Variations in the copper(I)-copper(I) distances in multinuclear clusters with identical coordination geometries. Short metal-metal contacts induced by oligomerization

Factors contributing to the variations in the Cu(I)-Cu(I) distances in two clusters with identical ligand and coordination geometries have been analyzed. While the hexamer, 4, exhibits metal-metal distances in the range 2.81-3.25 Angstrom, shorter contacts are found in the corresponding tetramer, 3 (2.60-2.77 Angstrom). EHT calculations reveal relatively little attractive interactions in the corresponding Cu-4(4+) and Cu-6(6+) cores. Introduction of the ligands lowers the reduced overlap populations between the metals further. MNDO calculations with model electrophiles have been carried out to determine the bite angle requirements of the ligands. These are satisfactorily met in the structures of both 3 and 4. The key geometric feature distinguishing 3 and 4 is the Cu-S-Cu angle involving the bridging S- unit. In 4, the corresponding angles are about 90 degrees, while the values in 3 are smaller (70-73 degrees). Wider angles are computed to be energetically favored and are characterized by an open three-center bond and a long Cu-Cu distance. The bridging angles are suggested to be primarily constrained by the mode of oligomerization. Implications of these results for the stability and reactivity of these clusters and for short metal-metal distances in d(10) systems in general are discussed.

Mechanistic studies on the effect of ferrocene bonding agents in composite solid propellents

Five compounds, viz. 1,1'-ferrocenediyldiethylidene bis(thiocarbonohydrazide) (DAFT), 1,1-diacetylferrocene disemicarbazone (DAFS), 1,1-diacetylferrocenebenzoyl hydrazone (FDBAH), 1,1-diacetylferrocene-p-nitrobenzoyl hydrazone (FDNBAH), and p-toluenesulfonic acid 1,1'-ferrocenediyldiethylidene dihydrazide (TFDD) were found to be bonding agents as well as burning-rate modifiers for the ammonium perchlorate + hydroxy-terminated polybutadiene system. The tensile strength and percentage elongation significantly increased in the presence of these bonding agents (except FDBAH). The bonding agents generally did not adversely affect the slurry viscosity during processing. The bonding sites were located by infrared spectroscopy, supported by determination of the dissolution kinetics of the bonding agents and scanning electron microscopy. The bonding agents did not undergo any side-reactions with the curing agents.

Mechanistic studies on the effect of ferrocene bonding agents in composite solid propellents

Five compounds, viz. 1,1'-ferrocenediyldiethylidene bis(thiocarbonohydrazide) (DAFT), 1,1-diacetylferrocene disemicarbazone (DAFS), 1,1-diacetylferrocenebenzoyl hydrazone (FDBAH), 1,1-diacetylferrocene-p-nitrobenzoyl hydrazone (FDNBAH), and p-tolenesulfonic acid, 1,1'-ferrocenediyldiethylidene dihydrazide (TFDD) were found to be bonding agents as well as burning-rate modifiers for the ammonium perchlorate + hydroxy-terminated polybutadiene system. The tensile strength and percentage elongation significantly increased in the presence of these bonding agents (except FDBAH). The bonding agents generally did not adversely affect the slurry viscosity during processing. The bonding sites were located by infrared spectroscopy, supported by determination of the dissolution kinetics of the bonding agents and scanning electron microscopy. The bonding agents did not undergo any side-reactions with the curing agents.

Composite material and piezoelectric coefficient uncertainty effects on structural health monitoring using feedback control gains as damage indicators

This article addresses uncertainty effect on the health monitoring of a smart structure using control gain shifts as damage indicators. A finite element model of the smart composite plate with surface-bonded piezoelectric sensors and actuators is formulated using first-order shear deformation theory and a matrix crack model is integrated into the finite element model. A constant gain velocity/position feedback control algorithm is used to provide active damping to the structure. Numerical results show that the response of the structure is changed due to matrix cracks and this change can be compensated by actively tuning the feedback controller. This change in control gain can be used as a damage indicator for structural health monitoring. Monte Carlo simulation is conducted to study the effect of material uncertainty on the damage indicator by considering composite material properties and piezoelectric coefficients as independent random variables. It is found that the change in position feedback control gain is a robust damage indicator.

Why is there a short-term increase in global precipitation in response to diminished CO2 forcing?

