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151. Fully biodegradable composites based on poly(butylene adipate-co-terephthalate)/peach palm trees fiber

Author

Sébastien Livi, Juliana Melo da Silva, Bluma G. Soares, Jessica S. Pereira da Silva, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon

Subjects
Filler (packaging), Supercritical carbon dioxide, Materials science, Mechanical Engineering, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Silane, Environmentally friendly, Industrial and Manufacturing Engineering, 0104 chemical sciences, Food packaging, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Mechanics of Materials, Blowing agent, Adipate, Ceramics and Composites, Fiber, Composite material, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

Lignocellulose agricultural residue from peach palm trees (Bactris gasipaes kunth), also well-known as “pupunha”, was employed as reinforcing filler of biodegradable matrix based on poly(butylene adipate- co -terephthalate) (PBAT) in order to develop new green composites for food packaging applications. Then, milled fibers (1.6 mm) were prepared with or without surface treatment with glycidoxypropyl-trimethoxy silane (GPTMS) and introduced into PBAT matrix. The mechanical, dynamic mechanical and rheological properties of these composites were investigated. The presence of fibers, mainly the functionalized one led to an increase of the mechanical performance of the corresponding composites. Finally, the preparation of polymer composite foams for possible packaging applications was also investigated under supercritical carbon dioxide (ScCO 2 ) which acts as environmentally friendly blowing agent. The foamed materials were characterized by SEM microscopy and creep-recovery testing.

Published
2017

152. Hemicellulose extraction and characterization for applications in paper coatings and adhesives

Author

Richard A. Venditti, Frédéric Becquart, Wissam Farhat, Ali Ayoub, Ashley Quick, Nathalie Mignard, Mohamed Taha, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
0106 biological sciences, Lignocellulosic biomass, 02 engineering and technology, Xylose, engineering.material, Lignin, 01 natural sciences, 7. Clean energy, Coating, chemistry.chemical_compound, 010608 biotechnology, Hardwood, Organic chemistry, Hemicellulose, Biomass, Cellulose, Chemistry, Hemicelluloses, Pulp (paper), Alkaline extraction, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Plasticization effect, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, engineering, Adhesive, 0210 nano-technology, Agronomy and Crop Science
Abstract

International audience; Hemicellulose materials are arguably the second most abundant renewable component of lignocellulosic biomass after cellulose. They are relatively under-utilized hetero-polysaccharides present in lignocellulosic biomass. In this research an alkaline treatment was optimized for extraction of polymeric hemicellulose from fully bleached hardwood pulp (B-HWP) and partially delignified switchgrass (SWG). The hemicellulose extracted from B-HWP was relatively pure with zero percent lignin and 89.5% xylose content whereas the partially delignified SWG hemicellulose contained about 6-3% lignin and 72–82% xylose, depending on the NaOH concentration during extraction (3–17% NaOH solution). A maximum molecular weight of SWG hemicellulose of 64,300 g/mol was achieved for the 10% NaOH solution extraction, whereas the MW of B-HWP hemicellulose at 10% NaOH solution extraction was lower at 49,200 g/mol. We have demonstrated that the residual lignin in SWG hemicellulose lowered the system Tg and this might be utilized as a way to increase the applications of hemicellulose in high value biomaterials. Furthermore, the hemicellulose could be crosslinked with zirconium to develop a water resistant gel for coating or adhesive applications. Our results showed that the loading stress required to break an hemicellulose based adhesive connection between two paper surfaces was 0.89, 2.02, 2.75, 3.46, and 3.11 (MPa) for 2, 4, 6, 8 and 10% AZC samples, indicating that up to about 8% AZC crosslinker in the hemicellulose increases the adhesive behavior of the material.

Published
2017

153. Box-relaxation based multigrid solvers for the variable viscosity Stokes problem

Author

Domenico Borzacchiello, Emmanuel Leriche, Benoît Blottière, Jacques Guillet, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Mécanique de Lille - FRE 3723 (LML), Université de Lille, Sciences et Technologies-Centrale Lille-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, and Université de Lille, Sciences et Technologies-Ecole Centrale de Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
General Computer Science, Discretization, Iterative method, Mathematical analysis, General Engineering, Relaxation (iterative method), [CHIM.MATE]Chemical Sciences/Material chemistry, 010103 numerical & computational mathematics, 01 natural sciences, Physics::Fluid Dynamics, 010101 applied mathematics, [CHIM.POLY]Chemical Sciences/Polymers, Multigrid method, Flow (mathematics), Robustness (computer science), Viscosity (programming), 0101 mathematics, ComputingMilieux_MISCELLANEOUS, ComputingMethodologies_COMPUTERGRAPHICS, Mathematics, Variable (mathematics)
Abstract

This paper concerns the numerical study of a class of box-relaxation (coupled) smoothers for multigrid solvers applied to the variable viscosity Stokes problem. In particular, we address the case of multi-phase flows of non miscible fluids with a high viscosity contrast, which are particularly challenging to solve using iterative methods and need robust preconditioning strategies. Three variants of box-relaxation are presented. These are defined based on the algebraic structure of the discrete operators only and therefore can be be compatible, in principle, with most of discretization techniques. Several tests are carried out to assess the robustness of the proposed approach against the varying viscosity contrast (up to 10 7 ), mesh size and mesh stretching factor. Finally, as a practical application, the box-relaxation smoother is used in the framework of flow simulation for multi-layer coextrusion of polymeric fluids.

Published
2017

154. Apparent anisotropy of adhesive bonds with weak adhesion and non-destructive evaluation of interfacial properties

Author

Jocelyne Galy, Michel Castaings, Mathieu Renier, Emmanuel Siryabe, Anissa Meziane, Institut de Mécanique et d'Ingénierie de Bordeaux (I2M), Institut National de la Recherche Agronomique (INRA)-Université de Bordeaux (UB)-École Nationale Supérieure d'Arts et Métiers (ENSAM), Arts et Métiers Sciences et Technologies, HESAM Université (HESAM)-HESAM Université (HESAM)-Arts et Métiers Sciences et Technologies, HESAM Université (HESAM)-HESAM Université (HESAM)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), Institut Jean Le Rond d'Alembert (DALEMBERT), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Mécanique Physique (LMP), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)-HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)-Arts et Métiers Sciences et Technologies, HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)-HESAM Université - Communauté d'universités et d'établissements Hautes écoles Sorbonne Arts et métiers université (HESAM)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), Institut Jean le Rond d'Alembert (DALEMBERT), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet - Saint-Étienne (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, and Centre National de la Recherche Scientifique (CNRS)-Université Sciences et Technologies - Bordeaux 1

Subjects
Materials science, Acoustics and Ultrasonics, Isotropy, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Epoxy, 021001 nanoscience & nanotechnology, 01 natural sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Aluminium, visual_art, 0103 physical sciences, visual_art.visual_art_medium, Ultrasonic sensor, Adhesive, Composite material, 0210 nano-technology, Anisotropy, 010301 acoustics, ComputingMilieux_MISCELLANEOUS, Curing (chemistry), Stiffness matrix
Abstract

The present research attempts to non-destructively characterize mechanical properties, which are representative of the interfacial adhesion and bond line cohesion of adhesively bonded assemblies, using an ultrasonic method. Eight bonded samples made of two aluminium substrates and of an epoxy-based adhesive layer were manufactured: four in which the adhesive is fully cured (100%) and four in which crosslinking is partial (80%). For each level of curing, four different surface treatments were applied to the aluminium substrates before assembling, in order to vary the quality of adhesion. Ultrasonic plane wave transmission coefficients (UPWTC) were either measured in a water tank, or simulated using the well-known stiffness matrix method that micmics the experiments, to produce input data for the inverse problem. This latest consists in the evaluation of the elastic properties of either the adhesive bond or the interphases between both substrates and the adhesive layer. If the interphases are of nominal quality, the values of the inferred properties of the adhesive bond match those previously measured on individual epoxy samples, whether the epoxy is fully or partially cured. However, when interphases are not of nominal quality level, the optimized bond moduli reveal an apparent anisotropy, although the epoxy layer is known to be isotropic. This apparent anisotropy is explained by an analytical rule of mixture, thus giving confidence in the proposed ultrasonic technique, which is then suggested as a potential way to detect weaknesses of interphases. Finally, the optimization of the interphases elastic properties is carried out. The measured normal and shear stiffnesses are shown to decrease as the interphases get degraded. All ultrasonically-measured parameters (apparent anisotropy of the bond and interfacial stiffnesses) vary monotonically with the bonds strength, which was measured via mechanical tests. The proposed UPWTC method was shown to have a strong potential to distinguish between adhesive and cohesive weaknesses of bonded joints, and to estimate corresponding mechanical properties.

Published
2017

155. Rheology of polypropylene filled with short-glass fibers: From low to concentrated filled composites

Author

Philippe Cassagnau, Grégory Martin, Martha Margarita Rueda, René Fulchiron, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, and Hutchinson SA

Subjects
Polypropylene, Materials science, 010304 chemical physics, Polymers and Plastics, Rheometry, Relative viscosity, Organic Chemistry, Glass fiber, General Physics and Astronomy, Percolation threshold, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, 021001 nanoscience & nanotechnology, 01 natural sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Rheology, 0103 physical sciences, Particle-size distribution, Materials Chemistry, Fiber, Composite material, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

Dynamic flow properties of two commercial short glass fiber reinforced polypropylene were carefully investigated. Rotational rheometry was employed to analyze the effect of the particle size distribution, the sizing and the fiber content on the flow properties. This experimental study allowed the examination of large fiber volume fractions up to 60 vol%, allowing the evidence of different phenomena. As generally known, the more the fiber level, the higher is the reinforcement effect on the matrix. The higher the average aspect ratio, the higher is the probability of creating a fiber network. Thus, higher aspect ratio leads to lower values of percolation threshold ( ϕ c ) . It was found that, small variations of the particle size distribution strongly affect the flow behavior of the composites. Dynamic frequency sweeps put in evidence the different concentration transitions regimes viz., dilute to semi-dilute and concentrated to nematic regimes. Finally, the elastic characteristic time has been found to increase when increasing the fiber content. This was in agreement with the behavior of the relative viscosity as a function of the filler level.

