Thermoset modified with polyethersulfone: Characterization and control of the morphology

Thermoset (TS) epoxy resins can be toughened with a thermoplastic (TP) for high-performance applications. The final structure morphology has to be controlled to achieve high mechanical properties and high impact resistance. Four polyethersulfone-modified epoxy resins are considered. They consist of different epoxy monomer structure (TGAP, triglycidyl-p-aminophenol and TGDDM, tetraglycidyl diaminodiphenylmethane) and a fixed amount of thermoplastic, and they are cured with two different amounts of curing agent. A reaction-induced phase separation occurs for all formulations generating morphologies, different in shapes and scales. The aim is to control the final morphology and in particular its dominant length scale. This morphology depends on the phase separation process, from the initiation to its final stage. The initiation relies on the relative miscibility of the components and on the stoichiometry between epoxy and curing agent. The kinetics depends on the viscosity of the systems. The different morphologies are characterized by electron microscopy or neutron scattering. Dynamic mechanical analysis allows confirming the presence of a phase separation even when it is not observable by electron microscopy. Vermicular morphologies with few hundreds nanometer width are obtained for the systems containing the TGAP as epoxy monomer. Systems formulated with TGDDM presents morphologies on much smaller scale of order a few tens of nanometers. We interpret the different sizes of the morphologies as a consequence of a larger viscosity for the TGDDM systems as compared to the TGAP ones rather than by a latter initiation of phase separation.     

Cycloisomerization of (arene)chromium complexes with enyne by gold(I) catalyst for axially chiral biaryls

Planar chiral arene chromium complexes with enyne bond gave stereoselectively axial biaryl chromium complexes by gold(I) catalyzed cycloisomerization in good yields. Arene chromium complexes with enyne bonds were treated with triphenylphosphine gold bis(trifluoromethanesulfonyl)imidate in methylene chloride to give anti-biaryl monochromium complexes without formation of stereoisomers.     

Experimental investigation and analytical description of a vibro-impact NES coupled to a single-degree-of-freedom linear oscillator harmonically forced

In this paper, the dynamics of a system composed of a harmonically forced single-degree-of-freedom linear oscillator coupled to a vibro-impact nonlinear energy sink (VI-NES) is experimentally investigated. The mass ratio between the VI-NES and the primary system is about \(1\%\). Depending on the external force’s amplitude and frequency, either a strongly modulated response (SMR) or a constant amplitude response (CAR) is observed. In both cases, an irreversible transfer of energy occurs from the linear oscillator toward the VI-NES: process known in the literature as passive targeted energy transfer. Furthermore, the problem is analytically studied by using the method of multiple scales. The obtained slow invariant manifold shows the existence of a stable and of an unstable branch of solutions, as well as of an energy threshold (a saddle-node bifurcation) for the solutions to appear. Subsequently, the fixed points of the problem are calculated. When a stable fixed point is reached, the system is naturally drawn to it and a CAR is established, whereas when no stable point is attained, the system exhibits a SMR regime. Finally, a good correlation between the experimental and the analytical results is presented.     

Microtermolides A and B from termite-associated Streptomyces sp. and structural revision of vinylamycin

Microtermolides A (1) and B (2) were isolated from a Streptomyces sp. strain associated with fungus-growing termites. The structures of 1 and 2 were determined by 1D- and 2D-NMR spectroscopy and high-resolution mass spectrometry. Structural elucidation of 1 led to the re-examination of the structure originally proposed for vinylamycin (3). Based on a comparison of predicted and experimental (1)H and (13)C NMR chemical shifts, we propose that vinylamycin's structure be revised from 3 to 4.     

Parametrically excited helicopter ground resonance dynamics with high blade asymmetries

The present work is aimed at verifying the influence of high asymmetries in the variation of in-plane lead-lag stiffness of one blade on the ground resonance phenomenon in helicopters. The periodical equations of motions are analyzed by using Floquet's Theory (FM) and the boundaries of instabilities predicted. The stability chart obtained as a function of asymmetry parameters and rotor speed reveals a complex evolution of critical zones and the existence of bifurcation points at low rotor speed values. Additionally, it is known that when treated as parametric excitations; periodic terms may cause parametric resonances in dynamic systems, some of which can become unstable. Therefore, the helicopter is later considered as a parametrically excited system and the equations are treated analytically by applying the Method of Multiple Scales (MMS). A stability analysis is used to verify the existence of unstable parametric resonances with first and second-order sets of equations. The results are compared and validated with those obtained by Floquet's Theory. Moreover, an explanation is given for the presence of unstable motion at low rotor speeds due to parametric instabilities of the second order.     

