Ornstein-Uhlenbeck processes on Lie groups

We consider Ornstein-Uhlenbeck processes (OU-processes) associated to hypo-elliptic diffusion processes on finite-dimensional Lie groups: let L be a hypo-elliptic, left-invariant “sum of the squares”-operator on a Lie group G with associated Markov process X, then we construct OU-processes by adding negative horizontal gradient drifts of functions U. In the natural case U(x)=−logp(1,x), where p(1,x) is the density of the law of X starting at identity e at time t=1 with respect to the right-invariant Haar measure on G, we show the Poincaré inequality by applying the Driver-Melcher inequality for “sum of the squares” operators on Lie groups. The resulting Markov process is called the natural OU-process associated to the hypo-elliptic diffusion on G. We prove the global strong existence of these OU-type processes on G under an integrability assumption on U. The Poincaré inequality for a large class of potentials U is then shown by a perturbation technique. These results are applied to obtain a hypo-elliptic equivalent of standard results on cooling schedules for simulated annealing on compact homogeneous spaces M.     

Isosteric heat of adsorption in liquid–solid equilibria: Theoretical determination and measurement by liquid chromatography/mass spectrometry

The isosteric heat of adsorption of a pure compound dissolved in a solution in equilibrium with a solid adsorbent was determined, based on the Gibbs surface excess model. The exact isosteric heat of adsorption differs from the usual value derived from the variation of the Henry’s constant with the reciprocal temperature because this procedure assumes ideal behavior of the bulk liquid solution, which, in most cases, is only approximately so. An experimental protocol, based on the determination of the excess adsorption isotherms by combining frontal analysis (for strongly adsorbed components) and spectrometric tracer pulse chromatography (for weakly adsorbed compounds) is proposed. It allows the determination of the exact isosteric heat of adsorption provided that the activity coefficient of the compound in the bulk solution can be explicitly expressed as a function of the bulk liquid composition.     

XMCD studies of magnetic polarization at Mo atoms in CoMo alloy and magnetically coupled Co/Mo multilayers

Magnetic polarization of Mo atoms in Co₉₆Mo₄ alloy film and Co/Mo multilayered structures has been studied by X‐ray magnetic circular dichroism. Samples with Mo spacers of two different thicknesses (0.9 nm and 1.8 nm) were investigated. Mo atoms receive a magnetic moment of ?0.21μ_B in the alloy. In the multilayer with the thinner Mo spacer (d_Mo = 0.9 nm) the magnetic moment is much smaller (?0.03μ_B). In both cases the measured induced moment at the Mo site is oriented antiparallel to the moment at the Co atoms. The presence of the induced moment in the Mo spacer coincides with antiferromagnetic coupling between the Co component slabs. In contrast, neither measurable induced moment at the Mo site nor interlayer coupling between the Co layers has been found for the multilayer with the thicker Mo spacer. Possible mechanisms of the coupling associated with the induced moment are discussed in detail.     

Reducing shear thickening of cement-based suspensions

Rheological measurements were made on concrete and mortars to characterize the shear thickening behavior of certain concrete mix designs. Shear thickening reduction levers were found by selecting and designing admixtures. Since the shear-thickening phenomena occur at the scale of the finest particles, industrial limestone fillers were studied that behave like cementitious materials. Theories based on previous academic works were relevant. The shear stress-dependent effects of shear thickening and size scaling were very helpful to distinguish between surface interactions, such as lubrication and volumetric contributions and also including the packing effects. The suspension viscosity curves vary accordingly to the Newtonian viscosity of the solvent medium. In both the shear thinning and shear thickening regimes, viscosity is controlled by adjusting the amount of two specific admixtures. The reduction of friction between polymer-coated materials appears to be a key phenomenon to delay onset shear thickening in industrial processes.     

