Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.     

Quantitative and high mass ToF-SIMS studies of siloxane segregation in hydrogel polymers using cryogenic sample handling techniques

This paper examines the capabilities of cryogenic sample handling to examine composition and structure of hydrogel materials where siloxane components are central to the analysis. XPS analysis of multicomponent polymers with cryogenic sample handling following exposure to aqueous environments has revealed the composition and kinetics of near surface reorganization for siloxane and fluorocarbon containing polymers. In this study we report results from a ToF-SIMS protocol for cryogenic sample handling applied to the analysis of surface changes upon hydration/dehydration of hydrogel polymers. Comparison of results from angle dependent XPS and ToF-SIMS are discussed for a range of commercial soft contact lens materials. Both methods detected changes in surface chemistry between the hydrated (frozen) and dehydrated surfaces. Analysis of the hydrated surfaces detected polymer components indicative of the commercial formulation as well as ice clusters. Analysis of the dehydrated materials detected changes in surface chemistry relative to the hydrated surface in addition to loss of water due to sample dehydration. A quantitative standard additions method for ToF-SIMS data was used to determine submonolayer amounts of PDMS impurities at the surface of the hydrogels. ToF-SIMS analysis of a series of seven poly (allyl methacrylate-g-dimethylsiloxane), AMA-g-DMS, graft copolymers in the hydrated state revealed high mass oligomeric ion distributions for systems with bulk PDMS content greater than 25 wt.%. This marks the first time that detection of high mass oligomeric ion distributions from hydrated (frozen) surfaces has been reported. Analysis of the dehydrated surface detected formation of high mass oligomeric ion distributions for systems with PDMS bulk content greater than 15 wt.%, but only detected these ion distributions in wet (frozen) samples when the bulk concentration was greater than 25 wt.%.     

高强混凝土弯压极限应变试验研究与计算

由于混凝土材料理化特性的差异,高强混凝土的弯压极限应变明显地小于普通混凝土,依据试验结果分析了高强混凝土的弯压极限应变变化规律,并给出了它的计算公式.     

应用加权列联表分析预测汛期（4─9月）洪涝趋势

本文根据汉寿县１９６０─１９８８年洪涝灾害资料，应用加权列联表分析法，与前期气候因子建立洪涝趋势预测模式。最后对１９８９─１９９０年洪涝试报，取得了满意的效果。     

Strength of cylinder joint adhesively bonded by coupling

Summary A method of joining two metal cylindrical shafts with adhesive coupling is proposed. Two cylindrical shafts with the same diameter are connected by bonding through a cylindrical coupling with epoxy resin. The strength of the shaft joint under tensile loading and torsional loading is investigated analytically and experimentally. The stress and strain distributions of the shaft joint is analyzed by the finite element method. The analyzed strain distributions in the joint are compared with experimental values. The joint strength is predicted by applying the strength laws of shafts, coupling, adhesive layer and adhesive interface between shaft and adhesive coupling. The effects of the coupling dimension on the joint strength are examined. It is shown that the adhesive shaft joint can transfer the load by which the cylindrical shafts are plastically deformed.This paper was refined by the author, K. Ikegami, during statying at Technische Universität München under the support of Deutscher Akademischer Austauschdients. The author is grateful to Professor Lippmann of Technische Universität München who is the host professor of the support.     

A numerical study of an unsteady laminar flow in a doubly constricted 3D vessel

Unsteady flow dynamics in doubly constricted 3D vessels have been investigated under pulsatile flow conditions for a full cycle of period T. The coupled non‐linear partial differential equations governing the mass and momentum of a viscous incompressible fluid has been numerically analyzed by a time accurate Finite Volume Scheme in an implicit Euler time marching setting. Roe's flux difference splitting of non‐linear terms and the pseudo‐compressibility technique employed in the current numerical scheme makes it robust both in space and time. Computational experiments are carried out to assess the influence of Reynolds' number and the spacing between two mild constrictions on the pressure drop across the constrictions. The study reveals that the pressure drop across a series of mild constrictions can get physiologically critical and is also found to be sensitive both to the spacing between the constrictions and the oscillatory nature of the inflow profile. The flow separation zone on the downstream constriction is seen to detach from the diverging wall of the constriction leading to vortex shedding with 3D features earlier than that on the wall in the spacing between the two constrictions. Copyright © 2002 John Wiley & Sons, Ltd.     

Asymptotic analysis of elastic curved rods

We consider a sequence of curved rods which consist of isotropic material and which are clamped on the lower base or on both bases. We study the asymptotic behaviour of the stress tensor and displacement under the assumptions of linearized elasticity when the cross‐sectional diameter of the rods tends to zero and the body force is given in the particular form. The analysis covers the case of a non‐smooth limit line of centroids. We show how the body force and the choice of the approximating curved rods can affect the strong convergence and the limit form of the stress tensor for the curved rods clamped on both bases. Copyright © 2006 John Wiley & Sons, Ltd.     

On the deformation and fracture of porous materials

The constitutive behavior of porous materials (including the yield loci, the void growth rate, the macro stress-strain relation and the strain to localization instability) is examined based on the lower bound approach proposed by the present authors. These results are then compared with the experimental and the finite element results as well as those predicted by Gurson's equations. Emphasis is placed on approaching the real behavior from the upper and the lower bound analysis. Calculation is also made on the influence of void nucleation on the critical strain to instability and a modified strain-controlled nucleation criterion is proposed. Finally the instability and fracture of AISI4340 steel in plane strain tension is examined and comparison is made between theoretical and experimental results.     

Amending cultures of selenium-resistant bacteria with dimethyl selenone

A possible biological intermediate in the reduction and methylation of selenium oxyanions, dimethyl selenone, was synthesized, and the first experiments involving the amendment of selenium resistant bacterial cultures with this compound are reported. The amount of volatile, reduced selenium-containing species released from these cultures into the headspace is significantly more than that produced in analogous experiments involving sodium selenate amended cultures. Dimethyl selenone is reduced in the presence of dimethyl sulfide and dimethyl disulfide in a complex growth medium, trypticase soy broth with 0.1% nitrate. This reduction occurs whether or not the reduced sulfur compounds are biologically produced.