Am unexpected entry into the silver(I) chemistry of diphosphazane ligands: Crystal and molecular structures of [Ag{Ph2PN(Pr-i)PPh2}(CF3SO3)](2), [Ag{Ph2PN(Pr-i)PPh(OC6H3Me2-2,6)}(2)]PF6, and [Ag-3(mu-Cl)(2){Ph2PN(R)PPh2}(3)]PF6 (R = H, Pr-i)

Mononuclear, binuclear and trinuclear silver(l) complexes were obtained unexpectedly while probing the reactivity of diphosphazane ligands of the type X2PN(Pr-i)PXY towards the ruthenium-based precursor Ru(bipy)(2)Cl-2 center dot 2H(2)O, in the presence of a silver salt as a chloride scavenger. Subsequently, the reactions of AgX [X = Cl, NO3 or CF3SO3] with Ph2PN(R)PPh(Y) [R = H, Y = Ph; R = Pr-i, Y = Ph or OC6H3Me2-2,6] in a 1: 1 or 1:2 molar ratio have been investigated. Mononuclear or binuclear Ag(I) complexes containing either chelating or bridging diphosphazane ligands are obtained. Trinuclear silver(l) complexes are accessible by the treatment of diphosphazane ligands, Ph2PN(R)PPh2 [R = H, Pr-i] with AgCl using piperidine as the solvent. In the presence of a suitable chloride donor species, the mononuclear and binuclear complexes of Ph2PN(Pr-i)PPh2 are transformed slowly to the trinuclear complex [Ag-3(mu-Cl)(2){Ph2PN(Pr-i)PPh2}(3)]X, over a period 20 h. The structures of representative complexes have been confirmed by X-ray crystallography and the salient structural features are discussed

Adhesively-bonded Patch Repair with Composites

Adhesively-bonded composite patch repairs over cracked or corrosion-damaged metallic aircraft structures have shown great promise for extending life of ageing structures. This study presents the numerical investigation into the interface behaviour of adhesively-bonded cracked aluminum alloy substrate patched with fibre-reinforced composite material. The adhesive is modelled as an elasto-plastic bilinear material to characterise the debond behaviour, while the defective substrate is regarded as linear elastic continuum. Two typical patch shapes were selected based on information available in the literature. Geometric and material nonlinear analyses for square and octagonal patches were performed to capture peel and shear stresses developed between the substrate and the patch to examine the possibility of interface delamination/debonding. Parametric studies on adhesive thickness and patch thickness were carried out to predict their infuence on damage tolerance of repaired structures.

Time Scale Separated Nonlinear Partial Integrated Guidance and Control of Interceptors in the Terminal Phase

The paper proposes a time scale separated partial integrated guidance and control of an interceptor for engaging high speed targets in the terminal phase. In this two loop design, the outer loop is an optimal control formulation based on nonlinear model predictive spread control philosophies. It gives the commanded pitch and yaw rates whereas necessary roll-rate command is generated from a roll-stabilization loop. The inner loop tracks the outer loop commands using the dynamicinversion philosophy. However, unlike conventional designs, in both the loops the Six degree of freedom (Six-DOF) interceptor model is used directly. This intelligent manipulation preserves the inherent time scale separation property between the translational and rotational dynamics, and hence overcomes the deficiency of current IGC designs, while preserving its benefits. Six-DOF simulation studies have been carried out accounting for three dimensional engagement geometry. Different comparison studies were also conducted to measure the performance of the algorithm.

Nonlinear Sliding Mode Control Design for an Air-breathing Engine with State Estimation

A modern system theory based nonlinear control design is discussed in this paper for successful operation of an air-breathing engine operating at supersonic speed. The primary objective of the control design of such an air-breathing engine is to ensure that the engine dynamically produces the thrust that tracks a commanded value of thrust as closely as possible by regulating the fuel flow to the combustion system. However, since the engine operates in the supersonic range, an important secondary objective is to manage the shock wave configuration in the intake section of the engine which is manipulated by varying the throat area of the nozzle. A nonlinear sliding mode control technique has been successfully used to achieve both of the above objectives. In this problem, since the process is faster than the actuators, independent control designs are also carried out for the actuators as well to assure the satisfactory performance of the system. Moreover, to filter out the sensor and process noises and to estimate the states for making the control design operate based on output feedback, an Extended Kalman Filter based state estimation design is also carried out. The promising simulation results suggest that the proposed control design approach is quite successful in obtaining robust performance of the air-breathing engine.

