Post-modification par irradiation g de polymères à base de fluorure de vinylidène (Applications aux membranes séparatrices de supercapacité)

Ce travail porte sur la modification de matrices polymères à base de fluorure de vinylidene pour permettre leur utilisation en tant que membrane séparatrice dans les supercapacités. Basé sur un procédé d irradiation par rayonnement g, l objectif principal était la limitation du gonflement du polymère lorsqu il est mis en contact d un milieu liquide relatif à l application tout en gardant d excellentes affinités avec celui-ci. Le processus de base exploité étant la formation et la réaction des radicaux lors de l irradiation du polymère, une partie de la thèse a été consacrée à leur étude par résonance paramagnétique électronique (RPE). Un modèle de simulation de spectre RPE a été mis en place pour identifier et quantifier chacune des espèces radicalaires. L effet de la dose d irradiation, de la durée d un recuit et de la nature de la matrice polymère (homo, copolymère) sur la proportion de ces espèces et sur leur réactivité a été évalué. Un lien avec la formation d un réseau a été proposé. Une attention particulière a ensuite été apportée à l augmentation de la densité de réticulation avec le concours d un agent réticulant, le TAIC. Pour terminer, une stratégie de modification des propriétés de surface du PVDF a été élaborée. Elle consiste dans un premier temps à radiogreffer un polymère à la surface du PVDF puis à modifier, dans un second temps, les greffons par une chimie douce et sélective. En conclusion, les approches complémentaires développées au cours de cette thèse ont permis de comprendre la radiolyse des polymères et de mettre à profit les processus élémentaires pour développer des stratégies robustes et prometteuses de modulation des propriétés.This work deals with the modification of VDF-based polymer induced by g-radiation as the polymer may be used in electrochemical supercapacitors. The main objective was to limit the swelling of the fluorinated matrix with a given electrolyte while a good wetting of the polymer by the liquid was also required. As the main basic process involved in polymer radiolysis is the formation of radicals, a part of the work was dedicated to the study of such species by using Electron Spin Resonance spectroscopy. A simulation model of ESR spectra was established in order to identify and quantify each radical species. The effect of several parameters such as radiation dose, annealing time or the nature of polymer matrix on the concentration of each species where investigated. A relation with the evolution of the crosslink density of the network formed during the radiolisys was proposed. In addition, one of the key steps of this work was to study the radiation crosslinking ability of VDF-based polymers and find a way to increase the crosslink density. This was achieved by incorporating, prior to the radiation process, a radiation sensitive crosslinker: TAIC. Finally, a new strategy based on the modification of surface properties of PVDF was investigated. It consists in the radiation grafting of pentafluorstyrene onto PVDF surface followed by the chemioselective functionalization of the grafted segments. As a conclusion, the different approaches used in this thesis allowed us to understand the radiolysis of VDF-based polymers and take advantage of the elementary process involved in this type of chemistry, to build up robust and promising strategies for tuning properties.VILLEURBANNE-DOC'INSA-Bib. elec. (692669901) / SudocSudocFranceF

A benzoxazine/substituted borazine composite coating: A new resin for improving the corrosion resistance of the pristine benzoxazine coating applied on aluminum

In this paper, laboratory synthesized Phenol-paraPhenyleneDiAmine (P-pPDA) benzoxazine containing different amounts of B-trimesityl-N-triphenylborazine was applied by spin coating on aluminum and thermally cured. The addition of the borazine derivative (borazine 1) does not appear to modify the curing characteristics of the P-pPDA matrix itself as shown by FTIR, DSC and DEA analyses; however, some interactions - chemical and/or physical (co-crystallization) – between P-pPDA and borazine 1 cannot be excluded. The microstructure of the composites is characterized by a two phase system consisting of a dispersion of nanosized (10–20 nm) clusters for the lowest borazine 1 concentration (0.5 wt%), evolving towards bigger (100–200 nm), agglomerated clusters for higher borazine 1 concentrations (3 wt%) and finally, continuous, dendritic structures within the P-pPDA matrix for the highest borazine 1 concentration (10 wt%). The benzoxazine composite coating containing 0.5 wt% trimesitylborazine derivative showed a largely increased and durable ability to protect the aluminum substrate. It is shown that a highly capacitive behavior and durable barrier properties can be obtained for P-pPDA coatings containing such a low amount of borazine derivative homogeneously dispersed in the benzoxazine matrix. For concentrations of 3 wt%, as agglomeration took place and dendrites appeared for the highest concentration of borazine derivative (10 wt%), the corrosion resistance decreased with time

Post-modification by γ-radiation of VDF-based polymers : Electrochemical capacitor membrane application