Published
2017

156. Data-driven non-linear elasticity: constitutive manifold construction and problem discretization

Author

Domenico Borzacchiello, Rubén Ibáñez, Jose Vicente Aguado, Francisco Chinesta, Elías Cueto, Emmanuelle Abisset-Chavanne, Pierre Ladevèze, ESI Group (ESI), ESI Group, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institut de Recherche en Génie Civil et Mécanique (GeM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-École Centrale de Nantes (ECN)-Centre National de la Recherche Scientifique (CNRS), Aragón Institute of Engineering Research [Zaragoza] (I3A), University of Zaragoza - Universidad de Zaragoza [Zaragoza], Laboratoire de Mécanique et Technologie (LMT), École normale supérieure - Cachan (ENS Cachan)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inverse problems, Mathematical optimization, Discretization, Computer science, Constitutive equation, Computational Mechanics, Ocean Engineering, 02 engineering and technology, 01 natural sciences, Data-driven, law.invention, Data-intensive simulation, [PHYS.MECA.STRU]Physics [physics]/Mechanics [physics]/Structural mechanics [physics.class-ph], 0203 mechanical engineering, law, Computational mechanics, Constitutive manifold, 0101 mathematics, Axiom, Applied Mathematics, Mechanical Engineering, Experimental data, Data-driven computational mechanics, Inverse problem, 010101 applied mathematics, Computational Mathematics, 020303 mechanical engineering & transports, Computational Theory and Mathematics, Manifold (fluid mechanics)
Abstract

The use of constitutive equations calibrated from data has been implemented into standard numerical solvers for successfully addressing a variety problems encountered in simulation-based engineering sciences (SBES). However, the complexity remains constantly increasing due to the need of increasingly detailed models as well as the use of engineered materials. Data-Driven simulation constitutes a potential change of paradigm in SBES. Standard simulation in computational mechanics is based on the use of two very different types of equations. The first one, of axiomatic character, is related to balance laws (momentum, mass, energy, $$\ldots $$ ), whereas the second one consists of models that scientists have extracted from collected, either natural or synthetic, data. Data-driven (or data-intensive) simulation consists of directly linking experimental data to computers in order to perform numerical simulations. These simulations will employ laws, universally recognized as epistemic, while minimizing the need of explicit, often phenomenological, models. The main drawback of such an approach is the large amount of required data, some of them inaccessible from the nowadays testing facilities. Such difficulty can be circumvented in many cases, and in any case alleviated, by considering complex tests, collecting as many data as possible and then using a data-driven inverse approach in order to generate the whole constitutive manifold from few complex experimental tests, as discussed in the present work.

Published
2017

157. Structural Peculiarities of Ion-Conductive Organic-Inorganic Polymer Composites Based on Aliphatic Epoxy Resin and Salt of Lithium Perchlorate

Author

Maksym Iurzhenko, Yevgen Mamunya, Volodymyr Synyuk, Igor Tkachenko, Liubov K. Matkovska, Gisèle Boiteux, Andriy Shadrin, V.L. Demchenko, Institute of Macromolecular Chemistry of NAS of Ukraine (IMC), National Academy of Sciences of Ukraine (NASU), Institute of Macromolecular Chemistry of NAS of Ukraine, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon

Subjects
Materials science, Scanning electron microscope, Coordinative complexes, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Oligomer, chemistry.chemical_compound, Differential scanning calorimetry, Polymer chemistry, lcsh:TA401-492, Glass transition temperature, General Materials Science, Epoxy resin, 62.23.St, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Nano Express, 66.30.hk, Epoxy, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Lithium perchlorate salt, Lithium perchlorate, 0104 chemical sciences, Amorphous solid, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Amorphous composite, visual_art, visual_art.visual_art_medium, lcsh:Materials of engineering and construction. Mechanics of materials, 81.07.Pr, 0210 nano-technology, Glass transition
Abstract

The article is concerned with hybrid amorphous polymers synthesized basing on epoxy oligomer of diglycide aliphatic ester of polyethylene glycol that was cured by polyethylene polyamine and lithium perchlorate salt. Structural peculiarities of organic-inorganic polymer composites were studied by differential scanning calorimetry, wide-angle X-ray spectra, infrared spectroscopic, scanning electron microscopy, elemental analysis, and transmission and reflective optical microscopy. On the one hand, the results showed that the introduction of LiClO4 salt into epoxy polymer leads to formation of the coordinative metal-polymer complexes of donor-acceptor type between central Li+ ion and ligand. On the other hand, the appearance of amorphous microinclusions, probably of inorganic nature, was also found.

Published
2017

158. Ionic conducting membranes based on new sulfonated poly(arylene ether ketone)s for fuel cell applications

Author

Eliane Espuche, Arnaud Morin, Edouard Chauveau, Catherine Marestin, Régis Mercier, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet - Saint-Étienne (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux (LITEN), Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, and Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL)

Subjects
Materials science, Polymers and Plastics, Ether, 02 engineering and technology, Sulfonic acid, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Polymer chemistry, Materials Chemistry, Ionic conductivity, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Diketone, chemistry.chemical_classification, Arylene, [CHIM.MATE]Chemical Sciences/Material chemistry, Polymer, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, Membrane, chemistry, 0210 nano-technology
Abstract

The synthesis and characterization of new di- and tetra-sulfonated ether diketone monomers are described. From these monomers, a wide series of sulfonated poly(arylene ether ketone)s (SPAEK) are synthesized by varying the sulfonic acid repartition along the polymer backbones. Their chemical structures are thoroughly characterized by NMR. From these polymers tough membranes are obtained from solution casting method and their water uptake, ionic conductivity, and water/gas permeation properties are determined and compared with those of Nafion membrane. Preliminary fuel cell tests show that SPAEK membranes are promising candidates for fuel cell application. This work brings new insights concerning the beneficial effects of introducing densely sulfonated monomers in a polyarylether macromolecular structure along with fluorinated groups improving conductivity while reducing unwanted excessive swelling. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 771–777

Published
2017

159. Nanoporous Cyanate Ester Resins: Structure-Gas Transport Property Relationships

Author

Kristina Gusakova, Eliane Espuche, Gisèle Boiteux, Alexander Fainleib, Jean-Marc Saiter, Daniel Grande, Fabrice Gouanvé, Olga Grigoryeva, Olga Starostenko, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Polymères, biopolymères, membranes (PBM), Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Morphology (linguistics), Materials science, 02 engineering and technology, Gas solubility, 010402 general chemistry, 01 natural sciences, Cyanate ester, Desorption, Polymer chemistry, lcsh:TA401-492, General Materials Science, Fourier transform infrared spectroscopy, ComputingMilieux_MISCELLANEOUS, Nanoporous thermosets, Inert, Nano Express, Gas diffusion, Nanoporous, Extraction (chemistry), [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Nanopore, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, Transport properties, lcsh:Materials of engineering and construction. Mechanics of materials, 0210 nano-technology, Cyanate ester resins
Abstract

This contribution addresses the relationships between the structure and gas transport properties of nanoporous thermostable cyanate ester resins (CERs) derived from polycyclotrimerization of 1,1′-bis(4-cyanatophenyl)ethane in the presence of 30 or 50 wt% of inert high-boiling temperature porogens (i.e., dimethyl- or dibutyl phthalates), followed by their quantitative removal. The nanopores in the films obtained were generated via a chemically induced phase separation route with further porogen extraction from the densely crosslinked CERs. To ensure a total desorption of the porogen moieties from the networks, an additional short-term thermal annealing at 250 °C was performed. The structure and morphology of such nanoporous CER-based films were investigated by FTIR and SEM techniques, respectively. Further, the gas transport properties of CER films were analyzed after the different processing steps, and relationships between the material structure and the main gas transport parameters were established.

Published
2017

160. Polybutylene terephthalate reactive blending with polymethylhydrosiloxane by ruthenium-catalyzed carbonyl hydrosilylation reaction

Author

Fernande Da Cruz-Boisson, Véronique Bounor-Legaré, Christine Lucas, Jing Ping Li, Flavien Mélis, Philippe Cassagnau, Pierre Alcouffe, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Polymères et des Biomatériaux (IMP-LMPB), Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut de Chimie du CNRS (INC), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)

Subjects
Polymethylhydrosiloxane, Materials science, Polymers and Plastics, Hydrosilylation, Organic Chemistry, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Catalysis, Ruthenium, chemistry.chemical_compound, Polybutylene terephthalate, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymer chemistry, Materials Chemistry, [CHIM]Chemical Sciences, Organic chemistry, Polymer blend, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2017

161. Modelling of an innovative liquid rotational moulding process

Author

Yves Bereaux, Jordan Biglione, Yao Agbessi, Ronan Le Goff, Jean-Yves Charmeau, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Mécanique des Contacts et des Structures [Villeurbanne] (LaMCoS), Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), and Centre Technique Industriel de la Plasturgie et des Composites (IPC)

Subjects
Work (thermodynamics), Rimming flow, Materials science, Stability criterion, business.industry, Flow (psychology), Process (computing), Liquid rotational moulding, Angular velocity, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Mechanics, Computational fluid dynamics, 021001 nanoscience & nanotechnology, Gravity driven film flow, [CHIM.POLY]Chemical Sciences/Polymers, 020401 chemical engineering, Orientation (geometry), General Materials Science, 0204 chemical engineering, Cube, CFD, 0210 nano-technology, business, Simulation
Abstract

International audience; An innovative liquid rotational moulding process aiming at using standard injection-moulding polymer grades, shortening cycle times and at accessing more higher-end markets is studied. In this new process, the polymer is melted beforehand in a conventional injection unit and injected into the mould rotating around two axes. This work focus on modelling the liquid polymer flow occurring in this process, as well as providing guidance on the choice of process parameters. First, a stability criterion for rimming flow is derived, defining the process and material parameters space available for a functional process. From this criterion, it appears that initial thickness, and density have a destabilising effect, while liquid viscosity and angular velocity have a stabilising effect. Next, using Lax-Friedrichs scheme, the one-dimensional transient gravity driven liquid film is numerically modelled, linking the total extent of spreading to the frequency of orientation reversals and to the major and minor angular velocities ratio : the closer this ratio to one, the larger the extent of spreading. Then, Computational Fluid Dynamics (CFD) simulations are carried out to take into account three-dimensional features in the moulding of a cube part. Finally, comparison with trials performed on the moulding of the same cube part validates entirely this approach. In particular, some peculiar features of spreading can only be explained and reproduced when employing three-dimensional CFD simulations.

Published
2017

162. Influence of the film-forming process on the nanostructuration of Pebax®/1-ethyl-3-methylimidazolium triflate ionic liquid: Consequences on the thermal, mechanical, gas, and water transport properties

Author

Fabrice Gouanvé, Eliane Espuche, Guillaume Sudre, Fabrice Cousin, S. Magana, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon

Subjects
Materials science, Water transport, Morphology (linguistics), Polymers and Plastics, Inorganic chemistry, Forming processes, Modulus, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Thermal mechanical, Ionic liquid, 1-ethyl-3-methylimidazolium triflate, Materials Chemistry, Copolymer, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2017

163. Dual functions of ILs in the core-shell particle reinforced epoxy networks: Curing agent vs dispersion aids

Author

Sébastien Livi, Thi Khanh Ly Nguyen, Bluma G. Soares, Jannick Duchet-Rumeau, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon

Subjects
Materials science, General Engineering, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Epoxy, Phosphinate, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Natural rubber, visual_art, Ionic liquid, Ceramics and Composites, visual_art.visual_art_medium, Particle, Amine gas treating, Phosphonium, Composite material, 0210 nano-technology, Dispersion (chemistry), ComputingMilieux_MISCELLANEOUS
Abstract

We present herein a comparative study on the dispersion of a commercial core-shell rubber particles denoted Genioperl P52 (CSR) in the epoxy networks cured with conventional amine 4,4'-methylene bis(3-chloro-2,6-diethylaniline) (MCDEA) and with two phosphonium ionic liquids (ILs) denoted: trihexyl (tetradecyl) phosphonium bis-2,4,4-(trimethyl pentyl) phosphinate (IL-TMP) and tributyl (ethyl) phosphonium (diethyl) phosphate (IL-DEP). Epoxy networks containing 10 and 20 phr of CSR were prepared and the effect of CSR on the final properties of epoxy networks was evaluated. We have demonstrated that the chemical nature of ILs play a key role on the morphology of modified epoxy networks resulting in a better dispersion of CSR compared to epoxy/amine networks. In addition, a correlation between morphology and properties of epoxy networks was also revealed in terms of thermal, mechanical properties as well as the hydrophobic behavior. In fact, a better distribution of CSR particles into epoxy/ILs networks led to an increase in fracture toughness compared to modified epoxy/amine networks i.e. 27% and 54% higher of KIc for DGEBA/MCDEA and DGEBA/IL-DEP system modified by 20 phr of CSR particles, respectively. Nevertheless, the toughening mechanism can also be influenced by the interaction between cured epoxy matrix and CSR particles.

