A practical way of grafting maleic anhydride onto polypropylene providing high anhydride contents without sacrificing excessive molar mass

This study reports a reactive extrusion process leading to very high levels of anhydride grafting (2.5–3 wt %) along polypropylene backbone without recovering grafted PP waxes at the die exit. Such high graftings are attainable without excessive degradation of the PP chain by using a brominated reagent. Simultaneously, this brominated reagent allows the tuning of the grafted PP crystallinity via epimerization of the PP backbone. Indeed, the synthesis of a mainly isotactic/atactic stereoblock polymer containing high levels of grafted succinic anhydride moieties is demonstrated by NMR and melting enthalpies recorded by DSC are definitely observed depressed and broadened. Grafting levels of around 3 wt % have been achieved and ascertained by both chemical titration and NMR spectroscopy. In addition, FTIR spectroscopy reveals an unusual observation: for the first time, only one single pair of symmetric and asymmetric carbonyl stretching bands are observed on those grafted PP, while, in other processes of anhydride grafting, those symmetric and asymmetric bands were both split in at least two bands. This suggests, for the here reported process, the absence of interacting grafted anhydride rings, i.e., absence of closely grafted anhydride moieties and absence of poly(maleic anhydride). All those observations support that this “bromine route” brings a really new grafting process for PP. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2936–2947, 2008     

Controlled reduction of polypropylene isotacticity and crystallinity by epimerization during reactive processing

Amorphous and low crystallinity polypropylenes were produced by reactive processing of commercial isotactic polypropylenes in the presence of a peroxide (2,5‐dimethyl‐2,5‐di(tert‐butylperoxy)hexane) and N‐bromosuccinimide. Characterization of the modified polypropylene microstructures using ¹³C NMR spectroscopy revealed that crystallinity loss is correlated with the epimerization of numerous methynes randomly along the polymer backbone, leading to decreasing isotacticities ([mmmm]) and average isotactic block lengths. Moreover, degradation usually induced by peroxide was shown to be comparatively limited in additional presence of N‐bromosuccinimide. This fast and easy process therefore allows the production of polypropylene plastomers and elastomers with controlled and homogeneous crystallinities and isotacticities, and relatively low molecular weight distributions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4505–4518, 2009     

Nonparametric Adverse Selection Problems

This article is devoted to adverse selection problems in which individual private information is a whole utility function and cannot be reduced to some finite-dimensional parameter. In this case, incentive-compatibility conditions can be conveniently expressed using some abstract convexity notions arising for instance in Mass Transfer Theory. After this characterization is provided, an existence result of optimal incentive-compatible contracts is proved. Finally, several economic examples are considered including applications to regulation and labor contracting.     

59Co, 23Na NMR and electric field gradient calculations in the layered cobalt oxides NaCoO2 and HCoO2

⁵⁹Co and ²³Na NMR has been applied to the layered cobalt oxides NaCoO₂ and HCoO₂ at three different magnetic field strengths (4.7, 7.1 and 11.7 T). The ⁵⁹Co and ²³Na quadrupole and anisotropic shift tensors have been determined by iterative fitting of the NMR line shapes at the three magnetic field strengths. Due to the large ⁵⁹Co quadrupole interaction in NaCoO₂, a frequency-swept irradiation procedure was used to alleviate the limited bandwidth of the excitation. While the ⁵⁹Co and ²³Na shift and quadrupole coupling tensors in NaCoO₂ are found to be coincident and axially symmetric in agreement with the crystal symmetry requirements, the fits of the ⁵⁹Co NMR spectra clearly show the presence of structural disorder in HCoO₂. The ²³Na chemical shift anisotropy can be reproduced by shift tensor calculations using a point dipole model and considering that the magnetic susceptibility in NaCoO₂ is due to Van Vleck paramagnetism for Co³⁺. Electric field gradient calculations using either the empirical point charge model or the ab initio full potential-linearized augmented plane wave method are compared with the experimental NMR data.     

Flow estimation using an intravascular imaging catheter

Coronary flow assessment can be useful for determining the hemodynamic severity of a stenosis and to evaluate the outcome of interventional therapy. We developed a method for measuring the transverse flow through the imaging plane of an intravascular ultrasound (IVUS) catheter. This possibility has raised great clinical interest since it permits simultaneous assessment of vessel geometry and function with the same device. Furthermore, it should give more accurate information than combination devices because lumen diameter and velocity are determined at the same location. Flow velocity is estimated based on decorrelation estimation from sequences of radiofrequency (RF) traces acquired at nearly the same position. Signal gating yields a local estimate of the velocity. Integrating the local velocity over the lumen gives the quantitative flow. This principle has been calibrated and tested through computer modeling, in vitro experiments using a flow phantom and in vivo experiments in a porcine animal model, and validated against a Doppler element containing guide wire (Flowire) in humans. Originally the method was developed and tested for a rotating single element device. Currently the method is being developed for an array system. The great advantage of an array over the single element approach would be that the transducer has no intrinsic motion. This intrinsic motion sets a minimal threshold in the detectable velocity components. Although the principle is the same, the method needs some adaptation through the inherent different beamforming of the transducer. In this paper various aspects of the development of IVUS flow are reviewed.     

Recovered efficiency of filter control in dispersion-managed solitons for optical regeneration applications: analysis and experimental validation

We demonstrate numerically that local conversion of dispersion-managed return-to-zero pulses into nonlinear Schr?dinger solitons fully restores optical filtering control for energy stabilization, thus permitting the association of optical regeneration with dispersion-managed propagation. Experimental validation is achieved by means of 40-Gbit/s regenerated dispersion-managed loop transmission over 10,000 km.     

Mass spectrometric study of conjugated bifunctional acetylenes. 1—Enynes

This study on the fragmentation of conjugated enynes demonstrates the relationships between the mass spectra and the structures of these compounds. The rearrangements of the molecular ions and the fragment ions are characterized; the mechanisms by which the most important peaks are formed have been established and detailed analysis of the metastable transitions reveals all the fragmentation steps. A complete scheme is presented for 2-methyl-1-nonene-3-yne since it includes all the transitions which can be detected for the lower homologues. The ion kinetic energy spectra for this family of compounds are distinct (even though the conventional spectra are similar) and could very well be used for identification purposes.     

The robust binomial approach to chance-constrained optimization problems with application to stochastic partitioning of large process networks

In this paper, we study an interpretation of the sample-based approach to chance-constrained programming problems grounded in statistical testing theory. On top of being simple and pragmatic, this approach is theoretically well founded, non parametric and leads to a general method for leveraging existing heuristic algorithms for the deterministic case to their chance-constrained counterparts. Throughout this paper, this algorithm design approach is illustrated on a real world graph partitioning problem which crops up in the field of compilation for parallel systems. Extensive computational results illustrate the practical relevance of the approach, as well as the robustness of the obtained solutions.