Three-dimensional characterization of strain localization bands in high-resolution elastoplastic polycrystals

In crystalline materials, the experimental observation of the localization of plastic strains in particular directions is generally restricted to the surface of a sample containing some hundreds of grains, because of the difficulties underlying microstructural analysis. In these conditions, the determination of the morphological characteristics of localization can be limited by the poor statistical representativity of the domain of observation. The purpose of this work is to extend the analysis of localization – localization bands or else – to the 3D elastoplastic strain fields of a high-resolution representative volume element of a polycrystal.     

High Glass‐Transition Temperature Polymer Networks Harnessing the Dynamic Ring Opening of Pinacol Boronates

Differential scanning calorimetry of high molar mass poly(4‐vinylphenylboronic acid, pinacol ester)s evidenced unusual reactive events above 120 °C, resulting in a high glass‐transition temperature of 220 °C. A reversible ring‐opening reactivity of pinacol boronates is proposed, involving a nucleophilic attack on the sp² boron and subsequent bridging between boron atoms by interconnected pinacol moieties to form a densely crosslinked network with high T_g. FTIR, solid‐state NMR investigations, and rheology studies on the polymer as well as double‐tagging analyses on molecular model structures and theoretical calculations further support this hypothesis and indicate a ring‐opening inducing crosslinking. When diluted in an apolar solvent such as toluene, the polymer network can be resolubilized via ring closing, thus recovering the entropically favored linear chains featuring cyclic boronate esters.     

Free radical photopolymerization process for fiber‐reinforced polymer: Effect on the mechanical properties

Glass–fiber‐reinforced polymers were manufactured either through a room temperature thermal curing or under ultraviolet (UV) light from a LED. The thermal system yields high performances when a post‐curing process at 65°C is applied. The photochemical curing leads to a composite in a faster timescale, albeit at the extent of the mechanical properties. It is found that in this case, impregnation and vacuum steps are too fast to allow a good wetting of the fibers, thereby leading to mechanical weaknesses and larger void volume. However, when applying longer vacuum and impregnation steps, the mechanical properties of the photochemically cured sample match the best thermally cured one. As a conclusion, it is shown that photochemical curing of glass–fiber‐reinforced polymer can lead to high performance composite provided that the preparation steps are well controlled.     

Dithia[3.3]paracyclophane Core: A Versatile Platform for Triplet State Fine‐Tuning and Through‐Space TADF Emission

Thermally activated delayed fluorescence (TADF) based on through‐space donor and acceptor interactions constitute a recent and promising approach to develop efficient TADF emitters. Novel TADF isomers using a dithia[3.3]‐paracyclophane building block as a versatile 3D platform to promote through‐space interactions are presented. Such a 3D platform allows to bring together the D and A units into close proximity and to probe the effect of their orientation, contact site and distance on their TADF emission properties. This study provides evidence that the dithia[3.3]paracyclophane core is a promising platform to control intramolecular through‐space interactions and obtain an efficient TADF emission with short reverse‐intersystem crossing (RISC) lifetimes. In addition, this study demonstrates that this design can tune the energy levels of the triplet states and leads to an upconversion from ³CT to ³LE that promotes faster and more efficient RISC to the ¹CT singlet state.     

Overview of Identification Methods of Mechanical Parameters Based on Full-field Measurements

This article reviews recently developed methods for constitutive parameter identification based on kinematic full-field measurements, namely the finite element model updating method (FEMU), the constitutive equation gap method (CEGM), the virtual fields method (VFM), the equilibrium gap method (EGM) and the reciprocity gap method (RGM). Their formulation and underlying principles are presented and discussed. These identification techniques are then applied to full-field experimental data obtained on four different experiments, namely (i) a tensile test, (ii) the Brazilian test, (iii) a shear-flexural test, and (iv) a biaxial test. Test (iv) features a non-uniform damage field, and hence non-uniform equivalent elastic properties, while tests (i), (ii) and (iii) deal with the identification of uniform anisotropic elastic properties. Tests (ii), (iii) and (iv) involve non-uniform strain fields in the region of interest. Working group “Identification” of the French CNRS research network (GDR 2519) “Mesures de champs et identification en Mécanique des Solides / Full-field Measurements and Identification in Solid Mechanics”.