EP3994205A1 - New ablative composite material - Google Patents

New ablative composite material

Info

Publication number
EP3994205A1
EP3994205A1 EP20735592.6A EP20735592A EP3994205A1 EP 3994205 A1 EP3994205 A1 EP 3994205A1 EP 20735592 A EP20735592 A EP 20735592A EP 3994205 A1 EP3994205 A1 EP 3994205A1
Authority
EP
European Patent Office
Prior art keywords
composite material
matrix
ablative composite
carbon fibers
ablative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20735592.6A
Other languages
German (de)
French (fr)
Inventor
Julien Beaudet
Emeline ARNAUD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Naval Group SA
Original Assignee
Naval Group SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Naval Group SA filed Critical Naval Group SA
Publication of EP3994205A1 publication Critical patent/EP3994205A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/04—Arrangements using dry fillers, e.g. using slag wool which is added to the object to be insulated by pouring, spreading, spraying or the like
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/24—Armour; Armour plates for stationary use, e.g. fortifications ; Shelters; Guard Booths
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length

Definitions

  • the present invention relates to a new ablative composite material, as well as its preparation process. It also relates to a part of said ablative composite material, the process for preparing said part, as well as the use of said material for thermal protection of the surface of a fuel-propelled munition launcher.
  • An ablative material derives its performance from its ability to absorb thermal and aerodynamic flow during the departure of a munition thanks to adapted thermal and mechanical characteristics.
  • thermal protection it is essential to identify the properties of the material that will promote energy dissipation during the ablation phenomenon. The more energy a material dissipates as it degrades, the better it will perform. In addition, the material must be a good insulator.
  • Ablation is a complex and strongly coupled phenomenon involving chemical, thermal and mechanical mechanisms.
  • the heat of ablation can be defined as the energy absorbed per mass of material consumed during ablation. The higher it is, the more energy it takes to degrade the material, or in other words, the less material it takes to protect a surface. It makes sense to seek to maximize it.
  • the heat of ablation is directly related to the specific heat, the enthalpies of reaction and the emissivity of the material.
  • Ultra-high temperature ceramic materials mainly consist of borides, nitrides, carbides and oxides of metals such as hafnium, zirconium, tantalum or titanium. These elements exhibit particularly high melting temperatures, above 2500 ° C. These are cutting-edge technologies the high cost of which is hardly compatible with use on large surfaces.
  • thermosetting resins in particular phenolic resin
  • materials based on elastomers as well as ceramic-based materials or materials of the carbon-carbon type.
  • the composite material Apart from the case of ceramic composites, it is possible to define the composite material with three main parameters: the resin, the reinforcement and the architecture of the reinforcement. Despite the number of combinations offered by these components, not all fiber-matrix combinations are as efficient as each other. The question of the cohesion of the material is as essential as the individual quality of each element constituting the composite.
  • the object of the present invention is therefore to resolve the problems of thermal insulation and of control of degradation during a retained fire or a missile departure fire.
  • the present invention relates to an ablative composite material comprising a matrix and a reinforcement, characterized in that:
  • the matrix is a phenolic resin or an epoxy resin
  • the reinforcement is formed of short carbon fibers with a length of between 0.5 mm and 20 mm, and a diameter of between 6 ⁇ m and 20 ⁇ m.
  • the material according to the invention is therefore formed of a matrix and of short carbon fibers as reinforcement.
  • the length of the carbon fibers is less than 20 mm.
  • the carbon fibers used according to the invention can be obtained from pitch or PAN (polyacrylonitrile) precursors.
  • the short carbon fibers have a porosity of less than 15%, preferably less than or equal to 10%, more preferably less than or equal to 5%.
  • the material according to the invention can be adapted to be subjected to severe aerothermal stress. Also, it is desirable, even essential, to limit the porosity, in particular the large pores which significantly accelerate the erosion of the material and to ensure that the material is as homogeneous and isotropic as possible. Preferably, the cohesion and density of the charcoal (carbon fibers) are maximized and the pullout sensitivity is limited.
  • the matrix of the material of the invention is a phenolic resin.
  • Phenolic resins are essentially resins derived from formaldehyde and phenol.
  • the phenolic resin is chosen from novolac resins (prepared by acid catalysis) or resols (prepared by basic catalysis).
  • the matrix of the material according to the invention is a phenolic matrix of the resole type.
  • the matrix of the material of the invention is a phenolic resin (phenolic matrix) and said material comprises a maximum rate of 60% by mass of short carbon fibers as defined above with respect to the mass total of said material, said short carbon fibers preferably exhibiting a porosity of less than 15%.
  • the material comprises at least 10% by mass of short carbon fibers as defined above relative to the total mass of said material.
  • the matrix of the material of the invention is a phenolic resin and said material comprises from 25% to 40% by mass of short carbon fibers. as defined above with respect to the total mass of said material, said short carbon fibers having a porosity of less than 5%.
  • the increase in the content of short carbon fibers makes it possible to increase the conductivity of the material without degrading its ablative properties, which makes it possible to limit the rise in temperature on the front face and to limit the loss of mass without compromising performance insulating material.
