Copper( 11) Complexes of Novel Tripodal Ligands containing Phenolate and Benzimidazole/Pyridine Pendants: Synthesis, Structure, Spectra and Electrochemical Behaviour

Mononuclear copper(II) complexes of tri- and tetra-dentate tripodal ligands containing phenolic hydroxyl and benzimidazole or pyridine groups have been isolated. They are of the type (CuL(X)].nH2O, [CuL(H2O)]X.nH2O or [CuL].nH2O where X = Cl-, ClO4-, N3- or NCS- and n = 0-4. The electronic spectra of all the complexes exhibit a broad absorption band around 14000 cm-1 and the polycrystalline as well as the frozen-solution EPR spectra are axial, indicating square-based geometries. The crystal structure of [CuL(Cl)] [HL = (2-hydroxy-5-nitrobenzyl)bis(2-pyridyl-methyl)amine] revealed a square-pyramidal geometry around Cu(II). The mononuclear complex crystallises in the triclinic space group P1BAR with a = 6.938(1), b = 11.782(6), c = 12.678(3) angstrom and alpha = 114.56(3), beta = 92.70(2), gamma = 95.36(2)-degrees. The co-ordination plane is comprised of one tertiary amine and two pyridine nitrogens and a chloride ion. The phenolate ion unusually occupies the axial site, possibly due to the electron-withdrawing p-nitro group. The enhanced pi delocalisation involving the p-nitrophenolate donor elevates the E1/2 values. The spectral and electrochemical results suggest the order of donor strength as nitrophenolate < pyridine < benzimidazole in the tridentate and nitrophenolate < benzimidazole < pyridine in the tetradentate ligand complexes.

A study of microstructure and wear behaviour of TiB2/Al metal matrix composites

The present paper deals with the study of microstructure and wear characteristics of TiB2 reinforced aluminium metal matrix composites (MMCs). Matrix alloys with 5, 10 and 15% of TiB2 were made using stir casting technique. Effect of sliding velocity on the wear behaviour and tribo-chemistry of the worn surfaces of both matrix and composites sliding against a EN24 steel disc has been investigated under dry conditions. A pin-on-disc wear testing machine was used to find the wear rate, in which EN24 steel disc was used as the counter face, loads of 10-60N in steps of 10N and speeds of 100, 200, 300, 400 and 500 rpm were employed. The results showed that the wear rate was increased with an increase in load and sliding speed for both the materials. However, a lower wear rate was obtained for MMCs when compared to the matrix alloys. The wear transition from slight to severe was presented at the critical applied loads. The transition loads for the MMCs were much higher than that of the matrix alloy. The transition loads were increased with increase in TiB2 and the same was decreased with the increase of sliding speeds. The SEM and EDS analyses were undertaken to demonstrate the effect of TiB2 particles on the wear mechanism for each conditions.

Structure, Spectra and Redox Behaviour of Copper(11) Complexes of Bis( benzimidazoly1)diamine Ligands

The linear quadridentate ligand N,N'-bis(benzimidazoI-2-ylethyl)ethane-l,2-diamine (L') and its 1 - methylbenzimidazole analogue (L2) and homologues form 1 : 1 complexes with Cu(CIO,),; L' also forms complexes of the types CuL'X, where X = NO,, PF,, Br or CI and CuL'(X)Y where X = CI or Br and Y = CIO, or Br. Deep blue CuL1Br,*2H20 crystallizes in the monoclinic space group C2/c with Z = 4, a = 9.91 9(2), b = 16.626(3), c = 14.1 02(3) le\ and p = 94.39(2)". The structure was solved by Patterson and Fourier difference methods and refined by the least-squares technique to R = 0.064 for 2195 independent reflections with / > 1.50(/). The molecule lies on a two-fold axis symmetrically around Cu". The co-ordination around Cu" is found to be square planar with two amino nitrogens and two benzimidazole nitrogens forming the equatorial plane [CU-N 1.983(3) and 2.037(4) A]. The bromides are at longer distances [3.349(1) A] in axial sites. Ligand field and EPR spectra indicate that one bromide or chloride ion is axially co-ordinated to Cu" in [CuL1l2+. This ion exhibits quasi-reversible redox behaviour. Electrochemical studies of the dihalides in methanol have established the presence of [CuL'X,], [CuL'(X)]+ and [CuL'I2+ in equilibrium. In complexes with 565 [CuL4I2+ [L4 = N,Nbis( benzimidazol-2-ylmethyl)ethane-l,2-diamine] and 555 [CuL3] [L3 = N,N'-bis(1 -methylbenzimidazol- 2-ylmethyl)propane-l,3-diamine] chelate rings, Cull does not seem to lie in the N, square plane, as revealed by their low A values and irreversible electrochemical behaviour. The Cu"-Cu' redox potentials in methanol are in the order [CuL1I2+ < [CuL3I2+ < [CuL4I2+; this illustrates that sixmembered chelate rings are suitable to stabilize Cu", when CU-N 0 interactions are favourable.