Published
2017

164. In situ emulsion cationic polymerization of isoprene onto the surface of graphite oxide sheets

Author

Claude Janin, Claire Barrès, Emmanuel Beyou, Alice Pazat, Florence Bruno, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon

Subjects
Thermogravimetric analysis, Materials science, General Physics and Astronomy, Graphite oxide, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Polymer chemistry, ComputingMilieux_MISCELLANEOUS, Isoprene, chemistry.chemical_classification, Cationic polymerization, [CHIM.MATE]Chemical Sciences/Material chemistry, Surfaces and Interfaces, General Chemistry, Polymer, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Grafting, 0104 chemical sciences, Surfaces, Coatings and Films, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, chemistry, Surface modification, 0210 nano-technology
Abstract

Grafting of polymers onto graphite oxide sheets (GO) has been widely studied in recent years due to the numerous applications of GO-based composites. Herein, polyisoprene (PI) chains were anchored on the surface of GO by in situ cationic polymerization using a “grafting through” approach with allyltrimethoxysilane-modified GO (GO-ATMS). First, the functionalization of GO sheets through the hydrolysis-condensation of allyltrimethoxysilane (ATMS) molecules was qualitatively evidenced by infra-red spectroscopy and X-ray photoelectron spectrometry and a weight content of 4% grafted ATMS was calculated from thermogravimetric analysis. Then, isoprene was in situ polymerized through a one-pot cationic mechanism by using a highly water-dispersible Lewis acid surfactant combined catalyst. For comparison, it was shown that the cationic polymerization of isoprene in presence of un-functionalized GO sheets led to a polyisoprene weight content on the solid filler divided by 3 compared to GO-ATMS. Finally, the compounding of the modified GO/PI composites was performed at a processing temperature of 80 °C with 2 phr and 15 phr loadings and it was shown a decrease of the air permeability coefficient of 27% for the vulcanizates with 15 phr loading.

Published
2017

165. Wear Protection without Surface Modification Using a Synergistic Mixture of Molecular Brushes and Linear Polymers

Author

Laurent David, Thierry Delair, Joanna Burdynska, Florina Moldovan, Xavier Banquy, Guojun Xie, Stéphane Benayoun, Krzysztof Matyjaszewski, Buddha Ratna Shrestha, Jimmy Faivre, Université de Montréal. Faculté de pharmacie, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Research Center, Sainte-Justine Hospital, Laboratoire de Tribologie et Dynamique des Systèmes (LTDS), École Centrale de Lyon (ECL), Université de Lyon-Université de Lyon-École Nationale des Travaux Publics de l'État (ENTPE)-Ecole Nationale d'Ingénieurs de Saint Etienne-Centre National de la Recherche Scientifique (CNRS), and Université de Montréal (UdeM)

Subjects
Wear resistance, Materials science, Surface forces, Linear polymer, Hyaluronic acid, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Saline solutions, General Materials Science, Composite material, ComputingMilieux_MISCELLANEOUS, Shearing (physics), chemistry.chemical_classification, Bottle-brush polymer, Surface force, General Engineering, [CHIM.MATE]Chemical Sciences/Material chemistry, Polymer, 021001 nanoscience & nanotechnology, 6. Clean water, Polyelectrolyte, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Biolubrication, Surface modification, 0210 nano-technology
Abstract

We describe the design of lubricating and wear protecting fluids based on mixtures of bottle-brushes (BB) and linear polymer solutions. To illustrate this concept, we used hyaluronic acid (HA), a naturally occurring linear polyelectrolyte, and a water-soluble synthetic BB polymer. Individually, these two polymers exhibit poor wear protecting capabilities compared to that of saline solutions. Mixture of the two polymers in pure water or in saline allows the wear protection of surfaces over a wide range of shearing conditions to drastically increase. We demonstrate that this synergy between the BB and HA polymers emerges from a strong cohesion between the two components forming the boundary film due to entanglements between both polymers. We show that this concept can be applied to other types of linear polymers and surfaces and is independent of the chemical and mechanical properties of the surfaces.

Published
2017

166. Going beyond the barriers of aza-Michael reactions: controlling the selectivity of acrylates towards primary amino-PDMS

Author

François Ganachaud, Emmanuel Pouget, Sandra Binauld, Daniel Portinha, Aymeric Genest, Etienne Fleury, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
chemistry.chemical_classification, Primary (chemistry), Polymers and Plastics, Double bond, 010405 organic chemistry, Chemistry, Organic Chemistry, Bioengineering, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Solvent, [CHIM.POLY]Chemical Sciences/Polymers, Hydrocarbon, Polymer chemistry, Organic chemistry, Amine gas treating, Metal catalyst, Selectivity, ComputingMilieux_MISCELLANEOUS
Abstract

The aza-Michael reaction of aliphatic primary amines with electron-deficient double bonds proceeds through two additions possibly leading to a mixture of amines with different degrees of substitution. We present here model reactions involving acrylates as Michael acceptors and amino-PDMS as Michael donors, and the impact of experimental conditions (temperature, organo-catalyst, and solvent) on the selectivity of such a reaction. While hydrocarbon alcohols favor monoaddition, halogenated alcohols favor double substitution. Tuning the operating conditions allowed the formation of either a monoadduct or a diadduct with no primary amine left, demonstrating that the structure of PDMS can be modified in a controlled manner without using any metal catalyst.

Published
2017

167. Controlled reduced-strength epoxy-aluminium joints validated by ultrasonic and mechanical measurements

Author

Abderrahim El Mahi, Jocelyne Galy, Joseph Moysan, Noëllie Ylla, Nicolas Massacret, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Laboratoire de Mécanique et d'Acoustique [Marseille] (LMA ), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM), Laboratoire d'Acoustique de l'Université du Mans (LAUM), Centre National de la Recherche Scientifique (CNRS)-Le Mans Université (UM), Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet - Saint-Étienne (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Polymers and Plastics, Adhesive bonding, General Chemical Engineering, Surface treatment, chemistry.chemical_element, 02 engineering and technology, Biomaterials, [SPI]Engineering Sciences [physics], 03 medical and health sciences, 0302 clinical medicine, Aluminium, Nondestructive testing, Composite material, ComputingMilieux_MISCELLANEOUS, Lap shear, business.industry, [CHIM.MATE]Chemical Sciences/Material chemistry, 030206 dentistry, Structural engineering, Epoxy, 021001 nanoscience & nanotechnology, Durability, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Acoustic emission, visual_art, visual_art.visual_art_medium, Ultrasonic sensor, Reduced-strength bond, Adhesive, 0210 nano-technology, business
Abstract

International audience; In this study a series of joint systems, consisting of aluminium substrates bonded using an epoxy adhesive, were produced. Several levels of adhesion were achieved by altering the substrate surface treatment and the curing cycle of the adhesive. The goal of this study was to produce reduced-strength epoxy-aluminium joints that could be used as reference samples for ultrasonic non-destructive testing (NDT) studies. There is clearly a continuing challenge to improve the quality of the adhesively-bonded joint inspection to ensure the durability of the bonds, to monitor repairs, and to evaluate the strength of the bonds. However, developing and qualifying innovative or advanced non-destructive testing requires an essential preliminary step: a method for repeatedly producing reduced-strength bonded test specimens must be developed. In this study, in addition to a rigorous protocol to produce bonded joints, complementary ultrasonic CSCAN were realised to validate the homogeneity of the joints and to ensure that samples met all requirements so as to be considered as reference samples. Mechanical tests were performed to evaluate the mechanical strength of each joint and Acoustic Emission (AE) was used during the tests in order to confirm the expected fracture mechanisms.

Published
2017

168. Tuning the Hydrophilic/Hydrophobic Balance to Control the Structure of Chitosan Films and Their Protein Release Behavior

Author

Thierry Delair, Cyrille Rochas, Roland Montserret, Laurent David, Guillaume Sudre, Bernard Verrier, Jose Becerra, Isabelle Royaud, Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de biologie et chimie des protéines [Lyon] (IBCP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Centre de Recherches sur les Macromolécules Végétales (CERMAV ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Université de Lorraine (UL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon

Subjects
Ovalbumin, Pharmaceutical Science, Biocompatible Materials, macromolecular substances, 02 engineering and technology, Aquatic Science, 010402 general chemistry, 01 natural sciences, law.invention, Hydrophobic effect, Chitosan, chemistry.chemical_compound, Crystallinity, Drug Delivery Systems, law, Drug Discovery, Polymer chemistry, medicine, Crystallization, ComputingMilieux_MISCELLANEOUS, Ecology, Evolution, Behavior and Systematics, Ecology, biology, Chemistry, technology, industry, and agriculture, [CHIM.MATE]Chemical Sciences/Material chemistry, General Medicine, equipment and supplies, 021001 nanoscience & nanotechnology, 0104 chemical sciences, carbohydrates (lipids), Solvent, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, biology.protein, Anhydrous, Swelling, medicine.symptom, 0210 nano-technology, Hydrophobic and Hydrophilic Interactions, Agronomy and Crop Science
Abstract

The control over the crystallinity of chitosan and chitosan/ovalbumin films can be achieved via an appropriate balance of the hydrophilic/hydrophobic interactions during the film formation process, which then controls the release kinetics of ovalbumin. Chitosan films were prepared by solvent casting. The presence of the anhydrous allomorph can be viewed as a probe of the hydrophobic conditions at the neutralization step. The semicrystalline structure, the swelling behavior of the films, the protein/chitosan interactions, and the release behavior of the films were impacted by the DA and the film processing parameters. At low DAs, the chitosan films neutralized in the solid state corresponded to the most hydrophobic environment, inducing the crystallization of the anhydrous allomorph with and without protein. The most hydrophilic conditions, leading to the hydrated allomorph, corresponded to non-neutralized films for the highest DAs. For the non-neutralized chitosan acetate (amorphous) films, the swelling increased when the DA decreased, whereas for the neutralized chitosan films, the swelling decreased. The in vitro release of ovalbumin (model protein) from chitosan films was controlled by their swelling behavior. For fast swelling films (DA = 45%), a burst effect was observed. On the contrary, a lag time was evidenced for DA = 2.5% with a limited release of the protein. Furthermore, by blending chitosans (DA = 2.5% and 45%), the release behavior was improved by reducing the burst effect and the lag time. The secondary structure of ovalbumin was partially maintained in the solid state, and the ovalbumin was released under its native form.