  • a particularly preferred material according to the invention comprises a phenolic matrix reinforced with 25% by mass of short carbon fibers as defined above, having low porosity, in particular less than 5%.
  • the pore size of the carbon fibers is less than 1 mm.
  • the matrix of the material of the invention is an epoxy resin.
  • the ablative composite material according to the invention comprises a matrix which is an epoxy resin, and comprises a maximum rate of 60% by mass of short carbon fibers as defined above relative to the total mass. of said material, said material having a porosity of less than 15%.
  • the material comprises at least 10% by mass of short carbon fibers as defined above relative to the total mass of said material.
  • the ablative composite material comprises, as a matrix, an epoxy resin chosen from flame retardant epoxy resins.
  • epoxy resins rich in carbon in particular with a carbonaceous residue at 1000 ° C. under nitrogen of between 20% and 80% by mass.
  • the material of the invention when the matrix is an epoxy resin, further comprises carbon powder, preferably in a mass content of between 5% and 20% relative to the total mass of said material.
  • the present invention also relates to a process for preparing the ablative composite material as defined above, comprising the mixing of the matrix and the reinforcement as defined above.
  • the present invention also relates to a process for preparing a part of ablative composite material as defined above.
  • This process essentially consists of performing compression molding (mold / mandrel).
  • the preparation process and the associated parameters make it possible to control the final quality and the characteristics of the material obtained.
  • the method of the invention comprises a step of mixing the matrix and the reinforcement, and a step of compression molding said mixture.
  • the present invention also relates to a process for preparing a part of ablative composite material as defined above, comprising a phenolic resin as a matrix.
  • the present invention therefore also relates to a process for preparing a part of ablative composite material as defined above, in which the matrix is a phenolic resin, and comprising from 10% to 60% by mass of short carbon fibers by weight. relative to the total mass of said material.
  • the manufacturing cycle includes pressurization and temperature of the mixture according to several different cycles (temperature / pressure pairs) to obtain the characteristics required for the material.
  • the processing cycle is adapted to the nature of the phenolic resin used.
  • the essential parameter for implementation is therefore the coupling between the pressure and the temperature.
  • An implementation by compression is imperative to obtain a material meeting the desired performance.
  • a homogeneous mixture and a perfect distribution of fibers in the mixture guarantee first-class performance.
  • the present invention also relates to a process for preparing a part of ablative composite material as defined above, comprising an epoxy resin as a matrix.
  • the present invention therefore also relates to a process for preparing a part of ablative composite material as defined above, in which the matrix is an epoxy resin, and comprising between 10% and 60% by mass of short carbon fibers by weight. relative to the total mass of said material.
  • Said method consists of several steps allowing the implementation of the invention.
  • the manufacturing cycle includes pressurization and temperature of the mixture according to several different cycles (temperature / pressure couples) making it possible to obtain the characteristics required for the material.
  • the processing cycle is adapted to the nature of the epoxy resin used.
  • the essential parameter for implementation is therefore the coupling between the pressure and the temperature.
  • An implementation by compression is imperative to obtain a material meeting the desired performance.
  • a homogeneous mixture and a perfect distribution of fibers in the mixture guarantee first-class performance.
  • the present invention also relates to a part of ablative composite material, said material being as defined above.
  • the present invention relates to a part of ablative composite material obtained by the aforementioned method.
  • the present invention also relates to a method of thermal protection of the surface of a fuel-propelled munition launcher, comprising the application of a part as defined above to said surface.
  • the thermal protection method of the invention is intended to protect the firing environment against the releases of ammunition, in particular those propelled by solid fuel.
  • the present invention therefore also relates to fuel-propelled munitions launchers, comprising at least one piece of ablative composite material as defined above.
  • Example 1 Preparation of a piece of ablative material comprising a phenolic resin
  • a piece of material comprising a phenolic resin according to the invention is prepared according to the method described in Table 1 below.
  • Example 2 Preparation of a piece of ablative material comprising an epoxy resin
  • a piece of material comprising an epoxy resin according to the invention is prepared according to the method described in Table 2 below.
  • Inventions based on phenolic and epoxy resins exhibit a homogeneous distribution of carbon fibers without preferential orientation.
  • thermo-physical characteristics are shown in the table below.
  • the material must degrade in a safe and linear manner. This means that the erosion must be gradual and controlled with good linearity of craterization as the exposure time increases.
  • the carbon resulting from the degradation must remain confined to the upper part of the plate and the thermal affectation must not lead to in-depth degradation of the thermal protection.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to an ablative composite material comprising a matrix and a reinforcement, characterized in that: the matrix is a phenolic resin or an epoxy resin, and the reinforcement is formed from short carbon fibers having a length of 0.5 mm to 20 mm and a diameter of 6 µm to 20 µm.