Singularity structure and chaotic behavior of the homopolar disk dynamo

We study in great detail a system of three first-order ordinary differential equations describing a homopolar disk dynamo (HDD). This system displays a large variety of behaviors, both regular and chaotic. Existence of periodic solutions is proved for certain ranges of parameters. Stability criteria for periodic solutions are given. The nonintegrability aspects of the HDD system are studied by investigating analytically the singularity structure of the system in the complex domain. Coexisting attractors (including period-doubling sequence) and coexisting strange attractors appear in some parametric regimes. The gluing of strange attractors and the ungluing of a strange attractor are also shown to occur. A period of bifurcation leading to chaos, not observed for other chaotic systems, is shown to characterize the chaotic behavior in some parametric ranges. The limiting case of the Lorenz system is also studied and is related to HDD.

Nonlinear dynamics and chaotic motions in feedback-controlled two- and three-degree-of-freedom robots

The dynamics of a feedback-controlled rigid robot is most commonly described by a set of nonlinear ordinary differential equations. In this paper we analyze these equations, representing the feedback-controlled motion of two- and three-degrees-of-freedom rigid robots with revolute (R) and prismatic (P) joints in the absence of compliance, friction, and potential energy, for the possibility of chaotic motions. We first study the unforced or inertial motions of the robots, and show that when the Gaussian or Riemannian curvature of the configuration space of a robot is negative, the robot equations can exhibit chaos. If the curvature is zero or positive, then the robot equations cannot exhibit chaos. We show that among the two-degrees-of-freedom robots, the PP and the PR robot have zero Gaussian curvature while the RP and RR robots have negative Gaussian curvatures. For the three-degrees-of-freedom robots, we analyze the two well-known RRP and RRR configurations of the Stanford arm and the PUMA manipulator respectively, and derive the conditions for negative curvature and possible chaotic motions. The criteria of negative curvature cannot be used for the forced or feedback-controlled motions. For the forced motion, we resort to the well-known numerical techniques and compute chaos maps, Poincare maps, and bifurcation diagrams. Numerical results are presented for the two-degrees-of-freedom RP and RR robots, and we show that these robot equations can exhibit chaos for low controller gains and for large underestimated models. From the bifurcation diagrams, the route to chaos appears to be through period doubling.

The thermodynamics and phase behaviour of Tb2Pd2O5 and Er2Pd2O5

Isothermal sections of the phase diagrams for the systems Ln-Pd-O (with Ln = Tb or Er) have been established by equilibration of samples at T = 1223 K, and phase identification after quenching by optical and scanning electron microscopy (OM, SEM), energy dispersive spectroscopy (EDS), and X-ray powder diffraction (XRPD). Two oxide phases were stable along the binary Tb-O: Tb2O3+x, a phase of variable composition, and Tb7O12 at T = 1223K. The oxide PdO was not stable at this temperature. Only one ternary oxide Tb2Pd2O5 was identified in the Tb-Pd-O system. No ternary compound was found in the system Er-Pd-O at T = 1223K. However, the compound Er2Pd2O5 could be synthesized at T = 1075 K by the hydrothermal route. In both systems, the alloys and inter-metallic compounds were all found to be in equilibrium with the lanthanide sesquioxide Ln(2)O(3) (where Ln is either Tb or Er). Two solid-state cells, each incorporating a buffer electrode, were designed to measure the Gibbs energy of formation of the ternary oxides, using yttria-stabilized zirconia as the solid electrolyte and pure oxygen gas as the reference electrode. Electromotive force measurements were conducted in the temperature range (900-1275) K for Th-Pd-O system, and at temperatures from (900-1075) K for the system Er-Pd-O. The standard Gibbs energy of formation Delta(f)G(m)degrees,, of the inter-oxide compounds from their component binary oxides Ln(2)O(3) and PdO are represented by equations linear in temperature. Isothermal chemical potential diagrams for the systems Ln-Pd-O (with Ln = Tb or Er) are developed based on the thermodynamic information. (C) 2002 Elsevier Science Ltd. All rights reserved.

