Effect of Water on α‐Methylstyrene Hydrogenation on Pd/Al2O3

α‐methylstyrene catalytic hydrogenation on Pd/Al₂O₃ is frequently used to characterize new reactors. However, whereas many authors report some problems of reproducibility or possible poisoning of the catalyst, no consistent advice is available in the literature to carry out the reaction without these problems. This work points out the inhibition of the reaction by trace amounts of water. An experimental procedure is explained to guarantee the reproducibility of the measures.     

Synthesis and Crystal Structure Characterization of Oxysilicate Apatites for Stabilization of Sr and Rare‐Earth Elements

Strontium (Sr) containing rare‐earth oxysilicate apatite A^I₄A^II₆(SiO₄)₆O₂ is considered a good matrix to accommodate radionuclide as its cation sites can incorporate lanthanide elements other than Sr. Here, we report a study on the synthesis of Nd₈Sr₂(SiO₄)₆O₂ and Yb₈Sr₂(SiO₄)₆O₂, which adopt P6₃/m apatite symmetry, as well as the characterization of crystallographic structures using X‐ray diffraction and electron microscopy. It is found that A^I position is shared by Nd, Yb and Sr, and A^IO₆ polyhedra are face‐connected, forming column structures, which are linked to SiO₄ tetrahedra, creating continuous channels. The Rietveld refinement shows that Nd and Yb prefer the A^II position in the channel. The twisted angle of adjacent triangle faces in an A^I‐O polyhedron along [001] is a critical parameter to identify the channel volume and its value varies when different cations are incorporated. The twisted angles for Nd‐apatite and Yb are 24.2° and 22.7° The findings provide a new insight into nuclear waste stabilization by apatite‐type structure.     

Dynamic methods and new reactors for liquid phase molecular catalysis

Kinetic data acquisition and screening of transition metal complexes for homogeneous liquid phase catalysis calls for numerous testing in multiphase G/L, L/L and G/L/L systems. It is shown first, with an example in asymmetric hydrogenation, why detailed kinetics must be performed. Then, new reactors leading to fast experimental techniques are proposed. A liquid–liquid centrifugal partition chromatography is evaluated for determining rate constants and partition isotherms by combining frontal analysis and elution chromatography, the catalyst being maintained in a stationary aqueous phase. Two microreactors offering short residence time have also been tested and compared with a fast test reaction (t_R ca. 5–20 s). The combination of reacting pulses, carrier liquids and micromixer is proposed as a general high throughput tool for the investigation of G/L, L/L and G/L/L catalytic systems in a fast sequential way.     

Emulsifying and foaming properties of native and chemically modified peptides from the 2S and 12S proteins of rapeseed (Brassica napus L.)

The 2S and 12S proteins of rapeseed were isolated and subsequently hydrolyzed by pepsin or a combination of pepsin plus trypsin. The resulting hydrolysates had a 15% degree of hydrolysis and were purified by gel filtration chromatography in order to obtain homogeneous peptide fractions. Three major fractions, having an average peptide chain length of 7.5–11 amino acids, were recovered. Purified peptide fractions were acylated with butyric anhydride and sulfamidated with p-toluenesulfonyl chloride. The degree of modification was always higher than 90%. Emulsifying and foaming properties of native and chemically modified peptides were studied and compared to those of sodium dodecyl sulfate (SDS) as standard. A peptide fraction from the 15% hydrolysis of the 12S protein exhibited the best foaming properties. After sulfamidation, this peptide fraction showed a foam formation similar to that of SDS. Whereas the attachment of toluene groups generally improved the surface properties, the incorporation of an aliphatic chain of four atoms of carbon was detrimental in most of the cases. On the other hand, none of the native or hydrophobized peptide fractions was able to form a stable emulsion.     

Behavior of Paramagnetic Iron during the Thermal Transformations of Kaolinite

Kaolinites with various degrees of structural order and iron content were heated and subsequently analyzed via electron paramagnetic resonance. Iron was present in two different states in the heated materials, either as dilute structural Fe³⁺ ions or in concentrated Fe³⁺ phases. During metakaolinization, the environment of dilute Fe³⁺ ions changed, following modifications of the Al³⁺ coordination, and the Fe³⁺ concentration increased. With the breakdown of metakaolinite, the diffusion of Fe³⁺ ions induced their exsolution in superparamagnetic iron-rich domains (Fe³⁺ clusters in γ-Al₂O₃ and/or Fe³⁺ oxide nanophases), which produced a decrease in the dilute Fe³⁺ concentration. The subsequent breakdown of γ-Al₂O₃ and the formation of mullite made the dilute Fe³⁺ concentration increase again, because of the incorporation of Fe³⁺ ions in the mullite structure.     

