A large orthotropic plate with misfit pin under arbitrarily oriented biaxial loading

The problem of misfit (interference or clearance) pin in a large orthotropic plate was solved earlier by the authors for biaxial loading in the principal directions of orthotropy. Here, a more general case of arbitrarily oriented loading is considered. The most important aspect of the problem studied is the partial contact at the pin-hole interface. The solution is obtained by extending the use of ‘inverse technique’ which was successfully applied earlier by the authors to problems of pins in isotropic and orthotropic domains. The loss of symmetry because of the arbitrary orientation of loading makes the problem more complex. Additional parameters are then involved in the inversion of the problem for the solution. Numerical results are presented primarily for a smooth interference fit pin in a typical orthotropic plate.

Analysis of Paschen Curves for air, N2 and SF6 Using the Townsend Breakdown Equation

It has been shown that it is possible to extend the validity of the Townsend breakdown criterion for evaluating the breakdown voltages in the complete pd range in which Paschen curves are available. Evaluation of the breakdown voltages for air (pd=0.0133 to 1400 kPa · cm), N2(pd=0.0313 to 1400 kPa · cm) and SF6 (pd=0.3000 to 1200 kPa · cm) has been done and in most cases the computed values are accurate to ±3% of the measured values. The computations show that it is also possible to estimate the secondary ionization coefficient ¿ in the pd ranges mentioned above.

On Calculation Of Breakdown Voltages Of Mixtures Of Electron Attaching Gases

In this paper we report the analysis of dc breakdown tests on mixtures of CC12F2, SF6, C-C4F8, 2-C4F8, N2, C02, CF4, CHF3, and 1,1,1-CH3CF3 gases on the basis of the NKH formula Vmix=k(pd)aNbUC developed by us earlier for the binary mixtures of SF6 with air, N2, N20, and CO2. It is shown that while a and c have the values 0.915 and 0.850 respectively as earlier, k and b depend on the component gases. There is a good agreement between the calculated values on the basis of the formula and measured values reported in the literature.

Noble Metal Ionic Catalysts

Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NOx, and unburned hydrocarbons-need to be fully converted to CO2, N-2, and H2O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al2O3 or SiO2 promoted by CeO2. However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce1-xMxO2-delta and Ce1-x-yTiyMxO2-delta (M = Pt, Pd, Rh; x = 0,01-0.02, delta approximate to x, y = 0.15-0.25) oxides in fluorite structure, In these oxide catalysts, pt(2+), Pd2+, or Rh3+ ions are substituted only to the extent of 1-2% of Ce4+ ion. Lower-valent noble metal ion substitution in CeO2 creates oxygen vacancies. Reducing molecules (CO, H-2, NH3) are adsorbed onto electron-deficient noble metal ions, while oxidizing (02, NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NOx reduction (with >80% N-2 selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO2 or Ce1-xTixO2 were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the more expensive Pt and Rh metals are not necessary in exhaust catalysts. We have also grown these nanocrystalline ionic catalysts on ceramic cordierite and have reproduced the results we observed in powder material on the honeycomb catalytic converter. Oxygen in a CeO2 lattice is activated by the substitution of Ti ion, as well as noble metal ions. Because this substitution creates longer Ti-O and M-O bonds relative to the average Ce-O bond within the lattice, the materials facilitate high oxygen storage and release. The interaction among M-0/Mn+, Ce4+/Ce3+, and Ti4+/Ti3+ redox couples leads to the promoting action of CeO2, activation of lattice oxygen and high oxygen storage capacity, metal support interaction, and high rates of catalytic activity in exhaust catalysis.

On Calculation Of Breakdown Voltages Of Mixtures Of Electron Attaching Gases

In this paper we report the analysis of dc breakdown tests on mixtures of CC12F2, SF6, C-C4F8, 2-C4F8, N2, C02, CF4, CHF3, and 1,1,1-CH3CF3 gases on the basis of the NKH formula Vmix=k(pd)aNbUC developed by us earlier for the binary mixtures of SF6 with air, N2, N20, and CO2. It is shown that while a and c have the values 0.915 and 0.850 respectively as earlier, k and b depend on the component gases. There is a good agreement between the calculated values on the basis of the formula and measured values reported in the literature.

