Simplified prediction of creep buckling of cylinders under external pressure. Part 1: finite element validation

In this paper, a simplified method is proposed for the prediction of creep buckling. This simplified approach relies upon a model which yields an analytical evaluation of creep buckling times for cylinders under external pressure. This model is fully developed herein, and a ‘closed-form’ solution is given for the evaluation of the critical creep collapse time. The collapse mechanism is assumed to be due to the formation of a plastic hinge which induces an unstable post-buckling of the ring. The analytical ‘closed-form’ creep collapse time is then compared to finite element buckling predictions using the quasi-axisymmetric COMU shell element in the INCA code of the CASTEM system. The model is then applied to four different cylinders under external pressure and compared to finite element predictions; the cylinders' radius-to-thickness ratio varies between 50 and 550. It is shown that the proposed model performs well for this type of prediction: in all cases, the times to failure predicted by the model are lower than the finite element predictions. These predictions prove to be rather conservative for thicker cylinders. It is shown that creep buckling is a very dangerous failure mode. If the shape of the structure is observed as a function of time, nothing seems to happen during a very long ‘incubation’ period; when the initial imperfection reaches some critical value, buckling then suddenly occurs. This phenomenon is shown by the two methods of evaluation presented herein.     

Cyclic Cohomology and Hopf Algebras

We associate canonically a cyclic module to any Hopf algebra endowed with a modular pair in involution, consisting of a group-like element and a character. This provides the key construction for allowing the extension of cyclic cohomology to Hopf algebras in the nonunimodular case and, further, to developing a theory of characteristic classes for actions of Hopf algebras compatible not only with traces but also with the modular theory of weights. This applies to both ribbon and coribbon algebras as well as to quantum groups and their duals.     

New aromatic annulation reaction via a C14 enaminone synthon: synthesis of ‘terpenoid-like chalcones’

Diverse functionalized synthons from a new enaminone are reported. These synthons were easily obtained in a one pot process starting from a compound derived from β-ionone. A new annulation reaction of this C-14 compound with several anions led to new ‘terpenoid-like’ chalcones.     

Adsorption kinetics of beta-lactoglobulin on a polyclonal immunochromatographic support

Beta-Lactoglobulin is one of the main components of whey proteins. Among other reasons, its allergenicity makes its determination in hypoallergenic foods and bio-pharmaceutical products necessary. Immunoaffinity chromatography is a widely accepted technique for purification and analysis of proteins. Knowledge of the apparent kinetics of the adsorption of beta-lactoglobulin onto the anti-beta-lactoglobulin immunochromatographic column is important to optimize the analytical process. High-performance frontal affinity chromatography was used to study the apparent kinetics of the adsorption process. Langmuir and bi-Langmuir kinetic models, assuming one and two kinds of binding sites, respectively, were used to characterize the adsorption kinetics of beta-lactoglobulin B on a polyclonal immunoadsorbent. Very good fits were obtained with the bi-Langmuir model for two different concentrations of beta-lactoglobulin and this allowed us to calculate the apparent adsorption rate constants and the column capacities for both kinds of sites. Experimental results indicate the possibility that the adsorption process is not irreversible. The values of the apparent dissociation rate constants leading to the best fit were estimated and the affinity constants were calculated.     

Synthesis of new polyaza heterocycles. Part 42: Diazines

Using Pd-catalyzed Stille cross-coupling reactions, we report here the synthesis of various mono- or bis(tri-n-butylstannyl)diazines which were reacted with various halogenated diazines to access to various polyaza heterocyclic derivatives.     

The dielectric function of LnSF rare-earth fluorosulfides (Ln=La, Ce): experiment and theory

The absorption properties of LaSF and CeSF in the UV-Visible range have been investigated on the basis of first principles density functional theory (DFT) calculations and from electron energy-loss spectroscopy (EELS) measurements. The extinction coefficient k, as well as the refractive index n, determined experimentally from the loss function Im(−1/ε), were compared with the corresponding factors extracted from the calculated dielectric tensor ε₂. The k and n values for the two compounds were expected to be very close to each other, owing to the chemical similarity of La and Ce. However, it was found that the nature of the electronic transitions in LaSF and CeSF strongly influences the k and n values with the result that the refractive index n and the extinction coefficient k are substantially larger for LaSF than for CeSF.     

