Sur le caractère thermo-extensif de la surface de charge d'un sol non saturéOn the thermo-extensive nature of the yield surface for an unsaturated soil

A study of temperature influence on the yield surface for one unsaturated soil at constant suction is presented. Mechanical consolidation tests are realized at different temperatures on clayey silty sand. A specific triaxial apparatus for unsaturated soils with temperatures included between 30 °C and 60 °C is used. Experimental results show without ambiguity a thermo-extensive nature of the yield surface. The physical interpretation proposed calls for microscopic considerations on the menisci capillary evolution according to temperature and suction. To cite this article: F. Jamin et al., C. R. Mecanique 332 (2004).     

Unraveling the Nature of Sites Active toward Hydrogen Peroxide Reduction in Fe-N-C Catalysts

Fe-N-C catalysts with high O₂ reduction performance are crucial for displacing Pt in low-temperature fuel cells. However, insufficient understanding of which reaction steps are catalyzed by what sites limits their progress. The nature of sites were investigated that are active toward H₂O₂ reduction, a key intermediate during indirect O₂ reduction and a source of deactivation in fuel cells. Catalysts comprising different relative contents of FeN_xC_y moieties and Fe particles encapsulated in N-doped carbon layers (0–100 %) show that both types of sites are active, although moderately, toward H₂O₂ reduction. In contrast, N-doped carbons free of Fe and Fe particles exposed to the electrolyte are inactive. When catalyzing the ORR, FeN_xC_y moieties are more selective than Fe particles encapsulated in N-doped carbon. These novel insights offer rational approaches for more selective and therefore more durable Fe-N-C catalysts.     

Morse theory and Lyapunov stability on manifolds

The aim of this article is to recall the main theorems of Morse theory and to infer some corollaries for the problem of Lyapunov stability on manifolds. It makes a link between Morse theory and the general theory of the Lyapunov stability for dynamical systems.     

One pot diastereoselective synthesis of new chiral spiro‐1,3,4‐thiadiazoles and 1,4,2‐oxathiazoles from (1R)‐thiocamphor

Herein we report an efficient one pot synthesis of new chiral 4,5‐dihydro‐4‐arylspiro[1,3,4‐thiadiazole]‐5,2′‐camphane‐2‐carboxylic acid ethyl esters 5–7 and 4,5‐dihydro‐3‐arylspiro[1,4,2‐oxathiazole]‐5,2′‐camphane 11–13 , using 1,3‐dipolar cycloaddition of nitrilimines 2–4 and nitrile oxides 8–10 to (1R)‐thiocamphor 1 respectively. The structure of the newly prepared 1,3,4‐thiadiazoles 5–7 (obtained as pure diastereoisomers) were fully established via spectroscopic analysis and X‐ray structural analysis which proved the absolute configuration of the C5 spiranic carbon to be (R). NMR spectral analysis were also very useful to show the new 1,4,2‐oxathiazoles 11–13 are mixtures of two (5R)/(5S) diastereoisomers with the ratio 6:4,7:3 and 6:4 respectively.     

Square‐Wave Voltammetric Determination of Paraquat at Carbon Paste Electrode Modified with Hydroxyapatite

The voltammetric behavior of paraquat was investigated at hydroxyapatite‐modified carbon paste electrode HAP‐CPE in K₂SO₄. A method was developed for the detection of the trace of this herbicide, based on their redox reaction. The reduction peaks of paraquat were observed around ?0.70 V and ?1.00 V (vs. SCE) in square‐wave voltammetry. Experimental conditions were optimized by varying the accumulation time, apatite loading and measuring solution pH. Calibration plots were linear under the optimized parameters over the herbicide's concentration range 8–200×10^?7 mol L^?1, with a detection and quantification limits about 1.5×10^?8 mol L^?1 and 6.4 10^?8 mol L^?1, respectively.     

