A combined experimental-numerical study to tensile behaviour of limestone

In this paper, a combined experimental-computational study of double-edge notched stone specimen subject to cyclic tensile loading is presented. In the experimental part, the load-deformation response and the local displacement field are recorded. Both experimental results are used to validate a numerical model for the description of fracture within finite elements. The model uses displacement discontinuities to model cracks. These discontinuities are implemented using the partition of unity property of finite element shape functions. In the discontinuity, a combined damage-plasticity cohesive law is used. Numerical simulations are compared with experimental observations

Impact des successions culturales (y compris intercultures) sur l'utilisation de produits phytosanitaires

Impact of crop sequences (including intercropping) on the use of pesticides. Crop sequences and the introduction of catch crops influence the development of agricultural pests (weeds, pests and diseases). This paper gives an overview of the problems that may arise for farmers in practice. Adaptation of crop interventions is often based on the use of plant protection products in the following crop, and these changes serve to solve problems that have been previously generated. Nevertheless, the poorly reasoned introduction of a catch crop can cause unwanted effects in terms of pest management and in relation to the protection of water resources

Assessment of atomic charge models for gas-phase computations on polypeptides

The concept of the atomic charge is extensively used to model the electrostatic properties of proteins. Atomic charges are not only the basis for the electrostatic energy term in biomolecular force fields but are also derived from quantum mechanical computations on protein fragments to get more insight into their electronic structure. Unfortunately there are many atomic charge schemes which lead to significantly different results, and it is not trivial to determine which scheme is most suitable for biomolecular studies. Therefore, we present an extensive methodological benchmark using a selection of atomic charge schemes [Mulliken, natural, restrained electrostatic potential, Hirshfeld-I, electronegativity equalization method (EEM), and split-charge equilibration (SQE)] applied to two sets of penta-alanine conformers. Our analysis clearly shows that Hirshfeld-I charges offer the best compromise between transferability (robustness with respect to conformational changes) and the ability to reproduce electrostatic properties of the penta-alanine. The benchmark also considers two charge equilibration models (EEM and SQE), which both clearly fail to describe the locally charged moieties in the zwitterionic form of penta-alanine. This issue is analyzed in detail because charge equilibration models are computationally much more attractive than the Hirshfeld-I scheme. Based on the latter analysis, a straightforward extension of the SQE model is proposed, SQE+Q0, that is suitable to describe biological systems bearing many locally charged functional groups

A Discontinuous Model to Study Fracture of Brittle Materials

In this paper, the partition of the unity property of finite element shape functions is used to introduce displacement discontinuities into finite elements. The discontinuous character of the displacement field is captured with the Heaviside step function. Using the partition of unity concept, the governing equation of the continuum and the discontinuity are separated and are consequently described by different constitutive laws. Inside the discontinuity, a plasticity based constitutive law is used to describe the decrease of tractions in function of the crack opening while the continuum is assumed to remain elastic. The methodology will be described and validated with a comparison between numerical simulations and experimental results.This paper is dedicated to J. Sejnoha, TU Prague, with respect and admiration for his scientific achievement.

A discrete model for cyclic mode I loading

AbstractThe cyclic behaviour of a double-edge notched specimen loaded in tension is studied. Cracks in the material are modelled by displacement discontinuities that can propagate during computation. Within these discontinuities, a cohesive zone model is used. The model assumes an additive split of the inelastic jump into a recoverable and an unrecoverable part. The influence of model parameters and discretisation is studied and the results have been compared with experimental data

Reactivity of three-membered heterocyclic rings with respect to sodium methoxide

Aziridines can be ‘activated’ or ‘non-activated’, depending on whether their N-substituent is an electron-withdrawing group or an electron-donating group, respectively. Activated aziridines are much more susceptible to ring opening than non-activated aziridines and epoxides are even more reactive. The difference in reactivity between activated 2-(bromomethyl)-1-tosylaziridines, non-activated 1-benzyl-2-(bromomethyl)aziridines and epibromohydrins with respect to sodium methoxide was comparatively analysed by means of DFT calculations, such as BMK, MPW1K and MPWB95 [1]. Nucleophilic substitution reactions are known to be influenced by the solvent environment. Therefore, the gas-phase results were extended towards a discrete solvent approach. The solvent effect was taken into account by inspecting the convergence behaviour of the energy of solvation in terms of a systematically increasing number of solvent molecules. To model each of the reactive profiles of the various substrates, a supermolecule model was used with five explicit methanol molecules. Solvation has significantly changed the landscape of the energy profiles, which nicely shows the necessity of taking into account explicit solvation molecules to obtain the correct reaction profiles. The barriers for direct displacement of bromide by methoxide in methanol are comparable for all three heterocyclic species under study. However, ring opening is only feasible for the epoxide and the activated aziridine and not for the non-activated aziridine

Time-dependent mesoscopic modelling of masonry using embedded weak discontinuities

In this contribution, a rate-dependent mesoscopic masonry model is presented in which the mortar joints are incorporated by embedded weak discontinuities based on partitions of unity. Within the discontinuities, both an isotropic damage and a Perzyna viscoplastic model are used to describe joint degradation. The elastic domain of the joint behaviour is bounded by a modified Drucker-Prager yield function. The performance of the developed masonry model is demonstrated by the simulation of a three-point bending test and a shear wall test

Reformulating the Woodward-Hoffmann Rules in a Conceptual Density Functional Theory Context: the Case of Sigmatropic Reactions

In this contribution, we have investigated the performance of the initial hardness response, a reactivity index from conceptual DFT, in the prediction of the allowed or forbidden character of a series of sigmatropic hydrogen shifts, which are traditionally explained using the famous Woodward-Hoffmann rules for pericyclic reactions. Previously, it was observed that this quantity can be linked to the activation hardness of a chemical reaction and, in this case, thus to the aromaticity of the transition state in these kinds of reactions. It is shown, both by considering approximate reaction coordinates and intrinsic reaction coordinates that the allowed mode of the sigmatropic rearrangement corresponds to the largest value of the initial hardness response, in agreement with earlier work on cycloadditions and electrocyclizations