Dehydrocyclization of Alkanes Over Zeolite-Supported Metal Catalysts: Monofunctional or Bifunctional Route

The direct catalytic conversion of alkanes into aromatics has found potentially important industrial applications. Initially only alkanes with 6 and more carbon atoms in the chain were concerned. Supported platinum catalysts were found active for the aromatization of alkanes; the drawbacks of these catalysts were their deactivation with time on stream and the existence of simultaneous parallel reactions. Much discussion has been published on the aromatization of C₆₊ alkanes. A bifunctional mechanism which involves both the metal and the acid sites of the support and a monofunctional mechanism involving only the metallic sites operate over, respectively, Pt supported on acidic support and Pt supported on nonacidic support. In the present review the mechanisms proposed for the aromatization of alkanes are described. Over monofunctional Pt catalysts two possible mechanisms prevail: 1,6 ring closure on the Pt surface involving primary and secondary C-H bond rupture, followed by dehydrogenation of the cycloalkanes into aromatics (1,5 ring closure to a lesser extent also contributes to aromatic production); or dehydrogenation of the alkanes into olefins, dienes, and trienes followed by thermal ring closure. Zeolites were found most suitable as support for preparing catalysts more active and more selective in the alkane aromatization. In addition catalysts based on noble metals supported on zeolite appeared more resistant against deactivation by coke. In this review the aromatization of hexane, heptane, and octane over Pt-zeolite catalysts is discussed in detail. Comparisons between different zeolite structures and different dehydrogenation sites are given. In particular a critical analysis of the results and interpretation concerning Pt-KL catalysts strongly suggests that the exceptional high selectivity towards aromatization of n-hexane exhibited by Pt-KL could not be explained by only the nest or constraint effect exerted by the channel dimension and morphology, not by only the terminal cracking properties, not by only the partial electron transfer from the zeolite support to the Pt particles, and not by only the Pt particle size. Zeolite structure also affects the aromatic product distribution, in particular when the alkane contains more than 7 carbon atoms. It is shown how Pt on medium-pore zeolites such as In-ZSM-5, silicalites will favor the aromatization of C₈ alkane isomers into ethylbenzene-styrene with respect to other C₈ aromatics. Aromatization of light alkanes, C₂-C₅, requires the increase of the hydrocarbon chain length up to 6 carbon atoms and higher, followed by cyclization reaction. Recently new processes to convert C₂-C₅ alkanes into aromatics have been disclosed, M2-forming from Mobil, Cyclar from BP-UOP, and Aroforming from IFP-Saluted. In general these processes use bifunctional catalysts possessing a dehydrogenating and an acid function. The catalysts consist of a metal ion or metal oxide supported on a microporous acid solid. In this review we analyze the results concerning mainly platinum supported on pentasil-type zeolite. It is shown that althoug Pt has better dehydrogenating properties as compared with gallium and zinc, the efficiency of catalysts based on Pt-ZSM-5 for light alkane aromatization is less because undersirable reactions such as hydrogenolysis and ethene (olefins) hydrogenation occur on the platinum surface, resulting in the production of unreactive alkanes, CH₂, C₂H₆. These drawbacks could be partially suppressed by alloying Pt and by increasing the reaction temperature.     

Crystallinity and mechanical properties of polylactide/ether‐amide copolymer blends

The present study focuses on the improvement of impact properties and particularly on the interaction between crystallinity development and mechanical properties of impact modified polylactide (PLA). The PLA was toughened by the addition of a random linear ether‐amide copolymer (PEBAX 3533?). A random copolymer of ethylene, methyl‐acrylate, and glycidyl‐methacrylate (LOTADER AX8900?) was also used to reactively compatibilize the ether‐amide copolymer with the PLA matrix. Melt rheology of the blends was investigated in small amplitude oscillatory shear and showed that the impact modifier could significantly influence the viscoelastic response of the material. The Izod impact resistance and tensile properties were measured using standard testing protocols. The blend morphology was also examined using scanning electron microscopy on cryofractured and microtomed surfaces, while the crystalline morphology was assessed by optical microscopy. A sub‐micron dispersion of the impact modifier was achieved in the presence of the reactive compatibilizer. Significantly improved impact strength was found with 10 wt % impact modifier. High crystallinity samples showed the highest impact strength with values reaching 68 kJ/m², hence a 20‐fold improvement with respect to the neat PLA. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44677.     

In‐line monitoring of the injection molding process by dielectric spectroscopy

In recent years, electrical techniques like microdielectrometry have increasingly been utilized for their ability to continuously monitor, in a nondestructive way, the advancement of the reaction of thermoset resins under cure. This paper discusses an extension of this technique for the “in‐situ” monitoring of the crystallization of thermoplastics applied during an injection molding process. Electric sensors were positioned at the walls of the mold cavity so that an analysis of the volume dielectric properties of material during the filling, the post‐filling, and the cooling steps could be carried out. Poly(vinylidene fluoride) was chosen for this study. A correlation between the evolution of the dielectric parameters and the succession of the steps in this process was undertaken. The dielectric response was sufficiently sensitive to identify the steps of the closing of the mold, filling, post‐filling, cooling, and ejection of the part. In addition, information concerning the crystallization phenomenon near the wall or in the middle of the sample was collected. The gradual filling of the cavity of the mold was also identified by dielectric measurements. The temperature dependence of dielectric properties of the sample was beneficial in evaluating the increase of the temperature of the mold with the succession of injection cycles. The influence of the packing pressure has been clearly identified and confirms the usefulness of the dielectric method as a probe for detecting the shrinkage of the part during the optimization phase of the machine parameters. The dielectric method detailed herein provides a new non‐invasive technique and could be applied to a closed‐loop control of the injection molding process.