of the strain components in the strain energy function. A simple method of deriving them directly from the energy function itself has been indicated for any general case and the same has been applied to the case of hydrostatic compression. The notion of an effective elastic energy-the energy require to effect an infinitesimal deformation over a state of finite strain-has been introduced, the coefficients in this expression being the effective elastic constants. A separation of this effective energy function into normal co-ordinates has been given for the particular case of cubic symmetry and it has been pointed out, that when any of such coefficients in this normal form becomes negative, elastic instability will set in, with associated release of energy.

Studies in the polarographic and coulometric behaviour of aromatic nitro compounds—III. nitrosobenzene in ethanol, acetone and dioxan

The green nitrosobenzene monomer is reduced polarographically to phenylhydroxylamine in the pH range 4—9. Though this reduction is known to be a two-electron process, coulometry invariably gives a lower value of n because of the reaction of unreacted nitrosobenzene and the phenylhydroxylamine formed. The green monomer is attacked by mercury in acid medium. In alkaline medium, the green monomer undergoes a change that follows first-order kinetics with respect to nitrosobenzene. The rate of the transformation depends on the solvent. It decreases in the order acetone > ethanol > dioxan.

Effect of disorder on the exponent in the coherence region in high temperature superconductors

Effect of disorder on the electrical resistance near the superconducting transition temperature in the paracoherence region of high temperature YBa2CU3O7-delta (YBCO) thin film superconductor is reported. For this, c-axis oriented YBa2Cu3O7-delta thin films having superconducting transition width varying between 0.27 K and 6 K were deposited using laser ablation and high pressure oxygen sputtering techniques. Disorder in these films was further created by using 100 MeV oxygen and 200 MeV silver ions with varying fluences. It is observed that the critical exponent in the paracoherence region for films with high transition temperature and small transition width is in agreement with the theoretically predicted value (gamma = 1.33) and is not affected by disorder, while for films with lower transition temperature and larger transition width the value of exponent is much larger as compared to that theoretically predicted and it varies from sample to sample and usually changes with disorder induced by radiation. This difference in the behaviour of the exponent has been explained on the basis of differences in the strength of weak links and the transition between temperatures T. and T, is interpreted as a percolation like transition with disorder. (c) 2006 Elsevier B.V. All rights reserved.

Dielectric relaxation and electrical conductivity in Bi5NbO10 oxygen ion conductors prepared by a modified sol–gel process

Crystalline Bi5NbO10 nanoparticles have been achieved through a modified sol–gel process using a mixture of ethylenediamine and ethanolamine as a solvent. The Bi5NbO10 nanoparticles were characterized by X-ray diffraction (XRD), differential scanning calorimetry/thermogravimetry (DSC/TG), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and Raman spectroscopy. The results showed that well-dispersed 5–60 nm Bi5NbO10 nanoparticles were prepared through heat-treating the precursor at 650 °C and the high density pellets were obtained at temperatures lower than those commonly employed. The frequency and temperature dependence of the dielectric constant and the electrical conductivity of the Bi5NbO10 solid solutions were investigated in the 0.1 Hz to 1 MHz frequency range. Two distinct relaxation mechanisms were observed in the plots of dielectric loss and the imaginary part of impedance (Z″) versus frequency in the temperature range of 200–350 °C. The dielectric constant and the loss in the low frequency regime were electrode dependent. The ionic conductivity of Bi5NbO10 solid solutions at 700 °C is 2.86 Ω−1 m−1 which is in same order of magnitude for Y2O3-stabilized ZrO2 ceramics at same temperature. These results suggest that Bi5NbO10 is a promising material for an oxygen ion conductor.

Natural history and behaviour of the primitively eusocial wasp Ropalidia marginata (Hymenoptera: Vespidae): a comparison of the two sexes

We report the natural history and behaviour of the primitively eusocial wasp Ropalidia marginata with a special reference to the males. We found that just as nests of this species are found throughout the year, so are the males. Females spend all their life in their nests but males stay in their natal nests only for 1-12 days and leave to lead a nomadic life. Males maintained in the laboratory can live for up to 140 days. Like all eusocial hymenopteran males, R. marginata males also do not perform any colony maintenance activities. We found that males did not forage or feed larvae. Compared with females, males showed fewer dominance and subordinate behaviours and being solicited behaviour and more feeding self and soliciting behaviours. By comparing males with young females, we found similar differences, except that the males showed similar rates of feeding self and higher rates of subordinate behaviour.

