Identification of constitutive model for rubber elasticity from micro-indentation tests on natural rubber and validation by macroscopic tests

Micro-hardness testing is widely used to measure the materials local response and is very valuable to describe gradients of physical properties. For polymers, the most common use is to measure a scalar value (hardness or modulus), which gives access to useful qualitative information but can clearly not be used to identify local constitutive models, strongly needed to achieve the numerical simulation of heterogeneous massive parts. In this study, load/displacement curves obtained at a micro-scale are used to identify the parameters of an Edwards-Vilgis hyperelastic model. The protocol proposed is coupling FE simulations achieved with Abaqus and optimization procedures using the dedicated software Boss Quattro. In order to limit the microstructure and viscous effects, the material studied is an unfilled natural rubber which exhibits a behavior very close to perfect hyperelasticity. Several numerical parameters (indent geometry, friction, thickness, …) as well as experimental protocols were tested in order to check the protocol reliability. The identified parameters are used to simulate macroscopic tests (tensile, compression and pure shear tests). The agreement with experimental data is very good, which is rarely found in the literature and which validates several numerical assumptions.     

Probing thermomechanics at the nanoscale: impulsively excited pseudosurface acoustic waves in hypersonic phononic crystals

High-frequency surface acoustic waves can be generated by ultrafast laser excitation of nanoscale patterned surfaces. Here we study this phenomenon in the hypersonic frequency limit. By modeling the thermomechanics from first-principles, we calculate the system's initial heat-driven impulsive response and follow its time evolution. A scheme is introduced to quantitatively access frequencies and lifetimes of the composite system's excited eigenmodes. A spectral decomposition of the calculated response on the eigemodes of the system reveals asymmetric resonances that result from the coupling between surface and bulk acoustic modes. This finding allows evaluation of impulsively excited pseudosurface acoustic wave frequencies and lifetimes and expands our understanding of the scattering of surface waves in mesoscale metamaterials. The model is successfully benchmarked against time-resolved optical diffraction measurements performed on one-dimensional and two-dimensional surface phononic crystals, probed using light at extreme ultraviolet and near-infrared wavelengths.     

Liquid-crystallization induced reactions. Microstructure and morphology of copolyesters synthesized by transesterification of PET with some LCP monomers

The transesterification of poly(ethylene terephthalate) (PET) with a mixture of sebacic acid (S), 4,4′-diacetoxybiphenyl (B) and 4-acetoxybenzoic acid (H), carried out under conditions expectedly favoring the formation of a p(ET-SBH) random copolyester, produces biphasic materials with an isotropic matrix and a highly fibrous, liquid-crystalline dispersed phase. Spectroscopic, calorimetric, microscopic and diffractometric characterization of the fractions separated by solvent extraction has shown that the two phases consist of practically random copolyesters having different average composition. Interestingly, the degree of aromaticity of the matrix is even lower than that of PET, whereas that of the minor phase is appreciably higher than that calculated for the SBH copolyester that would be produced from the monomer mixture in the absence of PET. This unexpected result is interpreted on the basis of an enthalpy-driven progressive diffusion of aromatic-rich material toward the mesophase which segregates at an early stage of the polycondensation within the isotropic mixture of low molar mass oligomers initially produced by the PET acidolysis. Thus, an increasing differentiation, rather than an equilibration, of the composition of the two phases takes place. It is noteworthy that, despite the strong compositional difference, the two phases of these products show fairly good compatibility and interfacial adhesion.     