Published
2016

169. Flame retardancy of phosphorus-containing ionic liquid based epoxy networks

Author

Henri Vahabi, Loïc Dumazert, Pascal Laheurte, Sébastien Livi, Rodolphe Sonnier, Thi Khanh Ly Nguyen, Jannick Duchet-Rumeau, Pôle Matériaux Polymères Avancés (Pôle MPA), Centre des Matériaux des Mines d'Alès (C2MA), IMT - MINES ALES (IMT - MINES ALES), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-IMT - MINES ALES (IMT - MINES ALES), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Laboratoire d'Informatique de Grenoble (LIG ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Laboratoire Matériaux Optiques, Photonique et Systèmes (LMOPS), CentraleSupélec-Université de Lorraine (UL), Laboratoire d'Etude des Microstructures et de Mécanique des Matériaux (LEM3), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Arts et Métiers Sciences et Technologies, and HESAM Université (HESAM)-HESAM Université (HESAM)

Subjects
Thermogravimetric analysis, Materials science, Polymers and Plastics, 02 engineering and technology, Ionic liquid, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Flame retardancy, Cone calorimeter, Materials Chemistry, Char, Composite material, Flammability, [CHIM.MATE]Chemical Sciences/Material chemistry, Epoxy, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Phosphorus flame retardant, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Mechanics of Materials, visual_art, visual_art.visual_art_medium, Charring, Epoxy networks, 0210 nano-technology, Pyrolysis
Abstract

International audience; Various amounts of a phosphonium ionic liquid (IL169) were used as curing agents as well as flame retardants of epoxy prepolymer in order to prepare epoxy networks with improved fire properties. The flame retardancy of these resins was investigated using thermogravimetric analysis (TGA), pyrolysis combustion flow calorimetry (PCFC) and cone calorimetry. Phosphonium ionic liquid significantly reduced flammability without further addition of flame retardants due to the high amount of phosphorus (up to 3.69 wt%). The Peak of heat release rate decreases from 1099 kW/m(2) to 300 kW/m(2) in cone calorimeter at 35 kW/m(2) when incorporating 30 phr of IL169. Phosphorus modifies pyrolysis pathway, promotes charring and may act as flame inhibitor. The char layer protects the underlying polymer, leading to a high unburnt polymeric fraction. Char properties were studied using PCFC, Raman spectroscopy and X-ray tomography. Phosphorus improved the graphitization of the char and its thermooxidative stability.

Published
2016

170. FROM A NEW GENERATION OF IONIC LIQUID MONOMERS TOWARDS THERMOSETTING EPOXY POLYMERS

Author

Livi, Sébastien, Chardin, Charline, Lins, Luanda Chaves, Baudoux, J., Gérard, Jean-François, Duchet-Rumeau, Jannick, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Macromoléculaires (IMP-LMM), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), and Centre National de la Recherche Scientifique (CNRS)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN)

Subjects
[CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2019

171. Gelation of Plasticized Polyvinyl Chloride Compounds in a Co‐Kneader

Author

Christian Carrot, Claude Raveyre, Benjamin Monchatre, Marwa Khemakhem, Lucas Sardo, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Mise en Forme des Matériaux (CEMEF), MINES ParisTech - École nationale supérieure des mines de Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Marketing, Materials science, Polymers and Plastics, General Chemical Engineering, 02 engineering and technology, General Chemistry, 021001 nanoscience & nanotechnology, Polyvinyl chloride, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, 020401 chemical engineering, chemistry, Materials Chemistry, 0204 chemical engineering, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Nuclear chemistry
Abstract

International audience

Published
2019

172. Design of new hardeners based on Ionic Liquids for epoxy prepolymer

Author

Chardin, Charline, Nguyen, Thi Khanh Ly, Baudoux, Jérôme, Livi, Sébastien, Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2019

173. From Ionic Liquid Epoxy Monomer to new Epoxy-Amine Networks with functional properties

Author

Livi, Sébastien, Baudoux, J., Lins, Luanda Chaves, Gérard, Jean-François, Duchet-Rumeau, Jannick, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Macromoléculaires (IMP-LMM), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), and Centre National de la Recherche Scientifique (CNRS)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN)

Subjects
[CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2019

174. Spent fuel transportation cask under accidental fire conditions: Numerical analysis of gas transport phenomena affecting heat transfer in shielding materials

Author

Olivier Bardon, Hervé Issard, Roula Ghazal, Matthieu Zinet, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Thermique de Lyon (CETHIL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Centre Sciences des Processus Industriels et Naturels (SPIN-ENSMSE), École des Mines de Saint-Étienne (Mines Saint-Étienne MSE), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)

Subjects
Materials science, 020209 energy, Nuclear engineering, Energy Engineering and Power Technology, 02 engineering and technology, 010501 environmental sciences, 01 natural sciences, Endothermic process, [SPI.MAT]Engineering Sciences [physics]/Materials, [SPI.MECA.MEFL]Engineering Sciences [physics]/Mechanics [physics.med-ph]/Fluids mechanics [physics.class-ph], Latent heat, [SPI.MECA.MEMA]Engineering Sciences [physics]/Mechanics [physics.med-ph]/Mechanics of materials [physics.class-ph], 0202 electrical engineering, electronic engineering, information engineering, Safety, Risk, Reliability and Quality, Waste Management and Disposal, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, Condensation, Thermal conduction, Spent nuclear fuel, [CHIM.POLY]Chemical Sciences/Polymers, Nuclear Energy and Engineering, Electromagnetic shielding, Heat transfer, [SPI.MECA.THER]Engineering Sciences [physics]/Mechanics [physics.med-ph]/Thermics [physics.class-ph], Transport phenomena
Abstract

In the nuclear industry, spent fuel is usually conveyed to the reprocessing or long term storage facilities in dedicated containers: the transportation casks. These structures are designed to meet rigorous standards intended to prevent any failure under both normal transport and severe accidental conditions. The design process includes thermal analyses in order to predict the temperature response of the cask to a 30 min engulfing fire at 800 °C. Materials presenting endothermic decomposition reactions are often used as thermal and radiologic protection in the cask walls. This paper focuses on numerically investigating the secondary effects induced by the vapor transfer phenomena specific to these endothermic shielding materials, using finite element modeling of heat transfer within the wall of a typical cask. Mechanisms such as vaporization, diffusion and recondensation of the water content, resulting in a transfer of latent heat within the medium, are taken into account in the model. Three materials are considered: polyester resin compound, plaster and phenolic foam. The predictions of this detailed model are compared to those of a model assuming only conduction heat transfer. It is shown that gas transport phenomena have a significant effect on the heating kinetics. Finally, the influence of model parameters such as the material porosity and the condensation coefficient is discussed.

Published
2019

175. Comb-like dextran copolymers: A versatile strategy to coat highly porous MOF nanoparticles with a PEG shell

Author

Borja Moreira-Alvarez, Daniel M. Foulkes, Xue Li, Juan M. Casas-Solvas, Mario Menendez-Miranda, Antonio Vargas-Berenguel, Catherine Ladavière, Giovanna Cutrone, Ruxandra Gref, Jorge Ruiz Encinar, Ahmet Aykaç, Jingwen Qiu, Didier Desmaële, Department of Surgery/Urology, Boston Children's Hospital-Harvard Medical School [Boston] (HMS), Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Institut Galien Paris-Sud (IGPS), University of Almeria, Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), University of Oviedo, Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Galien Paris-Saclay (IGPS), and Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)

Subjects
Polymers and Plastics, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, metal organic frameworks, nanomedecine, PEG ratio, Materials Chemistry, ComputingMilieux_MISCELLANEOUS, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, nanoparticle, Organic Chemistry, technology, industry, and agriculture, polymer coating, [SDV.SP]Life Sciences [q-bio]/Pharmaceutical sciences, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Dextran, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, dextran, Drug delivery, drug delivery, Click chemistry, Surface modification, 0210 nano-technology, Drug carrier, Ethylene glycol
Abstract

International audience; Nanoparticles made of metal-organic frameworks (nanoMOFs) are becoming of increasing interest as drug carriers. However, engineered coatings such as poly(ethylene glycol) (PEG) based ones are required to prevent nanoMOFs recognition and clearance by the innate immune system, a prerequisite for biomedical applications. This still presents an important challenge due to the highly porous structure and degradability of nanoMOFs. We provide here a proof of concept that the surface of iron-based nanoMOFs can be functionalized in a rapid, organic solvent-free and non-covalent manner using a novel family of comb-like copolymers made of dextran (DEX) grafted with both PEG and alendronate (ALN) moieties, which are iron complexing groups to anchor to the nanoMOFs surface. We describe the synthesis of DEX-ALN-PEG copolymers by click chemistry, with control of both the amount of PEG and ALN moieties. Stable DEX-ALN-PEG coatings substantially decreased their in-ternalization by macrophages in vitro, providing new perspectives for biomedical applications.

Published
2019

176. Embedment of Liposomes into Chitosan Physical Hydrogel for the Delayed Release of Antibiotics or Anaesthetics, and its First ESEM Characterization

Author

Catherine Ladavière, Pierre Alcouffe, S. Peers, Alexandra Montembault, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
liposomes, Polymers and Plastics, 02 engineering and technology, 010402 general chemistry, rifampicin, 01 natural sciences, Suspension (chemistry), Chitosan, Matrix (chemical analysis), chemistry.chemical_compound, drug delivery systems, Ultraviolet visible spectroscopy, Materials Chemistry, Molecule, [CHIM]Chemical Sciences, Environmental scanning electron microscope, ComputingMilieux_MISCELLANEOUS, Anesthetics, Liposome, Organic Chemistry, technology, industry, and agriculture, Hydrogels, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Fluoresceins, Fluorescence, 0104 chemical sciences, Anti-Bacterial Agents, Drug Liberation, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, lidocaine, Microscopy, Electron, Scanning, Rifampin, physical hydrogels, 0210 nano-technology, Rheology, Nuclear chemistry
Abstract

International audience; This work describes the characterization of an original liposomes/hydrogel assembly, and its application as a delayed-release system of antibiotics and anaesthetics. This system corresponds to drugloaded liposomes entrapped within a chitosan (CS) physical hydrogel. To this end, a suspension of pre-formed 1,2-dipalmitoyl-sn-glycero-3phosphocoline liposomes loaded with an antibiotic (rifampicin, RIF), an anaesthetic (lidocaine, LID), or a model fluorescent molecule (carboxyfluorescein, CF), was added to a CS solution. The CS gelation was subsequently carried out without any trace of chemical cross-linking agent or organic solvent in the final system. Liposomes within the resulting gelled CS matrix were characterized for the first time by environmental scanning electron microscopy. The release of drugs from the assembly was investigated by fluorescence or UV spectroscopy. The cumulative release profiles of RIF and LID (and also CF for comparison) were found to be lower from the "drug-in-liposomes-in-hydrogel" (DLH) assembly in comparison to "drug-in-hydrogel" (DH) system.