F-theory and N=1 Quivers from Polyvalent Geometry

We study four-dimensional quiver gauge models from F-theory compactified on fourfolds with hyper-K¨ahler structure.Using intersecting complex toric surfaces,we derive a class of N =1 quivers with charged fundamental matter placed on external nodes.The emphasis is on how local Calabi–Yau equations solve the corresponding physical constraints including the anomaly cancelation condition.Concretely,a linear chain of SU(N) groups with flavor symmetries has been constructed using polyvalent toric geometry.     

Hemisynthesis,crystal structure and inhibitory effect of sesquiterpenic thiosemicarbazones and thiazolidin‐4‐ones on the corrosion behaviour of stainless steel in 1 M H2SO4 solution

Treatment of thiosemicarbazones prepared from sesquiterpenes with ethyl 2‐bromoacetate in the presence of sodium acetate afforded the corresponding thiazolidin‐4‐ones. The structures of all the newly synthesized compounds were established by considering spectral and single‐crystal X‐ray diffraction data. The title compound, ethyl 2‐((Z)‐2‐{(Z)‐[(1aR,5aR,9aS)‐1,1‐dichloro‐1a,5,5,7‐tetramethyl‐1a,2,3,4,5,5a,8,9‐octahydro‐1H‐benzo[a]cyclopropa[b][7]annulen‐8‐ylidene]hydrazono}‐4‐oxothiazolidin‐3‐yl)acetate, C₂₃H₃₁Cl₂N₃O₃S, 5 , crystallizes in the orthorhombic noncentrosymmetric space group P2₁2₁2₁ with Z = 4. Within the molecule in the crystal structure, the cyclohexene ring has an envelope conformation and the cycloheptane ring, to which it is fused, has a boat conformation. In the crystal, molecules are linked by C—H…Cl hydrogen bonds forming chains propagating along the b‐axis direction. The absolute configuration of the molecule in the crystal could be fully confirmed from anomalous dispersion effects [Flack parameter = ?0.04 (2)]. Thiosemicarbazones 1 and 2 are efficient inhibitors for steel corrosion in 1 M H₂SO₄ solution, with a maximum efficiency of 92.28% at 10^?3 M. Furthermore, thiosemicarbazone compounds were found to be more efficient than thiazolidin‐4‐one derivatives. In addition, cyclic voltammetry was used to characterize the tested molecules, as well to estimate the experimental value of the energy band gap.     

Magnetocaloric Effect in Anisotropic Mixed Spin ½—1 System: Pair Approximation Method

We use the Pair Approximation method to analyze the magnetic and magnetocaloric behaviors of diluted mixed spin ${\rm S_A}$=1 and spin ${\rm S_B}$=1/2 with the anisotropic Heisenberg model, on a cubic lattice with coordination number $z$=6. Our system is described in presence of an external magnetic field; the phase diagram and thermodynamic properties related to the concentration of magnetic atom (A or B) and the single ion anisotropy are constructed and discussed. Special attention is paid to magnetocaloric properties provided by isothermal entropy change as well as the cooling capacity. These cooling power keys are plotted and discussed as a function of interaction anisotropy and magnetic component concentration of two sublattices ions A and B. Numerical results show a double peak structure in the entropy change curve and the inverse magnetocaloric effect related to the presence of the negative single-ion anisotropy.     

Microemulsion breakdown by pervaporation technique: effect of the alkyl chain length of n-alkanol, a cosurfactant of the microemulsion

Two sets of microemulsions, cyclohexane- and water-rich ones, were prepared with the following n-alkanols as cosurfactants: n-propanol, n-butanol, n-pentanol, and n-hexanol. The results showed the influence of the alkyl chain length of the n-alkanol on the permselectivity properties of the pervaporation technique in the breakdown of the microemulsions. The variations of the total flux rate J and the enrichment factor beta were in parallel with the effect of the cosurfactant on the swelling extent of the PDMS membrane.