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FR2875432A1 - Preparation of composite material, used in structure to carry out thermal exchange between coolant and structure, comprises incorporating microencapsulated phase change material into porous network of continuous matrix - Google Patents

Preparation of composite material, used in structure to carry out thermal exchange between coolant and structure, comprises incorporating microencapsulated phase change material into porous network of continuous matrix
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Publication number
FR2875432A1
FR2875432A1FR0452079AFR0452079AFR2875432A1FR 2875432 A1FR2875432 A1FR 2875432A1FR 0452079 AFR0452079 AFR 0452079AFR 0452079 AFR0452079 AFR 0452079AFR 2875432 A1FR2875432 A1FR 2875432A1
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matrix
thermal conductivity
change material
phase change
continuous matrix
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FR0452079A
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French (fr)
Inventor
Vincent Gueret
Pluton Pullumbi
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Priority to FR0452079ApriorityCriticalpatent/FR2875432A1/en
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Abstract

Preparation of a composite material with increased storage density and thermal conductivity, comprises incorporating at least a microencapsulated phase change material (PCM) in the form of polymeric microcapsules (having a diameter of 0.5-50 mu m) containing at least a phase change material, into the porous network of a continuous matrix (having strong thermal conductivity). Independent claims are also included for: (1) porous matrix (I) comprising polymeric microencapsules obtained by the process; and (2) structure comprising (I) arranged between at least two metallic sheets.

Description

Translated fromFrench

L'invention concerne un procédé de fabrication d'un matériau composite àThe invention relates to a method for producing a composite material for

densité de stockage et conductivité thermiques élevées, et un tel matériau  high storage density and thermal conductivity, and such material

utilisable en procédé de type PSA, VSA, TSA ou SERP (SERP pour Sorption Enhanced Reaction Process = procédé de réaction 'sorption' améliorée) II est connu que les matériaux à changement de phase (MCP) agissent comme des puits thermiques à leur température de changement de phase.  usable in the PSA, VSA, TSA or SERP (SERP method for enhanced sorption enhancement process) It is known that phase change materials (PCMs) act as heat sinks at their temperature of phase change.

Les MCP peuvent être organiques, telles que les paraffines et les io silicones, ou inorganiques, tels les sels hydratés et les alliages métalliques.  MCPs can be organic, such as paraffins and silicones, or inorganic, such as hydrated salts and metal alloys.

La capacité d'absorption de chaleur d'un MCP est d'autant plus grande que sa chaleur latente est élevée. Les paraffines ont une chaleur latente généralement inférieure à celles des sels hydratés. Pourtant, elles sont souvent préférentiellement utilisées comme MCP car elles présentent un certain nombre d'avantages, tels que réversiblité du changement de phase, stabilité chimique, température définie de changement de phase, possiblité d'encapsulation, faible coût, large plage de température selon le nombre d'atomes de carbone et la structure de la molécule, toxicité limitée.  The heat absorption capacity of a PCM is all the greater as its latent heat is high. Paraffins have a latent heat generally lower than those of hydrated salts. However, they are often preferentially used as MCP because they have a certain number of advantages, such as reversibility of the phase change, chemical stability, defined phase change temperature, encapsulation possibility, low cost, wide temperature range according to the number of carbon atoms and the structure of the molecule, limited toxicity.

Cependant, un inconvénient des paraffines est leur faible conductivité 20 thermique qui est de l'ordre de 0.1 ou 0.2 W/m/K selon que la paraffine est à l'état solide ou liquide.  However, a disadvantage of paraffins is their low thermal conductivity which is of the order of 0.1 or 0.2 W / m / K depending on whether the paraffin is in the solid or liquid state.

Cet inconvénient constitue une limitation majeure dès que les applications du MCP concernent des systèmes soumis à des échanges thermiques rapides, de temps caractéristiques compris entre quelques secondes et quelques minutes.  This disadvantage constitutes a major limitation as soon as the applications of the MCP concern systems subjected to rapid heat exchange, with characteristic times of between a few seconds and a few minutes.

