Template-free coordination-driven self-assembly of discrete hexanuclear prismatic cages employing half-sandwich octahedral Ru-2(II) acceptors and triimidazole donors

Coordination-driven self-assembly of dinuclear half-sandwich p-cymene ruthenium(II) complexes Ru-2(mu-eta(4)-C2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) and Ru-2(mu-eta(4)-C6H2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1b) separately with imidazole-based tritopic donors (L-1-L-2) in methanol yielded a series of hexanuclear 3+2] trigonal prismatic cages (2-5), respectively L-1 = 1,3,5-tris(imidazole-1-yl) benzene; L-2 = 4,4',4 `'-tris(imidazole-1-yl) triphenylamine]. All the self-assembled cages 2-5 were characterized by various spectroscopic techniques (multinuclear NMR, Infra-red and ESI-MS) and their sizes, shapes were obtained through geometry optimization using molecular mechanics universal force field (MMUFF) computation. Despite the possibility due to the free rotation of donor sites of imidazole ligands, of two different atropoisomeric prismatic cages (C-3h or C-s) and polymeric product, the self-selection of single (C(3)h) conformational isomeric cages as the only product is a noteworthy observation. (C) 2015 Elsevier B.V. All rights reserved.

A meso elastoplastic constitutive model for polycrystalline metals based on equivalent slip systems with latent hardening

A meso material model for polycrystalline metals is proposed, in which the tiny slip systems distributing randomly between crystal slices in micro-grains or on grain boundaries are replaced by macro equivalent slip systems determined by the work-conjugate principle. The elastoplastic constitutive equation of this model is formulated for the active hardening, latent hardening and Bauschinger effect to predict macro elastoplastic stress-strain responses of polycrystalline metals under complex loading conditions. The influence of the material property parameters on size and shape of the subsequent yield surfaces is numerically investigated to demonstrate the fundamental features of the proposed material model. The derived constitutive equation is proved accurate and efficient in numerical analysis. Compared with the self-consistent theories with crystal grains as their basic components, the present theory is much simpler in mathematical treatment.

Mechanism on Progressive Failure of a Faulted Rock Slope Due to Slip-Weakening

Slip-weakening is one of the characteristics of geological materials under certain loadings. Non-uniform rock structure may exist in the vicinity of the slip surface for a rock slope. Some portion of the slip surface may be penetrated but the other not. For the latter case, the crack or the fault surface will undergo shear deformation before it becomes a successive surface under a certain loading. As the slipped portion advances,slip-weakening occurs over a distance behind the crack tip. In the weakening zone, the shear strength will decrease from its peak value to residual friction level. The stress will redistribute along the surface of crack and in the weakening zone. Thus the changed local stress concentration leads the crack to extend and the ratio of penetration of the slip surface to increase. From the view of large-scale for the whole slip surface, the shear strength will decrease due to the damage of interior rock structure, and the faulted rock behaves as a softening material. Such a kind of mechanism performs in a large number of practical landslides in the zones experienced strong earthquakes. It should be noted that the mechanism mentioned above is different from that of the breakage of structural clay,in which the geological material is regarded as a medium containing structural lumps and structural bands. In this paper, the softening behavior of a faulted rock should be regarded as a comprehensive result of the whole complicated process including slip-weakening, redistribution of stress, extension of crack tip, and the penetration of the slip surface. This process is accompanied by progressive failure and abrupt structural damage. The size of slip-weakening zone is related to the undergoing strain. Once the relative slide is initiated (local or integrated), the effect of slip-weakening will behave in a certain length behind the crack tip until the formation of the whole slip surface.

Strain-Induced Grain Refinement of Cobalt During Surface Mechanical Attrition Treatment

The microstructural evolution during surface mechanical attrition treatment of cobalt (a mixture of hexagonal close packed (hep) and face-centered cubic (fcc) phases) was investigated. In order to reveal the mechanism of grain refinement and strain accommodation. The microstructure was systematically characterized by both cross-sectional and planar-view transmission electron microscopy. In the hcp phase, the process of grain refinement. Accompanied by an increase in strain imposed in the surface layer. Involved: (1) the onset of 110 111 deformation twinning, (2) the operation of (1 120) 110 1 0} prismatic and (1 120) (000 1) basal slip, leading to the formation of low-angle dislocation boundaries, and (3) the successive subdivision of grains to a finer and finer scale. Ressulting in the formation of highly misoriented nanocrystalline grains. Moreover. The formation of nanocrystalliies at the grain boundary and triple junction was also observed to occur concurrently with straining. By contrast. The fec phase accommodated strain in a sequence as follows: (1) slip of dislocations by forming intersecting planar arrays of dislocations, (2) {1 1 1} deformation twinning, and (3) the gamma(fcc) --> epsilon(hcp) martensitic phase transformation. The mechanism of grain refinement was interpreted in terms of the structural subdivision of grains together with dynamic recrystallization occurring in the hep phase and the gamma --> E: martensitic transformation in the fcc phase as well.

