Structural characterisation of the perovskite series Sr0.9−xCaxCe0.1MnO3: Influence of the Jahn-Teller effect

Fifteen perovskite-type compounds Sr_0.9−xCa_xCe_0.1MnO₃, x=0-0.9 in steps as fine as 0.05, have been synthesised by solid state methods, and the room temperature structures characterised using X-ray synchrotron powder diffraction. At low Ca contents (x?0.45) the structures are tetragonal in space group I4/mcm and at high Ca contents (x?0.55) the compounds are orthorhombic in space group Pbnm. At room temperature these two phases co-exist in the compound with x=0.5. XANES measurements show the Ce to be present as Ce⁴⁺ in all the oxides. High temperature structures are reported for selected members.     

Controlled hydrothermal synthesis and growth mechanism of various nanostructured films of copper and silver tellurides

Various nanostructured films of copper and silver tellurides were hydrothermally grown on the corresponding metal substrates through reactions between metal foils and tellurium powder in different media. Interesting morphologies including nanowires, nanorods, nanobelts, nanosheets, and hierarchical dendrites were obtained. The nanostructured films were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution TEM (HRTEM). A growth mechanism was proposed based on the characterization results. This study provides a low-temperature, solution-phase approach to grow low-dimensional, nanostructured metal tellurides with controllable morphologies.     

Preparation and evaluation of novel stationary phases for improved chromatographic purification of pneumocandin B0

Preparation and evaluation of a number of stationary phases for improved chromatographic purification of pneumocandin B0, a key intermediate in the synthesis of the antifungal agent, Cancidas, has led to the identification of several materials with potential for improved performance.     

Stereoselective preparation of a cyclopentane-based NK1 receptor antagonist bearing an unsymmetrically substituted sec-sec ether

A highly efficient synthesis of the potent and selective NK-1 receptor antagonist 1 is described. The key transformation involved the etherification reaction between cyclopentanol 12 and chiral imidate 30 which was catalyzed by HBF4 to initially give ether 14 as a 17:1 mixture of diastereomers and in 75% combined yield. The diastereoselectivity was upgraded to 109:1 by crystallization of the triethylamine solvate 44 which was isolated in 54% yield from 12. Mechanistic studies confirmed that the etherification reaction proceeds through an unprecedented S(N)2 reaction pathway under typical S(N)1 reaction conditions.     

Measurement of the Residual Stress Tensor in a Compact Tension Weld Specimen

Neutron diffraction measurements have been performed to determine the full residual stress tensor along the expected crack path in an austenitic stainless steel (Esshete 1250) compact tension weld specimen. A destructive slitting method was then implemented on the same specimen to measure the stress intensity factor profile associated with the residual stress field as a function of crack length. Finally deformations of the cut surfaces were measured to determine a contour map of the residual stresses in the specimen prior to the cut. The distributions of transverse residual stress measured by the three techniques are in close agreement. A peak tensile stress in excess of 600 MPa was found to be associated with an electron beam weld used to attach an extension piece to the test sample, which had been extracted from a pipe manual metal arc butt weld. The neutron diffraction measurements show that exceptionally high residual stress triaxiality is present at crack depths likely to be used for creep crack growth testing and where a peak stress intensity factor of 35 MPa√m was measured (crack depth of 21 mm). The neutron diffraction measurements identified maximum values of shear stress in the order of 50 MPa and showed that the principal stress directions were aligned to within ~20° of the specimen orthogonal axes. Furthermore it was confirmed that measurement of strains by neutron diffraction in just the three specimen orthogonal directions would have been sufficient to provide a reasonably accurate characterisation of the stress state in welded CT specimens.     

Mapping Multiple Components of the Residual Stress Tensor in a Large P91 Steel Pipe Girth Weld Using a Single Contour Cut

The contour method is applied in an innovative manner to measure the distribution of hoop residual stress in a large martensitic-ferritic steel pipe containing a multi-pass girth weld. First, a novel one-step wire electro-discharge machining cut is conducted to divide the pipe lengthways into two halves. The deformation of the cut halves is then measured and analysed in a way that simultaneously gives maps of hoop stress across the wall thickness on both sides of the pipe and automatically accounts for through-thickness hoop bending effects and how they may vary along the pipe. Finally the contour method results are combined with X-ray diffraction residual stress measurements using the principle of superposition to determine the distribution of the axial and radial residual stresses in the pipe. It is thereby demonstrated how the distribution of three direct components of the residual stress tensor in a welded pipe can be readily determined using a “hybrid” contour measurement approach.     

Regularity and Singularities of Optimal Convex Shapes in the Plane

We focus here on the analysis of the regularity or singularity of solutions Ω ₀ to shape optimization problems among convex planar sets, namely:

$J(\Omega_{0})={\rm min} \{J(\Omega), \Omega \quad {\rm convex},\Omega \in \mathcal{S}_{\rm ad}\},$

where \({\mathcal{S}_{\rm ad}}\) is a set of 2-dimensional admissible shapes and \({J:\mathcal{S}_{\rm ad}\rightarrow\mathbb{R}}\) is a shape functional. Our main goal is to obtain qualitative properties of these optimal shapes by using first and second order optimality conditions, including the infinite dimensional Lagrange multiplier due to the convexity constraint. We prove two types of results:

1. i)
   under a suitable convexity property of the functional J, we prove that Ω ₀ is a W ^2,p -set, \({p\in[1, \infty]}\). This result applies, for instance, with p = ∞ when the shape functional can be written as J(Ω) = R(Ω) + P(Ω), where R(Ω) = F(|Ω|, E _f (Ω), λ₁(Ω)) involves the area |Ω|, the Dirichlet energy E _f (Ω) or the first eigenvalue of the Laplace–Dirichlet operator λ₁(Ω), and P(Ω) is the perimeter of Ω;
    

1. ii)
   under a suitable concavity assumption on the functional J, we prove that Ω ₀ is a polygon. This result applies, for instance, when the functional is now written as J(Ω) = R(Ω) ? P(Ω), with the same notations as above.