Studies on phospholipid biosynthesis in hepatocytes from alcoholic rats by using radiolabeled exogenous precursors

We have studied the synthesis of phospholipids in hepatocytes isolated from chronically ethanol-treated rats by using isotopically labelled serine, ethanolamine, and choline as exogenous precursors. Our results demonstrate that ethanol induces specific effects on the biosynthesis of phosphatidyl-ethanolamine and phosphatidylcholinevia CDP-derivatives and also on the synthesis of phosphatidylserinevia the Ca⁺⁺-dependent base-exchange reaction. Thus, the synthesis of phosphatidylethanolamine from [³-H]ethanolamine and the incorporation of [³H]serine into phosphatidylserine were clearly higher in hepatocytes from ethanol-treated rats compared to controls. The synthesis of phosphatidylcholine from [methyl-¹⁴C] choline, on the other hand, decreased markedly, suggesting a specific inhibition of cholinephosphotransferase activity. We have also demonstrated that the phosphatidylcholine levels are markedly decreased in hepatocytes isolated from chronically ethanol-treated rats as a consequence of the lower phosphatidylcholine biosynthesis. The decrease in the incorporation of radioactivity from choline to betaine, which we also found, is interpreted as being the result of a higher use of betaine as methyl donor instead of methionine to maintain the hepaticS-adenosylmethionine levels in chronic alcoholism.     

Identification of two glutamic acid residues essential for catalysis in the {beta}-glycosidase from the thermoacidophilic archaeon Sulfolobus solfataricus

The Sulfolobus solfataricus, strain MT4, ß-glycosidase(Ssßgly) is a thermophilic member of glycohydrolasefamily 1. To identify active-site residues, glutamic acids 206and 387 have been changed to isosteric glutamine by site-directedmutagenesis. Mutant proteins have been purified to homogeneityusing the Schistosoma japonicum glutathione S-transferase (GST)fusion system. The proteolytic cleavage of the chimeric proteinwith thrombin was only obtainable after the introduction ofa molecular spacer between the GST and the Ssß-glydomains. The Glu387 Gin mutant showed no detectable activity,as expected for the residue acting as the nucleophile of thereaction. The Glu206 Gin mutant showed 10- and 60-fold reducedactivities on aryl-galacto and aryl-glucosides, respectively,when compared with the wild type. Moreover, a significant K_mdecrease with plo-nitrophenyl-ß-D-glucoside was observed.The residual activity of the Glu206 Gln mutant lost the typicalpH dependence shown by the wild type. These data suggest thatGlu206 acts as the general acid/base catalyst in the hydrolysisreaction.     

EPOXIDATION OF FUNCTIONALIZED OLEFINS OVER SOLID CATALYSTS

Heterogeneous catalytic epoxidation of functionalized olefins in the liquid phase has been reviewed, focusing on catalyst performance and its interrelation with the crucial parameters of the catalytic systems. Efficient catalysts include supported and mixed oxides, framework-substituted (“redox”) molecular sieves, layered-type materials, heterogenized homogeneous catalysts, and some others. Among the various substrates, allylic and homoallylic alcohols, and unsaturated carbonyl compounds have received most attention so far. The great variety of available catalysts enables selective epoxidation of most substituted olefins. The mechanistic understanding of heterogeneous catalytic epoxidation is still underdeveloped, rendering catalyst design rather empirical. A considerable potential for future development lies in the area of “heterogenization” of successful homogeneous catalysts especially for asymmetric epoxidation. Crucial requirements in the development of heterogeneous catalytic epoxidation catalysts are, besides good catalytic performance and cheap oxidant, recyclability and resistance to leaching of the active component. Some of the examples shown in the literature do not fulfill the latter requirement.     

Ion Irradiation of Preceramic Polymer Thin Films

Thin films of two preceramic polymers, namely polycarbosilane (PCS) and a silicone resin (SR350), were deposited on Si substrates. Instead of employing conventional annealing at high temperatures in an inert atmosphere, ion irradiation was used to achieve the polymer-to-ceramic conversion. A detailed investigation of the changes in the composition, chemical structure, and hardness was performed by means of ion beam analysis (Rutherford backscattering spectrometry, nuclear reaction analysis, and elastic recoil detection analysis), FTIR, Raman and nanoindentation, respectively. This processing method yielded amorphous Si-C and Si-O-C coatings possessing high hardness and density. Compared to films heat-treated under vacuum at 1000°C, ion-irradiated ones exhibited a similar hydrogen content, a lower oxygen contamination, and a higher carbon content. Annealing at 1000°C of previously irradiated films resulted in coatings still possessing a high carbon content and a high hardness.