Strain localization in ductile single crystals

This paper is concerned with an analysis of strain localization in ductile crystals deforming by single slip. The plastic flow is modelled as rate-insensitive, and localization, viewed as a bifurcation from a homogeneous deformation mode to one which is concentrated in a narrow ‘shear band’, is found to be possible only when the plastic hardening modulus for the slip system has fallen to a certain critical value h_cr, sensitive to the precise form of the constitutive law governing incremental shear. We develop the general form of this constitutive law, incorporating within it the possibility of deviations from the Schmid rule of a critical resolved shear stress, and we show that h_cr may in fact be positive when there are deviations from the Schmid rule. It is suggested that micromechanical processes such as ‘cross-slip’ in crystals provide specific cases for which stresses other than the Schmid stress may influence plastic response and, further, there is an experimental association of localization with the onset of large amounts of cross-slip. Thus, we give the specific form of h_cr for a constitutive model that corresponds to non-Schmid effects in cross-slip, and we develop a dislocation model of the process from which we estimate the magnitude of the parameters involved. The work supports the notion that localization can occur with positive strain-hardening, h_cr > 0, and the often invoked notions of the attainment of an ideally-plastic or strain-softening state for localization may be unnecessary.     

Synthesis and characterisation of luminescent rhenium tricarbonyl complexes with axially coordinated 1,2,3-triazole ligands

A series of 1-alkyl-4-aryl-1,2,3-triazoles (1-methyl-4-phenyl-1,2,3-triazole (1a); 1-propyl-4-phenyl-1,2,3-triazole (1b); 1-benzyl-4-phenyl-1,2,3-triazole (1c); 1-propyl-4-p-tolyl-1,2,3-triazole (1d)) have been prepared through a one-pot procedure involving in situ generation of the alkyl azide from a halide precursor followed by copper catalysed alkyne/azide cycloaddition (CuAAC) with the appropriate aryl alkyne. Cationic Re(I) complexes [Re(bpy)(CO)(3)(1a-d)]PF(6) (2a-d) were then prepared by stirring [Re(bpy)(CO)(3)Cl] with AgPF(6) in dichloromethane in the presence of ligands 1a-d. X-ray crystal structures were obtained for 2a and 2b. In the solid state, 2a adopts a highly distorted geometry, which is not seen for 2b, in which the plane of the triazole ligand tilts by 13° with respect to the Re-N bond as a result of a π-stacking interaction between the Ph substituent and one of the rings of the bpy ligand. This π-stacking interaction also results in severe twisting of the bpy ligand. Infrared spectra of 2a-d exhibit ν(CO) bands at ～2035 and ～1926 cm(-1) suggesting that these ligands are marginally better donors than pyridine (ν(CO) = 2037, 1932 cm(-1)). The complexes are luminescent in aerated dichloromethane at room temperature with emission maxima at 542 to 552 nm comparable to that of the pyridine analogue (549 nm) and blue shifted relative to the parent chloride complex. Long luminescent lifetimes are observed for the triazole complexes (475 to 513 ns) in aerated dichloromethane solutions at room temperature.     

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