Published
2019

177. Effect of the ultrastructure of chitosan nanoparticles in colloidal stability, quorum quenching and antibacterial activities

Author

C. Vila-Sanjurjo, L. David, Francisco M. Goycoolea, Carmen Remuñán-López, A. Vila-Sanjurjo, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidade de Santiago de Compostela [Spain] (USC ), inconnu, and Inconnu

Subjects
inorganic chemicals, Dispersity, education, Nanoparticle, 02 engineering and technology, macromolecular substances, 010402 general chemistry, 01 natural sciences, Biomaterials, Chitosan, chemistry.chemical_compound, Colloid and Surface Chemistry, X-Ray Diffraction, Scattering, Small Angle, Escherichia coli, Zeta potential, Colloids, health care economics and organizations, ComputingMilieux_MISCELLANEOUS, Small-angle X-ray scattering, technology, industry, and agriculture, Quorum Sensing, 021001 nanoscience & nanotechnology, Anti-Bacterial Agents, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Covalent bond, Quorum Quenching, Genipin, Nanoparticles, 0210 nano-technology
Abstract

We have fabricated two types of crosslinked chitosan-based nanoparticles (NPs), namely (1) ionically crosslinked with tripolyphosphate (TPP), designated as IC-NPs and (2) dually co-crosslinked (ionically and covalently with TPP and genipin, respectively) termed CC-NPs. The two types of NPs were physichochemically characterized by means of DLS-NIBS, synchrotron SAXS and M3-PALS (zeta potential). First, we found that covalent co-crosslinking of ionically pre-crosslinked nanoparticles yielded monodisperse CC-NPs in the size range of ∼200 nm, whereas the parental IC-NPs remained highly polydisperse. While both types of chitosan nanoparticles displayed a core-shell structure, as determined by synchrotron SAXS, only the structure of CC-NPs remained stable at long incubation times. This enhanced structural robustness of CC-NPs was likely responsible of their superior colloidal stability even in biological medium. Second, we explored the antimicrobial and quorum sensing inhibition activity of both types of nanoparticles. We found that CC-NPs had lower long-term toxicity than IC-NPs. In contrast, sub-lethal doses of IC-NPs consistently displayed higher levels of quorum quenching activity than CC-NPs. Thus, this work underscores the influence of the NP’s ultrastructure on their colloidal and biological properties. While the cellular and molecular mechanisms at play are yet to be fully elucidated, our results broaden the spectrum of use of chitosan-based nanobiomaterialsin the development of antibiotic-free approaches against Gram-negative pathogenic bacteria.

Published
2019

178. Numerical analysis of 3D mass diffusion in random (nano) composite systems: Effects of polydispersity and intercalation on barrier properties

Author

Eliane Espuche, Sarra Zid, Matthieu Zinet, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Polymères et des Biomatériaux (IMP-LMPB), Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Dispersity, Filtration and Separation, 02 engineering and technology, 010402 general chemistry, Thermal diffusivity, 01 natural sciences, Biochemistry, [SPI.MAT]Engineering Sciences [physics]/Materials, [SPI.MECA.MEFL]Engineering Sciences [physics]/Mechanics [physics.med-ph]/Fluids mechanics [physics.class-ph], [SPI.MECA.MEMA]Engineering Sciences [physics]/Mechanics [physics.med-ph]/Mechanics of materials [physics.class-ph], General Materials Science, Physical and Theoretical Chemistry, Composite material, Diffusion (business), ComputingMilieux_MISCELLANEOUS, Range (particle radiation), Nanocomposite, Numerical analysis, 021001 nanoscience & nanotechnology, Finite element method, 0104 chemical sciences, Membrane, [CHIM.POLY]Chemical Sciences/Polymers, [SPI.MECA.THER]Engineering Sciences [physics]/Mechanics [physics.med-ph]/Thermics [physics.class-ph], 0210 nano-technology
Abstract

Nanocomposite systems show promise as barrier materials for a wide range of applications. However, the enhancement of barrier properties requires a better understanding of the relationship between the system structure and the desired properties. The aim of the present study is to discuss first the effect of fillers size polydispersity on gas barrier properties through a step-by-step approach based on three-dimensional finite element modeling (FEM). Secondly, dispersions of monodisperse and polydisperse stacks are investigated coupled with a sensitive study of interplatelet diffusion effect on the overall diffusivity considering a wide range of diffusion coefficient values in the interplatelet area. The specificity of the developed model is its ability to account for interplatelet diffusion for a large range of fillers dimensions.

Published
2019

179. CBRAM devices with a water casted solid polymer electrolyte for flexible electronic applications

Author

Prabir Mahato, Etienne Puyoo, Sébastien Pruvost, Damien Deleruyelle, INL - Dispositifs Electroniques (INL - DE), Institut des Nanotechnologies de Lyon (INL), Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-École Centrale de Lyon (ECL), Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE), Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010302 applied physics, chemistry.chemical_classification, Materials science, Programmable metallization cell, Nanotechnology, 02 engineering and technology, Polymer, Electrolyte, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Flexible electronics, [SPI]Engineering Sciences [physics], chemistry, 0103 physical sciences, Electronics, 0210 nano-technology, Layer (electronics), Polyimide, ComputingMilieux_MISCELLANEOUS, Voltage
Abstract

In this work, an eco-friendly polymer consisting of Polyethylene Oxide (PEO) is employed to achieve the solid electrolyte layer of Conductive-Bridge Random Access Memory devices (CBRAM). In an attempt to move towards green solvent, water was used to fabricate the devices on polyimide substrates. The devices show promising electrical performance with low operating voltages ( 104) and resistance to mechanical stresses. These results achieve a promising step toward the sustainable development of flexible electronic devices.

Published
2019

180. From Ionic Liquid Epoxy Monomer to new Epoxy-Amine Networks with antibacterial Properties

Author

Livi, Sébastien, Lins, Luanda Chaves, Capeletti, Larissa, Baudoux, J., Cardoso, Mateus Borba, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), Laboratório Nacional de Luz Sìncrotron (LNLS), and Centro Nacional de Pesquisa em Energia e Materiais (CNPEM)

Subjects
[CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2019

181. Homogénéité thermique dans un procédé de transformation des polymères thermoplastiques

Author

Bu, Liangxiao, Agbessi, Yao, BIGLIONE, Jordan, Bereaux, Yves, Charmeau, Jean-Yves, Laboratoire de Mécanique des Contacts et des Structures [Villeurbanne] (LaMCoS), Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Mise en Forme des Matériaux (CEMEF), MINES ParisTech - École nationale supérieure des mines de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de génie des procédés - environnement - agroalimentaire (GEPEA), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Centre National de la Recherche Scientifique (CNRS)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut Universitaire de Technologie - Nantes (IUT Nantes), Université de Nantes (UN)-Institut Universitaire de Technologie Saint-Nazaire (IUT Saint-Nazaire), Université de Nantes (UN)-Institut Universitaire de Technologie - La Roche-sur-Yon (IUT La Roche-sur-Yon), Université de Nantes (UN)-Ecole Nationale Vétérinaire, Agroalimentaire et de l'alimentation Nantes-Atlantique (ONIRIS)-Université Bretagne Loire (UBL), Institut Universitaire de Technologie - Nantes (IUT Nantes), and Université de Nantes (UN)

Subjects
[PHYS.MECA.MEMA]Physics [physics]/Mechanics [physics]/Mechanics of materials [physics.class-ph], [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2019

182. Identification of a Transient but Key Motif in the Living Coordinative Chain Transfer Cyclocopolymerization of Ethylene with Butadiene

Author

Fernande Da Cruz-Boisson, Marie-Noëlle Poradowski, Vincent Monteil, Islem Belaid, Benoit Macqueron, Christophe Boisson, Julien Thuilliez, Franck D'Agosto, Lionel Perrin, Samira Bouaouli, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Interface Theory Experiment : Mechanism & Modeling (ITEMM), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Société Michelin, Ingénierie des Matériaux Polymères (IMP), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ethylene, 010405 organic chemistry, Chemistry, mechanism, Chain transfer, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, cyclohexane-unit, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, decalin-unit, [CHIM.POLY]Chemical Sciences/Polymers, Transfer agent, butadiene, Polymer chemistry, Copolymer, ethylene, [CHIM]Chemical Sciences, cyclo-copolymerization
Abstract

International audience; Copolymers of ethylene and butadiene were prepared using the ansa-bisfluorenyl Me2Si(C13H8)2NdR complex in combination with dialkylmagnesium as a chain transfer agent. Thorough kinetic studies and computational mechanistic investigations of this copolymerization reaction were performed. Combined with detailed analyses of the polymer microstructure and chain-ends, these studies demonstrate that the entitled copolymerization operates according to a living coordinative chain transfer copol-ymerization of ethylene and butadiene. Besides, in addition to the formation of the previously described 1,2-cyclohexane inner chain cyclic motif, the presence of bicyclic 1,5-decalin units via the formation of transient vinylcyclohexyl-methyl chain-end is discussed in the present communication. The non-accumulation of the vinylcyclohexane motif within the chains is explained by the reversibility of its formation, as interpreted with the help of DFT calculations, or by its rapid conversion into decalin motif after one ethylene insertion. Finally, this study also illustrates the ability of the fluorenyl ligand to adjust its binding mode on demand in order to avoid inhibition of catalyst.

Published
2019

183. Viscoelastic behaviour of cellulose acetate/triacetin blends by rheology in the melt state

Author

Alexandra Argoud, Xavier Dreux, Jean-Charles Majesté, Christian Carrot, Caroll Vergelati, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Polymères et Matériaux Avancés (LPMA), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Polymers and Plastics, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Viscoelasticity, chemistry.chemical_compound, Rheology, Plasticizers, Materials Chemistry, Elasticity (economics), Composite material, Cellulose, Triacetin, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Viscosity, Organic Chemistry, Temperature, Hydrogen Bonding, Polymer, Strain hardening exponent, 021001 nanoscience & nanotechnology, Cellulose acetate, Elasticity, Weissenberg effect, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, 0210 nano-technology
Abstract

The viscoelastic behaviour of cellulose acetate with a degree of substitution (DS) of 245 plasticized by triacetin was studied at short times by dynamic oscillatory measurements. Two distinct regimes and unexpected scaling behaviour according to plasticizer content were highlighted. The dynamics of chains and their structural organization are not modified up to 35 wt% of triacetin. The rheological behaviour is led by a constant correlation length corresponding to the distance between strong intermolecular interactions subsisting in the melt state at high temperature even in the presence of plasticizer. This particular structure involves the apparition of strain hardening effects during uniaxial extensional flow tests and an important elasticity corresponding to the apparition of a Weissenberg effect at really low shear rates during shear sweeps. Intramolecular hydrogen bonds are responsible of the high rigidity of cellulose acetate chains. Plasticized cellulose acetate in the melt state belongs to the class of associating polymers and its rheological behaviour is mainly led by stickers.

Published
2019

184. Exchange Process in the Dielectric Loss of Molecular and Macromolecular Ionic Conductors in the Interfacial Layers Formed by Electrode Polarization Effects

Author

A. Kallel, A. Kallel-Elloumi, Eric Drockenmuller, Anatoli Serghei, M. Samet, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Permittivity, [PHYS]Physics [physics], Materials science, 010304 chemical physics, Ionic bonding, Dielectric, Conductivity, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Ion, chemistry.chemical_compound, chemistry, Chemical physics, 0103 physical sciences, Ionic liquid, Materials Chemistry, Relaxation (physics), Dielectric loss, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

Here we report a first analytical approach to determine the spectral dependence of the complex permittivity function of molecular and macromolecular ionic conductors in the interfacial layers formed by electrode polarization effects. We show that a previous model of electrode polarization effects that was successfully applied for describing the dielectric behavior of ionic liquids ( Serghei, A.; Tress, M.; Sangoro, J. R.; Kremer, F. Electrode polarization and charge transport at solid interfaces. Phys. Rev. B 2009 , 80 , 184301 ) can be now generalized and applied for polymer/ionic liquid blends as well as for poly(ionic liquid)s. The determined dielectric function of the interfacial layers reveals a dramatic change in the charge transport process manifested by a large decrease in conductivity. Our approach brings the first evidence for a relaxation peak detected in the dielectric loss of the interfaces, which is attributed to an exchange process between the interface and the bulk. This study gives new insights into the mechanism of charge transport at interfaces and could thus contribute to a better correlation between the dielectric properties of ion conducting materials and their electrochemical behavior at interfaces.

