Rare earth exchanged (Ce3+, La3+ and RE3+) H-Y zeolites as solid acid catalysts for the synthesis of linear alkyl benzenes

Rare earth exchanged H–Y zeolites were prepared by simple ion exchange methods at 353 K and have been characterized using different physicochemical techniques. A strong peak around 58 ppm in the 27Al{1H} MAS NMR spectra of these zeolites suggests a tetrahedral coordination for the framework aluminium. Small peak at or near 0 ppm is due to hexa-coordinated extra-framework aluminium and a shoulder peak near 30 ppm is a penta-coordinated aluminium species; [Al(OH)4]−. The vapor-phase benzene alkylation with 1-decene and 1-dodecene was investigated with these catalytic systems. Under the reaction conditions of 448 K, benzene/olefin molar ratio of 20 and time on stream 3 h, the most efficient catalyst was CeH–Y which showed more than 70% of olefin conversion with 48.5% 2-phenyldecane and 46.8%, 2-phenyldodecane selectivities with 1-decene and 1-dodecene respectively.

Direct Synthesis of Terminally ``Clickable'' Linear and Hyperbranched Polyesters

1,3-Dipolar cycloaddition of an organic azide and an acetylenic unit,often referred to as the ``click reaction'', has become an important ligation tool both in the context of materials chemistry and biology. Thus, development of simple approaches to directly generate polymers that bear either an azide or an alkyne unit has gained considerable importance. We describe here a straightforward approach to directly prepare linear and hyperbranched polyesters that carry terminal propargyl groups. To achieve the former, we designed an AB-type monomer that carries a hydroxyl group and a propargyl ester, which upon self-condensation under standard transesterification conditions yielded a polyester that carries a single propargyl group at one of its chain-ends. Similarly, an AB(2) type monomer that carries one hydroxyl group and two propargyl ester groups, when polymerized under the same conditions yielded a hyperbranched polymer with numerous clickable'' propargyl groups at its molecular periphery. These propargyl groups can be readily clicked with different organic azides, such as benzyl azide, omega-azido heptaethyleneglycol monomethylether or 9-azidomethyl anthracene. When an anthracene chromophore is clicked, the molecular weight of the linear polyester could be readily estimated using both UV-visible and fluorescence spectroscopic measurements. Furthermore, the reactive propargyl end group could also provide an opportunity to prepare block copolymers in the case of linear polyesters and to generate nanodimensional scaffolds to anchor variety of functional units, in the case of the hyperbranched polymer. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3200-3208, 2010.

New type of high field electrooptic response in nematics

We have made concurrent measurements of ionic current and optical transmission between crossed polarisers on several nematics with positive dielectric anisotropy under the action of applied low frequency (< 1KHz) square wave voltages. When the field E is low, the measured current is linear in E and there is no electrooptic response. Beyond some value of the field (E(0)similar to 100 esu), the current becomes independent of the field (phenomenon of limiting current). Further an electrooptic signal is measured at twice the frequency of the applied voltage, which exhibits a peak as a function of the field. The width of the peak is 3 to 4 times the value of E-0, and the signal level at the peak decreases as the frequency is increased. These measurements have been made on three highly polar compounds with cyano end groups. Careful observations do not show any evidence of electrohydrodynamic instabilities in the sample. It is argued that the observations can be understood if at the onset of the phenomenon of the limiting current, a strong electric field gradient is established near one of the electrodes due to the sweeping of an ionic species with high mobility. The field gradient produces a flexoelectric deformation of the director field, which in turn gives rise to the electrooptic effect. At higher fields, the stabilising dielectric torque takes over to suppress this instability.

Nonlinear intrinsic instability of solid propellant combustion including gas-phase thermal inertia

The problem of homogeneous solid propellant combustion instability is studied with a one-dimensional flame model, including the effects of gas-phase thermal inertia and nonlinearity. Computational results presented in this paper show nonlinear instabilities inherent in the equations, due to which periodic burning is found even under steady ambient conditions such as pressure. The stability boundary is obtained in terms of Denison-Baum parameters. It is found that inclusion of gas-phase thermal inertia stabilizes the combustion. Also, the effect of a distributed heat release in the gas phase, compared to the flame sheet model, is to destabilize the burning. Direct calculations for finite amplitude pressure disturbances show that two distinct resonant modes exist, the first one near the natural frequency as obtained from intrinsic instability analysis and a second mode occurring at a much higher driving frequency. It is found that er rn in the low frequency region, the response of the propellant is significantly affected by the specific type of gas-phase chemical heat-release model employed. Examination of frequency response function reveals that the role of gas-phase thermal inertia is to stabilize the burning near the first resonant mode. Calculations made for different amplitudes of driving pressure show that the mean burning rate decreases with increasing amplitude. Also, with an increase in the driving amplitude, higher harmonics are generated in the burning rate.

On the momentum balance in linear-combination models for the transition zone

The momentum balance of the linear-combination integral model for the transition zone is investigated for constant pressure flows. The imbalance is found to be small enough to be negligible for all practical purposes. [S0889-504X(00)00703-0].

On the L2 stability of linear multidimensional time varying systems

This paper analyzes the L2 stability of solutions of systems with time-varying coefficients of the form [A + C(t)]x′ = [B + D(t)]x + u, where A, B, C, D are matrices. Following proof of a lemma, the main result is derived, according to which the system is L2 stable if the eigenvalues of the coefficient matrices are related in a simple way. A corollary of the theorem dealing with small periodic perturbations of constant coefficient systems is then proved. The paper concludes with two illustrative examples, both of which deal with the attitude dynamics of a rigid, axisymmetric, spinning satellite in an eccentric orbit, subject to gravity gradient torques.