Ce travail porte sur la modification de matrices polymères à base de fluorure de vinylidene pour permettre leur utilisation en tant que membrane séparatrice dans les supercapacités. Basé sur un procédé d‘irradiation par rayonnement γ, l‘objectif principal était la limitation du gonflement du polymère lorsqu‘il est mis en contact d‘un milieu liquide relatif à l‘application tout en gardant d‘excellentes affinités avec celui-ci. Le processus de base exploité étant la formation et la réaction des radicaux lors de l‘irradiation du polymère, une partie de la thèse a été consacrée à leur étude par résonance paramagnétique électronique (RPE). Un modèle de simulation de spectre RPE a été mis en place pour identifier et quantifier chacune des espèces radicalaires. L‘effet de la dose d‘irradiation, de la durée d‘un recuit et de la nature de la matrice polymère (homo, copolymère) sur la proportion de ces espèces et sur leur réactivité a été évalué. Un lien avec la formation d‘un réseau a été proposé. Une attention particulière a ensuite été apportée à l‘augmentation de la densité de réticulation avec le concours d‘un agent réticulant, le TAIC. Pour terminer, une stratégie de modification des propriétés de surface du PVDF a été élaborée. Elle consiste dans un premier temps à radiogreffer un polymère à la surface du PVDF puis à modifier, dans un second temps, les greffons par une chimie douce et sélective. En conclusion, les approches complémentaires développées au cours de cette thèse ont permis de comprendre la radiolyse des polymères et de mettre à profit les processus élémentaires pour développer des stratégies robustes et prometteuses de modulation des propriétés.This work deals with the modification of VDF-based polymer induced by γ-radiation as the polymer may be used in electrochemical supercapacitors. The main objective was to limit the swelling of the fluorinated matrix with a given electrolyte while a good wetting of the polymer by the liquid was also required. As the main basic process involved in polymer radiolysis is the formation of radicals, a part of the work was dedicated to the study of such species by using Electron Spin Resonance spectroscopy. A simulation model of ESR spectra was established in order to identify and quantify each radical species. The effect of several parameters such as radiation dose, annealing time or the nature of polymer matrix on the concentration of each species where investigated. A relation with the evolution of the crosslink density of the network formed during the radiolisys was proposed. In addition, one of the key steps of this work was to study the radiation crosslinking ability of VDF-based polymers and find a way to increase the crosslink density. This was achieved by incorporating, prior to the radiation process, a radiation sensitive crosslinker: TAIC. Finally, a new strategy based on the modification of surface properties of PVDF was investigated. It consists in the radiation grafting of pentafluorstyrene onto PVDF surface followed by the chemioselective functionalization of the grafted segments. As a conclusion, the different approaches used in this thesis allowed us to understand the radiolysis of VDF-based polymers and take advantage of the elementary process involved in this type of chemistry, to build up robust and promising strategies for tuning properties

Post-modification par irradiation γ de polymères à base de fluorure de vinylidène : Applications aux membranes séparatrices de supercapacité

This work deals with the modification of VDF-based polymer induced by γ-radiation as the polymer may be used in electrochemical supercapacitors. The main objective was to limit the swelling of the fluorinated matrix with a given electrolyte while a good wetting of the polymer by the liquid was also required. As the main basic process involved in polymer radiolysis is the formation of radicals, a part of the work was dedicated to the study of such species by using Electron Spin Resonance spectroscopy. A simulation model of ESR spectra was established in order to identify and quantify each radical species. The effect of several parameters such as radiation dose, annealing time or the nature of polymer matrix on the concentration of each species where investigated. A relation with the evolution of the crosslink density of the network formed during the radiolisys was proposed. In addition, one of the key steps of this work was to study the radiation crosslinking ability of VDF-based polymers and find a way to increase the crosslink density. This was achieved by incorporating, prior to the radiation process, a radiation sensitive crosslinker: TAIC. Finally, a new strategy based on the modification of surface properties of PVDF was investigated. It consists in the radiation grafting of pentafluorstyrene onto PVDF surface followed by the chemioselective functionalization of the grafted segments. As a conclusion, the different approaches used in this thesis allowed us to understand the radiolysis of VDF-based polymers and take advantage of the elementary process involved in this type of chemistry, to build up robust and promising strategies for tuning properties.Ce travail porte sur la modification de matrices polymères à base de fluorure de vinylidene pour permettre leur utilisation en tant que membrane séparatrice dans les supercapacités. Basé sur un procédé d‘irradiation par rayonnement γ, l‘objectif principal était la limitation du gonflement du polymère lorsqu‘il est mis en contact d‘un milieu liquide relatif à l‘application tout en gardant d‘excellentes affinités avec celui-ci. Le processus de base exploité étant la formation et la réaction des radicaux lors de l‘irradiation du polymère, une partie de la thèse a été consacrée à leur étude par résonance paramagnétique électronique (RPE). Un modèle de simulation de spectre RPE a été mis en place pour identifier et quantifier chacune des espèces radicalaires. L‘effet de la dose d‘irradiation, de la durée d‘un recuit et de la nature de la matrice polymère (homo, copolymère) sur la proportion de ces espèces et sur leur réactivité a été évalué. Un lien avec la formation d‘un réseau a été proposé. Une attention particulière a ensuite été apportée à l‘augmentation de la densité de réticulation avec le concours d‘un agent réticulant, le TAIC. Pour terminer, une stratégie de modification des propriétés de surface du PVDF a été élaborée. Elle consiste dans un premier temps à radiogreffer un polymère à la surface du PVDF puis à modifier, dans un second temps, les greffons par une chimie douce et sélective. En conclusion, les approches complémentaires développées au cours de cette thèse ont permis de comprendre la radiolyse des polymères et de mettre à profit les processus élémentaires pour développer des stratégies robustes et prometteuses de modulation des propriétés

