Unexpected products of the allyldiethylamine hydroformylation homogeneously catalyzed by rhodium complexes

Attempts to carry out the hydroformylation of allyldiethylamine homogeneously catalyzed by rhodium complexes led to unexpected formation of N,N,N,N-tetraethyl-1,4-diaminobutane and 4-(diethylamino)-1-butanole as final products. The role of the catalyst on the product formation and the reaction mechanism are briefly discussed.     

Transition layer thickness in microlaminar deposits

A theoretical analysis was carried out on the change of composition of a deposit obtained by the dual pulse method of forming laminar metal foils, with transition from a low current to a high current pulse, both in the galvanostatic and the potentiostatic mode of deposition. It was shown that the existence of a transition layer of varying composition between a layer of pure metal 1 and a layer consisting predominantly of the metal 2 is an inherent consequence of the electrochemical process, primarily because of an induction period in the concentration polarization with respect to ions of metal 1. The importance of this transition layer increases as the thickness of the layers of the two metals decreases. Eventually this limits the possibility of obtaining a sharp boundary between the layers, when the nanometre region of layer thickness is reached. Equations are given for calculating the deposition current density and rate of stirring of the electrolyte which provide a deposit of a required level of metal 1 in the layer of metal 2, as well as a required sharpness of the boundary between two layers. Experimental proof of the correctness of the analysis was sought. It was found that significant changes in the properties of the deposit occur in the same range of layer thickness in which the transition of the composition takes places.Nomenclature _c,1, a_c,2 transfer coefficient of the cathodic processes - C interfacial capacitance - C₁, C₂ concentration of the ions of metals 1 and 2 at the interface r - C ₀ ¹ , C ₀ ² concentration of ions of the metals 1 and 2 in solution - D ₁ diffusion coefficient for the diffusion of ions of the metal 1 - E _r,1,E _r,2 reversible potentials of metals 1 and 2, respectively - F the Faraday constant - J ₀ ¹ ,J ₀ ² exchange current density of the metals 1 and 2, respectively - M ₁,M ₂ atomic weights of the metals 1 and 2, respectively - kinematic viscosity of solution - ₁, ₂ densities of the metals 1 and 2 respectively - rotation speed (r.p.s.) - z number of electrons exchanged in the deposition process This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday, and in recognition of his outstanding contribution to electrochemistry.     

Synthesis of ZnO-based varistor precursor powders by means of the reaction spray process

High-purity, fine-grained oxide ceramic powders that are commonly used for ZnO-based varistors were synthesized by means of the reaction spray process. Processing steps included formation of the solutions of zinc nitrate and/or certain metal additives and spraying of the solution into a heated reaction column using a two-phase nozzle. After water evaporation from the droplets, the precursor salts were decomposed at elevated temperatures (up to 1473 K) in order to obtain homogeneous oxide powders with complex compositions corresponding to the final multicomponent varistor system. The decomposition behaviour of the precursors, as well as the characteristics of the resulting powders: crystallinity, phase composition, particle shape, morphology and particle-size distribution, were examined. It was shown that the characteristics of the reaction spray-derived powders can be controlled by adjusting the system and the solutions parameters.     

Evaluation of thermal conductivity from temperature profiles

A new dynamic technique for the measurement of thermal conductivity is being developed at IMGC. The experiment consists in bringing the specimen to high temperatures with a current pulse and in measuring the temperature profiles during the free cooling period. Different techniques can be used to extract the information on thermal conductivity from the profiles. The numerical computation of thermal conductivity from the experimental temperature profiles in absolute space is possible, but it is difficult and cumbersome because one must know and take into the account the exact position of the infinitesimal elements of the specimen in different profiles. Computations in tube-space (a fictitious space where no thermal expansion occurs) are simpler and lead to less complex numerical computations. Complementary techniques to evaluate thermal conductivity as a function of temperature or at constant temperature are presented with a discussion of advantages and disadvantages of each method. Computer simulations have tested the precision of the complex software. Numerically generated temperature profiles from known thermophysical properties have been obtained and thermal conductivity has been recomputed from the profiles. The relative difference using different computational approaches and different fitting functions is always less than 0.1%.Paper presented at the Third Workshop on Subsecond Thermophysics, September 17–18, 1992, Graz, Austria.     

