Organometallic chemistry of chiral diphosphazane ligands: Synthesis and structural characterisation

The diphosphazane ligands of the type, (C20H12O2)PN(R)P(E)Y2 (R = CHMe2 or (S)-*CHMePh; E = lone pair or S; Y2 = O2C20H12 or Y = OC6H5 or OC6H4Me-4 or OC6H4OMe-4 or OC6H4But-4 or C6H5) bearing axially chiral 1,1'-binaphthyl-2,2′-dioxy moiety have been synthesised. The structure and absolute configuration of a diastereomeric palladium complex, [PdCl2{ηsu2}-((O2C20H12)PN((S)-*CHMePh)PPh2] has been determined by X-ray crystallography. The reactions of [CpRu(PPh3)2Cl] with various symmetrical and unsymmetrical diphosphazanes of the type, X2PN(R)PYY′ (R = CHMe2 or (S)-*CHMePh; X = C6H5 or X2 = O2C20H12; Y=Y′= C6H5 or Y = C6H5, Y′ = OC6H4Me-4 or OC6H3Me2-3,5 or N2C3HMe2-3,5) yield several diastereomeric neutral or cationic half-sandwich ruthenium complexes which contain a stereogenic metal center. In one case, the absolute configuration of a trichiral ruthenium complex, viz. [Cp*Ruη2-Ph2PN((S)-*CHMePh)*PPh (N2C3HMe2-3,5)Cl] is established by X-ray diffraction. The reactions of Ru3(CO)12 with the diphosphazanes (C20H12O2)PN(R)PY2 (R = CHMe2orMe; Y2=O2C20H12or Y= OC6H5 or OC6H4Me-4 or OC6H4OMe-4 or OC6H4But-4 or C6H5) yield the triruthenium clusters [Ru3(CO)10{η-(O2C20H12)PN(R)PY2}], in which the diphosphazane ligand bridges two metal centres. Palladium allyl chemistry of some of these chiral ligands has been investigated. The structures of isomeric η3-allyl palladium complexes, [Pd(η3-l,3-R′2-C3H3){η2-(rac)-(02C20H12)PN(CHMe2)PY2}](PF6) (R′ = Me or Ph; Y = C6H5 or OC6H5) have been elucidated by high field two-dimensional NMR spectroscopic and X-ray crystallographic studies.

Nonlinear Dynamics of Beams with Stochastic Parameter Variations

The aim of this paper is to investigate the steady state response of beams under the action of random support motions. The study is of relevance in the context of earthquake response of extended land based structures such as pipelines and long span bridges, and, secondary systems such as piping networks in nuclear power plant installations. The following complicating features are accounted for in the response analysis: (a) differential support motions: this is characterized in terms of cross power spectral density functions associated with distinct support motions, (b) nonlinear support conditions, and (c) stochastically inhomogeneous stiffness and mass variations of the beam structure; questions on non-Gaussian models for these variations are considered. The method of stochastic finite elements is combined with equivalent linearization technique and Monte Carlo simulations to obtain response moments.

Nonlinear Finite-Element Modeling of Batter Piles under Lateral Load

In this paper, a finite-element model is developed in which the nonlinear soil behavior is represented by a hyperbolic relation for static load condition and modified hyperbolic relation, which includes both degradation and gap for a cyclic load condition. Although batter piles are subjected to lateral load, the soil resistance is also governed by axial load, which is incorporated by considering the P-Δ moment and geometric stiffness matrix. By adopting the developed numerical model, static and cyclic load analyses are performed adopting an incremental-iterative procedure where the pile is idealized as beam elements and the soil as elastoplastic spring elements. The proposed numerical model is validated with published laboratory and field pile test results under both static and cyclic load conditions. This paper highlights the importance of the degradation factor and its influence on the soil resistance-displacement (p-y) curve, number of cycles of loading, and cyclic load response.

Influence of matrix characteristics on fracture toughness of high volume fraction Al2O3/Al–AlN composites

The role of matrix microstructure on the fracture of Al-alloy composites with 60 vol% alumina particulates was studied. The matrix composition and microstructure were systematically varied by changing the infiltration temperature and heat treatment. Characterization was carried out by a combination of metallography, hardness measurements, and fracture studies conducted on compact tension specimens to study the fracture toughness and crack growth in the composites. The composites showed a rise in crack resistance with crack extension (R curves) due to bridges of intact matrix ligaments formed in the crack wake. The steady-state or plateau toughness reached upon stable crack growth was observed to be more sensitive to the process temperature rather than to the heat treatment. Fracture in the composites was predominantly by particle fracture, extensive deformation, and void nucleation in the matrix. Void nucleation occurred in the matrix in the as-solutionized and peak-aged conditions and preferentially near the interface in the underaged and overaged conditions. Micromechanical models based on crack bridging by intact ductile ligaments were modified by a plastic constraint factor from estimates of the plastic zone formed under indentations, and are shown to be adequate in predicting the steady-state toughness of the composite.

