DSC analysis of strengthening precipitates in ultrafine Al–Mg–Si alloys

Equal channel angular pressing (ECAP) was carried out on solution annealed samples of Al–Mg–Si–Zr and Al–Mg–Si–Zr–Sc alloys to achieve a substantial grain refinement of the materials. Post ECAP aging was then investigated on the ultrafine grained alloys by DSC and TEM analyses. DSC scans were carried out with heating rates ranging from 5 to 30°C min^–1. Peak identification was performed by the support of literature information and TEM analyses. Precipitation kinetics revealed to be similar for both alloys but the Sc-free alloy showed a recrystallization peak at temperatures ranging from 310 to 340°C, depending on the strain accumulated during ECAP. On the contrary, the Sc-containing alloy showed a greater grain stability. Analyses of peak positions and of activation energies as a function of ECAP passes experienced by the samples revealed large modifications of precipitation kinetics in the ultrafine-grained alloys with respect to the coarse-grained materials.     

Optimal Control in Heterogeneous Domain Decomposition Methods for Advection-Diffusion Equations

New domain decomposition methods (DDM) based on optimal control approach are introduced for the coupling of first and second order equations on overlapping subdomains. Several cost functionals and control functions are proposed. Uniqueness and existence results are proved for the coupled problem, and the convergence of iterative processes is analyzed. The work was supported by the Russian Foundation for Basic Research (04-01-00615) and it was partly carried out while the first author was visiting the IACS at EPFL.     

Propagation of mesons in asymmetric nuclear matter in a density-dependent coupling model

We study the propagation of the light mesons σ,ω,ρ, and a₀(980) in dense hadronic matter in an extended derivative scalar coupling model. Within the scheme proposed it is possible to unambiguously define effective density-dependent couplings at the Lagrangian level. We first apply the model to study asymmetric nuclear matter with fixed isospin asymmetry, and then we pay particular attention to hypermatter in β-equilibrium. The equation of state and the potential contribution to the symmetry coefficient arising from the mean-field approximation are investigated. Received: 16 October 2001 / Accepted: 10 January 2002     

Some properties of multi-degree-of-freedom potential systems and application to statistical equivalent non-linearization

This paper presents some properties of two restricted classes of multi-degree-of-freedom potential systems subjected to Gaussian white-noise excitations. Specifically, potential systems which exhibit damping terms with energy-dependent polynomial form are referred to. In this context, first systems with coupled stiffness terms and damping terms depending on the total energy are investigated. Then, systems with uncoupled stiffness terms and damping terms depending on the total energy in each degree-of-freedom are considered. For these two classes, it is found that algebraic relations among the stationary statistical moments of the energy functions can be derived by applying standard tools of Itô calculus. Further, it is noted that these relations are very useful within the framework of an equivalent statistical non-linearization technique to build approximate solutions for arbitrary non-linear systems.     

Ageing of wet-synthesized oxide powders

Wet chemical synthesis of precursor oxide ceramics is a method to obtain small particulate powders. Such powders are far more prone to ageing in air than more traditional precursors. Thermogravimetric analysis is used to highlight the species responsible for the ageing of ceramic precursors. Indeed water and carbon dioxide are observed to evolve from aged powders. Ceramics obtained from aged precursors can reach a very low final density with respect to the theoretical value. A large degree of the original sintering properties can be recovered after washing the aged powders with ethanol in a basic medium.     

Numerical analysis of a model of cure process for composites

We consider a composite material composed of fibres included in a resin which becomes solid when it is heated up (reaction of reticulation). The mathematical modelling of the cure process is given by a kinetic equation describing the evolution of the reaction of reticulation coupled with the heat equation. In this paper, we are interested in the computation of approximate solutions. We propose a family of discretized problems depending on two parameters (β₁, β₂) ε [0, 1]² which split the linear and non‐ linear terms in implicit and explicit parts. We prove the stability and convergence of the discretization for any (β₁, β₂) ε [½, 1 ] × [0, 1]. We present also some numerical results. Copyright © 2006 John Wiley & Sons, Ltd.     

