Catalytic olefin polymerisation at short times: Studies using specially adapted reactors

Despite the fact that the very early stages (several tens of seconds) of catalysed olefin polymerisation processes appear negligibly short with respect to the residence time of most industrial reactors, they are critical in terms of catalyst activation, obtaining good particle morphology, and avoiding irreparable problems caused by particle overheating. The different types of reactors that have been used over the course of the past few years are discussed in this feature article. It is shown that despite the difficulties encountered in finding the perfect experimental tool for this purpose, different configurations of stopped flow reactors can be used successfully to explore different aspects of what happens to the catalyst (supported and molecular) during these critical moments of polymerisation. © 2012 Canadian Society for Chemical Engineering     

Dielectric features of two grades of bi‐oriented isotactic polypropylene

The dielectric properties of two grades of bi‐oriented isotactic polypropylene were studied with a variety of techniques: breakdown field measurements, dielectric spectroscopy, thermally stimulated depolarization currents (Is), and direct‐current (dc) conduction I values. Standard polypropylene (STPP) and high‐crystallinity polypropylene (HCPP) films were investigated. Measurements were carried out over a wide temperature range (?150°C/+125°C). The breakdown fields in both materials showed a very small difference. On the other hand, the dielectric losses and dc conduction I values were significantly lower in HCPP. Both materials showed a decrease in the dielectric loss versus temperature in the range 20–90°C; this is favorable for application in alternating‐current power capacitors. The analysis of the dc I value allowed us to find evidence of two main conduction mechanisms: (1) below 80°C in both materials, a hopping mechanism due to the motion of electrons occurred in the amorphous phase, and (2) above 80°C, ionic conduction occurred in HCPP, and hopping conduction occurred in STPP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42224.     

Dietary intakes and food sources of fatty acids for Belgian women, focused on n-6 and n-3 polyunsaturated fatty acids

The intake of fat, saturated and monounsaturated FA (SFA and MUFA), and omega-6 and omega-3 PUFA has been estimated in 641 Belgian women (age 18-39 y). Their food intake was recorded using a 2-d food diary. The PUFA included were linoleic (LA), alpha-linolenic (LNA), arachidonic (AA), eicosapentaeonoic (EPA), docosapentaenoic (DPA) and docosahexaenoic (DHA) acids. The mean total fat intake corresponded to 34.3% of total energy intake (E). The mean intake of the FA groups corresponded to 13.7%, 13.1%, and 6.0% of E, for SFA, MUFA, and PUFA, respectively. The mean intake of LA was 5.3% of E and of LNA was 0.6% of E, with a mean LA/LNA ratio of 8.7. The mean intake of AA was 0.03% of E. The mean intake of EPA, DPA, and DHA was 0.4%, 0.01%, and 0.06% of E, respectively. According to the Belgian recommendations, the total fat and SFA intake was too high for about three-quarters of the population. The mean LA and overall n-6 PUFA intake corresponded with the recommendation, with part of the population exceeding the upper level. Conversely, the population showed a large deficit for LNA and n-3 PUFA. The major food source for LA and LNA was fats and oils, followed by cereal products. The main sources of long-chain PUFA were fish and seafood, and meat, poultry, and eggs. From a public health perspective, it seems desirable to tackle the problem of low n-3 PUFA intake.     

Binding Mode and Structure–Activity Relationships around Direct Inhibitors of the Nrf2–Keap1 Complex

An X‐ray crystal structure of Kelch‐like ECH‐associated protein (Keap1) co‐crystallised with (1S,2R)‐2‐[(1S)‐1‐[(1,3‐dioxo‐2,3‐dihydro‐1H‐isoindol‐2‐yl)methyl]‐1,2,3,4‐tetrahydroisoquinolin‐2‐carbonyl]cyclohexane‐1‐carboxylic acid (compound (S,R,S)‐ 1 a ) was obtained. This X‐ray crystal structure provides breakthrough experimental evidence for the true binding mode of the hit compound (S,R,S)‐ 1 a , as the ligand orientation was found to differ from that of the initial docking model, which was available at the start of the project. Crystallographic elucidation of this binding mode helped to focus and drive the drug design process more effectively and efficiently.     