Published
2019

185. Chemo-rheological studies and monitoring of high-Tg reactive polyphtalamides towards a fast innovative RTM processing of fiber-reinforced thermoplastic composites

Author

Mohamed Yousfi, Abderrahim Maazouz, Mohamed Dkier, Khalid Lamnawar, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Polymers and Plastics, Transfer molding, Organic Chemistry, General Physics and Astronomy, 02 engineering and technology, Reactive extrusion, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, [SPI.MAT]Engineering Sciences [physics]/Materials, Viscosity, [CHIM.POLY]Chemical Sciences/Polymers, Rheology, Materials Chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Fiber, Composite material, 0210 nano-technology, Glass transition, Prepolymer, Stoichiometry, ComputingMilieux_MISCELLANEOUS
Abstract

In this work, a High Temperature hybrid process coupling “reactive Extrusion” and “Resin Transfer Molding” (HT-ERTM) was designed for the manufacturing of continuous Glass Fiber-Reinforced Thermoplastic Composites (GFRTC) with an elevated glass transition temperature. Hereto, a high-performance polyphtalamide (PPA) obtained from the chain extension reaction of its prepolymer was studied with the optimal stoichiometry ratio and at several temperatures. Due to the extremely fast reaction, the present work highlights that both the reaction kinetics and the increase in viscosity are not easily monitored at short times and at high temperatures by usual techniques such as DSC and titration methods. The chemo-rheological evolutions were first studied ex-situ by coupling rheology with fast scan FTIR. In a second step, the HT-ERTM process was equipped with specific dielectric sensors in order to in-situ track the reaction evolution and the flow properties up to injection inside the cavity. Meanwhile, the viscosity increase was then determined depending on time, temperature and molar mass growth. Specifically, it was possible to model its evolution at less than one minute whereas the reaction conversion reaches 85% on two minutes of processing window. Interestingly, it was found that the in-situ results corroborated their ex-situ counterparts mentioned above. Finally, GFRTC parts with fiber contents up to 60 wt% were obtained with a better control of both mechanical and thermo mechanical properties intended especially for high service temperature applications such as in the automotive or aerospace industries.

Published
2019

186. Reducing-end 'clickable' functionalizations of chitosan oligomers for the synthesis of chitosan-based diblock copolymers

Author

Catherine Ladavière, Stéphane Trombotto, Amani Moussa, Agnès Crépet, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Polymères et des Biomatériaux (IMP-LMPB), Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, Polymers and Plastics, Organic Chemistry, Alkyne, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Hydrazide, 01 natural sciences, Aldehyde, Combinatorial chemistry, Reductive amination, 0104 chemical sciences, Chitosan, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Materials Chemistry, Click chemistry, Azide, 0210 nano-technology, Ethylene glycol, ComputingMilieux_MISCELLANEOUS
Abstract

Chitooligosaccharides (COS) produced by nitrous acid depolymerization of chitosan are unique chitosan oligomers due to the presence of the 2,5-anhydro-d-mannofuranose (amf) unit at their reducing end. In this work, we focused on the reductive amination and the oximation of the amf aldehyde group towards various functionalized anilines, hydrazides and O-hydroxylamines. The aim of this work was to synthesize new COS-based building blocks functionalized at their reducing end by different "clickable" chemical groups such as alkene, alkyne, azide, hydrazide and thiol. Targeted functionalized COS were synthesized in excellent mass yields and fully characterized by NMR spectroscopy and MALDI-TOF mass spectrometry. Our results showed these functionalizations are quantitative, versatile and can be easily performed in mild reaction conditions. Finally, these COS-based building blocks could be useful intermediates for the development of advanced functional COS-based conjugates, as illustrated in this work by the synthesis of new COS-poly(ethylene glycol) (PEG) diblock copolymers.

Published
2019

187. The morphology of rigid polyurethane foam matrix and its evolution with time during foaming – New insight by cryogenic scanning electron microscopy

Author

Joël Reignier, Françoise Méchin, Françoise Fenouillot, Pierre Alcouffe, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Polyurethane, Materials science, Scanning electron microscope, Bubble, nucleation, microstructure, Nucleation, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, [SPI.MAT]Engineering Sciences [physics]/Materials, Biomaterials, chemistry.chemical_compound, cryogenic scanning electron microscopy (cryo-SEM), Colloid and Surface Chemistry, Blowing agent, Phase (matter), emulsion, [SPI.FLUID]Engineering Sciences [physics]/Reactive fluid environment, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Isopentane, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, chemistry, Emulsion, 0210 nano-technology, foam
Abstract

International audience; This paper presents an investigation of the morphology of growing polyurethane (PU) rigid foams during the very first seconds of the process by cryogenic scanning electron microscopy (cryoSEM) performed at -150°C. The heterogeneous nature of the initial mixture has been revealed withthe presence of sub-micron size physical blowing agent droplets (isopentane), micron size dispersed phase nodules, and large air bubbles dispersed in a continuous matrix. Following the evolution of the microstructure during foaming by cryo-SEM suggested that the isopentane liquid droplets (undissolved part of the physical blowing agent) did not vaporize to create their own bubbles. These observations were confirmed by showing that the number of air bubbles per unit volume (~10^6 bubble/cm3) was similar to the cell population density of the final foam (~10^6 cell/cm3), while the number of isopentane droplets initially present was found to be six orders of magnitude higher (~10^12 droplet/cm3). This all means that isopentane molecules initially dissolved in the continuous phase diffuse into the pre-existing air bubbles with no energy barrier to overcome (non-classical nucleation) whereas the isopentane droplets simply act like reservoirs. Finally, despite our best efforts, there is still some doubt whether polymeric 4,4-diphenylmethane diisocyanate (PMDI) is dispersed in the polyol phase, or polyol dispersed in PMDI.

Published
2019

188. Chitosan hydrogel micro-bio-devices with complex capillary patterns via reactive-diffusive self-assembly

Author

Vincent A. Martinez, Marziye Mirbagheri, Pierre-Luc Latreille, Jean-François Bouchard, Thierry Delair, Xavier Banquy, Jimmy Faivre, Laurent David, Vahid Adibnia, Jordan Robert, Bruno Cécyre, Dae Kun Hwang, Université de Montréal. Faculté de pharmacie, Faculté de Pharmacie [Montréal], Université de Montréal (UdeM), Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Capillary action, 0206 medical engineering, Microfluidics, Biomedical Engineering, Metal Nanoparticles, Nanotechnology, macromolecular substances, 02 engineering and technology, Biochemistry, Diffusion, Biomaterials, Biopolymers, Drug Delivery Systems, Tissue engineering, Materials Testing, Animals, Sodium Hydroxide, Dimethylpolysiloxanes, Molecular Biology, Chitosan, Microscopy, Confocal, Tissue Scaffolds, Microcirculation, technology, industry, and agriculture, Hydrogels, General Medicine, Self-assembly, Fibroblasts, 021001 nanoscience & nanotechnology, 020601 biomedical engineering, Capillaries, [CHIM.POLY]Chemical Sciences/Polymers, Capillary length, Colloidal gold, Self-healing hydrogels, Drug delivery, Nanoparticles, Nanomedicine, Cattle, Gold, 0210 nano-technology, Biotechnology, Micropatterning
Abstract

International audience; We present chitosan hydrogel microfluidic devices with self-assembled complex microcapillary patterns, conveniently formed by a diffusion-reaction process. These patterns in chitosan hydrogels are formed by a single-step procedure involving diffusion of a gelation agent into the polymer solution inside a microfluidic channel. By changing the channel geometry, it is demonstrated how to control capillary length, trajectory and branching. Diffusion of nanoparticles (NPs) in the capillary network is used as a model to effectively mimic the transport of nano-objects in vascularized tissues. Gold NPs diffusion is measured locally in the hydrogel chips, and during their two-step transport through the capillaries to the gel matrix and eventually to embedded cell clusters in the gel. In addition, the quantitative analyses reported in this study provide novel opportunities for theoretical investigation of capillary formation and propagation during diffusive gelation of biopolymers.Statement of SignificanceHydrogel micropatterning is a challenging task, which is of interest in several biomedical applications. Creating the patterns through self assembly is highly beneficial, because of the accessible and practical preparation procedure. In this study, we introduced complex self-assembled capillary patterns in chitosan hydrogels using a microfluidic approach. To demonstrate the potential application of these capillary patterns, a vascularized hydrogel with microwells occupied by cells was produced, and the diffusion of gold nanoparticles travelling in the capillaries and diffusing in the gel were evaluated. This model mimics a simplified biological tissue, where nanomedicine has to travel through the vasculature, extravasate into and diffuse through the extracellular matrix and eventually reach targeted cells.

Published
2019

189. Chitosan Films for Microfluidic Studies of Single Bacteria and Perspectives for Antibiotic Susceptibility Testing

Author

Julie Tréguier, Loic Bugnicourt, Guillaume Gay, Mamoudou Diallo, Salim Islam, Alexandre Toro, Laurent David, Olivier Théodoly, Guillaume Sudre, Tâm Mignot, Laboratoire de chimie bactérienne (LCB), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet - Saint-Étienne (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Morphogénie Logiciels, Centre Hospitalier de Martigues, Adhésion et Inflammation (LAI), Aix Marseille Université (AMU)-Assistance Publique - Hôpitaux de Marseille (APHM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), CNRS Prematuration grant 'Speedybiotics' and a SATT-Sud Est Maturation grant (Antiobio-R) to T.M., O.T., and G.S., Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, MORPHOGENIE LOGICIELS SAS, Assistance Publique - Hôpitaux de Marseille (APHM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and LEROI, Delphine

Subjects
Biocompatibility, medicine.drug_class, [SDV]Life Sciences [q-bio], Microfluidics, Antibiotics, microfluidics, Biocompatible Materials, Nanotechnology, Microbial Sensitivity Tests, 02 engineering and technology, medicine.disease_cause, Microbiology, Bacterial Adhesion, Chitosan, 03 medical and health sciences, chemistry.chemical_compound, single cells, Virology, Materials Testing, medicine, Escherichia coli, Pathogen, Klebsiella pneumonia, Cell Proliferation, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, Bacteria, biology, 030306 microbiology, Polymer, Therapeutics and Prevention, 021001 nanoscience & nanotechnology, biology.organism_classification, QR1-502, Anti-Bacterial Agents, [SDV] Life Sciences [q-bio], antibiotic susceptibility testing, Klebsiella pneumoniae, Biochemistry, chemistry, Polylysine, Glass, chitosan, 0210 nano-technology, Research Article
Abstract

Current microfluidic techniques are powerful to study bacteria and determine their response to antibiotic treatment, but they are currently limited by their complex manipulation. Chitosan films are fully biocompatible and could thus be a viable replacement for existing commercial devices that currently use polylysine. Thus, the low cost of chitosan slides and their simple implementation make them highly versatile for research as well as clinical use., Single-cell microfluidics is a powerful method to study bacteria and determine their susceptibility to antibiotic treatment. Glass treatment by adhesive molecules is a potential solution to immobilize bacterial cells and perform microscopy, but traditional cationic polymers such as polylysine deeply affect bacterial physiology. In this work, we chemically characterized a class of chitosan polymers for their biocompatibility when adsorbed to glass. Chitosan chains of known length and composition allowed growth of Escherichia coli cells without any deleterious effects on cell physiology. Combined with a machine learning approach, this method could measure the antibiotic susceptibility of a diversity of clinical strains in less than 1 h and with higher accuracy than current methods. Finally, chitosan polymers also supported growth of Klebsiella pneumoniae, another bacterial pathogen of clinical significance.

