Void Geometry Driven Spin Crossover in Zeolite-Encapsulated Cobalt Tris(bipyridyl) Complex Ion

The cobalt(II) tris(bipyridyl) complex ion encapsulated in zeolite-Y supercages exhibits a thermally driven interconversion between a low-spin and a high-spin state-a phenomenon not observed for this ion either in solid state or in solution. From a comparative study of the magnetism and optical spectroscopy of the encapsulated and unencapsulated complex ion, supported by molecular modeling, such spin behavior is shown to be intramolecular in origin. In the unencapsulated or free state, the [Co(bipy)(3)](2+) ion exhibits a marked trigonal prismatic distortion, but on encapsulation, the topology of the supercage forces it to adopt a near-octahedral geometry. An analysis using the angular overlap ligand field model with spectroscopically derived parameters shows that the geometry does indeed give rise to a low-spin ground state, and suggests a possible scenario for the spin state interconversion.

Bearing capacity of circular footing on geocell-sand mattress overlying clay bed with void

The potential benefits of providing geocell reinforced sand mattress over clay subgrade with void have been investigated through a series of laboratory scale model tests. The parameters varied in the test programme include, thickness of unreinforced sand layer above clay bed, width and height of geocell mattress, relative density of the sand fill in the geocells, and influence of an additional layer of planar geogrid placed at the base of the geocell mattress. The test results indicate that substantial improvement in performance can be obtained with the provision of geocell mattress, of adequate size, over the clay subgrade with void. In order to have beneficial effect, the geocell mattress must spread beyond the void at least a distance equal to the diameter of the void. The influence of the void over the performance of the footing reduces for height of geocell mattress greater than 1.8 times the diameter of the footing. Better improvement in performance is obtained for geocells filled with dense soil. (C) 2008 Elsevier Ltd. All rights reserved.

Numerical simulations of void growth near a notch tip in ductile single crystals

The objective of this work is to study the growth of a cylindrical void ahead of a notch tip in ductile FCC single crystals under mode I, plane strain, small scale yielding (SSY) conditions. To this end, finite element simulations are performed within crystal plasticity framework neglecting elastic anisotropy. Attention is focussed on the effects of crystal hardening, ratio of void diameter to spacing from the notch and crystal orientation on plastic flow localization in the ligament connecting the notch and the void as well as their growth. The results show strong interaction between shear bands emanating from the notch and angular sectors of single slip forming around the void leading to intense plastic strain development in the ligament. Further, the ductile fracture processes are retarded by increase in hardening of the single crystal and decrease in ratio of void diameter to spacing from the notch. Also, a strong influence of crystal orientation on near-tip void growth and plastic slip band development is observed. Finally, the synergistic, cooperative growth of multiple voids ahead of the notch tip is examined.

Constraint effects on multiple void interaction in pressure sensitive plastic solids

In this work, effects of pressure sensitive yielding and plastic dilatancy on void growth and void interaction mechanisms in fracture specimens displaying high and low constraint levels are investigated. To this end, large deformation finite element simulations are carried out with discrete voids ahead of the notch. It is observed that multiple void interaction mechanism which is favored by high initial porosity is further accelerated by pressure sensitive yielding, but is retarded by loss of constraint. The resistance curves predicted based on a simple void coalescence criterion show enhancement in fracture resistance when constraint level is low and when pressure sensitivity is suppressed.

Modelling of void initiation and breaking phenomena in a packed bed

Void breaking and formation in a packed bed are important phenomena in stabilising and optimising the performance of reactors such as the blast furnace, spouted bed and catalytic regenerator. These phenomena have been studied using a mathematical model. The model is based on a previously published force balance approach to predict the cavity size. Limited numbers of experiments, at room temperature, have been carried out in order to compare the experimental results with theory. A good agreement has been found between the experimental and theoretical results. In addition, the predictions have been compared with published data, which give reasonable agreement. The role of various forces (friction, pressure and bed weight) on void initiation and breaking has been investigated. The effect of bed height, particle diameter and density, void fraction, as well as gas flow rate on void formation and breaking has also been studied.

Influence of crack tip constraint on void growth in ductile FCC single crystals

Effect of constraint (stress triaxiality) on void growth near a notch tip in a FCC single crystal is investigated. Finite element simulations within the modified boundary layer framework are conducted using crystal plasticity constitutive equations and neglecting elastic anisotropy. Displacement boundary conditions based on model, elastic, two term K-T field are applied on the outer boundary of a large circular domain. A pre-nucleated void is considered ahead of a stationary notch tip. The interaction between the notch tip and the void is studied under different constraints (T-stress levels) and crystal orientations. It is found that negative T-stress retards the mechanisms of ductile fracture. However, the extent of retardation depends on the crystal orientation. Further, it is found that there exists a particular orientation which delays the ductile fracture processes and hence can potentially improve ductility. This optimal orientation depends on the constraint level. (C) 2010 Published by Elsevier B.V.

