Micro–macro analysis of granular material behavior along proportional strain paths

When granular materials are subjected to proportional strain loading paths, they manifest a variety of behaviors depending on the initial void ratio of the specimen as well as the imposed dilatancy/contractancy rate. In some cases, the stress components may vanish over the duration of the test, and the specimen may progressively liquefy. To investigate this behavior, the authors have developed a kinematic approach to be deployed in two parts. First, numerical simulations are performed by means of a discrete element method. Secondly, two micromechanical models have corroborated the DEM results. The performance of these models may explain a number of microstructural mechanisms responsible for the macroscopic constitutive behavior.     

Relationships between molar mass and fracture properties of segmented urethane and amide copolymers modified by chemical degradation

This publication highlights the structure–property relationships in several thermoplastic elastomers (TPEs): one poly(ether-block-amide) and two thermoplastic polyurethane elastomers with ester and ether soft blocks. Structural changes are induced by chemical degradation from virgin samples through hydrolysis and oxidation. Molar mass measurements show an exclusive chain scission mechanism for all TPEs, regardless of the chemical modification condition. Mechanical behavior was nevertheless obtained from uniaxial tensile testing and fracture testing while considering the essential work of fracture (EWF) concept. During the macromolecular scission process, elongation at break shows a plateau followed by a drop, while stress at break decreases steadily. Once again, the trend is identical for all TPEs in all conditions considered. The βw_p parameter determined using the EWF concept exhibits an interesting sensitivity to scissions (i.e., molar mas decrease). Plotting elongation at break as a function of molar mass reveals a strong correlation between these two parameters. This master curve is particularly remarkable considering the range of TPEs and chemical breakdown pathways considered (hydrolysis and oxidation at several temperatures). Relevant structure–property relationships are proposed, highlighting that molar mass is a predominant parameter for determining the mechanical properties of thermoplastic elastomers.     

Multiresidue determination of 256 pesticides in lavandin essential oil by LC/ESI/sSRM: advantages and drawbacks of a sampling method involving evaporation under nitrogen

The determination of 256 multiclass pesticides in lavandin essential oil has been performed by liquid chromatography–electrospray ionization tandem mass spectrometry using the scheduled selected reaction monitoring mode available on a quadrupole-linear ion trap mass spectrometer. With the aim of improving the limits of quantification (LOQs) of the target molecules, a sampling step based on evaporation of the essential oil under a nitrogen flow assisted by controlled heating was tested. The LOQs determined in this case were compared with the values obtained with the classic dilution preparation method. With sampling by dilution, 247 pesticides were detected and quantified at low concentration, with 74 % of the pesticides having LOQs of 10 μg L^-1 or less. With the evaporation method, a global improvement of the LOQs was observed, with lower LOQs for 92 active substances and LOQs of 10 μg L^-1 or less for 82.8 % of the pesticides. Almost twice as many active substances had an LOQ of 1 μg L^-1 or less when the evaporation method was used. Some pesticides exhibited poor recovery or high variance caused by volatilization or degradation during the evaporation step. This behavior was evidenced by the case of thiophanate-methyl, which is degraded to carbendazim.

Micromechanical analysis of the behavior of stiff clay

Cementations formed in geological timescale are observed in various stiff clays.A micromechanical stress strain model is developed for modeling the effect of cementation on the deformation behavior of stiff clay.The proposed approach considers explicitly cementations at intercluster contacts,which is different from conventional model.The concept of inter-cluster bonding is introduced to account for an additional cohesion in shear sliding and a higher yield stress in normal compression.A damage law for inter-cluster bonding is proposed at cluster contacts for the debonding process during mechanical loading.The model is used to simulate numerous stress-path tests on Vallericca stiff clay.The applicability of the present model is evaluated through comparisons between the predicted and the measured results.In order to explain the stress-induced anisotropy arising from externally applied load,the evolution of local stresses and local strains at inter-cluster planes are discussed.     

Asymmetric synthesis of the four stereoisomers of 5-deoxystrigol

Two approaches to the strigolactone tricyclic lactone skeleton 2 were investigated using ketene/ketene-iminium cycloaddition to olefins. Finally, the first enantioselective access to the four stereoisomers of 5-deoxystrigol 1 is reported using an intramolecular [2+2] cycloaddition of homochiral ketene-iminium salts 5. Very high asymmetric control was achieved with C-2 symmetric pyrrolidines as chiral auxiliary.     

Synthesis and palladium-catalysed isomerisation of fused polycyclic tetrahydrofurans: efficient and stereoselective one-pot domino construction of functionalised bridged bicyclo[n.2.1] ring systems

A new one-pot domino reaction for a general entry to functionalised bridged bicyclo[n.2.1] ring systems from α ,α’-diactivated cyclic ketones and trans-1,4-dihalides is described. The sequence combines a base promoted C–O cycloalkylation reaction leading to fused polycyclic enol ethers and their in situ palladium-catalysed isomerisation.     

Micromechanical modelling for effect of inherent anisotropy on cyclic behaviour of sand

The inherent anisotropy more or less exists in sand when preparing samples in laboratory or taking from field. The purpose of this paper is to model cyclic behaviour of sand by means of a micromechanical approach considering inherent anisotropy. The micromechanical stress–strain model developed in an earlier study by Chang and Hicher (2005) is enhanced to account for the stress reversal on a contact plane and the density state-dependent dilatancy. The enhanced model is first examined by simulating typical drained and undrained cyclic tests in conventional triaxial conditions. The model is then used to simulate drained cyclic triaxial tests under constant p′ on Toyoura sand with different initial void ratios and different levels of p′, and undrained triaxial tests on dense and loose Nevada sand. The applicability of the present model is evaluated through comparisons between the predicted and the measured results. The evolution of local stresses and local strains at inter-particle planes due to externally applied load are discussed. All simulations have demonstrated that the proposed micromechanical approach is capable of modelling the cyclic behaviour of sand with inherent and induced anisotropy.