End-bearing capacity of driven piles in sand using the stress characteristics method: analysis and implementation

The method of stress characteristics has been employed to compute the end-bearing capacity of driven piles. The dependency of the soil internal friction angle on the stress level has been incorporated to achieve more realistic predictions for the end-bearing capacity of piles. The validity of the assumption of the superposition principle while using the bearing capacity equation based on soil plasticity concepts, when applied to deep foundations, has been examined. Fourteen pile case histories were compiled with cone penetration tests (CPT) performed in the vicinity of different pile locations. The end-bearing capacity of the piles was computed using different methods, namely, static analysis, effective stress approach, direct CPT, and the proposed approach. The comparison between predictions made by different methods and measured records shows that the stress-level-based method of stress characteristics compares better with experimental data. Finally, the end-bearing capacity of driven piles in sand was expressed in terms of a general expression with the addition of a new factor that accounts for different factors contributing to the bearing capacity. The influence of the soil nonassociative flow rule has also been included to achieve more realistic results.

Gibbs energy formation of lead titanate

The Gibbs energy of formation of titania-saturated lead titanate has been determined by e.m.f. measurements on the solid state cell;Pt,Ir,Pb + Pb1−xTiO3−x + TiO2(rutile)/CaO-ZrO2/Ni + NiO,Pt in the temperature range 1075–1350 K. The results obtained are significantly different from those reported in the literature based upon vapour pressure measurements, employing Knudsen effusion and transportation techniques, and assuming that the vapor phase consisted entirely of monomeric PbO molecules. A reanalysis of the data obtained in the earlier vapor pressure studies using mass spectrometric measurements on polymeric PbO species in the gas phase, gives Gibbs energies of formation of lead titanate which are in better agreement with those obtained in this study. Earlier electrochemical measurements by Mehrotra et al. and more recent electrochemical measurements by Schmahl et al. both employing CaO-ZrO2 solid electrolytes are in good agreement with the present study. The electro-chemical measurements by Schmahl et al. using PbF 2 solid electrolyte give a slightly more positive Gibbs energy of formation. There was no evidence supporting the formation of compounds other than Pb1−xTiO3−x from yellow PbO and rutile form of TiO2 in the temperature range covered in this study.Résumé L'enthalpie libre de formation du titanate de plomb saturé en oxyde de titane a été déterminée par des mesures de FEM de la pile: Pt,Ir,Pb + Pb1−xTiO3−x + TiO2(rutile)/CaO-ZrO2/Ni + NiO,Pt dans le domaine de températures 1075–1350 K. Les résultats obtenus, different appréciablement de ceux publiés, déterminés par mesures de tensions de vapeur (techniques de transport et d'effusion de Knudsen) en supposant que la phase gazeuse etait uniquement constituée de molécules monomériques de PbO. Une réanalyse des résultats de la littérature, à partir de mesures par spectrométrie de masse sur les polymères de PbO gazeux, donne des enthalpies libres de formation du titanate de plomb se rapprochant de celles obtenues dans cette étude. Les mesures de Mehrotra et al. et plus récemment de Schmahl et al. utilisant toutes deux l'électrolyte CaO-ZrO2 concordent bien avec celles de la présente étude. Les mesures de Schmahl et al., à l'aide de l' électrolyte solide PbF2, donnent une enthalpie de formation légèrement plus positive. Pour la gammede températures étudiée, rien ne permet de supposer que des composés autres que Pb1−x TiO3−x puissent se former à partir du PbO Gaune) et du rutile (TiO2).

