Alumina foam catalyst supports for industrial steam reforming processes

The manufacture and the characterisation of alumina foams as alternative catalysts supports for industrial steam reforming processes are presented here. The possibility of use of alumina foams as catalysts supports in such processes is evaluated by studying their resistance toward mechanical and chemical stresses. The alumina foams produced are characterised owing to their processing parameters (slurry infiltration, sintering temperature, template pore size). Their ability to work in hydrothermal atmosphere is assessed by characterising the evolution of microstructures and mechanical strengths upon aging. Thermodynamic studies of the stability of alumina in industrial steam reforming working conditions are performed and correlated to the experiments to demonstrate the stability of such a system.     

Synthesis and structural characterization of a liquid polyisoprene bearing amidoxime end groups

Azo-bis(isobutyroamidoxime) was synthesized and used as functionalized initiator to prepare a liquid isoprene bearing amidoxime end groups via radical polymerization. The polymer was characterized by FT-IR, Gel Permeation Chromatography and NMR. In particular, the structure of the polymer was investigated using 1D and 2D NMR techniques. The distribution of the different isoprene units (1,4-trans, 1,4-cis, 1,2 and 3,4), as well as the structure of the amidoxime end-groups was determined. It was found that the structure of the end groups was governed by the steric hindrance of the initiator. Only 1,4 and 4,1 functionalized end units were evidenced, with a majority of 4,1 end units.     

Continuous Crystallization of Submicrometer Energetic Compounds

This study introduces the conception of an apparatus to crystallize continuously nanosized explosive or more generally nanosized organic materials. These materials can be elaborated in pure state or in form of mixtures of energetic and inert materials. The installation can produce nano‐RDX or nano‐PETN from 1 to 10 g h⁻¹ using a reactor containing one ultrasonic piezoelectric transducer. The present study describes the different parameters which influence the crystallization process. It presents first results of the parametric study of the influence of these parameters. The most important parameters which were already identified are the frequency of the ultrasonic piezoelectric transducer, the nature of the solvent, the liquid level in the reactor, the temperatures in the system, and the passing time of the aerosol droplets in the oven.     

Interaction between laser beam and BaTiO3 powders in selective laser sintering treatments

The research work reported in this paper is an investigation of the behavior of barium titanate powders under selective laser irradiation. Our goal is to determine suitable conditions to sinter the powders and form dense layers usable in some electronic components. On that purpose, compacts of micro/nano BaTiO₃ powder mixes are used for a parametric investigation of the laser scans parameters (power, speed, etc.) with a Nd-YVO₄ laser (23 W). The microstructures obtained after laser treatments are evaluated by XRD, SEM and EDS and compared to a reference specimen manufactured in a conventional way. From this work it can be concluded that a high laser beam power is required to obtain a consolidation of the powder grains and the use of a high scan speed avoids the melting. The scanning speed also influences the final crystallographic state of BaTiO₃. Optimal parameters were founded in order to form a dense and homogeneous tetragonal BaTiO₃ surface.     

Iridium complexes incorporating coumarin moiety as catalyst photoinitiators: Towards household green LED bulb and halogen lamp irradiation

Household LED bulbs and halogen lamps are used to promote the ring-opening photopolymerization of epoxides in the presence of a new series of iridium(III) complexes (IrCs) exhibiting enhanced visible light absorption properties through the introduction of a coumarin moiety. These latter complexes are used as catalyst photoinitiators in an oxidative cycle in combination with a silane and an iodonium salt. Remarkably, even under the selected very soft irradiations (e.g. light intensity lower than 2 mW/cm²), excellent polymerization profiles are obtained (conversions > 80%). The mechanisms are investigated by ESR and luminescence experiments.     

Structural evolution at short and medium range distances during crystallization of a P2O5-Li2O-Al2O3-SiO2 glass

Li₂O-Al₂O₃-SiO₂ (LAS) glass-ceramics have important industrial applications and bulk nucleation is usually achieved by using nucleating agents. In particular, P₂O₅ is an efficient agent in glasses containing a low level of Al₂O₃ but its role in the first stages of nucleation is not well established. In this study, we combine structural investigations from local to mesoscales to describe the structural evolution during crystallization of LAS glass-ceramics. Local environment is probed using ²⁹Si and ³¹P MAS-NMR, indicating organization of P in poorly crystallized Li₃PO₄ species prior to any crystallization. To better understand the detailed nanoscale changes of the glass structure, ³¹P-³¹P DQ-DRENAR homonuclear correlation experiments have been carried out, revealing the gradual segregation of P atoms associated with the formation of disordered Li₃PO₄. Small-angle neutron scattering data also show the apparition of nanoscale heterogeneities associated with Li₃PO₄ species upon heating treatments and allow the determination of their average sizes. These new structural information enhance our understanding of the role of P in nucleation mechanisms. Nucleation is initiated by gradual change in P environment implying P segregation upon heating treatments, forming disordered Li₃PO₄ heterogeneities. The segregation of P atoms enables the precipitation of meta- and disilicate phases.     