Preparation and catalytic studies of palladium nanoparticles stabilized by dendritic phosphine ligand-functionalized silica

Silica is a prominently utilized heterogeneous metal catalyst support. Functionalization of the silica with poly(ether imine) based dendritic phosphine ligand was conducted, in order to assess the efficacy of the dendritic phosphine in reactions facilitated by a silica supported metal catalyst. The phosphinated poly(ether imine) (PETIM) dendritic ligand was bound covalently to the functionalized silica. For this purpose, the phosphinated dendritic ligand containing an amine at the focal point was synthesized initially. Complexation of the dendritic phosphine functionalized silica with Pd(COD)Cl-2 yielded Pd(II) complex, which was reduced subsequently to Pd(0), by conditioning with EtOH. The Pd metal nanoparticle thus formed was characterized by physical methods, and the spherical nanoparticles were found to have >85% size distribution between 2 nm and 4 nm. The metal nanoparticle was tested as a hydrogenation catalyst of olefins. The catalyst could be recovered and recycled more than 10 times, without a loss in the catalytic efficiency.

Efficient implementations of a pseudodynamical stochastic filtering strategy for static elastography

A computationally efficient pseudodynamical filtering setup is established for elasticity imaging (i.e., reconstruction of shear modulus distribution) in soft-tissue organs given statically recorded and partially measured displacement data. Unlike a regularized quasi-Newton method (QNM) that needs inversion of ill-conditioned matrices, the authors explore pseudodynamic extended and ensemble Kalman filters (PD-EKF and PD-EnKF) that use a parsimonious representation of states and bypass explicit regularization by recursion over pseudotime. Numerical experiments with QNM and the two filters suggest that the PD-EnKF is the most robust performer as it exhibits no sensitivity to process noise covariance and yields good reconstruction even with small ensemble sizes.

Sequence dependence and role of 5'-phosphate in the B to Z transition

Spectroscopic studies on pd(CG)3 and pd(GC)3 have been carried out to elucidate the sequence dependence and effect of free 5'-phosphate on the B to Z transition. Unlike d(CG)3, pd(CG)3 fails to undergo salt-induced B to Z transition at ambient temperature. Model building studies have been carried out to determine the inhibitory role of the 5'-phosphate group, but have been unsuccessful.

Molecular-complexes of metallo tetraphenyl porphyrins with 2,4,5,7-tetranitro fluorenone

The interactions of mesotetraphenyl porphyrin and its metallo derivatives with 2,4,5,7-tetra nitrofluorenone have been studied using spectroscopic methods. The association constants (K) for 1:1 complexes in Ch2Cl2Cl2 follow the order Pd+2>Co+2> Cu+2>VO+2>Ni+2>Zn+2. The values of K are accounted in terms of stereochemistry of MTPPs and the electronic configuration of the metal ions. The magnitude and direction of the proton NMR shifts of the acceptor and donor in the complexes and their ESR parameter furnish information as to the possible structures of these complexes in solution.

Prediction of Breakdown Voltages of Binary Gas Mixtures in Uniform Electric Fields

A simple equation to predict the breakdown voltages for binary mixtures (Vmix) of electronegative gases (SF6, CCl2F2) and buffer gases (N2, N2O, CO2, air) under uniform electric field has been proposed. Values of Vmix evaluated using this equation for mixtures of SF6-N2, SF6-air, SF6-N2O, SF6-CO2 and CCl2F2-N2 over a wide range of pd show an excellent agreement with the experimentally measured data available in the literature.

Electrophilic Addition of Phenylisocyanate at gamma-CH of Thio-beta-diketonates of Some Transition Metals

The quasi-aromatic property of metal chelates of thio-beta-diketones has been studied by reacting them with phenylisocyanate, where addition takes place at the gamma-CH in a stepwise manner. Mono-thiodiketonates of Ni(II), Pd(II), cu(II) and Co(III) and the dithio-acetylacetonate of Ni(II) react with phenylisocyanate to produce mono-, di- and triphenylamido [with cobalt (III) only] substituted derivatives. In the case of tris (ethylthioacetoacetato) cobalt (III), it is found that the reaction with phenylisocyanate gives two isomers, a chocolate coloured isomer in which the phenylamido carbonyl is not coordinated while the green coloured isomer has bonding through phenylemido carbonyl oxygen. The reactions of the thiodiketonates have been compared with those of beta-diketonates and beta-ketoiminates. The reaction products have been characterised by elemental analyses, magnetic moments, and electronic, IR and 1H NMR spectral studies.