Waste Heat Recovery by Means of Organic Rankine Cycle (ORC) System Coupled with Two-Phase Closed Thermosyphons

peer reviewedThis paper aims at assessing the performance of a waste heat-to-power plant by means of an ORC (Organic Rankine Cycle) system coupled with two-phase closed thermosyphons (or gravity-assisted heat pipes or wickless heat pipes). The heat exchanger, made up of two-phase closed thermosyphons, is used for conveying heat from exhaust stream to ORC working fluid. In reality, a hot oil loop or a pressurized hot water loop or a saturated ste am loop or even a direct evaporator is often used to transfer heat from the heat source to the ORC system. However, installing a heat exchanger directly in the hot gas paths of ORC system evokes the concerns for the flammability and/or toxicity of organic working fluids especially when the heat source has a relatively high temperature. Also the use of an intermediate heat carrier loop such as thermal oil or saturated steam or pressurized water loop is costly and involves installation of comparatively heavy components. In principle, the use of two-phase closed thermosyphons for capturing and transporting heat from a waste heat source to organic working fluid is less expensive than utilizing an intermediate heat transfer loop and eliminates safety issues as in the case of direct installation of an ORC evaporator in the hot gas paths.ORCA

Performance evaluation of an Organic Rankine Cycle (ORC) connected to two-phase closed thermosyphons

peer reviewedThis paper aims at evaluating the performance of a waste heat-to-power plant using an organic Rankine cycle (ORC) connected to two-phase closed thermosyphons (or gravity-assisted heat pipes or wickless heat pipes). The heat exchanger, made up of two-phase closed thermosyphons, is used for transferring heat from exhaust stream to ORC working fluid. In practice, a hot oil loop or a pressurized hot water loop or a saturated steam loop or even a direct evaporator is often used to transfer heat from heat source to ORC system. However, installing a heat exchanger directly in the hot gas paths of ORC system evokes the concerns for the flammability and/or toxicity of organic working fluids especially when the heat source has a relative high temperature. Also the use of an intermediate heat carrier loop such as thermal oil or saturated steam or pressurized water loop is relatively expensive and involves installation of relatively heavy components. A priori, the use of two-phase closed thermosyphons for capturing and transferring heat from a waste heat source to organic working fluid is less expensive than the use of an intermediate heat transfer loop and eliminates safety concerns as in the case of direct installation of an ORC evaporator in the hot gas paths.ORCA

Modulation des propriétés surfaciques et volumiques des polymères - Cas du PVDF sous rayonnement gamma

International audienc

Wettability adjustment of PVDF surfaces by combining radiation-induced grafting of (2,3,4,5,6)-pentafluorostyrene and subsequent chemoselective "click-type" reaction

International audienceA novel strategy combining (2,3,4,5,6)-pentafluorostyrene (PFS) grafting and subsequent wthiol/parafluorine "click" type post-grafting modification is presented to impart specific surface properties to bulky PVDF samples. First, PFS was radiation-induced grafted on the surface of PVDF using gamma-rays as the radiation source, and both pre-irradiation and simultaneous irradiation techniques were attempted. The extent of modification was higher with the latter strategy, as determined by semi-quantitative ATR-FT1R analyses. Subsequent coupling was then undertaken using 3-mercapto-1,2-propanediol (MPD). The chemoselective functionalization was qualitatively and semi-quantitatively evidenced by ATR-FTIR, and led to PVDF-g-PPFS decorated with hydroxyl groups. The resulting surface properties were investigated by wettability measurements, and hysteresis with water and contact angle with acetonitrile both evidenced the successful and appropriate modification. This strategy opens the scope of a new means to modify both swelling and surface properties of PVDF samples, as required for specific applications (such as separator in electrochemical devices or in pipe systems for handling specific chemicals)

Modulation des propriétés surfaciques et volumiques des polymères - Cas du PVDF sous rayonnement gamma

International audienc

Modulation des propriétés surfaciques et volumiques des polymères - Cas du PVDF sous rayonnement gamma

International audienc