Palladium-arene interactions in catalytic intermediates: an experimental and theoretical investigation of the soft rearrangement between eta1 and eta2 coordination modes

A series of dichloro-bridged arylbicycloheptylpalladium complexes have been synthesized and characterized by means of NMR spectroscopy. The compound [(C16H19)PdCl]2*CH2Cl2 with ortho and para methyl substituents at the arene has been characterized by means of X-ray diffraction techniques. The C(ipso) atom of the arene lies almost at the fourth planar coordination site of the metal [Pd-C(ipso) = 2.22(1) A (average)], and due to the arene's tilting, the substituted C(ortho) atom is relatively close to the metal atom [2.54(1) A (average)]. The coordinated C(ipso)-C(ortho) linkage, in a seemingly dihapto coordination, is anti with respect to the CH2 bridge of the bicycloheptyl unit. Variable-temperature NMR experiments for the para-substituted dimer 9 reveal restricted rotation of the two aryl groups about the corresponding C-C(ipso) bonds (DeltaE < or =17 kcal x mol(-1)). DFT-B3LYP calculations have been carried out on the known and similar monomer (phenylbicycloheptenyl)Pd(PPh3)I (4) and its related substituted derivatives. The essential results are as follows: (i) The potential energy surface for twisting the phenyl ring away from the symmetric eta(1) coordination in 4 is very flat (DeltaE < or = 1 kcal x mol(-1)) whereas an Atoms in Molecules analysis excludes the existence of an actual Pd-C(ortho) bond in the seemingly eta2-type conformer. (ii) Complete rotation of the unsubstituted phenyl ring is not facile but feasible. A significant strain affects the transition-state structure featuring a Pd-HC(aryl) agostic-type bond. The calculated destabilization of 10.3 kcal x mol(-1), with respect to the ground state, can be compared to the experimental barrier of the dimer 9. (iii) Various methyl-substituted derivatives of 4 have been optimized, and their structural and energetic trends are discussed. An almost ideal eta1 coordination is shown by the anti conformer of the C(ortho)-substituted complex due steric effects. For all of the other cases, a slipped eta2 coordination may be described. As a general conclusion, the unsaturated metal center receives pi electron density of the arene mainly through its C(ipso) atom. The effect may be slightly improved if the C(ortho) atom also gets closer to the metal, but in no case, does the slipped eta2 coordination seem to be crucial for the stability of the system.     

A thorough study of the surface wax of apple fruits

The composition of the surface waxes of three apple ( Malus domestica L.) cultivars ("Florina", "Golden B" and "Ozark Gold") has been studied by means of spectroscopic and GC–MS analysis of the class-fractionated mixture of components. Odd n -alkanes, mainly C₂₇ and C₂₉ molecules, are prevalent in the saturated fraction. Small concentrations of alkenes were also found; the C_28:1 component is strongly (72%) in excess over the other 1-alkenes. Straight-chain esters (mainly of palmitic acid) of saturated primary alcohols (C₁₈–C₃₀) were also detected; whereas the acyl moiety is made up essentially of an even number of carbons, the alcohol counterpart does not exhibit this characteristic. Aldehydes are present (C₂₀–C₃₀) with the homologue patterns C₂₆–C₃₀ most strongly represented. Straight-chain free secondary alcohols characterize the waxes of "Florina" and "Ozark Gold"; the hydroxy function is located far from the extremity of the carbon framework. Outstanding is the presence of three alcohols with 29 carbon centres. These alcohols are accompanied by free straight-chain primary alcohols, mainly with even-numbered carbon chains in the range C₂₆–C₃₀. Free fatty acids are present; all of have a framework of even-numbered carbon chains mainly in the range C₁₆–C₂₀. C_18:1 (oleic acid) is well represented.     

A conductive elastomer based on EPDM and polyaniline: II. Effect of the crosslinking method

Electrically conductive heterogeneous binary polymer blends based on ethylene-propylene-diene-monomer (EPDM) and polyaniline (PAni) were prepared in a Haake Rheocord 90 rheometer, coupled with an internal mixer (counter rotating cam rotors) using different amounts of PAni doped with dodecylbenzenosulfonic acid (DBSA). Blends were crosslinked using two methods: (i) phenolic resin (SP-1045) as crosslinking agent and (ii) electron beam irradiation. The last method avoids the interference of the acid dopant in the crosslinking process and produces blends with higher conductivity.     

Structure of the hydrated and dimethyl sulfoxide solvated rubidium ions in solution

The structure of the hydrated and the dimethyl sulfoxide solvated rubidium ions in solution has been determined by means of large-angle X-ray scattering (LAXS) and extended X-ray absorption fine structure (EXAFS) studies. The models of the hydrated and dimethyl sulfoxide solvated rubidium ions fitting the experimental data best are square antiprisms with Rb-O bond distances of 2.98(2) and 2.98(3) A, respectively. The EXAFS data show a significant asymmetry in the Rb-O bond distance distribution with C(3) values of 0.0076 and 0.015 A(3), respectively. No second hydration sphere is observed around the hydrated rubidium ion. The dimethyl sulfoxide solvated rubidium ion displays a Rb-O-S bond angle of ca. 130 degrees, which is typical for a medium hard electron acceptor such as rubidium.