Published
2019

190. Sustainable Modification of Carboxymethyl Cellulose by Passerini Three-Component Reaction and Subsequent Adsorption onto Cellulosic Substrates

Author

Céline Moreau, Bernard Cathala, Aurélia Charlot, Etienne Fleury, Adélie Daunay, Asja Pettignano, Università di Bologna [Bologna] (UNIBO), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Macromoléculaires (IMP-LMM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères (IMP), Alma Mater Studiorum Università di Bologna [Bologna] (UNIBO), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
General Chemical Engineering, Ether, macromolecular substances, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Carboxymethyl cellulose, chemistry.chemical_compound, Adsorption, Surface modification, medicine, Environmental Chemistry, Organic chemistry, Cellulose, ComputingMilieux_MISCELLANEOUS, Renewable Energy, Sustainability and the Environment, Chemistry, Component (thermodynamics), technology, industry, and agriculture, Chemical modification, General Chemistry, 021001 nanoscience & nanotechnology, Passerini reaction, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Quartz crystal microbalance with dissipation (QCM-D) analysis, 0210 nano-technology, Multicomponent reaction (MCR), medicine.drug
Abstract

International audience; The present work describes the chemical modification of carboxymethyl cellulose (CMC), a widely diffused commercial cellulose ether, by means of the Passerini three-component reaction (P-3CR). The reaction, performed in homogeneous aqueous medium, was proven to be effective at combining the carboxyl groups of CMC with different aldehydes and isocyanides, leading to the formation of a wide library of Passerini-modified CMC derivatives, in a simple and environmentally friendly one-pot process. The derivatized CMC products were thoroughly characterized to confirm the modification and determine the degrees of substitution (DS). The impact of experimental parameters (i.e., reaction T, time and pH, amount of employed reagents) and structure of the reactants (different aldehydes and isocyanides) on the reaction outcome was also discussed to explore the potential of this original approach for polysaccharide modification. Finally, the adsorption ability of selected CMC samples onto a model cellulosic surface was characterized by means of quartz crystal microbalance with energy dissipation monitoring (QCM-D). The analysis confirmed the successful adsorption of the Passerini-modified CMC derivatives and highlighted a positive effect of the derivatization on the amount of adsorbed polymer. Not only does the developed strategy appear as a mild and sustainable route for CMC functionalization, but also the promising adsorption ability of the functionalized derivatives opens the path toward the straightforward modification of surface properties of cellulosic substrates.

Published
2019

191. Programmable Hierarchical Construction of Mixed/Multilayered Polysaccharide Nanocapsules through Simultaneous/Sequential Nanoprecipitation Steps

Author

Ricardo Ramos, François Ganachaud, Rostyslav Bilyy, Xibo Yan, Julien Bernard, Pierre Alcouffe, Luis E. Muñoz, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidad de Cantabria [Santander], Danylo Halytskiy Lviv National Medical University, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)

Subjects
chemistry.chemical_classification, Materials science, Polymers and Plastics, Polymers, Bioengineering, Nanotechnology, 02 engineering and technology, Polymer, Silicon Dioxide, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Nanocapsules, 0104 chemical sciences, Biomaterials, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polysaccharides, Materials Chemistry, Technology, Pharmaceutical, Nanocarriers, 0210 nano-technology, Oils, ComputingMilieux_MISCELLANEOUS
Abstract

We report here on a one-pot construction of oil-filled hierarchical capsular assemblies using the nanoprecipitation technique. Relying on multicomponent phase diagrams, we show that simultaneous and/or sequential nanoprecipitations involving polymer combinations can be precisely programmed to design a new class of mixed/multilayered multicomponent nanocapsules, with a precise control of the dimensions, shell thickness/composition, and spatial distribution of the building blocks. The simplicity and tunability of this approach are exemplified here with a library of neutral and ionic polysaccharides giving access to a range of functional multilayered nanocarriers of interest for biomedical applications.

Published
2019

192. Rheological study of quaternary ammonium‐containing star‐shaped polylactic acid

Author

Mohamed Taha, Corinne Jegat, Kedafi Belkhir, Jean-Charles Majesté, Unité Matériaux et Transformations - UMR 8207 (UMET), Institut de Chimie du CNRS (INC)-Institut National de la Recherche Agronomique (INRA)-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Ecole Nationale Supérieure de Chimie de Lille (ENSCL), Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National de la Recherche Agronomique (INRA)-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet - Saint-Étienne (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Materials science, Polymers and Plastics, Ionic bonding, Thermodynamics, 02 engineering and technology, General Chemistry, Activation energy, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Ion, chemistry.chemical_compound, Viscosity, Polylactic acid, chemistry, Rheology, Time–temperature superposition, Materials Chemistry, 0210 nano-technology
Abstract

International audience; Quaternary ammonium-containing star-shaped polylactic acid (PLA-Q) is analyzed in melt rheology and found to follow a clustering behavior. The viscosity of this polymer is largely higher than its analog, of the same structure, without ammonium ions. This difference is attributed to physical interactions taking place between the ammoniums and hindering the flow of the melt polymer. The frequency sweeps of the storage (G′) and loss (G′′) modulus of the melt PLA-Q are achieved at different temperatures and different shearing times. The iso-temperature and iso-time superposition of the resulting curves were achieved using, respectively, a temperature and a time shift factors, this superposition allowed the determination of the flow activation energy; its value corresponds to an ionic process confirming the ionic interactions. When the two shift factors are used simultaneously, a unique master curve of both G′ and G′′ is obtained; this curve follows the Rouse model indicating the presence of two types of ionic associations within the melt polymer: a large number of multiplets having small size and a small number of clusters of larger size.

Published
2019

193. Improving the thermal and electrical properties of polymer composites by ordered distribution of carbon micro- and nanofillers

Author

Yevgen Mamunya, Sławomira Pusz, Gisèle Boiteux, Oleksii Maruzhenko, Urszula Szeluga, Sébastien Pruvost, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Filler (packaging), Materials science, Composite number, 02 engineering and technology, 01 natural sciences, 010305 fluids & plasmas, law.invention, chemistry.chemical_compound, Thermal conductivity, law, Phase (matter), 0103 physical sciences, Composite material, ComputingMilieux_MISCELLANEOUS, Fluid Flow and Transfer Processes, Graphene, Mechanical Engineering, Percolation threshold, [CHIM.MATE]Chemical Sciences/Material chemistry, Polyethylene, 021001 nanoscience & nanotechnology, Condensed Matter Physics, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Percolation, 0210 nano-technology
Abstract

This article presents the study of electrical and thermal properties of segregated polymer composites based on ultra-high-molecular-weight polyethylene (UHMWPE) filled with carbon fillers (nanofiller graphene (Gr), microfiller anthracite (A) and hybrid filler Gr/A). It is shown that the formation of a segregated structure with an ordered distribution of the filler leads to a high local concentration in the intergrain boundaries, which causes a lower percolation threshold. Thus, in the composite UHMWPE + A, the percolation threshold is an order of magnitude lower than for a system with a random distribution of the filler. The segregated composite with nanofiller UHMWPE + Gr provides a 14-fold lower percolation threshold than the composite with microfiller UHMWPE + A. Composite with the hybrid filler Gr/A also exhibits a low percolation threshold close to the UHMWPE + Gr. The plot of the thermal conductivity versus filler content does not show the percolation behavior and obeys the equation of the Lichtenecker. The thermal conductivity parameter λf in the segregated system is 4.4 times higher than for the uniform distribution of the filler that indicates an increased thermal transport through the filler phase located at the boundaries in the segregated structure.

Published
2019

194. Rheology and crystallization behavior of polypropylene and high‐density polyethylene in the presence of a low molar mass polyethylene

Author

Michaël Robert, Philippe Cassagnau, René Fulchiron, Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Polymères et des Biomatériaux (IMP-LMPB), Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut de Chimie du CNRS (INC), Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Polypropylene, Molar mass, Materials science, Polymers and Plastics, Materials Science (miscellaneous), 02 engineering and technology, Polyethylene, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Miscibility, 0104 chemical sciences, law.invention, chemistry.chemical_compound, chemistry, Chemical engineering, Rheology, Mechanics of Materials, law, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], High-density polyethylene, Physical and Theoretical Chemistry, Crystallization, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2019

195. Silicone rheological behavior modification for 3D printing: Evaluation of yield stress impact on printed object properties

Author

Arthur Colly, René Fulchiron, David Mariot, Clément Perrinet, Christophe A. Marquette, Jean-Marc Frances, Edwin-Joffrey Courtial, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères (IMP), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Elkem Silicones

Subjects
0209 industrial biotechnology, 3d printed, Materials science, business.industry, Biomedical Engineering, 3D printing, 02 engineering and technology, 021001 nanoscience & nanotechnology, Industrial and Manufacturing Engineering, Viscoelasticity, chemistry.chemical_compound, 020901 industrial engineering & automation, Silicone, chemistry, Rheology, Deposition (phase transition), General Materials Science, Composite material, 0210 nano-technology, business, Engineering (miscellaneous), [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft], ComputingMilieux_MISCELLANEOUS
Abstract

Silicone-based materials are commonly used in medical applications such as pre-surgery models or implants, leading to interesting biomimetic mechanical properties. Emergence of 3D printing and particularly liquid deposition modelling (LDM) has shown that specific rheological behaviors, particularly yield stress characters, were required to achieve efficient LDM. Unfortunately, standard silicone formulations seldom present such behaviors and are then proved to have low applicability in LDM-based 3D printing. In the present study, polyethylene glycol of different lengths were added as yield stress agents in a bi-component silicone and were demonstrated to operate a drastic improvement of the material rheological behaviors, without significant impact on the final mechanical properties of the material. An interesting relationship was demonstrated between dynamic yield stress values and reachable 3D geometries (the higher σ y s , the more complex the 3D printed shape can be) but the study also revealed that it is not the only key factor to ensure the printability of viscoelastic materials when highly complex geometries are seek; tack and melt strength have also to be investigated.

Published
2019

196. Advanced Fluorescent Polymer Probes for the Site-Specific Labeling of Proteins in Live Cells Using the HaloTag Technology

Author

Andrea Raimondi, Laura Fabre, Marie Therese Charreyre, Thomas Berki, Anush Bakunts, Catherine Ladavière, Andrea Orsi, Arnaud Favier, Eelco van Anken, Damien Duret, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Systèmes Macromoléculaires et Physiopathologie Humaine (SMPH), BIOMERIEUX-Centre National de la Recherche Scientifique (CNRS), San Raffaele Scientific Institute, Vita-Salute San Raffaele University and Center for Translational Genomics and Bioinformatics, Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Macromoléculaires (IMP-LMM), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Berki, T, Bakunts, A, Duret, D, Fabre, L, Ladaviere, C, Orsi, A, Charreyre, Mt, Raimondi, A, van Anken, E, and Favier, A

Subjects
chemistry.chemical_classification, Bioconjugation, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, 010405 organic chemistry, Chemistry, [SDV]Life Sciences [q-bio], General Chemical Engineering, General Chemistry, Polymer, 010402 general chemistry, 01 natural sciences, Article, 0104 chemical sciences, lcsh:Chemistry, [CHIM.POLY]Chemical Sciences/Polymers, lcsh:QD1-999, Covalent bond, Biophysics, [CHIM]Chemical Sciences, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, [SDV.IB]Life Sciences [q-bio]/Bioengineering, Fluorescent polymer, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; We report the site-specific and covalent bioconjugation of fluorescent polymer chains to proteins in live cells using the HaloTag technology. Polymer chains bearing a Halo-ligand precisely located at their α-chain-end were synthesized in a controlled manner owing to the RAFT polymerization process. They were labeled in lateral position by several organic fluorophores such as AlexaFluor 647. The resulting Haloligand polymer probe was finally shown to selectively recognize and label HaloTag proteins present at the membrane of live cells using confocal fluorescence microscopy. Such a polymer bioconjugation approach holds great promises for various applications ranging from cell imaging to cell surface functionalization.