Study of the electronic structures of high Tc cuprate superconductors by electron energy loss and secondary electron emission spectroscopies

Energy loss spectra of superconducting YBa2Cu3O6.9' Bi1.5Pb0.5Ca2.5Sr1.5Cu3O10+δ and Tl2CaBa2Cu3O8 obtained at primary electron energies in the 170–310 eV range show features reflecting the commonalities in their electronic structures. The relative intensity of the plasmon peak shows a marked drop across the transition temperature. Secondary electron emission spectra of the cuprates also reveal some features of the electronic structure.

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.

Novel organic porous solids with channel and layered structures from 1,3,5-triazine-2,4,6-triaminehexaacetic acid and its calcium salt

Single crystals of a symmetrically substituted molecule, 1,3,5-triazine-2,4,6-triaminehexaacetic acid, (TTHA) and its Ca2+ salt have been synthesized, the analysis of which reveals the existence of novel channel type cavities and helical packing organizations in the crystals.

Solution cation-binding properties of segmented polyethylene oxide-A C-13 NMR spectroscopic study

Two segmented polyethylene oxides, SPEO-3 and SPEO-4, were prepared using a novel transetherification methodology. Their structures were confirmed by H-1 and C-13 NMR spectroscopy. The complexation of these SPEO's with alkali-metal ions in solution was investigated by C-13 NMR spectroscopy. The mole-fraction method was used to determine the complexation ratio of SPEO with LIClO4 at 25 degrees C, which showed that these formed 1:1 (polymer repeat unit/salt) complexes. The association constant, K, for the complex formation was calculated from the variation of the chemical shift values with salt concentration, using a standard nonlinear least-square fitting procedure. The maximum change in chemical shift (Delta delta) and the K values suggest that both SPEO-3 and SPEO-4 formed stronger complexes with lithium salts than with sodium salts. Unexpectedly, the K values were found to be different, when the variation of delta of different carbons was used in the fitting procedure. This suggests that several possible complexed species may be in equilibrium with the uncomplexed one. Structurally similar model compounds were also prepared and their complexation studies indicated that all of them also formed 1:1 complexes with Li salts. Interestingly, it was observed that the polymers gave higher K values suggesting the formation of more stable complexes in polymers when compared to the model analogues. (C) 2000 John Wiley & Sons, Inc.

Evolution and decay of cylindrical and spherical nonlinear acoustic waves generated by a sinusoidal source

The present work gives a comprehensive numerical study of the evolution and decay of cylindrical and spherical nonlinear acoustic waves generated by a sinusoidal source. Using pseudospectral and predictor–corrector implicit finite difference methods, we first reproduced the known analytic results of the plane harmonic problem to a high degree of accuracy. The non-planar harmonic problems, for which the amplitude decay is faster than that for the planar case, are then treated. The results are correlated with the known asymptotic results of Scott (1981) and Enflo (1985). The constant in the old-age formula for the cylindrical canonical problem is found to be 1.85 which is rather close to 2, ‘estimated’ analytically by Enflo. The old-age solutions exhibiting strict symmetry about the maximum are recovered; these provide an excellent analytic check on the numerical solutions. The evolution of the waves for different source geometries is depicted graphically.

Trajectory controllability of nonlinear integro-differential system

A stronger concept of complete (exact) controllability which we call Trajectory Controllability is introduced in this paper. We study the Trajectory Controllability of an abstract nonlinear integro-differential system in the finite and infinite dimensional space setting. (C) 2010 The Franklin Institute. Published by Elsevier Ltd. All rights reserved.

New computational approaches for wrinkled and slack membranes

The static response of thin, wrinkled membranes is studied using both a tension field approximation based on plane stress conditions and a 3D nonlinear elasticityformulation, discretized through 8-noded Cosserat point elements. While the tension field approach only obtains the wrinkled/slack regions and at best a measure of the extent of wrinkliness, the 3D elasticity solution provides, in principle, the deformed shape of a wrinkled/slack membrane. However, since membranes barely resist compression, the discretized and linearized system equations via both the approaches are ill-conditioned and solutions could thus be sensitive to discretizations errors as well as other sources of noises/imperfections. We propose a regularized, pseudo-dynamical recursion scheme that provides a sequence of updates, which are almost insensitive to theregularizing term as well as the time step size used for integrating the pseudo-dynamical form. This is borne out through several numerical examples wherein the relative performance of the proposed recursion scheme vis-a-vis a regularized Newton strategy is compared. The pseudo-time marching strategy, when implemented using 3D Cosserat point elements, also provides a computationally cheaper, numerically accurate and simpler alternative to that using geometrically exact shell theories for computing large deformations of membranes in the presence of wrinkles. (C) 2010 Elsevier Ltd. All rights reserved.