Finite element analysis of moving contact in mechanically fastened joints

The Finite Element Method (FEM) has made a number of otherwise intractable problems solvable. An important aspect for achieving an economical and accurate solution through FEM is matching the formulation and the computational organisation to the problem. This was realised forcefully in the present case of the solution of a class of moving contact boundary value problems of fastener joints. This paper deals with the problem of changing contact at the pin-hole interface of a fastener joint. Due to moving contact, the stresses and displacements are nonlinear with load. This would, in general, need an interactive-incremental approach for solution. However, by posing the problem in an inverse way, a solution is sought for obtaining loads to suit given contact configuration. Numerical results are given for typical isotropic and composite plates with rigid pins. Two cases of loading are considered: (i) load applied only at the edges of the plate and (ii) load applied at the pin and reacted at a part of the edge of the plate. Load-contact relationships, compliance and stress-patterns are investigated. This paper clearly demonstrates the simplification achieved by a suitable formulation of the problem. The results are of significance to the design and analysis of fastener joints.

Finite element analysis of moving contact in mechanically fastened joints

The Finite Element Method (FEM) has made a number of otherwise intractable problems solvable. An important aspect for achieving an economical and accurate solution through FEM is matching the formulation and the computational organisation to the problem. This was realised forcefully in the present case of the solution of a class of moving contact boundary value problems of fastener joints. This paper deals with the problem of changing contact at the pin-hole interface of a fastener joint. Due to moving contact, the stresses and displacements are nonlinear with load. This would, in general, need an interactive-incremental approach for solution. However, by posing the problem in an inverse way, a solution is sought for obtaining loads to suit given contact configuration. Numerical results are given for typical isotropic and composite plates with rigid pins. Two cases of loading are considered: (i) load applied only at the edges of the plate and (ii) load applied at the pin and reacted at a part of the edge of the plate. Load-contact relationships, compliance and stress-patterns are investigated. This paper clearly demonstrates the simplification achieved by a suitable formulation of the problem. The results are of significance to the design and analysis of fastener joints.

Ambidentate coordination of isonitrosoacetylacetone imines in their nickel(II) and palladium(II) complexes

Nickel(I1) and palladium(I1) complexes of the types Ni(R-IAI)(IAI'), Pd(IAI)(IAI'), and Pd(R-IAI), , where IAI and IAI' represent isonitrosoacetylacetone imine and R-IAI represents its Aralkyl derivative, have been prepared. The molar conductance, molecular weight, magnetic moment, and ir, pmr, and electronic spectra of these com- plexes have been studied. It is suggested that the isonitroso group of R-IAI coordinates through the nitrogen and that of IAI' thiough the oxygen in Ni(R-IAI)(IAI'). In Pd(R-IAI), the isonitroso groups of both ligands coordinate through nitrogen while Pd(IAI)(IAI') has a structure similar to that of Ni(R-IAI)(IAI'). The amine- exchange reactions of nickel(I1) and palladium(I1) complexes are discussed and compared on the basis of their structures.

Optical and magnetic resonance studies of the interaction of metallo tetraphenylporphyrins with nitrobenzofuroxan

Metallo tetraphenylporphyrins form I : I molecular complexes with 4,6-dinitrobenzofuroxan. The molecular association is described in terms of T-n. interaction with porphyrins functioning as donors. The association constants and thermodynamic parameters have been evaluated using optical absorption and 'H nmr spectral methods. Based on the binding constants, the donor ability of various metalloporphyrins can be arranged in the following order: Pd(I1) > Co(I1) > Cu(I1) > Ni(I1) - VO(1V) - 2H > Zn(l1). Electron paramagnetic resonance studies of the complexes reveal that the IT-complexation results in changes in the electronic structure of the central metal ions which are reflected in the changes in the M-N 5 bonding. The dipolar contribution to the acceptor proton chemical shifts in the CoTPP complex has been partitioned from ring current contributions using the shifts observed in the ZnTPP complex. The shifts, along with the line broadening ratios observed for the CoTPP complex, are used to arrive at the possible solution structures of the complexes.