Bounded-input/bounded-output stability of linear multidimensional time- varying systems

The present study of the stability of systems governed by a linear multidimensional time-varying equation, which are encountered in spacecraft dynamics, economics, demographics, and biological systems, gives attention the lemma dealing with L(inf) stability of an integral equation that results from the differential equation of the system under consideration. Using the proof of this lemma, the main result on L(inf) stability is derived according; a corollary of the theorem deals with constant coefficient systems perturbed by small periodic terms. (O.C.)

Adhesion-Induced Instability in Asperities

Adhesive forces between two approaching asperities will deform the asperities, and under certain conditions this will result in a sudden runaway deformations leading to a jump-to-contact instability. We present finite element-based numerical studies on adhesion-induced deformation and instability in asperities. We consider the adhesive force acting on an asperity, when it is brought near a rigid half-space, due to van der Waals interaction between the asperity and the half-space. The adhesive force is considered to be distributed over the volume of the asperity (body force), thus resulting in more realistic simulations for the length scales considered. Iteration scheme based on a ``residual stress update'' algorithm is used to capture the effect of deformation on the adhesion force, and thereby the equilibrium configuration and the corresponding force. The numerical results are compared with the previous approximate analytical solutions for adhesion force, deformation of the asperity and adhesion-induced mechanical instability (jump-to-contact). It is observed that the instability can occur at separations much higher,and could possibly explain the higher value of instability separation observed in experiments. The stresses in asperities, particularly in case of small ones, are found to be high enough to cause yielding before jump -to-contact. The effect of roughness is considered by modeling a spherical protrusion on the hemispherical asperity.This small-scale roughness at the tip of the asperities is found to control the deformation behavior at small separations, and hence are important in determining the friction and wear due to the jump-to-contact instability.

Asynchronous behaviour in some three-atom linear concerted radical-exchange reactions

A few simple three-atom thermoneutral radical exchange reactions (i.e. A + BC --> AB + C) are examined by ab initio SCF methods. Emphasis is laid on the detailed analysis of density matrices rather than on energetics. Results reveal that the sum of the bond orders of the breaking and forming bonds is not conserved to unity, due to development of free valence on the migrating atom 'B' in the transition state. Bond orders, free valence and spin densities on the atoms are calculated. The present analysis shows that the bond-cleavage process is always more advanced than the bond-formation process in the transition state. Further analysis shows a development of the negative spin density on the migrating atom 'B' in the transition state. The depletion of the alpha-spin density on the radical site "A" in the reactant during the reaction lags behind the growth of the alpha-spin density on the terminal atom "C" of the reactant bond, 'B-C' in the transition state. But all these processes are completed simultaneously at the end of the reaction. Hence, the reactions are asynchronous but kinetically concerted in most cases.

Modified linear prediction method for directions of arrival estimation of narrow-band plane waves

A modified linear prediction (MLP) method is proposed in which the reference sensor is optimally located on the extended line of the array. The criterion of optimality is the minimization of the prediction error power, where the prediction error is defined as the difference between the reference sensor and the weighted array outputs. It is shown that the L2-norm of the least-squares array weights attains a minimum value for the optimum spacing of the reference sensor, subject to some soft constraint on signal-to-noise ratio (SNR). How this minimum norm property can be used for finding the optimum spacing of the reference sensor is described. The performance of the MLP method is studied and compared with that of the linear prediction (LP) method using resolution, detection bias, and variance as the performance measures. The study reveals that the MLP method performs much better than the LP technique.

Actuator fault detection and isolation in linear systems

A scheme for the detection and isolation of actuator faults in linear systems is proposed. A bank of unknown input observers is constructed to generate residual signals which will deviate in characteristic ways in the presence of actuator faults. Residual signals are unaffected by the unknown inputs acting on the system and this decreases the false alarm and miss probabilities. The results are illustrated through a simulation study of actuator fault detection and isolation in a pilot plant doubleeffect evaporator.

A note on the observed anisotropy in linear compressibility and thermal expansion of quasicrystals

The linear compressibility and the thermal expansion of Al-Fe and Al-Mn quasicrystals have been reported to be anisotropic. The authors suggest that the observed anisotropy in these properties could be due to the presence of decagonal quasicrystals rather than icosahedral quasicrystals.

A systolic evaluator for linear, quadratic, and cubic expressions

High-speed evaluation of a large number of linear, quadratic, and cubic expressions is very important for the modeling and real-time display of objects in computer graphics. Using VLSI techniques, chips called pixel planes have actually been built by H. Fuchs and his group to evaluate linear expressions. In this paper, we describe a topological variant of Fuchs' pixel planes which can evaluate linear, quadratic, cubic, and higher-order polynomials. In our design, we make use of local interconnections only, i.e., interconnections between neighboring processing cells. This leads to the concept of tiling the processing cells for VLSI implementation.

Capillary-gravity waves against a corrugated vertical cliff

An analysis involving a transformation of the velocity potential and a Fourier Sine Transform technique is described to study the effect of surface tension on incoming surface waves against a vertical cliff with a periodic wall perturbation. Known results are recovered as particular cases of the general problem considered. An analytical expression is derived for the surface elevation, at far distances from the shore-line, by using Watson's lemma and a representative table of numerical values of the coefficients of the resulting asymptotic expansion is also presented.