Radiance temperatures (at 658 and 898 nm) of niobium at its melting point

Radiance temperatures (at 658 and 898 nm) of niobium at its melting point were measured by a pulse-heating technique. A current pulse of subsecond duration was imparted to a niobium strip and the initial part of the melting plateau was measured by high-speed pyrometry. Experiments were performed with two techniques and the results do not indicate any dependence of radiance temperature (at the melting point) on initial surface or system operational conditions. The average radiance temperature at the melting point of niobium is 2420 K at 658 nm and 2288 K at 898 nm, with a standard deviation of 0.4 K at 658 nm and 0.3–0.6 K at 898 nm (depending on the technique used). The total uncertainty in radiance temperature is estimated to be not more than ±6 K. The results are in good agreement with earlier measurements at the National Institute of Standards and Technology (USA) and confirm that both radiance temperature and normal spectral emissivity (of niobium at its melting point) decrease with increasing wavelength in the region 500–900 nm.Paper presented at the Third Workshop on Subsecond Thermophysics, September 17–18, 1992, Graz, Austria.     

Influence of Particle Size Distribution,Moisture Content,and Particle Shape on the Flow Properties of Bulk Solids

Abstract

There has been a great deal of research on characterising bulk solids. However, some of the characteristics, particularly the time‐dependent and random changes of properties, still remain insufficiently understood. The focus of this article is to study the influence of particle size, size distribution, moisture content, and particle shape on the unconfined yield strength of bulk solids. We present some interesting results about the influence of the particle size distribution on the unconfined yield strength of a bulk solid and a new method for determining the influence of particle shape on the unconfined yield strength of a bulk solid, which was made possible by the design and use of a novel attritor.     

An improved two-party identity-based authenticated key agreement protocol using pairings

Two-party authenticated key agreement protocols using pairings have gained much attention in the cryptographic community. Several protocols of this type where proposed in the past of which many were found to be flawed. This resulted in attacks or the inability to conform to security attributes. In this paper, we propose an efficient identity-based authenticated key agreement protocol employing pairings which employs a variant of a signature scheme and conforms to security attributes. Additionally, existing competitive and the proposed protocol are compared regarding efficiency and security. The criteria for efficiency are defined in this paper, whereas the criteria for security are defined by the fulfilment of security attributes from literature.     

Analysis for a class of singularly perturbed hybrid systems via averaging

A class of singularly perturbed hybrid dynamical systems is analyzed. The fast states are restricted to a compact set a priori. The continuous-time boundary layer dynamics produce solutions that are assumed to generate a well-defined average vector field for the slow dynamics. This average, the projection of the jump map in the direction of the slow states, and flow and jump sets from the original dynamics define the reduced, or average, hybrid dynamical system. Assumptions about the average system lead to conclusions about the original, higher-dimensional system. For example, forward pre-completeness for the average system leads to a result on closeness of solutions between the original and average system on compact time domains. In addition, global asymptotic stability for the average system implies semiglobal, practical asymptotic stability for the original system. We give examples to illustrate the averaging concept and to relate it to classical singular perturbation results as well as to other singular perturbation results that have appeared recently for hybrid systems. We also use an example to show that our results can be used as an analysis tool to design hybrid feedbacks for continuous-time plants implemented by fast but continuous actuators.     

Supervisory control synthesis of discrete-event systems using a coordination scheme

Supervisory control of distributed DES with a global specification and local supervisors is a difficult problem. For global specifications, the equivalent conditions for local control synthesis to equal global control synthesis may not be met. This paper formulates and solves a control synthesis problem for a generator with a global specification and with a combination of a coordinator and local controllers. Conditional controllability is proven to be an equivalent condition for the existence of such a coordinated controller. A procedure to compute the least restrictive solution within our coordination control architecture is provided and conditions under which the result coincides with the supremal controllable sublanguage are stated.