Pour tenter d'y remédier, il a été proposé de combiner le MCP avec un matériau conducteur, ce qui consiste par exemple à imprégner les pores d'une matrice continue à forte conductivité thermique, tels les nids d'abeille, mousses, treillis, tissu métallique ou carboné, ou encore fibres continues de carbone, avec le MCP, ce qui permet d'atteindre des conductivités supérieures à celles obtenue précédemment, principalement du fait de la constitution d'un réseau conducteur continu.  In an attempt to remedy this, it has been proposed to combine the MCP with a conductive material, which consists, for example, in impregnating the pores of a continuous matrix with a high thermal conductivity, such as honeycombs, foams, lattices, metal or carbon fabric, or continuous carbon fibers, with the MCP, which achieves conductivities higher than those obtained previously, mainly because of the formation of a continuous conductive network.

Ainsi, le document US-A-6,399,149 propose de remplir les pores d'une mousse de carbone (pitch-derived) avec le MCP. La mousse de carbone est fermée par des parois métalliques ou carbonées.  Thus, US-A-6,399,149 proposes to fill the pores of a carbon foam (pitch-derived) with the MCP. The carbon foam is closed by metal or carbon walls.

Cependant, l'inconvénient de cette méthode est qu'elle nécessite la fabrication préalable d'une mousse de carbone avec des dimensions spécifiques. D'autre part, l'usinage d'une mousse de carbone n'est pas aisé, surtout si des tranches inférieures au centimètre sont requises. Enfin, si la mousse de carbone se brise à l'intérieur du dispositif, la conduction thermique n'est plus assurée et il faut démonter le système.  However, the disadvantage of this method is that it requires the prior manufacture of a carbon foam with specific dimensions. On the other hand, machining a carbon foam is not easy, especially if slices less than one centimeter are required. Finally, if the carbon foam breaks inside the device, thermal conduction is no longer ensured and the system must be dismantled.

La solution consistant à imprégner des fibres carbonées poreuses par des MCP est, quant à elle, limitée par la quantité de MCP logeable car les MCP ne sont retenus dans les pores des fibres que par des forces de capillarité. L'ensemble comporte donc des volumes morts ne contenant pas de MCP.  The solution consisting in impregnating porous carbonaceous fibers with PCMs is, in turn, limited by the amount of MCP that can be accommodated because the PCMs are retained in the pores of the fibers only by capillary forces. The set therefore includes dead volumes that do not contain PCM.

En définitive, les solutions ci-dessus ne sont pas idéales et présentent toutes des limites au plan industriel.  Ultimately, the above solutions are not ideal and all have industrial limitations.

La présente invention se propose dès lors de pallier ces limitations et inconvénients en proposant un procédé amélioré de fabrication d'un matériau composite à densité de stockage et conductivité thermiques élevées, ainsi qu'un tel matériau composite.  The present invention therefore proposes to overcome these limitations and disadvantages by proposing an improved method of manufacturing a composite material with high storage density and thermal conductivity, as well as such a composite material.

La solution de l'invention est alors un procédé de fabrication d'un matériau composite à densité de stockage et conductivité thermiques élevées, dans lequel on incorpore dans le réseau poreux d'une matrice continue à forte conductivité thermique, au moins un matériau à changement de phase (MCP) microencapsulé se présentant sous forme de microcapsules polymériques de diamètres compris entre 0.5 pm et 50 pm contenant au moins un matériau à changement de phase.  The solution of the invention is then a method of manufacturing a composite material with a high storage density and thermal conductivity, in which is incorporated in the porous network of a continuous matrix with high thermal conductivity, at least one material to change microencapsulated phase (MCP) in the form of polymer microcapsules of diameters between 0.5 μm and 50 μm containing at least one phase change material.

Dans le cadre de l'invention, on appelle matrice continue à forte conductivité thermique , une matrice composé d'un materiaux possédant une conductivité thermique propre élevée (supérieure à 200 W/m/K) qui en fonction de sa porosité (75 à 90%) peut avoir une conductivité thermique supérieure à 10 W/m/K.  In the context of the invention, a continuous matrix with a high thermal conductivity is called a matrix composed of a material having a high intrinsic thermal conductivity (greater than 200 W / m / K) which, depending on its porosity (75 to 90 %) may have a thermal conductivity greater than 10 W / m / K.