Study of ITER equatorial port plug handling system and vacuum sealing interface

In the field of the ITER port plug engineering and integration task, CEA has contributed to define proposals concerning the port plugs vacuum sealing interface with the vessel flange and the equatorial plug handling.The 2001 baseline vacuum flange sealing consisted of TIG welding of a 316L strip plate on to U shapes. This arrangement presented some issues like welding access, implementation of tools, lip consumption, complex local leak test, continuous leak checking. Therefore, an alternate sealing solution based on the use of metallic gaskets is proposed. The different technical aspects are discussed to explain how this design can simplify the maintenance and deal with safety and vacuum requirements.The design of the mechanical attachment and vacuum sealing of the plug has constantly evolved, but the associated remote handling equipment was not systematically reviewed. An update of the cask and maintenance procedure was studied in order to design it in accordance with the last generic plug flange design. This includes a concept of a gripping system that uses the plug flange bolting area and, to help the remote handling process, a cantilever assisting system is suggested to increase the reliability of the transfer operation between vacuum vessel and cask.     

“Greening Up” Cross-Coupling Chemistry

New methodologies that enable palladium catalyzed cross-coupling reactions to be performed under environmentally benign conditions (in water and/or at room temperature) have been developed. Described approaches involve in situ activation of carbon–halogen or carbon–hydrogen bonds using zinc metal, or cationic palladium, respectively.     

Mechanical Property of HVOF Inconel 718 Coating for Aeronautic Repair

The module of elasticity is one of the most important mechanical properties defining the strength of a material which is a prerequisite to design a component from its early stage of conception to its field of application. When a material is to be thermally sprayed, mechanical properties of the deposited layers differ from the bulk material, mainly due to the anisotropy of the highly textured coating microstructure. The mechanical response of the deposited layers significantly influences the overall performance of the coated component. It is, therefore, of importance to evaluate the effective module of elasticity of the coating. Conventional experimental methods such as microindentation, nanoindentation and four-point bending tests have been investigated and their results vary significantly, mainly due to inhomogeneous characteristics of the coating microstructure. Synchrotron radiation coupled with a tensile test rig has been proposed as an alternative method to determine the coating anisotropic elastic behavior dependence on crystallographic orientations. The investigation was performed on Inconel 718 (IN718) HVOF coatings sprayed on IN718 substrates. Combining these experimental techniques yield a deeper understanding of the nature of the HVOF coating Young’s modulus and thus a tool for Design Practice for repair applications.     

5-Axis tool path smoothing based on drive constraints

In high speed machining, the real feedrate is often lower than the programmed one. This reduction of the feedrate is mainly due to the physical limits of the drives, and affects machining time as well as the quality of the machined surface. Indeed, if the tool path presents sharp geometrical variations the feedrate has to be decreased to respect the drive constraints in terms of velocity, acceleration and jerk. Thus, the aim of this paper is to smooth 5-axis tool paths in order to maximize the real feedrate and to reduce the machining time.Velocity, acceleration and jerk limits of each drive allow to compute an evaluation of the maximum reachable feedrate which is then used to localize the areas where the tool path has to be smoothed. So starting from a given tool path, the proposed algorithm iteratively smoothes the joint motions in order to raise the real feedrate. This algorithm has been tested in 5-axis end milling of an airfoil and in flank milling of an impeller for which a N-buffer algorithm is used to control the geometrical deviations. An important reduction of the measured machining time is demonstrated in both examples.     

Retail competition in electricity markets

The introduction of competition into retail electricity supply gave rise to great expectations. However, to date, its performance has proven less than stellar, owing primarily to the theoretical concepts underpinning this reform, which draw heavily on the Austrian school. Neither consumers’ decision processes nor this sector's technical paradigm were adequately accounted for, leading to an uncorrect estimation of the expected impact of opening to competition. Short- and medium-term prospects for the evolution of retail markets must be reconsidered from the perspective of greater stability: not a generalization of competition, but rather a persistent segmentation between active and inactive clients; not a large and rapid diffusion of radical innovations in commercialisation, with the potential for undermining the incumbents’ positions.