A hybrid nine-level inverter for IM drive

This paper proposes a new hybrid nine-level inverter topology for IM drive. The nine-level structure is realized by using two three-phase two-level inverters fed by isolated DC voltage sources and six H-bridges fed by capacitors. The number of switches required in this topology is only 36 where as the conventional nine-level topologies require 48 switches. The voltages across the capacitors, feeding the H-bridges that operate at asymmetric voltages, are effectively balanced by making use of the switching state redundancies. In this topology, the requirement of DC link voltage is only half of the maximum magnitude of the voltage space vector. As the two-level inverters are powered by isolated voltage sources, the circulation of triplen harmonic current in the motor winding is prevented. The proposed drive system is capable of functioning in three-level mode in case of any switch failure in H-bridges. The performance of the proposed topology in the entire modulation range is verified by simulation study and experiment.

Bypass operation in bridge convertors for high-voltage d.c. transmission

Bypass operation with the aid of a special bypass valve is an important part of present-day schemes of protection for h.v. d.c. transmission systems. In this paper, the possibility of using two valves connected to any phase in the bridge convertor for the purpose of bypass operation is studied. The scheme is based on the use of logic circuits in conjunction with modified methods of fault detection. Analysis of the faults in a d.c. transmission system is carried out with the object of determining the requirements of such a logic-circuit control system. An outline of the scheme for the logic-circuit control of the bypass operation for both rectifier and invertor bridges is then given. Finally, conclusions are drawn regarding the advantages of such a system, which include reduction in the number of valves, prevention of severe faults and fast clearance of faults, in addition to the immediate location of the fault and its nature.

The effect of particle size on performance of cathode materials of Li-ion batteries

Beginning with the ‘frog-leg experiment’ by Galvani (1786), followed by the demonstrations of Volta pile by Volta (1792) and lead-acid accumulator by Plante´ (1859), several battery chemistries have been developed and realized commercially. The development of lithium-ion rechargeable battery in the early 1990s is a breakthrough in the science and technology of batteries. Owing to its high energy density and high operating voltage, the Li-ion battery has become the battery of choice for various portable applications such as note-book computers, cellular telephones, camcorders, etc. Huge efforts are underway in succeeding the development of large size batteries for electric vehicle applications. The origin of lithium-ion battery lies in the discovery that Li+-ions can reversibly be intercalated into/de-intercalated from the Van der Walls gap between graphene sheets of carbon materials at a potential close to the Li/Li+ electrode. By employing carbon as the negative electrode material in rechargeable lithium-ion batteries, the problems associated with metallic lithium in rechargeable lithium batteries have been mitigated. Complimentary investigations on intercalation compounds based on transition metals have resulted in establishing LiCoO2 as the promising cathode material. By employing carbon and LiCoO2, respectively, as the negative and positive electrodes in a non-aqueous lithium-salt electrolyte,a Li-ion cell with a voltage value of about 3.5 V has resulted.Subsequent to commercialization of Li-ion batteries, a number of research activities concerning various aspects of the battery components began in several laboratories across the globe. Regarding the positive electrode materials, research priorities have been to develop different kinds of active materials concerning various aspects such as safety, high capacity, low cost, high stability with long cycle-life, environmental compatibility,understanding relationships between crystallographic and electrochemical properties. The present review discusses the published literature on different positive electrode materials of Li-ion batteries, with a focus on the effect of particle size on electrochemical performance.

Rotation field in wedge indentation of metals

A study is made of the rotation field in wedge indentation of metals using copper as the model material system. Wedges with apical angles of 60 and 120 are used to indent annealed copper, and the deformation is mapped using image correlation. The indentation of annealed and strain-hardened copper is simulated using finite element analysis. The rotation field, derived from the deformation measurements, provides a clear way of distinguishing between cutting and compressive modes of deformation. Largely unidirectional rotation on one side of the symmetry line with small spatial rotation gradients is characteristic of compression. Bidirectional rotation with neighboring regions of opposing rotations and locally high rotation gradients characterizes cutting. In addition, the rotation demarcates such characteristic regions as the pile-up zone in indentation of a strain-hardened metal. The residual rotation field obtained after unloading is essentially the same as that at full load, indicating that it is a scalar proxy for plastic deformation as a whole.

Gap model of one-way cyclic lateral load on vertical files in soft clay

For the analysis and design of pile foundation used for coastal structures the prediction of cyclic response, which is influenced by the nonlinear behavior, gap (pile soil separation) and degradation (reduction in strength) of soil becomes necessary. To study the effect of the above parameters a nonlinear cyclic load analysis program using finite element method is developed, incorporating the proposed gap and degradation model and adopting an incremental-iterative procedure. The pile is idealized using beam elements and the soil by number of elastoplastic sub-element springs at each node. The effect of gap and degradation on the load-deflection behavior. elasto-plastic sub-element and resistance of the soil at ground-line have been clearly depicted in this paper.

