Biaxial deformation of polyamide‐6: Assessment of orientation by means of infrared trichroism

Infrared spectroscopy was used to study the evolution of structure in films of polyamide‐6 drawn on a Cellier tenter frame laboratory tester under conditions of simultaneous equibiaxial stretching and planar uniaxial stretching. The “tilted film” method was used to obtain trichroic spectra corresponding to the machine, transverse, and normal directions, as well the “structural factor” spectrum. From these it was possible to obtain information on the molecular orientation and the evolution of the crystalline structure. The starting films, prepared by melt casting from an extruder on a chilled roll, contained predominantly the mesomorphic β form. The structural factor spectra confirmed that strain‐induced transformation into the α form occurred upon drawing, and that the amount of α form increased with the extent of drawing. The trichroic spectra showed that the molecular orientation was localized mainly, but not exclusively, in the α form. Orientation functions could be determined for both the molecular chain axis and the normal to the hydrogen‐bonded sheets. For both the equibiaxial and planar uniaxial films, these sheets were found to be strongly oriented parallel to the plane of the film, with the degree of orientation increasing with overall draw ratio. For the biaxial samples, the molecular chain orientation was found to be equibiaxial, as expected. Mechanical test results indicated that the chains are evenly distributed in the film plane rather than showing a preference for the two orthogonal draw directions. For the planar uniaxial samples, the chain orientation was predominantly in the draw direction, but some degree of orientation in the transverse direction was also observed. The variation of orientation functions with draw ratio suggested that the α structure evolves in two stages, the first involving chain orientation in the draw direction and the second involving rotation of the sheets into the plane of the film.     

Structures and morphologies of cast and plastically strained polyamide 6 films as evidenced by confocal Raman microspectroscopy and atomic force microscopy

Both confocal Raman microspectroscopy and atomic force microscopy (AFM) have been undertaken to study the crystalline and the morphological aspects of cast PA 6 films at a sub-microscopic scale. The percentages of the different crystalline structures present within PA 6 cast films, i.e. the monoclinic α, the pseudo-hexagonal β, and the monoclinic γ, have been measured by confocal Raman microspectroscopy. In cast films, the prevailing structure is the β one. AFM has been used to characterize the morphology of the PA 6 films. Simultaneously, the deformed state has been considered as well. Our main interest has been to follow the evolution of the percentage of each crystalline structure as a function of the plastic deformation mechanisms which are responsible of the yielding of PA 6 films: shear banding for temperatures T lower than 160 °C and formation of fibrils for      

Effect of recycling and injection parameters on gloss properties of smooth colored polypropylene parts: Contribution of surface and skin layer

The aim of this article is to investigate the optical properties of a recycled polymer during numerous processes. The effects of different process parameters (number of grinding‐injection cycles, material temperature, mold temperature, and injection rate) on gloss and color properties of a buff‐colored polypropylene containing 2wt%/wt of pigment was considered. The variations of properties are in the same range that is observed by changing processing parameters. It is found that the roughness is not able to explicate the variation of the optical properties for these variations of conditions. In addition, the optical properties of the skin layer of the injected parts are associated with the observed gloss and color variations. Moreover, the change of spherulite dimensions is related with optical changes. POLYM. ENG. SCI., 59:1288–1299 2019. © 2019 Society of Plastics Engineers     

Adaptive partitioning schemes for bipartite ranking

Recursive partitioning methods are among the most popular techniques in machine learning. The purpose of this paper is to investigate how to adapt this methodology to the bipartite ranking problem. Following in the footsteps of the TreeRank approach developed in Clémençon and Vayatis (Proceedings of the 2008 Conference on Algorithmic Learning Theory, 2008 and IEEE Trans. Inf. Theory 55(9):4316–4336, 2009), we present tree-structured algorithms designed for learning to rank instances based on classification data. The main contributions of the present work are the following: the practical implementation of the TreeRank algorithm, well-founded solutions to the crucial issues related to the splitting rule and the choice of the “right” size for the ranking tree. From the angle embraced in this paper, splitting is viewed as a cost-sensitive classification task with data-dependent cost. Hence, up to straightforward modifications, any classification algorithm may serve as a splitting rule. Also, we propose to implement a cost-complexity pruning method after the growing stage in order to produce a “right-sized” ranking sub-tree with large AUC. In particular, performance bounds are established for pruning schemes inspired by recent work on nonparametric model selection. Eventually, we propose indicators for variable importance and variable dependence, plus various simulation studies illustrating the potential of our method.     