Photoinduced electron transfer in zinc porphyrin-crown ether supramolecule with Eu3+ electron acceptor in crown void

Photoinduced electron transfer (ET) reactions in the zinc porphyrin-crown ether (ZnPCE) supramolecule, in which one crown ether moiety containing Eu3+ as electron acceptor is covalently linked to zinc porphyrin (ZnP), were studied by flash photolysis. In methanol solutions, highly efficient charge separation occurs via intramolecular ET from (ZnP)-Zn-3 to Eu3+ encapsulated in the crown ether void (k(1) = (3 +/- 1) X 10(3) s(-1)) and intramolecular ET from 3ZnP to uncomplexed Eu2+ (k(2) = (2.5 +/- 0.5) X 10(3) s(-1)). Intermolecular ET from Eu2+ escaped from the crown ether void to ZnP.+ (k(tau) = (4.3 +/- 0.7) X 10(8) M(-1) s(-1)) seems to be the main pathway of charge recombination.

Water content - void ratio swell-shrink paths of compacted expansive soils

This paper addresses the behaviour of compacted expansive soils under swell-shrink cycles. Laboratory cyclic swell-shrink tests were conducted on compacted specimens of two expansive soils at surcharge pressures of 6.25, 50.00, and 100.00 kPa. The void ratio and water content of the specimens at several intermediate stages during swelling until the end of swelling and during shrinkage until the end of shrinkage were determined to trace the water content versus void ratio paths with an increasing number of swell-shrink cycles. The test results showed that the swell-shrink path was reversible once the soil reached an equilibrium stage where the vertical deformations during swelling and shrinkage were the same. This usually occurred after about four swell-shrink cycles. The swelling and shrinkage path of each specimen subjected to full swelling - full shrinkage cycles showed an S-shaped curve (two curvilinear portions and a linear portion). However, the swelling and shrinkage path occurred as a part of the S-shaped curve, when the specimen was subjected to full swelling - partial shrinkage cycles. More than 80% of the total volumetric change and more than 50% of the total vertical deformation occurred in the central linear portion of the S-shaped curve. The volumetric change was essentially parallel to the saturation line within a degree of saturation range of 50-80% for the equilibrium cycle. The primary value of the swell-shrink path is to provide information regarding the void ratio change that would occur for a given change in water content for any possible swell-shrink pattern. It is suggested that these swell-shrink paths can be established with a limited number of tests in the laboratory.

Ductile fracture by multiple void growth and interaction ahead of a notch tip in polycrystalline plastic solids

The objectives of this paper are to study the effects of plastic anisotropy and evolution in crystallographic texture with deformation on the ductile fracture behaviour of polycrystalline solids. To this end, numerical simulations of multiple void growth and interaction ahead of a notch tip are performed under mode I, plane strain, small scale yielding conditions using two approaches. The first approach is based on the Hill yield theory, while the second employs crystal plasticity constitutive equations and a Taylor-type homogenization in order to represent the ductile polycrystalline solid. The initial textures pertaining to continuous cast Al-Mg AA5754 sheets in recrystallized and cold rolled conditions are considered. The former is nearly-isotropic, while the latter displays pronounced anisotropy. The results indicate distinct changes in texture in the ligaments bridging the voids ahead of the notch tip with increase in load level which gives rise to retardation in porosity evolution and increase in tearing resistance for both materials.

Effect of Annealing Temperature in Al 1145 Alloy Sheets on Formability, Void Coalescence, and Texture Analysis

This paper deals with a combined forming and fracture limit diagram and void coalescence analysis for the aluminum alloy Al 1145 alloy sheets of 1.8 mm thickness, annealed at four different temperatures, namely 200, 250, 300, and 350 A degrees C. At different annealing temperatures these sheets were examined for their effects on microstructure, tensile properties, formability, void coalescence, and texture. Scanning electron microscope (SEM) images taken from the fractured surfaces were examined. The tensile properties and formability of sheet metals were correlated with fractography features and void analysis. The variation of formability parameters, normal anisotropy of sheet metals, and void coalescence parameters were compared with texture analysis.