Synthesis of syn-facial (Cr,Mn) benzyl complexes by the stereoselective thermolytic coupling of unsymmetric diazomethanes with cyclomanganated (η-arene)tricarbonylchromium complexes

The heat-promoted reaction of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene with cyclomanganated 2-[tricarbonyl(η⁶-phenyl)chromium]pyridine afforded, upon departure of a molecule of CO, a new stable manganese alkylidene complex in which, according to X-ray diffraction analyses, the heterocyclic ligand is anti-facial with respect to the Cr(CO)₃ moiety. Similar heat-promoted reactions of unsymmetrically substituted diazoalkanes such as (Me₃Si)(H)CN₂, (Ph)(Me)CN₂, (Ph)(t-Bu)CN₂ and (Ph)(FcCH₂CH₂)CN₂, which are precursors of more electrophilic alkylidenes, with cyclomanganated 2-[tricarbonyl(η⁶-phenyl)chromium]pyridine derivatives afforded new syn-facial heterobimetallic benzyl complexes. The stereoselectivity of these reactions depends on the steric demand of the substituents at the diazoalkane. A phenyl substituent at the diazoalkane favors the formation of syn-facial heterobimetallic benzyl complexes with the Ph group in the endo position. Combining this “phenyl directing effect” to the steric effect operated by a bulky group at the phenyldiazoalkane, like noticed with (Ph)(t-Bu)CN₂, led to total stereoselectivity. This study discloses four new X-ray structures of syn-facial Cr,Mn benzyl complexes, which all present the same short Cr-to-Mn distance of ca. 3.04 Å.     

Nitroxydes 94 : decomposition thermique d'un radical oxazolidine-oxyle.

Pyrolysis of spiro ((4-t-butyl cyclohexane)-1,2′-(4′,4′-dimethyl oxazolidine-3′ oxyl)) $\text{1}$ leads to spiro ((4-t-butyl cyclohexane)-1,2′-(4′,4′ oxazolidine 3′-hydroxy)) $\text{2}$, 4-t-butyl cyclohexanone and 4-t-butyl cyclohexanoxime. Kinetic studies show that the reaction proceeds through an autocatalytic process.     

New manganese-scaffolded organic triple-deckers based on quinoxaline, pyrazine and pyrimidine cores

The thermolytic coupling of Ph(2)CN(2) and (t-Bu)(Ph)CN(2) with doubly cyclomanganated 2,5-diphenylpyrazine and 4,6-diphenylpyrimidine afforded substantial amounts of new triple decker compounds of either C(i) and C(2) symmetry respectively containing, in both series, two eta(3)-bonded Mn(CO)(3) fragments which intervene as scaffolds sustaining the helical non-conjugated triaryl backbone. The molecular structures of two pyrazine derivatives show a typical non-parallel stacking of the aromatic rings and the encapsulation of the central pyrazyl fragment with interplanar centroid-to-centroid distances of ca. 3.5 A. The stacking of the aromatics in the triple-decker pyrimidine derivatives has been assessed by (1)H NMR experiments at low temperature. All the triple-decker-type compounds are electroactive. Pyrimidine triple-deckers can reversibly be electrochemically reduced to the corresponding anions.     

Modelling of steel scrap movement

Uneven movement of steel scrap during electric arc furnace melting causes operational problems, such as cave-ins. To understand the phenomenon, a small-scale apparatus has been built to simulate the flow of scrap that may be interlocked. It was found that flow starts at the point where the suspended length of the pile bottom reaches the average scrap size. The force balance in a suspended scrap pile has been analyzed to estimate the effective cohesion of interlocking. A numerical model has been developed to simulate the scrap flow.     

Thermodynamic analysis of the shape, anisotropy and formation process of InAs/InP(0 0 1) quantum dots and quantum sticks grown by metalorganic vapor phase epitaxy

This study describes the origin of the size and shape anisotropy of InAs/InP(0 0 1) quantum dots (QDs) grown by metalorganic vapor phase epitaxy (MOVPE). The geometry of the QDs is determined by carefully analyzing transmission electron microscopy (TEM) images. An analytical model adapted to our QD geometry is used to understand the formation mechanism of the QDs, and to describe the origin of their size dispersion. A shape transition from QDs to elongated quantum sticks (QS) is observed under As-poor growth conditions. This transition, driven by thermodynamics, is clearly described by our model.