Studies on thermal degradation of acrylonitrile–butadiene–styrene copolymer (ABS-Br) containing brominated flame retardant

The thermal degradation of acrylonitrile-butadiene-styrene copolymer (ABS-Br; 10 g) containing brominated flame retardant (Br: 9.59 wt.%) was carried out at 450 °C using a semi batch operation using two different temperature programs. The heating rate was found to affect the quality of the degradation oil and yield of products (liquid, gas and residue). Data on the effect of the temperature program on the accumulation of liquid products was presented. It was found that the majority of the bromine was concentrated in the carbon residue and while majority of the nitrogen accumulates in the liquid products irrespective of degradation mode. The use of a one step constant heating rate process (I) produced a higher liquid yield (39%), than a two step process (29%). Differences were also noted in the Br and N contained in the liquids produced by the two processes.     

Oxidative addition of different electrophiles with rhodium(I) carbonyl complexes of unsymmetrical phosphine–phosphine monoselenide ligands

Dimeric chlorobridge complex [Rh(CO)₂Cl]₂ reacts with two equivalents of a series of unsymmetrical phosphine–phosphine monoselenide ligands, Ph₂P(CH₂)_nP(Se)Ph₂ {n = 1( a ), 2( b ), 3( c ), 4( d )}to form chelate complex [Rh(CO)Cl(P∩Se)] ( 1a ) {P∩Se = η²‐(P,Se) coordinated} and non‐chelate complexes [Rh(CO)₂Cl(P～Se)] ( 1b–d ) {P～Se = η¹‐(P) coordinated}. The complexes 1 undergo oxidative addition reactions with different electrophiles such as CH₃I, C₂H₅I, C₆H₅CH₂Cl and I₂ to produce Rh(III) complexes of the type [Rh(COR)ClX(P∩Se)] {where R = ? C₂H₅ ( 2a ), X = I; R = ? CH₂C₆H₅ ( 3a ), X = Cl}, [Rh(CO)ClI₂(P∩Se)] ( 4a ), [Rh(CO)(COCH₃)ClI(P～Se)] ( 5b–d ), [Rh(CO)(COH₅)ClI‐(P～Se)] ( 6b–d ), [Rh(CO)(COCH₂C₆H₅)Cl₂(P～Se)] ( 7b–d ) and [Rh(CO)ClI₂(P～Se)] ( 8b–d ). The kinetic study of the oxidative addition (OA) reactions of the complexes 1 with CH₃I and C₂H₅I reveals a single stage kinetics. The rate of OA of the complexes varies with the length of the ligand backbone and follows the order 1a > 1b > 1c > 1d . The CH₃I reacts with the different complexes at a rate 10–100 times faster than the C₂H₅I. The catalytic activity of complexes 1b–d for carbonylation of methanol is evaluated and a higher turnover number (TON) is obtained compared with that of the well‐known commercial species [Rh(CO)₂I₂]^?. Copyright © 2006 John Wiley & Sons, Ltd.     

Dielectric friction and solvation dynamics: Novel results on relaxation in dipolar liquids

In this article we present a new, general but simple, microscopic expression for time-dependent solvation energy of an ion. This expression is surprisingly similar to the expression for the time-dependent dielectric friction on a moving ion. We show that both the Chandra-Bagchi and the Fried-Mukamel formulations of solvation dynamics can be easily derived from this expression. This expression leads to an almost perfect agreement of the theory with all the available computer simulation results. Second, we show here for the first time that the mobility of a light solute ion can significantly accelerate its own solvation, specially in the underdamped limit. The latter result is also in excellent agreement with the computer simulations.     

On the behaviour of small clusters near the spinodal decomposition

The canonical average of the Boltzmann factor of the interaction potential, as measured by a test particle, is shown to be equal to the inverse of the fraction of the average number of 1-particle Mayer clusters. The potential distribution theory is used to derive an analytic expression for a mean number of small clusters 1≤n<N, in anN-particle system) in the mean-field expression. Near the spinodal density, the average number of small clusters undergo a sharp change. Computation of pressure shows that only the first four clusters produce surprisingly good agreement with known pressure even beyond the spinodal density. Contribution No. 439 from the Solid State and Structural Chemistry Unit     

Parameter identification for stochastic diffusion equations with unknown boundary conditions

Stochastic diffusion equations with unknown boundary conditions are encountered in practice whenever the boundary is observed only through measurement errors. Parameter identification for such systems is studied in the present paper. The boundary condition is treated as an unknown parameter in a function space as an intermediate step in solving the identification problem.     

The mechanics and physics of thin film decohesion and its measurement

The intent of this review is to utilize the mechanics of thin films in order to define quantitative procedures for predicting interface decohesion motivated by residual stress. The emphasis is on the role of the interface debond energy, especially methods for measuring this parameter in an accurate and reliable manner. Experimental results for metal films on dielectric substrates are reviewed and possible mechanisms are discussed.     

Control limit policies for early detection of failure

This paper considers a class of Markov Decision problems subjects to partial observation. We develop a methodology for early detection of failure of systems that do not display symptoms of failure. We assume that the inspections used for detection are error prone and there is a fixed probability of not detecting the failure. The problem is studied as a non-stationary, finite horizon Markovian Decision Process with two states. We demonstrate that the optimal policy has a two region structure that intuition suggests. This characterization can be used to reduce the computational burden of finding the optimum inspection schedule. We also show that the form of the optimum policy remains unchanged for the unbounded horizon problem. Finally, we discuss a potential application of the model to medical diagnosis.     

Truncated harmonic oscillator and parasupersymmetric quantum mechanics

We discuss in detail the parasupersymmetric quantum mechanics of arbitrary order where the parasupersymmetry is between the normal bosons and those corresponding to the truncated harmonic oscillator. We show that even though the parasusy algebra is different from that of the usual parasusy quantum mechanics, still the consequences of the two are identical. We further show that the parasupersymmetric quantum mechanics of arbitrary orderp can also be rewritten in terms ofp supercharges (i.e. all of which obeyQ _i ² =0). However, the Hamiltonian cannot be expressed in a simple form in terms of thep supercharges except in a special case. A model of conformal parasupersymmetry is also discussed and it is shown that in this case, thep supercharges, thep conformal supercharges along with HamiltonianH, conformal generatorK and dilatation generatorD form a closed algebra.