Nanocrystalline Formation During Mechanical Attrition of Cobalt

The nanocrystalline (nc) formation was studied in cobalt (a mixture of c (hexagonal close packed) and gamma (face-centered cubic) phases) subjected to surface mechanical attrition treatment. Electron microscopy revealed the operation of {10(1) over bar 0}< 11(2) over bar 0 > prismatic and {0001}< 11(2) over bar 0 > basal slip in the E phase, leading to the successive subdivision of grains to nanoscale. In particular, the dislocation splitting into the stacking faults was observed to occur in ultrafine and nc grains. By contrast, the planar dislocation arrays, twins and martensites were evidenced in the gamma phase. The strain-induced gamma ->epsilon martensitic transformation was found to progress continuously in ultrafine and nc grains as the strain increased. The nc formation in the gamma phase was interpreted in terms of the martensitic transformation and twinning.

Experimental Investigation On The Slip Between Oil And Water In Horizontal Pipes

This work is devoted to study of the slip phenomenon between phases in water-oil two-phase flow in horizontal pipes. The emphasis is placed on the effects of input fluids flow rates, pipe diameter and viscosities of oil phase on the slip. Experiments were conducted to measure the holdup in two horizontal pipes with 0.05 m diameter and 0.025 m diameter, respectively, using two different viscosities of white oil and tap water as liquid phases. Results showed that the ratios of in situ oil to water velocity at the pipe of small diameter are higher than those at the pipe of big diameter when having same input flow rates. At low input water flow rate, there is a large deviation on the holdup between two flow systems with different oil viscosities and the deviation becomes gradually smaller with further increased input water flow rate. (C) 2008 Elsevier Inc. All rights reserved.

Deformation Twin Formed By Self-Thickening, Cross-Slip Mechanism In Nanocrystalline Ni

We report the observation of a deformation twin formed by a recently proposed self-thickening, cross-slip twinning mechanism. This observation verifies one more twinning mechanism, in addition to those reported before, in nanocrystalline face-centered-cubic metals. In this mechanism, once the first Shockley partial is emitted from a grain boundary, and cross slips onto another slip plane, a deformation twin could nucleate and grow in both the primary and cross-slip planes without requiring the nucleation of additional Shockley partials from the grain boundary.

Extended Stoney'S Formula For A Film-Substrate Bilayer With The Effect Of Interfacial Slip

The curvature-stress relation is studied for a film-substrate bilayer with the effect of interfacial slip and compared with that of an ideal interface without interfacial slip. The interfacial slip together with the dimensions, elastic and interfacial properties of the film and substrate layers can cause a significant deviation of curvature-stress relation from that with an ideal interface. The interfacial slip also results in the so-called free edge effect that the stress, constraint force, and curvature vary dramatically around the free edges. The constant curvature as predicted by Stoney's formula and the Timoshenko model of an ideal interface is no longer valid for a bilayer with a nonideal interface. The models with the assumption of an ideal interface can also lead to an erroneous evaluation on the true stress state inside a bilayer with a nonideal interface. The extended Stoney's formula incorporating the effects of both the layer dimensions and interfacial slip is presented.

Search For Critical Slip Surface In Slope Stability Analysis By Spline-Based Ga Method

The stability of a soil slope is usually analyzed by limit equilibrium methods, in which the identification of the critical slip surface is of principal importance. In this study the spline curve in conjunction with a genetic algorithm is used to search the critical slip surface, and Spencer's method is employed to calculate the factor of safety. Three examples are presented to illustrate the reliability and efficiency of the method. Slip surfaces defined by a series of straight lines are compared with those defined by spline curves, and the results indicate that use of spline curves renders better results for a given number of slip surface nodal points comparing with the approximation using straight line segments.

Attractor crisis and bursting in a fluid flow with two no-slip directions

Characteristic burtsing behavior is observed in a driven, two-dimensional viscous flow, confined to a square domain and subject to no-slip boundaries. Passing a critical parameter value, an existing chaotic attractor undergoes a crisis, after which the flow initially enters a transient bursting regime. Bursting is caused by ejections from and return to a limited subdomain of the phase space, whereas the precrisis chaotic set forms the asymptotic attractor of the flow. For increasing values of the control parameter the length of the bursting regime increases progressively. Passing another critical parameter value, a second crisis leads to the appearance of a secondary type of bursting, of very large dynamical range. Within the bursting regime the flow then switches in irregular intervals from the primary to the secondary type of bursting. Peak enstrophy levels for both types of bursting are associated to the collapse of a primary vortex into a quadrupolar state.