Effect of strain rate on tensile and compression behaviour of Al-Si/graphite composite

Effects of strain rate (10(-4)-10(-2) s(-1)) on tensile and compressive strength of the Al-Si alloy and Al-Si/graphite composite are investigated. The strain hardening exponent value of the composite was more than that of the alloy for all strain rates during tensile and compressive loading. The yield stress of the composite was more than that of the ultimate tensile strength of the alloy for all strain rates. Tensile and compressive properties of the alloy and composite are dependent on strain rates. The negative strain rate sensitivity was observed for the composite and alloy at lower strain rates during the compression and tension loading respectively. (C) 2011 Elsevier B.V. All rights reserved.

Atomic layer deposition of ZrO2 thin films: Study of growth kinetics and dielectric behaviour

Thin films of ZrO2 have been deposited by ALD on Si(100) and SIMOX using two different metalorganic complexes of Zr as precursors. These films are characterized by X-ray diffraction, transmission and scanning electron microscopies, infrared spectroscopy, and electrical measurements. These show that amorphous ZrO2 films of high dielectric quality may be grown on Si(100) starting about 400degreesC. As the growth temperature is raised, the films become crystalline, the phase formed and the microstructure depending on precursor molecular structure. The phase of ZrO2 formed depends also on the relative duration of the precursor and oxygen pulses. XPS and IR spectroscopy show that films grown at low temperatures contain chemically unbound carbon, its extent depending on the precursor. C-V measurements show that films grown on Si(100) have low interface state density, low leakage current, a hysteresis width of only 10-250 mV and a dielectric constant of similar to16-25.

Observation of pseudo-gap and Kondo behaviour in Al70Pd30−xMnx quasicrystals

We report here the electrical and magnetic properties of Al70Pd30−xMnx quasicrystals (x=9 and 11), from resistivity and point contact spectroscopy measurements. Electrical resistivity shows a resistivity maximum for both of these compositions. The positive TCR at lower temperature is attributed to spin–orbit scattering. For x=11, we observe an upturn in the resistivity below 20 K, which follows a lnT dependence indicating Kondo-like behaviour. In the point contact spectroscopy studies we observe two regimes showing a V2 dependence at low bias voltages (for V<10 meV) crossing over to the V0.5 dependence at higher voltages. This is attributed to the signature of a pseudo-gap in the density of states at zero bias. We suggest that this V2 dependence can also arise due to magnetic scattering effects, which are signatures of the Kondo-like behaviour.

Microstructure and damping behaviour of consolidated magnesium chips

Chips produced by turning a commercial grade pure magnesium billet were consolidated by solid state recycling technique of cold compaction followed by hot extrusion. The cold compacted billets were extruded at four different temperatures: 250 degrees C, 300 degrees C, 350 degrees C and 400 degrees C. For the purpose of comparison, cast magnesium (pure) billets were extruded under similar conditions. Extruded products were characterized for damping properties. Damping capacity and dynamic modulus was measured as a function of time and temperature at a fixed frequency of 5 Hz 10 to 14% increase in damping capacity was observed in chip consolidated products compared to reference material. Microstructural changes after the temperature sweep tests were examined. Chip boundaries present in consolidated products were observed to suppress grain coarsening which otherwise was significant in reference material. The present work is significant from the viewpoint of recycling of machined chips and development of sustainable manufacturing processes. (C) 2012 Elsevier B.V. All rights reserved.

