Development of Innovating Materials for Distributing Mixtures of Hydrogen and Natural Gas. Study of the Barrier Properties and Durability of Polymer Pipes

International audienceWith the growing place taken by hydrogen, a question still remains about its delivery and transport from the production site to the end user by employing the existing extensive natural gas pipelines. Indeed, the key challenge is the significant H 2 permeation through polymer infrastructures (PolyEthylene (PE) pipes, components such as connecting parts). This high flow rate of H 2 through PE has to be taken into account for safety and economic requirements. A 3-year project was launched, the aim of which was to develop and assess material solutions to cope with present problems for hydrogen gas distribution and to sustain higher pressure compared to classical high density polyethylene pipe. This project investigated pure hydrogen gas and mixtures with natural gas (20% of CH 4 and 80% of H 2) in pipelines with the aim to select engineering polymers which are more innovative than polyethylene and show outstanding properties, in terms of perme-ation, basic mechanical tests but also more specific characterizations such as long term ageing and behaviour. The adequate benches, equipments and scientific approach for materials testing had been developed and validated. In this context, the paper will focus on the evaluation of the barrier properties of 3 polymers (PE, PA11 and PAHM). Experiments were performed for pure H 2 and CH 4 and also in the presence of mixtures of hydrogen and natural gas in order to study the possible mixing effects of gases. It will report some round-robin tests that have been carried out. Secondly, by comparing data obtained on film, polymer membrane and on pipe section, the influence of the polymer processing will be studied. Innovative multilayers systems will be proposed and compared on the basis of the results obtained on monolayer systems. Finally, the evolution of the transport properties of the studied polymers with an ageing under representative service conditions will be discussed

Water transport in polyurethane/polydimethylsiloxane membranes: Influence of the hydrophobic/hydrophilic balance and of the crosslink density

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Étude et modélisation du transport de petites molécules dans des nanocomposites à charges lamellaires (optimisation des propriétés barrière)

The aim of this work is to study and to improve barrier properties of nanocomposites prepared from lamellar nanofillers and two different semi-crystalline polymers. The permeability of the nanocomposites films is relates to the state of dispersion of the fillers, to the crystalline structure of the polymer matrix and to the filler / matrix interactions. In PA6-based nanocomposites, the permeability decreases are mainly due to a tortuosity effect induced by the well-dispersed inorganic layers. A quantitative description of the states of dispersion at different filler loadings allows a precise modelling of the gas transport properties. In HDPE-based nanocomposites, the increase in barrier properties is not directly related to the nanofillers dispersion state. They greatly depend on the interactions occurring between the fillers and the compatibilizersCe travail a pour but d'étudier et d'optimiser les propriétés barrière de nanocomposites à charges lamellaires pour deux matrices semi-cristallines de polarité différente. La perméabilité des films nanocomposites, réalisés dans des conditions contrôlées, est reliée à l'état de dispersion des charges, à la texture cristalline et aux interactions charges / matrices. Dans les systèmes à base de PA6, les réductions de perméabilité sont principalement dues à un effet de tortuosité induit par les charges qui sont dispersées de manière homogène. Une description quantitative des états de dispersion à différents taux de charges a permis une modélisation précise des propriétés de transport. Dans les systèmes à base de PEHD, les propriétés optimales ne sont pas obtenues pour les systèmes dans lesquels les charges sont les mieux exfoliées : elles dépendent fortement des interactions développées entre la charge et les agents compatibilisants introduits dans la formulationLYON1-BU.Sciences (692662101) / SudocSudocFranceF

Electrolytes polymère nano-structurés à base de liquides ioniques pour les piles à combustible hautes températures