Nonlinear cyclic load analysis for lateral response of batter piles in soft clay with a rigorous degradation model

Nonlinear analysis of batter piles in soft clay is performed using the finite element technique. As the batter piles are not only governed by lateral load but also axial load, the effect of P- Delta moment and geometric stiffness matrix is included in the analysis. For implementing the nonlinear soil behavior, reduction in soil strength (degradation), and formation of gap with number of load cycles, a numerical model is developed where a hyperbolic relation is adopted for the soil in static condition and hyperbolic relation considering degradation and gap for cyclic load condition. The numerical model is validated with published experimental results for cyclic lateral loading and the hysteresis loops are developed to predict the load-deflection behavior and soil resistance behavior during consecutive cycles of loading. This paper highlights the importance of a rigorous degradation model for subsequent cycles of loading on the pile-soil system by a hysteretic representation.

Smart polymer mediated purification and recovery of active proteins from inclusion bodies

Obtaining correctly folded proteins from inclusion bodies of recombinant proteins expressed in bacterial hosts requires solubilization with denaturants and a refolding step. Aggregation competes with the second step. Refolding of eight different proteins was carried out by precipitation with smart polymers. These proteins have different molecular weights, different number of disulfide bridges and some of these are known to be highly prone to aggregation. A high throughput refolding screen based upon fluorescence emission maximum around 340 nm (for correctly folded proteins) was developed to identify the suitable smart polymer. The proteins could be dissociated and recovered after the refolding step. The refolding could be scaled up and high refolding yields in the range of 8 mg L-1 (for CD4D12, the first two domains of human CD4) to 58 mg L-1 (for malETrx, thioredoxin fused with signal peptide of maltose binding protein) were obtained. Dynamic light scattering (DLS) showed that polymer if chosen correctly acted as a pseuclochaperonin and bound to the proteins. It also showed that the time for maximum binding was about 50 min which coincided with the time required for incubation (with the polymer) before precipitation for maximum recovery of folded proteins. The refolded proteins were characterized by fluorescence emission spectra, circular dichroism (CD) spectroscopy, melting temperature (T-m), and surface hydrophobicity measurement by ANS (8-anilinol-naphthalene sulfonic acid) fluorescence. Biological activity assay for thioredoxin and fluorescence based assay in case of maltose binding protein (MBP) were also carried out to confirm correct refolding. (C) 2012 Elsevier B.V. All rights reserved.

Two Novel Heterometallic Chains Featuring Mn-II and Na-I Ions in Trigonal-Prismatic Geometries Alternately Linked to Octahedral Mn-IV Ions: Synthesis, Structures, and Magnetic Behavior

Two new one-dimensional heterometallic complexes, Mn3Na(L)(4)(CH3CO2)(MeOH)(2)]-(ClO4)(2)center dot 3H(2)O (1), Mn3Na(L)(4)(CH3CH2CO2)-(MeOH)(2)](ClO4)(2)center dot 2MeOH center dot H2O (2) LH2 = 2-methyl-2-(2-pyridyl)propane-1,3-diol], have been synthesized and characterized by X-ray crystallography. Both complexes feature Mn-II and Na-I ions in trigonal-prismatic geometries that are linked to octahedral Mn-IV ions by alkoxy bridges. Variable-temperature direct- and alternating-current magnetic susceptibility data indicated a spin ground state of S = 11/2 for both complexes. Density functional theory calculations performed on 1 supported this conclusion.

Evaluation of damage in reinforced concrete bridge beams using acoustic emission technique

Acoustic emission (AE) testing is a well-known method for damage identification of various concrete structures including bridges. This article presents a method to assess damage in reinforced concrete (RC) bridge beams subjected to incremental cyclic loading. The specifications in the standard NDIS-2421 were used to classify the damage in RC bridge beams. Earlier researchers classified the damage occurring in bridge beams by using crack mouth opening displacement (CMOD) and AE released and proposed a standard (NDIS-2421: the Japanese Society for NonDestructive Inspection). In general, multiple cracks take place in RC beams under bending; therefore, utilisation of CMOD for crack detection may not be appropriate. In the present study, the damage in RC beams is classified by using the AE released, deflection, strains in steel and concrete, because the measurement of the strains in steel and concrete is easy and the codes of practice are specified for different limit states (IS-456:2000). The observations made in the present experimental study have some important practical applications in assessing the state of damage of concrete structural members.