Versatile N,C,N coordination behavior of a monoanionic aryldiamine ligand in ruthenium(II) complexes: Syntheses and crystal structures of [Ru-II(C6H3(CH(2)NMe(2))(2)-2,6)X(L)] (L equals norbornadiene, X=Cl, SO3CF3; L=PPh(3), X=I) and [Ru-II{C6H3(CH(2)NMe(2))(2)-2,6}(2,2':6:2''-terpyridine)]Cl

The monoanionic ligand [C6H3(CH(2)NMe(2))(2)-2,6](-), a potentially terdentate N,C,N bonding system, has been employed to synthesize a series of new ruthenium(II) complexes [Ru{C6H3(CH(2)NMe(2))(2)-2,6}X(L)] (L = PPh(3) X = Cl (2a), I (2b); L = norbornadiene (nbd), X = Cl (4), eta(1)-OSO2CF3 (5)) and [Ru{C6H3(CH(2)NMe(2))(2)-2,6}(2,2':6',2 ''-terpyridine)]Cl (3). X-ray crystal structures of 2b and 3-5 have been determined, in which the N,C,N coordination geometry with respect to the metal center is found to differ considerably. In each complex the aryldiamine ligand is terdentate, eta(3)-N,C,N-bonded as a six electron donor system. However, depending on the other ligands in the Ru(II) coordination sphere, this ligand demonstrates considerable flexibility in adopting coordination geometries which range from meridional in 3 through pseudomeridional in 2b to pseudofacial in 4 and 5. In the structures of 4 and 5 significant distortions of the aryl ring, involving bending of the six-membered ring into a boatlike conformation, are found. The different combinations of the N,C,N ligand with sets of other ligands lead to a range of metal geometries, i.e. square pyramidal in 2b, octahedral in 3, and bicapped tetrahedral in 4 and 5.

STUDYING THE MIGRATORY BEHAVIOR OF INDIVIDUAL BATS: CURRENT TECHNIQUES AND FUTURE DIRECTIONS

Migrating bats are among the most poorly understood of migratory taxa, with relatively little information available on their behavior and ecology during migration compared to other taxa. This arises because of the

Phase behavior of mixtures of colloidal platelets and nonadsorbing polymers

The phase behavior of a model system of colloidal platelets and nonadsorbing polymers is studied using computer simulations and perturbation theory. The equation of state for the pure platelet reference system is obtained by Monte Carlo simulations, and the free volume fraction accessible to polymers is measured by a trial insertion method. The free volume fraction is also calculated using scaled particle theory. Subsequently, the phase diagram for platelet-polymer mixtures is calculated. For a platelet aspect ratio L/D=0.1 and a polymer to platelet size ratio d/D>0.2, we observe coexistence between two isotropic phases with different densities. For smaller polymers d/D

Numerical study of the effects of reinforcement/matrix interphase on stress-strain behavior of YAl2 particle reinforced MgLiAl composites

For the potential influence produced by the reinforcement/matrix interphase in particle reinforced metal matrix composites (PMMCs), a unit cell model with transition interphase was proposed. Uniaxial tensile loading was simulated and the stress/strain behavior was predicted. The results show that a transition interphase with both appropriate strength and thickness could affect the failure mode, reduce the stress concentration, and enhance the maximum strain value of the composite.

An evaluation of the effect of altering nutrition and nutritional strategies in early lactation on reproductive performance and estrous behavior of high-yielding Holstein-Friesian dairy cows