Description

NOUVEAU MATÉRIAU COMPOSITE ABLATIF NEW ABLATIVE COMPOSITE MATERIAL
La présente invention a pour objet un nouveau matériau composite ablatif, ainsi que son procédé de préparation. Elle a également pour objet une pièce dudit matériau composite ablatif, le procédé de préparation de ladite pièce, ainsi que l’utilisation dudit matériau pour la protection thermique de la surface d’un lanceur de munition propulsée par un carburant. The present invention relates to a new ablative composite material, as well as its preparation process. It also relates to a part of said ablative composite material, the process for preparing said part, as well as the use of said material for thermal protection of the surface of a fuel-propelled munition launcher.
Lors de la mise en oeuvre d’armes sur les bâtiments de surface, le départ de munitions engendre une agression aérothermique très sévère qui nécessite la protection des zones de pas de tirs par des matériaux spécifiques. Que ce soit sur le pont des navires ou sur des systèmes plus complexes, les performances des matériaux de protection thermique sont essentielles pour garantir la sécurité de l’équipage et du navire et permettre une disponibilité maximale du système de combat. During the deployment of weapons on surface vessels, the departure of ammunition generates a very severe aerothermal aggression which requires the protection of the zones of no fire by specific materials. Whether on the decks of ships or on more complex systems, the performance of thermal protection materials is essential to ensure the safety of the crew and the ship and to allow maximum availability of the combat system.
Un matériau ablatif tire ses performances de sa capacité à absorber le flux thermique et aérodynamique lors du départ d’une munition grâce à des caractéristiques thermiques et mécaniques adaptées. Dans le cadre de travaux de développement d’une protection thermique, il est essentiel d’identifier les propriétés du matériau qui favoriseront la dissipation d’énergie au cours du phénomène d’ablation. Plus un matériau dissipera d’énergie en se dégradant plus il sera performant. Par ailleurs, le matériau doit être un bon isolant. An ablative material derives its performance from its ability to absorb thermal and aerodynamic flow during the departure of a munition thanks to adapted thermal and mechanical characteristics. When developing thermal protection, it is essential to identify the properties of the material that will promote energy dissipation during the ablation phenomenon. The more energy a material dissipates as it degrades, the better it will perform. In addition, the material must be a good insulator.
L’ablation est un phénomène complexe et fortement couplé faisant intervenir des mécanismes chimiques, thermiques et mécaniques. La chaleur d’ablation peut être définie comme l’énergie absorbée par masse de matière consommée au cours de l’ablation. Plus elle est élevée, plus il faut d’énergie pour dégrader le matériau, ou en d’autres termes, moins il faut de matière pour protéger une surface. Il est logique de chercher à la maximiser. La chaleur d’ablation est directement liée à la chaleur spécifique, aux enthalpies de réaction et à l’émissivité du matériau. Ablation is a complex and strongly coupled phenomenon involving chemical, thermal and mechanical mechanisms. The heat of ablation can be defined as the energy absorbed per mass of material consumed during ablation. The higher it is, the more energy it takes to degrade the material, or in other words, the less material it takes to protect a surface. It makes sense to seek to maximize it. The heat of ablation is directly related to the specific heat, the enthalpies of reaction and the emissivity of the material.
Ces solutions peuvent être séparées en deux grandes familles de matériaux très différentes, les composites à matrice organique et les composites céramiques. Les matériaux céramiques ultra-haute température sont principalement constitués de borures, nitrures, carbures et oxyde de métaux tels que le hafnium, le zirconium, le tantale ou le titane. Ces éléments présentent des températures de fusion particulièrement élevées, supérieures à 2500°C. Il s'agit de technologies de pointe dont le coût élevé est difficilement compatible avec une mise en oeuvre sur de grandes surfaces. These solutions can be separated into two large families of very different materials, composites with an organic matrix and ceramic composites. Ultra-high temperature ceramic materials mainly consist of borides, nitrides, carbides and oxides of metals such as hafnium, zirconium, tantalum or titanium. These elements exhibit particularly high melting temperatures, above 2500 ° C. These are cutting-edge technologies the high cost of which is hardly compatible with use on large surfaces.