Selon le cas, le procédé de l'invention peut comprendre l'une ou plusieurs des caractéristiques suivantes: - les microcapsules de MPC ont un diamètre compris entre 1 et 10 pm.  Depending on the case, the process of the invention may comprise one or more of the following characteristics: the microcapsules of MPC have a diameter of between 1 and 10 μm.

- la matrice continue à forte conductivité thermique est une mousse.  the continuous matrix with high thermal conductivity is a foam.

- la matrice continue à forte conductivité thermique est choisie parmi les mousses céramiques, métalliques ou carbonées.  - The continuous matrix with high thermal conductivity is selected from ceramic foams, metal or carbon.

- la matrice est agencée entre au moins deux feuilles métalliques.  the matrix is arranged between at least two metal sheets.

- le MCP est choisi parmi les paraffines, les acides gras, les composés azotés, les composés oxygénés (alcool ou acides), les phényles et les sels lo hydratés.  the MCP is chosen from paraffins, fatty acids, nitrogen compounds, oxygenated compounds (alcohol or acids), phenyls and hydrated salts.

L'invention concerne aussi une matrice poreuse comprenant des microencapsules polymériques contenant au moins un matériau à changement de phase (MCP) et ayant un diamètre compris entre 0,5 pm et 50 pm, susceptible d'être obtenu par le procédé de fabrication de l'invention.  The invention also relates to a porous matrix comprising polymeric microencapsules containing at least one phase-change material (PCM) and having a diameter of between 0.5 μm and 50 μm, obtainable by the method of manufacturing the 'invention.

De préférence, la matrice est choisie parmi les mousses céramiques, métalliques ou carbonées.  Preferably, the matrix is chosen from ceramic, metal or carbonaceous foams.

L'invention porte aussi sur une structure comprenant une matrice selon l'invention agencée entre au moins deux plaques métalliques, ainsi que sur l'utilisation d'une structure selon l'invention pour réaliser un échange thermique entre un fluide caloporteur et ladite structure.  The invention also relates to a structure comprising a matrix according to the invention arranged between at least two metal plates, as well as to the use of a structure according to the invention for effecting a heat exchange between a coolant and said structure.

En d'autres termes, contrairement à ce que propose le document US-A-6,399, 149, à savoir une introduction directe du MPC dans une matrice continue à forte conductivité thermique, la solution de l'invention est basée sur une incorporation de MCP sous forme microencapsulée dans la matrice.  In other words, contrary to the document US Pat. No. 6,399,149, namely a direct introduction of the MPC in a continuous matrix with a high thermal conductivity, the solution of the invention is based on an incorporation of MCP. in microencapsulated form in the matrix.

En effet, le fait d'utiliser un MPC microencapsulé permet de passer outre les limitations de l'enseignement du document US-A-6,399,149.  Indeed, the fact of using a microencapsulated MPC makes it possible to overcome the limitations of teaching US-A-6,399,149.

Plus précisément, la technique de microencapsulation, le MCP est inséré dans des microsphères polymériques, de mélamine formaldéhyde ou d'acrylique par exemple, de diamètre compris entre 0,5 pm et 50 pm. A ces échelles, la conductivité thermique à travers la coque polymère et le MCP est très bonne. Les MCP microencapsulés ainsi obtenus se présentent sous la forme d'une poudre micronique particulièrement facile à manipuler et à mettre en oeuvre. La micro- encapsulation permet d'augmenter la surface d'échange du MCP avec le milieu extérieur et d'améliorer ainsi la cinétique thermique.  More specifically, the microencapsulation technique, MCP is inserted in polymeric microspheres, melamine formaldehyde or acrylic for example, with a diameter of between 0.5 pm and 50 pm. At these scales, the thermal conductivity through the polymer shell and the MCP is very good. The microencapsulated MCPs thus obtained are in the form of a micron powder which is particularly easy to handle and to use. Microencapsulation makes it possible to increase the exchange surface of the PCM with the external medium and thus to improve the thermal kinetics.

Les mousses contenant des MCP microencapsulés selon l'invention sont utilisables dans des applications impliquant des variations rapides de température, c'est-à-dire comprises entre 5 secondes et 10 minutes, notamment en procédés VSA, PSA, TSA ou SERP pour la séparation ou la purification des gaz.  The foams containing microencapsulated MCPs according to the invention can be used in applications involving rapid temperature variations, that is to say between 5 seconds and 10 minutes, in particular in the VSA, PSA, TSA or SERP methods for separation. or the purification of gases.