Published
2019

197. Effects of Chain Length of Chitosan Oligosaccharides on Solution Properties and Complexation with siRNA

Author

Jimmy Faivre, Mirjam Hofmaier, Stéphane Trombotto, François Dole, Maxime Mock-Joubert, Olivier Sandre, Jean-Paul Chapel, Agnès Crépet, Tim Delas, Christophe Schatz, Thierry Delair, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 3 LCPO : Polymer Self-Assembly & Life Sciences, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE09-0020,TANGO,Marquage non-covalent de siRNA par de petites séquences de copolymères à blocs pour une meilleure administration ciblée(2016)

Subjects
[SDV.BIO]Life Sciences [q-bio]/Biotechnology, Polymers and Plastics, complexation, Context (language use), 02 engineering and technology, Gene delivery, Article, lcsh:QD241-441, Chitosan, 03 medical and health sciences, chemistry.chemical_compound, Colloid, lcsh:Organic chemistry, polyionic complexation, oligosaccharide, Solubility, polyelectrolyte, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, General Chemistry, Oligosaccharide, 021001 nanoscience & nanotechnology, electrostatics, Polyelectrolyte, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, siRNA, Biophysics, chitosan, 0210 nano-technology, [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft]
Abstract

In the context of gene delivery, chitosan has been widely used as a safe and effective polycation to complex DNA, RNA and more recently, siRNA. However, much less attention has been paid to chitosan oligosaccharides (COS) despite their biological properties. This study proposed to carry out a physicochemical study of COS varying in degree of polymerization (DP) from 5 to 50, both from the point of view of the solution properties and the complexing behavior with siRNA. The main parameters studied as a function of DP were the apparent pKa, the solubility versus pH, the binding affinity with siRNA and the colloidal properties of complexes. Some parameters, like the pKa or the binding enthalpy with siRNA, showed a marked transition from DP 5 to DP 13, suggesting that electrostatic properties of COS vary considerably in this range of DP. The colloidal properties of siRNA/COS complexes were affected in a different way by the COS chain length. In particular, COS of relatively high DP (&ge, 50) were required to form small complex particles with good stability.

Published
2019

198. Development of alternative textile treatment based on epoxide derivatives

Author

Landa, Matthieu, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon, Etienne Fleury, and STAR, ABES

Subjects
Cellulose fiber, Fibre de cellulose, Cationic polymerization, Textile substrate, Matériaux, Chimie des polymères, Mechanical properties, [SPI.MAT] Engineering Sciences [physics]/Materials, Epoxyde, Polymère, [SPI.MAT]Engineering Sciences [physics]/Materials, Polymérisation cationique, Technical textile, Propriétés mécaniques, Substrat textile, Polymer chemistry, Polymer, Polysaccharide, Materials, Epoxide, Textile technique
Abstract

The aim of this thesis is the development of epoxide-based aqueous formulation, which can be used as "easy-care" textile treatment."Easy -care" treatment is applicated to improve wrinkle recovery properties and the dimensionnal stability of textile (cellulosic substrates). This treatment is based on the chemical crosslinking of cellulose microfibers by a crosslinking agent. The formulations developed in this thesis have to substitute the one using formaldehyde derivatives. After a bibliographic study, the epoxide derivatives under acid catalyst (Lewis Acid: zinc tetrafluoroborate) have been selected. Different reactions are possible in the course of the treatment of textile by epoxide in acid media: -Crosslinking of cellulose by etherification, -Acid hydrolysis of epoxide functions, -Cationic polymerization of epoxide derivatives. First, the complex reaction media "epoxide + alcohol + water + acid catalyst" have been investigated by different model reaction studies. The etherification of an alcohol by an epoxide in this media have been highlighted. Then, different epooxid-based aqueous formulation have been developed and experimented as textile treatment at laboratory scale. The formulation are distinguished by the type of epoxide, the quantity of epoxide and the quantity of catalyst. The effect of the treatment on the wrinkle recovery and mechanical properties have been investigated., Ce travail de thèse est consacré au développement de formulations aqueuses époxyde pouvant être utilisées comme traitement textile « easy-care » sur substrat cellulosique. Ce traitement consiste en l’amélioration des propriétés défroissables et de la stabilité dimensionnelle. Les propriétés « easy-care » sont apportées par des formulations réactives pouvant réticuler chimiquement les microfibrilles de cellulose (via les fonctions hydroxyle). Les formulations, développées lors de ces travaux de thèse, ont pour objectif de substituer celles utilisées actuellement car elles libèrent du formaldéhyde (produit CMR). Après une étude bibliographique des alternatives aux dérivés formaldéhyde, l’utilisation de dérivés époxyde en présence d’un catalyseur acide (acide de Lewis : le tétrafluoroborate de zinc) a été sélectionnée comme stratégie principale. Différentes réactions peuvent subvenir lors du traitement d’un substrat cellulosique par ce type de formulation : -La réticulation des chaînes de cellulose par éthérification (souhaitée pour notre application),-L’hydrolyse acide des fonctions époxyde, -L’oligomérisation cationique des dérivés époxyde. Les deux dernières réactions ont un impact néfaste sur la réactivité de la formulation. Tout d’abord, nous avons souhaité contribuer à une meilleure compréhension du milieu réactionnel « époxyde + alcool + eau + catalyseur », peu étudié dans la littérature, à travers différentes réactions modèles. L’éthérification d’alcool par des dérivés époxyde a notamment été vérifiée. Des formulations, se différenciant par la quantité de catalyseur, la quantité de dérivés époxyde et la nature de l’époxyde, ont été appliquées à l’échelle laboratoire sur un substrat textile modèle (100% coton). Le greffage du dérivé époxyde a été mis en évidence par XPS et IRTF-ATR. L’impact du traitement sur les propriétés défroissables et mécaniques a été évaluée. Une formulation époxyde a été sélectionnée, puis appliquée à un substrat industriel à l’échelle pilote afin de comparer les propriétés obtenues à celles d’un tissu référence.

Published
2019

199. Synthèse, caractérisation et propriétés des oligoesters et composites sulfonés biosourcés

Author

Hadj kacem, Yosra, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon, Université de Sfax (Tunisie), Etienne Fleury, and Majdi Abid

Subjects
Thermomechanical Behaviour, Hydrolytic degradation, Propriété thermomécanique, Matériaux, Composite, Matériau polymère, [SPI.MAT]Engineering Sciences [physics]/Materials, Biomasse, Biobased monomer, Monomère biosourcé, Dégradation hydrolytique, Oligoester, Polymer materials, Biomass, Materials
Abstract

The research conducted in this thesis was achieved in the context of vegetal biomass valorization. It aims to develop a new family of aliphatic oligoesters from biobased monomers and incorporating into their structure sulfonated groups. This choice is justified by the following three considerations. (i) This is a contribution to the valorization of vegetal biomass. (ii) The presence of sulfonated units in the structure of this type of polymers gives them specific physicochemical properties favoring their use in various industrial sectors. (iii) These oligoesters can be subsequently used for the preparation of poly (ester-urethane) networks and ionic liquid-based composites with potentially interesting thermomechanical properties and a great tendency towards hydrolytic degradation.; La transformation de la biomasse végétale en composés simples pouvant servir comme monomères pour l’élaboration de nouveaux matériaux polymères susceptibles de se substituer à leurs homologues d’origine pétrochimique a été l’un des thèmes de recherche développés au cours des deux dernières décennies. c’est dans ce vaste contexte que s’inscrivent les travaux rapportés dans ce mémoire dont l’objectif était d’élaborer une nouvelle famille d’oligoesters aliphatiques en partant de monomères biosourcés et en intégrant dans leur structure des groupes sulfonés. Cette orientation est justifié par les trois considérations suivantes (i) cela constitue une contribution à la valorisation de la biomasse végétale (ii) la présence des unités sulfonés dans leur structure leur confère des propriétés physico-chimiques particulières favorisant leur utilisation dans divers secteurs industriels. (iii) Ces oligoesters peuvent être par la suite utilisés pour la préparation des composites à base de réseaux de poly (ester-uréthane) et de liquide ionique ayant des propriétés thermomécaniques potentiellement intéressantes et une grande tendance à la dégradation hydrolytique.

Published
2019

200. Synthesis, characterization and properties of biobased, sulfonated oligoesters and composites

Author

Hadj Kacem, Yosra, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon, Université de Sfax (Tunisie), Etienne Fleury, Majdi Abid, and STAR, ABES

Subjects
Thermomechanical Behaviour, Hydrolytic degradation, Propriété thermomécanique, Matériaux, Composite, [SPI.MAT] Engineering Sciences [physics]/Materials, Matériau polymère, [SPI.MAT]Engineering Sciences [physics]/Materials, Biomasse, Biobased monomer, Monomère biosourcé, Dégradation hydrolytique, Oligoester, Polymer materials, Biomass, Materials
Abstract

The research conducted in this thesis was achieved in the context of vegetal biomass valorization. It aims to develop a new family of aliphatic oligoesters from biobased monomers and incorporating into their structure sulfonated groups. This choice is justified by the following three considerations. (i) This is a contribution to the valorization of vegetal biomass. (ii) The presence of sulfonated units in the structure of this type of polymers gives them specific physicochemical properties favoring their use in various industrial sectors. (iii) These oligoesters can be subsequently used for the preparation of poly (ester-urethane) networks and ionic liquid-based composites with potentially interesting thermomechanical properties and a great tendency towards hydrolytic degradation., La transformation de la biomasse végétale en composés simples pouvant servir comme monomères pour l’élaboration de nouveaux matériaux polymères susceptibles de se substituer à leurs homologues d’origine pétrochimique a été l’un des thèmes de recherche développés au cours des deux dernières décennies. c’est dans ce vaste contexte que s’inscrivent les travaux rapportés dans ce mémoire dont l’objectif était d’élaborer une nouvelle famille d’oligoesters aliphatiques en partant de monomères biosourcés et en intégrant dans leur structure des groupes sulfonés. Cette orientation est justifié par les trois considérations suivantes (i) cela constitue une contribution à la valorisation de la biomasse végétale (ii) la présence des unités sulfonés dans leur structure leur confère des propriétés physico-chimiques particulières favorisant leur utilisation dans divers secteurs industriels. (iii) Ces oligoesters peuvent être par la suite utilisés pour la préparation des composites à base de réseaux de poly (ester-uréthane) et de liquide ionique ayant des propriétés thermomécaniques potentiellement intéressantes et une grande tendance à la dégradation hydrolytique.

Published
2019

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