Recently, it was found that a reduction in atmospheric CO2 concentration leads to a temporary increase in global precipitation. We use the Hadley Center coupled atmosphere-ocean model, HadCM3L, to demonstrate that this precipitation increase is a consequence of precipitation sensitivity to changes in atmospheric CO2 concentrations through fast tropospheric adjustment processes. Slow ocean cooling explains the longer-term decrease in precipitation. Increased CO2 tends to suppress evaporation/precipitation whereas increased temperatures tend to increase evaporation/precipitation. When the enhanced CO2 forcing is removed, global precipitation increases temporarily, but this increase is not observed when a similar negative radiative forcing is applied as a reduction of solar intensity. Therefore, transient precipitation increase following a reduction in CO2-radiative forcing is a consequence of the specific character of CO2 forcing and is not a general feature associated with decreases in radiative forcing. Citation: Cao, L., G. Bala, and K. Caldeira (2011), Why is there a short-term increase in global precipitation in response to diminished CO2 forcing?, Geophys. Res. Lett., 38, L06703, doi:10.1029/2011GL046713.

Ionic Polymer Metal Composite Flapping Actuator Mimicking Dragonflies

In this study, variational principle is used for dynamic modeling of an Ionic Polymer Metal Composite (IPMC) flapping wing. The IPMC is an Electro-active Polymer (EAP) which is emerging as a useful smart material for `artificial muscle' applications. Dynamic characteristics of IPMC flapping wings having the same size as the actual wings of three different dragonfly species Aeshna Multicolor, Anax Parthenope Julius and Sympetrum Frequens are analyzed using numerical simulations. An unsteady aerodynamic model is used to obtain the aerodynamic forces. A comparative study of the performances of three IPMC flapping wings is conducted. Among the three species, it is found that thrust force produced by the IPMC flapping wing of the same size as Anax Parthenope Julius wing is maximum. Lift force produced by the IPMC wing of the same size as Sympetrum Frequens wing is maximum and the wing is suitable for low speed flight. The numerical results in this paper show that dragonfly inspired IPMC flapping wings are a viable contender for insect scale flapping wing micro air vehicles.

Nonlinear static and dynamic damped response of a composite rectangular plate resting on a two-parameter elastic foundation

Nonlinear static and dynamic response analyses of a clamped. rectangular composite plate resting on a two-parameter elastic foundation have been studied using von Karman's relations. Incorporating the material damping, the governing coupled, nonlinear partial differential equations are obtained for the plate under step pressure pulse load excitation. These equations have been solved by a one-term solution and by applying Galerkin's technique to the deflection equation. This yields an ordinary nonlinear differential equation in time. The nonlinear static solution is obtained by neglecting the time-dependent variables. Thc nonlinear dynamic damped response is obtained by applying the ultraspherical polynomial approximation (UPA) technique. The influences of foundation modulus, shear modulus, orthotropy, etc. upon the nonlinear static and dynamic responses have been presented.

Modeling of a reacting nanofilm on a composite substrate

This article provides a detailed computational analysis of the reaction of dense nanofilms and the heat transfer characteristics on a composite substrate. Although traditional energetic compounds based on organic materials have similar energy per unit weight, non-organic material in nanofilm configuration offers much higher energy density and higher flame speed. The reaction of a multilayer thin film of aluminum and copper oxide has been studied by varying the substrate material and thicknesses. The numerical analysis of the thermal transport of the reacting film deposited on the substrate combined a hybrid approach in which a traditional two-dimensional black box theory was used in conjunction with the sandwich model to estimate the appropriate heat flux on the substrate accounting for the heat loss to the surroundings. A procedure to estimate this heat flux using stoichiometric calculations is provided. This work highlights two important findings. One is that there is very little difference in the temperature profiles between a single substrate of silica and a composite substrate of silicon silica. Secondly, with increase in substrate thickness, the quenching effect is progressively diminished at a given speed. These findings show that the composite substrate is effective and that the average speed and quenching of flames depend on the thickness of the silica substrate, and can be controlled by a careful choice of the substrate configuration. (C) 2011 Elsevier Ltd. All rights reserved.

Structure and properties of fibre reinforced zn-27% al alloy based cast MMCs

Metal matrix composites (MMCs) based on a zinc-27% aluminium alloy (ZA-27) were produced using a pressure infiltration technique. Preforms of alumina fibres and aluminosilicate fibres were used for reinforcement. Uniform distribution of fibres and satisfactory interfacial bonding were achieved. UTS, specific strength, hardness and wear resistance were improved significantly by the alumina fibre reinforcement, but UTS decreased when using aluminosilicate fibres for reinforcement mainly due to unavoidable clustering of particles in the fibre preforms. Structure-property relations have been analysed in all cases.

Stiffened composite cylindrical panels�Optimum lay-up for buckling by ranking

Buckling of discretely stiffened composite cylindrical panels made of repeated sublaminate construction is studied using a finite element method. In repeated sublaminate construction, a full laminate is obtained by repeating a basic sublaminate, which has a smaller number of plies. This paper deals with the determination of the optimum lay-up for buckling by ranking of such stiffened (longitudinal and hoop) composite cylindrical panels. For this purpose we use the particularized form of a four-noded, 48 degrees of freedom doubly curved quadrilateral thin shell finite element together with a fully compatible two-noded, 16 degrees of freedom composite stiffener element. The computer program developed has been used, after extensive checking for correctness, to obtain an optimum orientation scheme of the plies in the sublaminate so as to achieve maximum buckling load for a specified thickness of typical stiffened composite cylindrical panels.