Innovative polyelectrolytes/poly(ionic liquid)s for energy and the environment

This paper presents the work carried out within the European project RENAISSANCE‐ITN, which was dedicated to the development of innovative polyelectrolytes for energy and environmental applications. Within the project different types of innovative polyelectrolytes were synthesized such as poly(ionic liquid)s coming from renewable or natural ions, thiazolium cations, catechol functionalities or from a new generation of cheap deep eutectic monomers. Further, macromolecular architectures such as new poly(ionic liquid) block copolymers and new (semi)conducting polymer/polyelectrolyte complexes were also developed. As the final goal, the application of these innovative polymers in energy and the environment was investigated. Important advances in energy storage technologies included the development of new carbonaceous materials, new lignin/conducting polymer biopolymer electrodes, new iongels and single‐ion conducting polymer electrolytes for supercapacitors and batteries and new poly(ionic liquid) binders for batteries. On the other hand, the use of innovative polyelectrolytes in sustainable environmental technologies led to the development of new liquid and dry water, new materials for water cleaning technologies such as flocculants, oil absorbers, new recyclable organocatalyst platforms and new multifunctional polymer coatings with antifouling and antimicrobial properties. All in all this paper demonstrates the potential of poly(ionic liquid)s for high‐value applications in energy and enviromental areas. © 2017 Society of Chemical Industry     

Fictive-Temperature Mapping in Highly Ge-Doped Multimode Optical Fibers

In this paper, a Fourier transform infrared focal-plane-array detector was used to image the "bond-stretching" vibration mode observed near sigma=1120 cm^-1 of highly Ge-doped graded-index multimode optical fibers (GI-MMFs). We show that the distribution of the peak wavenumber sigma is nonuniform across the core and cladding of the MMF, i.e., sigma is smaller in the core due to the Ge-doping. Next, as calibration curves between sigma and the fictive temperature T_f are not available in the literature for highly Ge-doped glasses (above 7w%), we have determined calibration curves from 1w% to 30w% in Ge. Then, we have applied these corrections in order to estimate, for the first time to our knowledge, the fictive-temperature distribution within multimode-fiber cross section. Using these curves, we show that T_f is higher at the fiber edges, presumably due to faster cooling. Furthermore, there is also a T_f increase in the center of the core (i.e., higher Ge content)     

Surface energy, adsorption, and wetting transitions in ternary liquid alloys

Surface energy measurements have been performed on liquid Ga-Sn binary and on Ga-Pb-Sn as well as Ga-Pb-Tl ternary alloys, by the sessile drop technique under ultrahigh vacuum conditions. The purpose of these measurements was to investigate the change in adsorption behavior of Pb in Garich alloys as a consequence of ternary additions. In order to aid in the interpretation of the results, a multilayer model of surface segregation was formulated in the regular solution approximation. The results show evidence of site competition effects between the two solutes, which reduce the surface concentration of Pb in relation to binary Ga-Pb alloys. The effects of Sn on previously studied wetting-related adsorption transitions in Ga-Pb were also investigated. It was concluded that Sn additions are likely to raise the wetting temperature of the Ga-Pb alloy.     

Thermal stability of the 248-nm-induced presensitization process in standard H2-loaded germanosilicate fibers

Grating growths through exposure of presensitized standard fibers to KrF light were recorded in various experimental condition. It is shown that there exists an optimum sensitization fluence at which the efficiency of the sensitization process is higher. Isochronal thermal annealing of pre-exposed fibers led to a decrease in the sensitization-induced enhancement of photosensitivity. IR-absorption spectroscopy was carried out in fibers or preform plates to monitor the attenuation ascribed to H-bearing species in the same samples. The annealing-induced decay in photosensitivity cannot be correlated with those of the H-bearing species in the whole temperature range (110 degrees C-800 degrees C). This indicates that the enhancement of photosensitivity comes from the transformation of more than one species.     

Structural organization and drawability in polyamide blends

The thermal behavior of polyamide 6/amorphous polyamide blends has been investigated as a function of blend composition and temperature. Crystal phase nature and stability are probed by a combination of thermal analysis, X‐ray diffraction and Fourier transform infrared spectroscopy. Ductility appears to be strongly affected by the addition of the amorphous polyamide, but the corresponding decrease of the yield stress, either taken at the same draw temperature or under a comparable state of mobility of the amorphous phase, may not be simply accounted for by the reduction of overall ordered phase content.     

An empirical comparison of learning algorithms for nonparametric scoring: the TreeRank algorithm and other methods

The TreeRank algorithm was recently proposed in [1] and [2] as a scoring-based method based on recursive partitioning of the input space. This tree induction algorithm builds orderings by recursively optimizing the Receiver Operating Characteristic curve through a one-step optimization procedure called LeafRank. One of the aim of this paper is the in-depth analysis of the empirical performance of the variants of TreeRank/LeafRank method. Numerical experiments based on both artificial and real data sets are provided. Further experiments using resampling and randomization, in the spirit of bagging and random forests are developed [3, 4] and we show how they increase both stability and accuracy in bipartite ranking. Moreover, an empirical comparison with other efficient scoring algorithms such as RankBoost and RankSVM is presented on UCI benchmark data sets.