Studies in the polarographic and coulometric behaviour of aromatic nitro compounds—III. nitrosobenzene in ethanol, acetone and dioxan

The green nitrosobenzene monomer is reduced polarographically to phenylhydroxylamine in the pH range 4—9. Though this reduction is known to be a two-electron process, coulometry invariably gives a lower value of n because of the reaction of unreacted nitrosobenzene and the phenylhydroxylamine formed. The green monomer is attacked by mercury in acid medium. In alkaline medium, the green monomer undergoes a change that follows first-order kinetics with respect to nitrosobenzene. The rate of the transformation depends on the solvent. It decreases in the order acetone > ethanol > dioxan.

Influence of drying on the liquid limit behaviour of a marine clay

The possible mechanisms of particle aggregation and reduction in liquid limit of the Cochin marine clay on drying are investigated. Mineralogical analysis showed the absence of halloysite in the marine specimen. Experimental results also ruled out the possibility of cementitious material being responsible for particle aggregation and reduction in clay plasticity on drying. The presence of calcium and magnesium as the predominant exchangeable ions and of a high pore salt concentration facilitates strong interparticle attraction and small particle separations; the latter leads to development of significant capillary stresses that permits an intimate contact of particles and growth of strong van der Waals' and Coulombic bonds.

Asymptotic behaviour and boundedness of linear systems with time varying coefficients

Motivated by developments in spacecraft dynamics, the asymptotic behaviour and boundedness of solution of a special class of time varying systems in which each term appears as the sum of a constant and a time varying part, are analysed in this paper. It is not possible to apply standard textbook results to such systems, which are originally in second order. Some of the existing results are reformulated. Four theorems which explore the relations between the asymptotic behaviour/boundedness of the constant coefficient system, obtained by equating the time varying terms to zero, to the corresponding behaviour of the time varying system, are developed. The results show the behaviour of the two systems to be intimately related, provided the solutions of the constant coefficient system approach zero are bounded for large values of time, and the time varying terms are suitably restrained. Two problems are tackled using these theorems.

Behaviour of Bi-adhesive Joints

The use of relatively low modulus adhesive at the ends of overlap in a bi-adhesive bondline of a bonded joint can reduce the stress concentration significantly and, therefore, potentially lead to higher strength of the joint. This study presents the two-dimensional and three-dimensional nonlinear (geometric and material) finite element analyses of adhesively bonded single lap joints having modulus-graded bondline under monotonic loading conditions. The adhesives were modelled as an elasto-plastic multi-linear material, while the substrates were regarded as both linear elastic and bi-linear elasto-plastic material. The computational simulations have been performed to investigate the bondline behaviour by studying the stress and strain distributions both at the mid-plane as well as at the interface of the bondline. It has been observed that the static strength is higher for joints with bi-adhesive bondlines compared to those with single adhesives in bondline. Higher joint strength has also been observed for optimum bi-adhesive bondline ratio through parametric studies. Effects of load level, and bondline thickness on stress distribution in the bi-adhesive bondline have also been studied. 3D analysis results reveal the existence of complex multi-axial stress/strain state at the ends of the overlap in the bondline which cannot be observed in 2D plane strain analysis. About 1/3rd of the width of the joint from the free edge in the width direction has 3D stress state, especially in the compliant adhesive of the bondline. Magnitudes of longitudinal and lateral stress/strain components are comparable to peel stress/strain components. It has also been analytically shown that the in-plane global stiffness of the joint remains unaffected by modulus gradation of the bondline adhesive. (C) Koninklijke Brill NV, Leiden, 2010.

Real-Time Simulation of Electrical Machines on FPGA Platform

This paper presents real-time simulation models of electrical machines on FPGA platform. Implementation of the real-time numerical integration methods with digital logic elements is discussed. Several numerical integrations are presented. A real-time simulation of DC machine is carried out on this FPGA platform and important transient results are presented. These results are compared to simulation results obtained through a commercial off-line simulation software

Polymer composite/nanocomposite processing and its effect on the electrical properties

One of the biggest challenges when considering polymer nanocomposites for electrical insulation applications lies in determining their electrical properties accurately, which in turn depend on several factors, primary being dispersion of particles in the polymer matrix. With this background, this paper reports an experimental study to understand the effects of different processing techniques on the dispersion of filler particles in the polymer matrix and their related effect on the dielectric properties of the composites. Polymer composite and nanocomposite samples for the study were prepared by mixing 10% by weight of commercially available TiO2 particles of two different sizes in epoxy using different processing methods. A considerable effect of the composite processing method could be seen in the dielectric properties of nanocomposites.