Reproductive performance in the high-yielding dairy cow has severely decreased in the last 40 yr. The aim of this study was to compare the effectiveness of 4 nutritional strategies in improving the reproductive performance of high-yielding dairy cows. It was hypothesized that offering cows a high-starch ration in early lactation would enhance the onset of luteal activity, and that decreasing the severity of negative energy balance in the early postcalving period would improve reproductive parameters. Nutritional regimens aimed at improving fertility were applied to 96 Holstein-Friesian dairy animals. Upon calving, animals were allocated in a balanced manner to one of 4 dietary treatments. Primiparous animals were balanced according to live weight, body condition score and calving date. Multiparous animals were balanced according to parity, previous lactation milk yield, liveweight, body condition score and calving date. Treatment 1 was based on an industry best practice diet (control) to contain 170 g of crude protein/kg of dry matter. Treatment 2 was an individual cow feeding strategy, whereby the energy balance (EB) of individual animals was managed so as to achieve a predetermined target daily EB profile (+/- 10 MJ/d). Treatment 3 was a high-starch/high-fat combination treatment, whereby an insulinogenic (high-starch) diet was offered in early lactation to encourage cyclicity and followed by a lipogenic (low-starch, high-fat) diet to promote embryo development. Treatment 4 was a low-protein diet, containing 140 g of crude protein/kg of dry matter, supplemented with protected methionine at an inclusion level of 40 g per animal per day. The nutritional strategies implemented in this study had no statistically significant effects on cow fertility measures, which included the onset of luteal activity, conception rate, in-calf rate, and the incidence of atypical cycles. The individual cow feeding strategy improved EB in early lactation but had no benefit on conception rate to first insemination. However, conception rate to second insemination, 100-d pregnancy rate (from the commencement of breeding), and overall pregnancy rate tended to be higher in this group. The high-starch/high-fat treatment tended to decrease the proportion of delayed ovulations and increase the proportion of animals cycling by d 50 postcalving. Animals that failed to conceive to first insemination had a significantly longer luteal phase in the first cycle postpartum and a longer inter-ovulatory interval in the second cycle postpartum. With regards to estrous behavior, results indicate that as the size of the sexually active group increased, the intensity of estrus and the expression of mounting or attempting to mount another cow also increased. Furthermore, cows that became pregnant displayed more intense estrous behavior than cows that failed to become pregnant.

MODELED DIFFUSION-CONTROLLED RESPONSE AND RECOVERY BEHAVIOR OF A NAKED OPTICAL FILM SENSOR WITH A HYPERBOLIC-TYPE RESPONSE TO ANALYTE CONCENTRATION

The diffusion-controlled response and recovery behaviour of a naked optical film sensor (i.e., with no protective membrane) with a hyperbolic-type response [i.e., S0/S = (1 + Kc), where S is the measured value of the absorbance or luminescence intensity of one form of the sensor dye in the presence of the analyte, S0 is the observed value of S in the absence of analyte and K is a constant] to changes in analyte concentration, c, in a system under test is approximated using a simple model, and described more accurately using a numerical model; in both models it is assumed that the system under test represents an infinite reservoir. Each model predicts the variations in the response and recovery times of such an optical sensor, as a function of the final external analyte concentration, the film thickness (I) and the analyte diffusion coefficient (D). From an observed signal versus time profile for a naked optical film sensor it is shown how values for K and D/I2 can be extracted using the numerical model. Both models provide a qualitative description of the often cited asymmetric nature of the response and recovery for hyperbolic-type response naked optical film sensors. It is envisaged that the models will help in the interpretation of the response and recovery behaviour exhibited by many naked optical film sensors and might be especially apposite when the analyte is a gas.

The Behavior of compressively loaded stiffener runout specimens - Part II: Finite element analysis

The termination of stiffeners in composite aircraft structures give rise to regions of high interlaminar shear and peel stresses as the load in the stiffener is diffused into the skin. This is of particular concern in co-cured composite stiffened structures where there is a relatively low resistance to through-thickness stress components at the skin-stiffener interface. In Part I, experimental results of tested specimens highlighted the influence of local design parameters on their structural response. Indeed some of the observed behavior was unexpected. There is a need to be able to analyse a range of changes in geometry rapidly to allow the analysis to form an integral part of the structural design process.

This work presents the development of a finite element methodology for modelling the failure process of these critical regions. An efficient thick shell element formulation is presented and this element is used in conjuction with the Virtual Crack Closure Technique (VCCT) to predict the crack growth characteristics of the modelled specimens. Three specimens were modelled and the qualitative aspects of crack growth were captured successfully. The shortcomings in the quantitative correlation between the predicted and observed failure loads are discussed. There was evidence to suggest that high through-thickness compressive stresses enhanced the fracture toughness in these critical regions.

The Behavior of compressively loaded stiffener runout specimens - Part I: Experiments

The development of the next generation of civil and military transport aircraft will inevitably see an increased use of advanced carbon fibre composite material in the primary structure if performance targets are to be met. One concern in this development is the vulnerability of co-cured and co-bonded stiffened structures to through-thickness stresses at the skin-stiffener interfaces, particularly in stiffener runout regions. These regions are a consequence of the requirement to terminate stiffeners at cutouts, rib intersections, or other structural features which interrupt the stiffener load path.