Synthetic Peroxides Promote Apoptosis of Cancer Cells by Inhibiting P-Glycoprotein ABCB5

This article discloses a new horizon for the application of peroxides in medical chemistry. Stable cyclic peroxides are demonstrated to have cytotoxic activity against cancer cells; in addition a mechanism of cytotoxic action is proposed. Synthetic bridged 1,2,4,5-tetraoxanes and ozonides were effective against HepG2 cancer cells and some ozonides selectively targeted liver cancer cells (the selectivity indexes for compounds 11 b and 12 a are 8 and 5, respectively). In some cases, tetraoxanes and ozonides were more selective than paclitaxel, artemisinin, and artesunic acid. Annexin V flow-cytometry analysis revealed that the active ozonides 22 a and 23 a induced cell death of HepG2 by apoptosis. Further study showed that compounds 22 a and 23 a exhibited a strong inhibitory effect on P-glycoprotein (P-gp/ABCB5)-overexpressing HepG2 cancer cells. ABCB5 is a key player in the multidrug-resistant phenotype of liver cancer. Peroxides failed to demonstrate a direct correlation between oxidative potential and their biological activity. To our knowledge this is the first time that peroxide diastereoisomers have been found to show stereospecific antimalarial action against the chloroquine-sensitive 3D7 strain of Plasmodium falciparum. Stereoisomeric ozonide 12 b is 11 times more active than stereoisomeric ozonide 12 a (IC₅₀=5.81 vs 65.18 μm ). Current findings mean that ozonides merit further investigation as potential therapeutic agents for drug-resistant hepatocellular carcinoma.     

Geopolymer assembly by emulsion templating: Emulsion stability and hardening mechanisms

This work investigates emulsion templating to synthesize hexadecane oil/geopolymer composites. In a system with hexadecane as the internal (dispersed) phase and an alkali activated continuous phase without added surfactant, adding aluminosilicate clay particles does not increase resistance against creaming or coalescence, while adding a surfactant (L35 or CTAB) stabilizes the solid-liquid interface. Infrared studies and rheological studies of the associated geopolymerization determined that the presence of the organic phase or surfactant has no significant effect on the geopolymerization kinetics, as determined by the change in time of the Si-O-T IR stretching frequency and the rheological moduli involved during the process. The stabilization of the organic template is reminiscent of Pickering emulsion even though we employ a much greater amount of inorganic material for geopolymer formation. Although the addition of surfactant has a significant effect on the behavior of the paste, the percolation of the network remains unmodified, highlighting the fact that the phenomenon is not dependent on viscosity. Finally, rheological measurements were used to obtain the mass fractal dimension of the as-made gel network, which is able to differentiate the interfacial effect between surfactant molecules with a slightly denser interphase when a cationic surfactant is used.     

Simple Views on Metal/Oxide Interfaces: Contributions of the Long-Range Interactions to the Adhesion Energy

The image and van der Waals contributions to the metal/oxide work of adhesion are compared through the extent to which they follow the known prevalent trends, i.e. the increase in work of adhesion (a) with narrowing oxide band gap and (b) with increasing conduction electron density of the metal. The van der Waals interaction is shown to follow both trends, while the image term is suggested to be significant only for dense metals in contact with very ionic oxides. The relative contribution of these long-range interactions to the overall metal/oxide work of adhesion is found to be maximized for systems involving metals with low electronic densities and oxides with wide band gaps. At variance, high metallic electronic densities and narrow oxide gaps likely favour short-range interactions arising from charge transfer.     

Nanocomposite piezoelectric films of P(VDF‐TrFE)/LiNbO3

Piezoelectric films were prepared by incorporation of lithium niobate (LiNbO₃) nanoparticles into copolymer of vinylidene difluoride and trifluoroethylene. Nanoparticles of LiNbO₃ with ferroelectric phase were successfully synthesized and dispersed homogenously by ultrasonication in the copolymer matrix without any surfactant or surface functionalization. The nanocomposites were fully characterized by electronic microscopy, X‐ray diffraction, differential scanning calorimetry, dynamical mechanical analysis, and piezometer. Surprisingly, the copolymer matrix crystallinity and morphology were not affected by the incorporation of nanoparticles. Therefore the nanocomposites remained good mechanicals properties and high ferroelectricity coupled to nonlinear optical activity thanks to the noncentro symmetric space group of lithium niobate. This could be a novel approach to develop new multifunctional materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013