Search

A setup dedicated to measure the influence of the biaxial stress on the magnetic properties of thin laminations is described. The obtained results are consistent with recently published work and indicate that the Schneider criterion is an interesting one.

A simplified mechanical analysis is used to estimate long-range residual stresses induced by punching and a magnetoeleastic coupled model predicts their influence on the global magnetic behavior of the device. These residual stresses have a small local influence on the permeability, compared to plasticity, but they affect a larger volume of material so that at the end their global magnetic impact is as large as the one of the plasticity.

TiO2 nanoparticles are successively functionalized with [Mn(κ2N1,N2-ttpy)(CO)3Br] as catalyst and [Ru(bpy)3]2+ as photosensitizer to yield RuII/TiO2/MnI. Under continuous irradiation at 470 nm and in the presence of a sacrificial electron donor, this triad reduces CO2 to HCOOH (TONmax = 27) with 100% selectivity. [ABSTRACT FROM AUTHOR]

[Cr(ttpy)2]3+ (ttpy = 4′-(4-methylphenyl)-2,2′:6,2′′-terpyridine) exhibits rich electrochemical and photophysical properties. Cyclic voltammetry performed in CH3CN shows in the cathodic part the presence of three one-electron reversible systems at −0.47, −0.85 and −1.35 V vs. Ag/AgNO3 10−2 M. These systems are attributed to the reduction of the terpyridine ligands with a partial delocalization of the charge on the tolyl for the last reduction event. The three different reduced species were generated by exhaustive electrolysis and characterized by EPR and UV-visible spectroscopy; DFT calculations were performed to locate the spin density of the electrons added during the reduction. Visible light irradiation of [Cr(ttpy)2]3+ induces the population of a luminescent metal-centered excited state with a lifetime of 270 ns in deoxygenated CH3CN. This excited state can be quenched by an electron transfer process with triphenylphosphine (PPh3) or triethanolamine (TEOA). Using TEOA as a sacrificial electron donor, the doubly reduced species (i.e.[Cr(ttpy)2] +) can be generated under continuous irradiation. In the presence of [Ru(bpy)3]2+ as an additional photosensitizer, the photoreduction of [Cr(ttpy)2]3+ towards [Cr(ttpy)2]+ is accelerated. The trinuclear [{RuII(bpy)2(bpy-O-tpy)}2CrIII]7+ complex ([Ru2Cr]7+) in which a CrIII-bis-terpyridine centre is covalently linked to two RuII-tris-bipyridine moieties by oxo bridges has been synthesised. Its electrochemical, photophysical and photochemical properties were investigated in deoxygenated CH3CN. Cyclic voltammetry indicates only a poor electronic communication between the different subunits, whereas luminescence experiments show a strong quenching of the RuII* excited state by an intramolecular process. Continuous irradiation of [Ru2Cr]7+ under visible conditions in the presence of TEOA leads to [Ru2Cr]4+ where three electrons are stored on the [Cr(ttpy)] subunit. [ABSTRACT FROM AUTHOR]

The synthesis and crystallization of two verdazyl radicals, 1,5‐dimethyl‐3‐(4′‐carboxyphenyl)‐6‐oxoverdazyl HIMe and 1,5‐diisopropyl‐3‐(4′‐carboxyphenyl)‐6‐oxoverdazyl HIiPr, are described. The electrochemical studies reveal that the oxidation of the two radicals is reversible, whereas their reduction is irreversible. The EPR spectrum of both radicals essentially exhibits a nine‐line pattern related to the mean hyperfine interaction of the unpaired electron with the nitrogen atoms of the verdazyl cycle. The single‐crystal X‐ray diffraction of the intermediates towards HIiPr allows a fine description of the cyanoborane adduct, which is the key intermediate of this synthesis. The verdazyl radicals themselves are obtained as single crystals. In the case of HIiPr, depending on the solvent, two polymorphs are crystallized. The structure resolution reveals that, in the solid state, the organization of the verdazyl radicals is governed by both H‐bonding and π–π interactions and is reminiscent of the H‐bonded structures that can be present in solution. Within the 1D π stacks observed in the three compounds, the verdazyl–verdazyl distance varies from 4.88 Å in HIMe to 7.90 Å in HaIiPr. This modulation of the distance strongly influences the antiferromagnetic intermolecular exchange interaction between π‐stacked radicals, which goes from J = –90 cm–1 (H = –JΣSiSi+1) for HIMe to –12.96(3) cm–1 for HbIiPr and –0.92 cm–1 for HaIiPr. [ABSTRACT FROM AUTHOR]