L'invention va être expliquée plus en détail en références aux figures annexées.  The invention will be explained in more detail with reference to the appended figures.

io La figure 1 représente des vues grossies d'une mousse poreuse métallique selon l'invention, laquelle incorpore, dans son réseau poreux, un matériau à changement de phase (MCP) microencapsulé se présentant sous forme de microcapsules polymériques de diamètres compris entre 0.5 pm et 50 pm, typiquement entre 2 et 10 pm, contenant ledit matériau à changement de phase, par exemple les paraffines et les silicones.  FIG. 1 represents magnified views of a porous metal foam according to the invention, which incorporates, in its porous network, a microencapsulated phase change material (MCP) in the form of polymer microcapsules with diameters of between 0.5 μm. and 50 μm, typically between 2 and 10 μm, containing said phase change material, for example paraffins and silicones.

La mousse peut être, selon le cas, de nature métallique, céramique ou carbonée et est préférentiellement agencée, c'est-à-dire prise en sandwich , entre deux feuilles ou plaques métalliques, comme visible sur la figure 2.  The foam may be, as the case may be, of a metallic, ceramic or carbonaceous nature and is preferably arranged, that is to say sandwiched, between two sheets or metal plates, as can be seen in FIG. 2.

Il existe plusieurs manières de fabriquer une matrice selon l'invention.  There are several ways to make a matrix according to the invention.

Une première méthode schématisée sur la Figure 3 consiste à remplir ou à incorporer aux espaces vides, c'est-à-dire au réseau poreux, d'une matrice 1 métallique ou carbonée agencée entre deux plaques métalliques 2, le MCP microencapsulé lequel y est introduit sous forme d'une solution 3 de MCP microencapsulé. La structure formée par la matrice 1 et les plaques 2 est posée sur un filtre ayant des pores de 1 pm, lequel sert à arrêter les microcapsules contenant le MCP et à les retenir dans la matrice continue à forte conductivité thermique.  A first method shown diagrammatically in FIG. 3 consists in filling or incorporating into the empty spaces, that is to say the porous network, a metallic or carbon matrix 1 arranged between two metal plates 2, the microencapsulated MCP which is introduced in the form of a solution 3 of microencapsulated MCP. The structure formed by the matrix 1 and the plates 2 is placed on a filter having pores of 1 μm, which serves to stop the microcapsules containing the MCP and to retain them in the continuous matrix with high thermal conductivity.

Une autre méthode repose sur l'incorporation du MCP microencapsulé dans une mousse polymérique, tel du polyurétane expansé avec distribution de tailles de pores contrôlées, suivie d'un dépôt électrolytique de métal sur la mousse polymérique.  Another method relies on the incorporation of microencapsulated MCP into a polymeric foam, such as expanded polyurethane with controlled pore size distribution, followed by electrolytic deposition of metal on the polymeric foam.

La mousse de l'invention peut être utilisée dans des systèmes impliquant des cycles de température rapides (entre 5 s et 10 min) tels les procédés VSA, PSA ou TSA pour la séparation ou la purification des gaz, par lesquelles sont produits un ou plusieurs composés parmi 02, H2, CO2, Ar, N2..., à partir de l'air, d'un mélange H2ICO, d'un syngas, d'un gaz résiduel de combustion par exemple, par adsorption sélective de N2, 02, CO, CO2, H2O, d'hydrocarbures saturés ou insaturés, de composés sulfurés ou d'oxydes d'azote; ou encore les procédés SERP.  The foam of the invention can be used in systems involving fast temperature cycles (between 5 s and 10 min) such as VSA, PSA or TSA processes for gas separation or purification, by which one or more products are produced. O2, H2, CO2, Ar, N2 ... compounds, from air, a H2ICO mixture, a syngas, a combustion residual gas for example, by selective adsorption of N2, O2 CO, CO2, H2O, saturated or unsaturated hydrocarbons, sulfur compounds or oxides of nitrogen; or the SERP methods.

