Static shakedown theorems in piecewise linearized poroplasticity

Summary A fully saturated two-phase solid or structure subjected to variable, in particular cyclic, external actions is described as a nonhardening poroelastoplastic material with piecewise linearized yield loci. With reference to a multifield finite element model, sufficient and necessary conditions for shakedown are established by the static Melan's approach. Shakedown analysis by linear programming is briefly discussed. Received 29 December 1997, accepted for publications 25 June 1998     

Quadratic programming and theory of elastic-perfectly plastic structures

Summary For elastic perfectly plastic discretized structures acted upon by given loads and dislocations, it is shown, under holonomic constitutive laws or no local unloading hypothesis, that the formulation of the analysis problem in terms of finite (not incremental) stresses, is amenable to the Kuhn-Tucker conditions of a quadratic program. Then it is readily derived a generalized form of the principle of Haar and Kármán, together with an extremum theorem for displacements and plastic strains, which is the dual of the preceding one. As special cases of this theorems known variational principles follow, which thus turn out to be related in pairs by the duality notion as understood in programming theory. Also the statical and kinematical theorems of limit analysis are proved by means of the unitary conceptual framework supplied by quadratic programming.

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Sommario Con riferimento a strutture discretizzate idealmente elastoplastiche, soggette a dati carichi e distorsioni, si mostra che nell'ipotesi di olonomia dei legami costitutivi o di assenza di ritorni elastici, la formulazione del problema strutturale negli sforzi finiti (non incrementali) è riducibile alle condizioni di Kuhn e Tucker di un programma quadratico. Se ne deducono direttamente una forma generalizzata del principio di Haar e Kármán ed un teorema di estremo negli spostamenti e nelle deformazioni plastiche, duale al precedente. Dai due teoremi discendono come casi speciali noti principi variazionali, che cosi risultano collegati in coppie dalla nozione di dualitá propria della teoria delle ottimizzazioni.Si mostra come anche i teoremi statico e cinematico del calcolo a rottura trovano una nuova dimostrazione nell'inquadramento teorico unitario fondato sulla programmazione quadratica.

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The results presented here form part of a series of studies supported by the C.N.R. (National Research Council).     

Exciplexes in highly excited triplet states

A mechanism of energy transfer from highly excited triplet aromatic molecules has been developed, which involves a stage of formation of an exciplex between a highly excited energy-donor molecule and an unexcited energy-acceptor molecule. Interpretation of the experimental data on the shape and the intensity of triplet-triplet absorption bands and the energy transfer probability is presented. In this interpretation, the results of quantum-chemical calculations of the energies of highly excited triplet states of toluene and benzene molecules are used.     

Renner-Teller and Fermi resonance interactions for the v3=1 and v7=2 vibronic levels in the A2Πu and X2Πg electronic states of HC4H+

The excitation of the v(3) = 1 (σ(g)(+) C-C stretch) and the v(7) = 2 (π(g)(2) C≡C-C bend) modes in the A(2)Π(u) electronic state of diacetylene cations results in Renner-Teller (R-T) and Fermi interactions. The 3(0)(1) and 7(0)(2) vibronic bands in the A(2)Π(u)-X(2)Π(g) transition of HC(4)H(+) have been measured with rotational resolution using cavity ringdown spectroscopy in a supersonic slit jet discharge. The analysis yields T(00) = 20520.828(4) cm(-1), B' = 0.14047(2) cm(-1), and A' = -17.95(1) cm(-1) for the v(3) = 1 and T(00) = 20573.659(4) cm(-1), B' = 0.14018(3) cm(-1), and A' = -11.55(1) cm(-1) for the v(7) = 2 level in the A(2)Π(u) electronic state. A vibronic analysis has been carried out taking into consideration the R-T, spin-orbit, and Fermi resonance interactions between the ν(3) and ν(7) modes. The levels are fitted to the eigenvalues of an appropriate Hamiltonian matrix. This yields the vibrational frequencies ω(3)′ = 811.8 cm(-1) and ω(7)′ = 403.2 cm(-1), Renner parameter ε(7)′ = 0.065, Fermi coefficients W(1)′ = 10.3 cm(-1) and W(2)′ = 5.1 cm(-1), and spin-orbit interaction constant A(SO)′ = -31.1 cm(-1). A corresponding R-T analysis has been carried out for the X(2)Π(g) ground state of HC(4)H(+) using data available in the literature [Callomon, J. H. Can. J. Phys. 1956, 34, 1046]. This gives ω(3)" = 956.2 cm(-1), ω(7)" = 435.4 cm(-1), ε(7)" = 0.028, W(1)" = 7.2 cm(-1), W(2)" = 10.9 cm(-1), and A(SO)" = -33.3 cm(-1).     

Direct observation of lithium staging in partially delithiated LiFePO4 at atomic resolution

Lithium ions in LiFePO(4) were observed directly at atomic resolution by an aberration-corrected annular-bright-field scanning transmission electron microscopy technique. In addition, it was found in partially delithiated LiFePO(4) that the remaining lithium ions preferably occupy every second layer, along the b axis, analogously to the staging phenomenon observed in some layered intercalation compounds. This new finding challenges previously proposed LiFePO(4)/FePO(4) two-phase separation mechanisms.     

Conformational studies of the robust 2-Cys peroxiredoxin Salmonella typhimurium AhpC by solution phase hydrogen/deuterium (H/D) exchange monitored by electrospray ionization mass spectrometry

This is the first comprehensive HX-MS study of a "robust" 2-Cys peroxiredoxin (Prx), namely Salmonella typhimurium AhpC (StAhpC). Prx proteins control intracellular peroxide levels and are abundant antioxidant proteins in eukaryotes, archaea and bacteria. Crystal structural analyses and structure/activity studies of several bacterial and mammalian 2-Cys Prxs have revealed that the activity of 2-Cys Prxs is regulated by redox-dependent oligmerization and a sensitivity of the active site cysteine residue to overoxidation. The propensity to overoxidation is linked to the conformational flexibility of the peroxidatic active site loop. The HX-MS results emphasize the modulation of the conformational motility of the active site loop by disulfide formation. To obtain information on the conformational impact of decamer formation on the active site loop motility, mutants with Thr77 substituted by Ile, a decamer-disrupting mutation or by Val, a decamer-stabilizing mutation, were studied. For the isoleucine mutant, enhanced mobility was observed for regions encompassing the α4 helix located in the dimer-dimer interface and regions surrounding the peroxidatic loop. In contrast, the T77V mutation resulted in an increase in conformational stability in most regions of the protein except for the active site loop and the region encompassing the resolving cysteine.     

Mixed conductivity in nanocrystalline highly acceptor doped cerium oxide thin films under oxidizing conditions

We report on the investigation of 10 mol% gadolinium-doped cerium oxide thin films of various microstructures prepared by pulsed laser deposition. Depending on substrate, growth conditions and hence microstructure, the electric conductivity values vary considerably by several orders of magnitude. Remarkably, in the sample with the highest grain boundary density, we even have evidence of substantial electronic conductance under oxidizing conditions despite the large acceptor level. This possibly surprising result can be explained by an increased space charge potential at the grain boundaries in combination with the small grain size of 10 nm that leads to an enrichment of excess electrons while the ion conduction is simultaneously blocked by vacancy-depleted regions.