Study of Fluid Flow and Mixing Behaviour of a Vacuum Degasser

In recent times the demand of ultra-low carbon steel (ULCS) with improved mechanical properties such as good ductility and good workability has been increased as it is used to produce cold-rolled steel sheets for automobiles. For producing ULCS efficiently, it is necessary to improve the productivity of the vacuum degassers such as RH, DH and tank degasser. Recently, it has been claimed that using a new process, called REDA (revolutionary degassing activator), one can achieve the carbon content below 10 ppm in less time. As such, REDA process has not been studied thoroughly in terms of fluid flow and mass transfer which is a necessary precursor to understand and design this process. Therefore, momentum and mass transfer of the process has been studied by solving momentum and species balance equations along with k-epsilon turbulent model in two-dimension (2D) for REDA process. Similarly, computational fluid dynamic studies have been made in 2D for tank and RH degassers to compare them with REDA process. Computational results have been validated with published experimental and theoretical data. It is found that REDA process is the most efficient among all these processes in terms of mixing efficiency. Fluid flow phenomena have been studied in details for REDA process by varying gas flow rate, depth of immersed snorkel in the steel, diameter of the snorkel and change in vacuum pressure. It is found that design of snorkel affects the melt circulation in the bath significantly.

Synthesis, structural analysis and solvatochromic behaviour of 4,6-bis (4-butoxyphenyl)-2-methoxynicotinonitrile mesogen

In this communication, we report the synthesis and characterisation of a new luminescent liquid crystalline material, 4,6-bis (4-butoxyphenyl)-2-methoxynicotinonitrile (3). We have confirmed its structure by Fourier transform infrared and 1H nuclear magnetic resonance spectroscopy, elemental analysis and X-ray single crystal diffraction studies. The newly synthesised compound crystallises in a monoclinic system with the space group C2/c and its cell parameters are found to be a?=?25.181(4) angstrom, b?=?15.651(4)angstrom, c?=?12.703(19) angstrom, V?=?4880.4 (16) angstrom, Z?=?8. The results indicate that the presence of weak CH center dot center dot center dot O and CH center dot center dot center dot N hydrogen bonding as short-range intermolecular interactions are responsible for the formation of its crystal assembly. The measured torsion angle shows the existence of a distorted structure for the molecule wherein 4-butoxyphenylene ring substituent at the fourth position of the central pyridine ring forms a torsion angle chiC(4), C(3), C(10), C(19)] of 40.55 degrees. Its liquid crystalline behaviour was investigated with the aid of polarised optical microscopy and differential scanning calorimetry. The study reveals that the compound displays a broad nematic phase in the range of 78112 degrees C. Further, solution phase optical studies indicate that it is a blue light emitter in different non-polar and polar organic solvents at a concentration of 10-5M.

Predictability and chaotic nature of daily streamflow

The predictability of a chaotic series is limited to a few future time steps due to its sensitivity to initial conditions and the exponential divergence of the trajectories. Over the years, streamflow has been considered as a stochastic system in many approaches. In this study, the chaotic nature of daily streamflow is investigated using autocorrelation function, Fourier spectrum, correlation dimension method (Grassberger-Procaccia algorithm) and false nearest neighbor method. Embedding dimensions of 6-7 obtained indicates the possible presence of low-dimensional chaotic behavior. The predictability of the system is estimated by calculating the system’s Lyapunov exponent. A positive maximum Lyapunov exponent of 0.167 indicates that the system is chaotic and unstable with a maximum predictability of only 6 days. These results give a positive indication towards considering streamflow as a low dimensional chaotic system than as a stochastic system.

Evidence of novel quasiparticles in a strongly interacting two-dimensional electron system: giant thermopower and metallic behaviour

We report thermopower (S) and electrical resistivity (rho (2DES) ) measurements in low-density (10(14) m(-2)), mesoscopic two-dimensional electron systems (2DESs) in GaAs/AlGaAs heterostructures at sub-Kelvin temperatures. We observe at temperatures a parts per thousand(2)0.7 K a linearly growing S as a function of temperature indicating metal-like behaviour. Interestingly this metallicity is not Drude-like, showing several unusual characteristics: (i) the magnitude of S exceeds the Mott prediction valid for non-interacting metallic 2DESs at similar carrier densities by over two orders of magnitude; and (ii) rho (2DES) in this regime is two orders of magnitude greater than the quantum of resistance h/e (2) and shows very little temperature-dependence. We provide evidence suggesting that these observations arise due to the formation of novel quasiparticles in the 2DES that are not electron-like. Finally, rho (2DES) and S show an intriguing decoupling in their density-dependence, the latter showing striking oscillations and even sign changes that are completely absent in the resistivity.