Theq-state Potts model in the standard Pirogov-Sinai theory: Surface tensions and Wilson loops

Theq-state Potts model (both scalar and gauge versions) is rewritten, with the help of the duality transformation, into a form of the Pirogov-Sinai theory with noninteracting contours that can be controlled by cluster expansions onceq is large enough. This is then used in a new proof of the existence of a unique transition (inverse) temperature _t , where the mean internal energy is discontinuous. Moreover, we prove for the scalar model (again forq large enough) that there are discontinuities at _t of the magnetization and of the mass gap, with the magnetization vanishing below _t and the mass gap vanishing above _t . We also show that the surface tensions between ordered stable phases are strictly positive up to _t , and the surface tension between an ordered phase and the disordered one is strictly positive at _t . For the three-dimensional gauge model, the Wilson parameter exhibits a direct transition from an area law decay (quark confinement) to a perimeter law decay (deconfinement).On leave from ENS Rabat, Morocco.     

Monomer adsorption on equilateral triangular lattices with attractive first-neighbor interactions

We have recently studied a model of monomer adsorption on infinitely long equilateral triangular lattices with terraces of finite width M and nonperiodic boundaries. This study was restricted to the case of repulsive adsorbate-adsorbate first-neighbor interactions but included attractive, repulsive, and negligible second-neighbor interactions. The present work extends this study to the case of attractive first-neighbors, and the phases are determined, as before, with a confidence exceeding 10 significant figures. Phase diagrams are included for terrace widths M < or =11. Most of the occupational characteristics of the phases fit exact analytic expressions in M. The infinite-M limit of these expressions, combined with other analyses, provide the complete phase diagram for the infinite two-dimensional lattice. In addition to the empty and full coverage phases, there are three phases exhibiting stripe and cluster features that were not observed in the case of repulsive first-neighbors.     

Factors influencing mononuclear versus multinuclear coordination in a series of potentially hexadentate acyclic N6 ligands: the roles of flexibility and chelate ring size

The synthesis of the new potentially hexadentate ligands N,N'-bis(2,2'-bipyridin-6-ylmethyl)butane-1,4-diamine (bmbu), N,N'-bis(2,2'-bipyridin-6-ylmethyl)pentane-1,5-diamine (bmpt) and N,N'-bis(2,2'-bipyridin-6-ylmethyl)octane-1,8-diamine (bmot) from the condensation of 2,2'-bipyridine-6-carbaldehyde with the appropriate diamine (butane-1,4-diamine, pentane-1,5-diamine and octane-1,8-diamine, respectively) and subsequent reduction, is reported. Bmet, bmpp and bmbu all form mononuclear complexes with first-row transition metal ions (Co(3+), Fe(2+), Ni(2+), Mn(2+)), and X-ray structures of [Mn(bmet)](ClO(4))(2), [Ni(bmet)](ClO(4))(2), [Fe(bmet)](ClO(4))(2), [Mn(bmpp)](ClO(4))(2)·2MeCN and [Co(bmpp)](ClO(4))(3)·H(2)O are reported. As the aliphatic methylene chain increases in length, formation of dinuclear, and in some cases trinuclear, complexes becomes more pronounced, as evidenced by mass spectral analysis of solutions containing Ni(2+) and bmpt, and Ni(2+), Fe(2+) and Mn(2+) with bmot. The increasing preference for multinuclear complexes with increasing chain length is ascribed to the difficulty of incorporating a medium-sized (8 to 13-membered) chelate ring in a mononuclear complex.     

Ethylene–propylene copolymerization initiated with solubilized Ziegler–Natta macromolecular complexes. I. Determination of kinetic parameters

Copolymerization of ethylene with propylene (E–P) was initiated with soluble polystyrene –butadiene–Li/TiCl₄ complexes in toluene leading to vinylic-olefinic based block copolymers. The activity of the system was measured at a constant ratio r = Li/Ti for different feed compositions. From measurements of the amount of copolymers produced, a direct determination of the efficiency of the catalytic system was made. This efficiency was found to be close to that obtained for homopolymerizations of C₂H₄ and C₃H₆ initiated with the same catalytic complex (? 80% with respect to the concentration of “carbon-titanium” bonds). Both the measured values of the efficiency and the determination of the molar masses of the polyolefinic block are consistent with a living character of the system involved in the E–P copolymerization. In such conditions well-defined linear [styrene]-b-[ethylene-co-propylene] copolymers were obtained. Furthermore, ¹³C NMR analyses allowed determination of the comonomer reactivity ratios, the values of which indicate an E–P random copolymerization. From both these values and those of the absolute rate constants of propagation determined for the homopolymerization of C₂H₄ and C₃H₆ initiated with the same catalytic system, the absolute rate constants of cross-propagation were deduced.