Les membranes à base de liquides ioniques à conduction protonique (PCIL) sont très prometteuses comme électrolytes des piles à combustible haute température (HT- PEMFC) du fait de leur forte conductivité et stabilité à des températures supérieures à 100C. L'objectif de cette thèse est de réaliser une étude approfondie sur l'évolution de la morphologie et des propriétés fonctionnelles, des membranes à base de liquides ioniques, avec i) la concentration en PCIL, ii) la méthode d élaboration et iii) la structure chimique du PCIL. Afin de prouver la potentialité de ces membranes dans le HT-PEMFC, des tests préliminaires en pile sont réalisés et les phénomènes de dégradation des PCIL et des membranes en présence de peroxyde d'hydrogène sont étudiés. La première partie de ce travail est focalisée sur la caractérisation des membranes de Nafion® neutralisées avec le triéthylamine (Nafion-TEA) et gonflées avec triflate de triéthylammonium (TFTEA). Il a été montré que dans le Nafion-TEA sec, les cations présentent une organisation de type string like à l'interface hydrophobe-hydrophile. L introduction du TFTEA dans la membrane Nafion-TEA ne détruit pas sa nano-structuration, mais augmente de manière significative la conductivité ionique du système. La deuxième partie de ce travail nous a permis d'établir que les membranes dopées élaborées par coulée-évaporation présentent une meilleure organisation et une meilleure tenue thermomécanique par rapport à celles obtenues par gonflement. La troisième partie de ce travail est focalisée sur l étude de l'impact de la nature chimique du PCIL sur la morphologie et les propriétés fonctionnelles des membranes de Nafion-TEA. Il a été démontré que les PCILs avec longues chaînes perfluorées ne modifient pas la nano-structuration du Nafion-TEA. Ceci a un impact fort sur les propriétés de conductivité, de sorption d eau et sur les propriétés thermomécaniques de la membrane. Dans la dernière partie, des Ionomères aromatiques ont été synthétisés afin de remplacer le Nafion-TEA. Malgré la structure similaire de la chaîne latérale des Ionomères aromatiques et du Nafion®, les membranes à base d Ionomères aromatiques et TFTEA ne présentent aucune nano-structuration. De plus l effet plastifiant du TFTEA est plus notable dans le cas des Ionomères aromatiques probablement du fait d une distribution aléatoire des fonctions ioniques dans la membrane polymère.The polymer electrolyte membranes based on Proton Conducting Ionic liquids (PCIL) are very promising systems for the high temperature-PEMFC technology owing to their good ionic conductivity and stability at temperatures above 100oC. The objective of this thesis work is to achieve a profound study on the evolution of morphology and consequent functional properties of the PCIL based polymer electrolyte membranes in function of: i). concentration of the PCIL, ii). the method of elaboration and iii). chemical structure of the PCIL. To demonstrate the potential of these membranes in HT-PEMFC, preliminary tests have been carried out in the fuel cell stack and degradation phenomena associated with PCILs and membranes in the presence of hydrogen peroxide have been studied. The first part of this work is focused on the characterization of Nafion® membranes neutralized with triethylamine (Nafion-TEA) and swollen with triethylammonium Triflate (TFTEA). It has been shown that Nafion-TEA exhibits a single layer string-like organization of inter-digited Triethylammonium cations at the hydrophobic-hydrophilic interface when in anhydrous state. The introduction of TFTEA into Nafion-TEA membrane does not destroy its nano-structuration but significantly boosts the anhydrous ionic conductivity and hydrophilicity of the system. The second part of this work has permitted us to establish the fact that doped membranes prepared by casting method have better organization and better thermo-mechanical properties compared to those obtained by swelling method. Third part of this work focuses on the impact of the chemical nature of the PCIL on the morphology and functional properties of Nafion-TEA membranes. It has been demonstrated that the PCILs with long perfluorinated chain length do not modify the nano-structuration of Nafion-TEA membranes at all. This has a strong impact on the ion-conducting, water-sorption and thermo-mechanical properties of the membrane. In the last part, aromatic ionomers were synthesized in order to replace Nafion-TEA in such PCIL based system. Despite the similar structure of the side chain of the synthesized aromatic ionomers and Nafion®, the membranes based on aromatic ionomers and TFTEA do not present any nano-structuration. Moreover, the plasticizing effect of TFTEA is more noticeable in the case of aromatic ionomers probably due to a random distribution functions in the ionic polymer membrane.SAVOIE-SCD - Bib.électronique (730659901) / SudocGRENOBLE1/INP-Bib.électronique (384210012) / SudocGRENOBLE2/3-Bib.électronique (384219901) / SudocSudocFranceF

Modification of a hydrophilic linear polyurethane by crosslinking with a polydimethylsiloxane. Influence of the crosslink density and of the hydrophobic/hydrophilic balance on the water transport properties

International audienceA hydrophilic thermoplastic polyurethane (TPU) was modified by reactive extrusion to obtain in a first step a grafted and soluble material and to finally form by a hydrolysis condensation process a weakly crosslinked network. Different isocyanates were used as grafting agents and a a,x-dihydroxypoly(dimethylsiloxane) (PDMS) was used to modify the hydrophilic/hydrophobic balance of the material and the chain length between the crosslinks. The influence of the isocyanate functionality and of the PDMS content were studied on the network formation and on the thermomechanicaland water sorption properties. The networks properties were also compared with those of a TPU/PDMS blend

Water transport properties of thermoplastic polyurethane films

International audienceTwo linear segmented polyurethanes, based on poly(oxyethylene) (POE) as a soft segment and 4,4'-diphenylmethane diisocyanate and 1,4-butanediol as hard segments and differing in their soft segment length, have been studied from a water vapor transport point of view. For both polyurethanes, the water sorption is governed by a Fickian process, and the thermoplastic polyurethane with the longer POE segments displays the higher water diffusion rate. The water sorption isotherms are Brunauer Emmet Teller (BET) type III for both thermoplastic polyurethanes, and the water uptakes are directly related to the polymer POE content. The Flory-Huggins theory cannot correctly describe the sorption isotherms. More sophisticated approaches (Koningsveld-Kleinjtens or Guggenheim-Anderson-de Boer (GAB) models) are needed to fit the experimental water uptakes. The positive deviation from Henry's law and the decrease in the apparent diffusion coefficient observed at a high activity have been particularly studied. In this activity range, an isotherm analysis based on the cluster integral of Zimm and Lundberg suggests some clustering phenomenon, which seems consistent with the diffusion coefficient variation. In agreement with the sorption results, the water permeability coefficients are small at low activities, and they increase greatly with the relative pressure of water

Sol-gel route: An original strategy to chemically stabilize proton exchange membranes for fuel cell

International audienceWe present the elaboration, via a Sol-Gel (SG) route, of a new generation of hybrid membranes for PEMFC applications, in order to improve their performances and durability. The strategy was to create, within a commercial sPEEK membrane, a reactive SG phase able to reduce the oxidative species generated during FC operation and to improve the proton conductivity. The SG content is adjusted by tuning the SG precursors/sPEEK ratio used for the impregnation step. Raman analyses show that a uniform distribution of the SG phase in the membrane section is obtained when NMR analyses demonstrate its high extent of condensation, and reveal the structuring effect of the sPEEK membrane on the SG phase at the nanoscale. The membranes exhibit a better liquid water uptake and proton conductivity than pristine sPEEK membrane up to a SG uptake of 18%, with a gas permeability slightly higher than sPEEK but still lower than the benchmark Nafion. H2O2 accelerated aging tests evidenced the ability of the SG phase to prevent the oxidative degradation of sPEEK. Finally, the FC operability tests showed better and more durable performances for the hybrid membranes, without any increase of the gas permeability during operation

Membranes hybrides multi-stabilisées pour piles à combustible et électrolyseurs

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