Effect of Short Duration of Load increment on the Compressibility of Soils

This study concerns the effect of duration of load increment (up to 24 h) on the consolidation properties of expansive black cotton soil (liquid limit = 81%) and nonexpansive kaolinite (liquid limit = 49%). It indicates that the amount and rate of compression are not noticeably affected by the duration of loading for a standard sample of 25 mm in height and 76.2 mm in diameter with double drainage. Hence, the compression index and coefficient of consolidation can be obtained with reasonable accuracy even if the duration of each load increment is as short as 4 h. The secondary compression coefficient (C-alpha epsilon) for kaolinite can be obtained for any pressure range with 1/2 h of loading, which, however, requires 4 h for black cotton soil. This is because primary consolidation is completed early in the case of kaolinite. The paper proves that the conventional consolidation test can be carried out with much shorter duration of loading (less than 4 h) than the standard specification of 24 h or more even for remolded fine-grained soils.

Short-bite chiral diphosphazanes derived from (S)-?-methyl benzyl amine and their Pd, Pt and Rh metal complexes

New chiral diphosphazane ligands of the type Ph(2)PN(S-*CHMePh)PYY' {YY'= Ph(2) (2), O2C6H4 (3); Y= Ph, Y'= Cl {4a (SS), 4b (SR)}, N(2)C(3)HMe(2)-3,5 {5a (SR), 5b (SS)} are synthesised starting from a chiral aminophosphine, Ph(2)PNH(S-*CHMePh) (1). The structure of one of the diastereomer 5a has been confirmed by single crystal X-ray diffraction {Orthorhombic system, P2(1)2(1)2(1); a=10.456 (4), b=15.362 (7), c=17.379 (6) Angstrom, Z=4}. Transition metal mononuclear complexes [Rh{eta(2)-(Ph(2)P)(2)N- (S-*CHMePh)}(2)](+)(BF4)(-) (6), [PdCl2{eta(2)-(Ph(2)P)(2)N(S-*CHMePh)}] (7) and [PtCl2{eta(2)-(Ph(2)P)(2)N- (S-*CHMePh)}] (8) have also been synthesised. The structure of the palladium complex 7 is solved by X-ray crystallography {Orthorhombic system, P2(1)2(1)2(1); a=8.746 (2), b=18.086 (2), c=20.811 (3) Angstrom, Z=4}. All these compounds are characterised by micro analyses, IR and NMR spectroscopic data.

Some observations on the ignition of composite solid propellants

Heat-up times derived from studies on the ignition characteristics of a few model composite solid propellants, containing polystyrene, carboxy-terminated polybutadiene, plasticised polyvinyl chloride and polyphenol formaldehyde as binders, show that they are directly proportional to the mass of the sample and inversely proportional to the hear flux. Propellant weight-loss prior to ignition and high pressure ignition temperature data on the propellants, ammonium per chlorate, and binders show that the ignition is governed by the gasification of the binder pyrolysis products. The activation energy for the gasification of the pyrolysed polymer products corresponds to their ignition behaviour suggesting that propellant ignition is controlled by the binder.

Large deformation finite element analysis of laminated circular composite plates

A 48 d.o.f., four-noded quadrilateral laminated composite shell finite element is particularised to a sector finite element and is used for the large deformation analysis of circular composite laminated plates. The strain-displacement relationships for the sector element are obtained by reducing those of the quadrilateral shell finite element by substituting proper values for the geometric parameters. Subsequently, the linear and tangent stiffness matrices are formulated using conventional methods. The Newton-Raphson method is employed as the nonlinear solution technique. The computer code developed is validated by solving an isotropic case for which results are available in the literature. The method is then applied to solve problems of cylindrically orthotropic circular plates. Some of the results of cylindrically orthotropic case are compared with those available in the literature. Subsequently, application is made to the case of laminated composite circular plates having different lay-up schemes. The computer code can handle symmetric/unsymmetric lay-up schemes. The large displacement analysis is useful in estimating the damage in composite plates caused by low-velocity impact.

Production and properties of carbon fibre/particle reinforced cast metal matrix composites

Carbon fibres/particles can be satisfactory reinforcing material in polymer, ceramic and metal matrices. Carbon fibres/particles reinforced polymer matrix composites and ceramic matrix composites are being used extensively in critical areas of application, but carbon fibre - metal matrix composites have not reached that stage yet. This paper discusses the salient aspects of production and specific properties of carbon fibre/particle reinforced cast metal matrix composites. It is envisaged that these materials will find extensive applications where cost, weight and thermal expansion are the key factors.