Titanium dioxide nanoparticles were synthesized by laser pyrolysis, their surface and electronic properties were modified by gold and/or nitrogen. These materials were characterized by different techniques like X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). Time resolved conductivity (TRMC) was used to study the charge separation of electron/hole pairs. Altogether (XPS, EPR, TRMC), the physicochemical characterizations are well correlated with chemical photoactivity of the different samples. Their photocatalytic activity was evaluated for the degradation of linear carboxylic acids (C2-C3) under UV and visible illumination. The decomposition rate of acids was measured, it shows that the modification with gold increases the photoactivity while the presence of nitrogen slows down the process. Such observations are in good agreement with evolution of TRMC signals. A degradation pathway has been determined by identification of intermediate products by chromatography and EPR, results show different intermediate species. In particular EPR confirms the presence of NO2− paramagnetic centers and shows two novel N centered paramagnetic centers. A decrease of the degradation rate is observed with increase of carboxylic acid chain length. [ABSTRACT FROM AUTHOR]

Titanium dioxide nanoparticles were synthesized by laser pyrolysis, their surface and electronic properties were modified by gold and/or nitrogen. These materials were characterized by different techniques like X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). Time resolved conductivity (TRMC) was used to study the charge separation of electron/hole pairs. Altogether (XPS, EPR, TRMC), the physicochemical characterizations are well correlated with chemical photoactivity of the different samples. Their photocatalytic activity was evaluated for the degradation of linear carboxylic acids (C2-C3) under UV and visible illumination. The decomposition rate of acids was measured, it shows that the modification with gold increases the photoactivity while the presence of nitrogen slows down the process. Such observations are in good agreement with evolution of TRMC signals. A degradation pathway has been determined by identification of intermediate products by chromatography and EPR, results show different intermediate species. In particular EPR confirms the presence of NO2−paramagnetic centers and shows two novel N centered paramagnetic centers. A decrease of the degradation rate is observed with increase of carboxylic acid chain length. [ABSTRACT FROM AUTHOR]

Thisreport describes the study of a dimer d2+and a linear trimer t3+of amminium radical cations coupled by 3,4′-biphenylspin coupling units. The synthesis of the parent diamine and triamineand their optical and electrochemical properties obtained by UV–visibleand cyclic voltammetry are presented. The chemical doping of the parentdiamine dand triamine twas performed quantitativelyto obtain samples containing the corresponding dimer d2+and trimer t3+in almost pure high-spin states as evidenced by pulsed EPRnutation spectroscopy. The Jcoupling constants ofthe corresponding S= 1 and S=3/2 spin states were measured (J/k= 135 K) and compared quantitatively to DFT calculations. [ABSTRACT FROM AUTHOR]

This paper introduces a new local plastic correction algorithm that is aimed at accelerating elasto-plastic finite element (FE) simulations for structural problems exhibiting localised plasticity (around e.g. notches, geometrical defects). The proposed method belongs to the category of generalised multi-axial Neuber-type methods, which process the results of an elastic prediction point-wise in order to calculate an approximation of the full elasto-plastic solution. The proposed algorithm relies on a rule of local proportionality, which, in the context of J2 plasticity, allows us to express the plastic correction problem in terms of the amplitude of the full mechanical tensors only. This lightweight correction problem can be solved for numerically using a fully implicit time integrator that shares similarities with the radial return algorithm. The numerical capabilities of the proposed algorithm are demonstrated for a notched structure and a specimen containing a distribution of spherical pores, subjected to monotonic and cyclic loading. As a second point of innovation, we show that the proposed local plastic correction algorithm can be further accelerated by employing a simple meta-modelling strategy, with virtually no added errors. At last, we develop and investigate the merits of a deep-learning-based corrective layer designed to reduce the approximation error of the plastic corrector. A convolutional architecture is used to analyse the neighbourhoods of material points and outputs a scalar correction to the point-wise Neuber-type predictions. This optional brick of the proposed plastic correction methodology relies on the availability of a set of full elasto-plastic finite element solutions to be used as a training data-set. [ABSTRACT FROM AUTHOR]