Claims (1)

Translated fromFrench
6 REVENDICATIONS6 claims 1. Procédé de fabrication d'un matériau composite à densité de stockage et conductivité thermiques élevées, dans lequel on incorpore dans le réseau poreux d'une matrice continue à forte conductivité thermique, au moins un matériau à changement de phase (MCP) microencapsulé se présentant sous forme de microcapsules polymériques de diamètres compris entre 0,5 pm et 50 pm contenant au moins un matériau à changement de phase.  A method of manufacturing a composite material with high storage density and thermal conductivity, in which a continuous matrix of high thermal conductivity is incorporated in the porous network, at least one microencapsulated phase-change material (MCP) is in the form of polymeric microcapsules of diameters between 0.5 μm and 50 μm containing at least one phase change material. io 2. Procédé selon la revendication 1, caractérisé en ce que les microcapsules de MPC ont un diamètre compris entre 1 et 10pm.  2. Process according to claim 1, characterized in that the microcapsules of MPC have a diameter of between 1 and 10 μm. 3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que la matrice continue à forte conductivité thermique est une mousse.  3. Method according to one of claims 1 or 2, characterized in that the continuous matrix with high thermal conductivity is a foam. 4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la matrice continue à forte conductivité thermique est choisie parmi les mousses céramiques, métalliques ou carbonées.  4. Method according to one of claims 1 to 3, characterized in that the continuous matrix with high thermal conductivity is selected from ceramic foams, metal or carbon. 5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la matrice est agencée entre au moins deux feuilles métalliques.  5. Method according to one of claims 1 to 4, characterized in that the matrix is arranged between at least two metal sheets. 6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que le MCP est choisi parmi les paraffines, les acides gras, les composés azotés, les 25 composés oxygénés (alcool ou acides), les phényles et les sels hydratés.  6. Method according to one of claims 1 to 5, characterized in that the MCP is selected from paraffins, fatty acids, nitrogen compounds, oxygenates (alcohol or acids), phenyls and hydrated salts. 7. Matrice poreuse comprenant des microencapsules polymériques contenant au moins un matériau à changement de phase (MCP) et ayant un diamètre compris entre 0,5 pm et 50,um, susceptible d'être obtenue par le  7. A porous matrix comprising polymeric microencapsules containing at least one phase-change material (PCM) and having a diameter of between 0.5 μm and 50 μm, obtainable by the procédé selon l'une des revendications 1 à 6.  process according to one of claims 1 to 6. 8. Matrice selon la revendication 7, caractérisé en ce qu'elle est choisie parmi les mousses céramiques, métalliques ou carbonées.  8. Matrix according to claim 7, characterized in that it is selected from ceramic foams, metal or carbon. 9. Structure comprenant une matrice selon l'une des revendications 7 5 ou 8 agencée entre au moins deux plaques métalliques.  9. Structure comprising a matrix according to one of claims 7 5 or 8 arranged between at least two metal plates. 10. Utilisation d'une structure selon la revendication 9 pour réaliser un échange thermique entre un fluide caloporteur et ladite structure. io  10. Use of a structure according to claim 9 for performing a heat exchange between a heat transfer fluid and said structure. io
FR0452079A2004-09-172004-09-17Preparation of composite material, used in structure to carry out thermal exchange between coolant and structure, comprises incorporating microencapsulated phase change material into porous network of continuous matrixWithdrawnFR2875432A1 (en)

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CZ308571B6 (en)*2019-09-132020-12-09Technická univerzita v LiberciComposite for thermal protection, in particular for cooling electronic components
FR3131772A1 (en)*2022-01-072023-07-14Commissariat A L'energie Atomique Et Aux Energies Alternatives MODULAR THERMAL STORAGE ASSEMBLY WITH PHASE CHANGE MATERIAL, WHOSE MANUFACTURE IS SIMPLIFIED
EP4212814A1 (en)*2022-01-072023-07-19Commissariat à l'énergie atomique et aux énergies alternativesModular thermal storage assembly with phase-change material, the production of which is simplified
US12264882B2 (en)2022-01-072025-04-01Commissariat A L'energie Atomique Et Aux Energies AlternativesModular heat-storage assembly with phase-change material, the manufacture of which is simplified

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