This work presents the results of an experimental programme investigating the failure of thick-sectioned stiffener runout specimens loaded in uniaxial compression. For all tests, failure initiated at the edge of the runout and propagated across the skin-stiffener interface. It was found that the failure load of each specimen was greatly influenced by intentional changes in the geometric features of these specimens. High frictional forces at the edge of the runout were also deduced from a fractographic analysis, indicating a predominantly Mode II initial failure mode.

Oscillatory Behavior of Supersonic Impinging Jet Flows

Oscillatory flows of a choked underexpanded supersonic impinging jet issuing from a convergent nozzle have been computed using the axisymmetric unsteady Navier–Stokes system. This paper focuses on the oscillatory flow features associated with the variation of the nozzle-to-plate distance and nozzle pressure ratio. Frequencies of the surface pressure oscillation and flow structural changes from computational results have been analyzed. Staging behaviour of the oscillation frequency has been observed for both cases of nozzle-to-plate distance variation and pressure ratio variation. However, the staging behavior for each case exhibits different features. These two distinct staging behaviors of the oscillation frequency are found to correlate well if the frequency and the distance are normalized by the length of the shock cell. It is further found that the staging behaviour is strongly correlated with the change of the pressure wave pattern in the jet shear layer, but not with the shock cell structure.

Fatigue behavior of laser-welded NiTi wires in small-strain cyclic bending

NiTi wires and their weldments are commonly used in micro-electro-mechanical systems (MEMS), and in such applications, cyclic loading are commonly encountered. In this paper, the bending-rotation fatigue (BRF) test was used to study the bending fatigue behavior of NiTi wire laser weldment in the small-strain regime. The fracture mechanism, which includes crack initiation, crack growth and propagation of the weldment in the BRF test, was investigated with the aid of SEM fractography and discussed in terms of the microstructure. It was found that crack initiation was primarily surface-condition dependent. The cracks were found to initiate at the surface defects at the weld zone (WZ) surface, and the crack propagation was assisted by the gas inclusions in the WZ. The weldment was finally fractured in a ductile manner. The fatigue life was found to decrease with increasing surface strain and also with increasing bending frequency (controlled by the rotational speed in the BRF test). In comparison, the fatigue life of the unwelded NiTi wires was higher than their welded counterparts at all strain levels and bending frequencies. The decrease in fatigue resistance of the weldment could be attributed to the surface and microstructural defects introduced during laser welding.

Effect of postweld heat treatment on the microstructure and cyclic deformation behavior of laser-welded NiTi-shape memory wires

NiTi wires of 0.5 mm diameter were laser welded using a CW 100-W fiber laser in an argon shielding environment with or without postweld heat-treatment (PWHT). The microstructure and the phases present were studied by scanning-electron microscopy (SEM), transmission-electron microscopy (TEM), and X-ray diffractometry (XRD). The phase transformation behavior and the cyclic stress–strain behavior of the NiTi weldments were studied using differential scanning calorimetry (DSC) and cyclic tensile testing. TEM and XRD analyses reveal the presence of Ni4Ti3 particles after PWHT at or above 623 K (350 °C). In the cyclic tensile test, PWHT at 623 K (350 °C) improves the cyclic deformation behavior of the weldment by reducing the accumulated residual strain, whereas PWHT at 723 K (450 °C) provides no benefit to the cyclic deformation behavior. Welding also reduces the tensile strength and fracture elongation of NiTi wires, but the deterioration could be alleviated by PWHT.

Viscous behavior of imidazolium-based ionic liquids

The viscosity of four imidazolium-based ionic liquids is analyzed as a function of pressure and temperature. Experimental measurements were carried out using an electromagnetic moving piston viscometer in the 303-353 K and 0.1-70 MPa ranges on synthesized ultrapure samples, and compared with available literature data. Molecular dynamics simulations were used to analyze the fluids' dynamic properties from a nanoscopic viewpoint, with special attention paid to self-diffusion coefficients and dynamic viscosity. Simulated properties are in excellent agreement with experimental results in spite of the glasslike dynamics of some of the studied fluids. © 2013 American Chemical Society.