A ce jour, il existe plusieurs types de matériaux utilisés comme protections thermiques ou dont la résistance ablative a été testée, ainsi que quelques matériaux développés par des industriels. On peut citer les matériaux basés sur des résines thermodurcissables, notamment la résine phénolique, les matériaux basés sur des élastomères ainsi que des matériaux à base céramique ou matériaux du type carbone-carbone. To date, there are several types of materials used as thermal protections or whose ablative resistance has been tested, as well as some materials developed by manufacturers. Mention may be made of materials based on thermosetting resins, in particular phenolic resin, materials based on elastomers as well as ceramic-based materials or materials of the carbon-carbon type.
Le cas des composites céramiques mis à part, il est possible de définir le matériau composite avec trois paramètres principaux : la résine, le renfort et l'architecture du renfort. Malgré le nombre de combinaisons offertes par ces composants, toutes les associations fibre-matrice ne sont pas aussi performantes les unes que les autres. La question de la cohésion du matériau est aussi essentielle que la qualité individuelle de chaque élément constituant le composite. Apart from the case of ceramic composites, it is possible to define the composite material with three main parameters: the resin, the reinforcement and the architecture of the reinforcement. Despite the number of combinations offered by these components, not all fiber-matrix combinations are as efficient as each other. The question of the cohesion of the material is as essential as the individual quality of each element constituting the composite.
Les agressions très sévères générées lors des mises à feu impliquent une forte érosion de la surface des protections thermiques employées. Il est donc essentiel de proposer des solutions matériaux dont le comportement est maîtrisé pour garantir la disponibilité des équipements. The very severe attacks generated during fires imply a strong erosion of the surface of the thermal protections used. It is therefore essential to offer material solutions whose behavior is controlled to guarantee the availability of equipment.
Il existe donc un besoin pour disposer d’un matériau ablatif pour obtenir des propriétés satisfaisantes d’isolation thermique adaptées notamment pour des lanceurs de munition. There is therefore a need for an ablative material to obtain satisfactory thermal insulation properties suitable in particular for munition launchers.
La présente invention a donc pour but de résoudre les problématiques d’isolation thermique et de maîtrise de la dégradation pendant un tir retenu ou un tir départ de missile. The object of the present invention is therefore to resolve the problems of thermal insulation and of control of degradation during a retained fire or a missile departure fire.
Elle a également pour but de fournir un matériau ablatif présentant des propriétés de protection thermique adaptées, notamment pour une utilisation notamment pour la préparation de lanceurs de munitions. It also aims to provide an ablative material having suitable thermal protection properties, in particular for use in particular for the preparation of munitions launchers.
Ainsi, la présente invention concerne un matériau composite ablatif comprenant une matrice et un renfort, caractérisé en ce que : Thus, the present invention relates to an ablative composite material comprising a matrix and a reinforcement, characterized in that:
la matrice est une résine phénolique ou une résine époxy et the matrix is a phenolic resin or an epoxy resin and
le renfort est formé de fibres courtes de carbone de longueur comprise entre 0,5 mm et 20 mm, et de diamètre compris entre 6 pm et 20 pm. the reinforcement is formed of short carbon fibers with a length of between 0.5 mm and 20 mm, and a diameter of between 6 μm and 20 μm.
Le matériau selon l’invention est donc formé d’une matrice et de fibres courtes de carbone à titre de renfort. De préférence, la longueur des fibres de carbone est inférieure à 20 mm.The material according to the invention is therefore formed of a matrix and of short carbon fibers as reinforcement. Preferably, the length of the carbon fibers is less than 20 mm.
Les fibres de carbone mises en oeuvre selon l’invention peuvent être obtenues à partir des précurseurs brai ou PAN (polyacrylonitrile). The carbon fibers used according to the invention can be obtained from pitch or PAN (polyacrylonitrile) precursors.
Avantageusement, les fibres courtes de carbone présentent une porosité inférieure à 15%, de préférence inférieure ou égale à 10%, plus préférentiellement inférieure ou égale à 5%. Advantageously, the short carbon fibers have a porosity of less than 15%, preferably less than or equal to 10%, more preferably less than or equal to 5%.
Il est important que le matériau selon l’invention puisse être adapté pour être soumis à une sollicitation aérothermique sévère. Aussi, il est souhaitable, voire primordial, de limiter la porosité, notamment les pores de dimension importante qui accélèrent sensiblement l'érosion du matériau et de veiller à ce que le matériau soit le plus homogène et isotrope possible. De préférence, la cohésion et la densité du charbon (fibres de carbone) sont maximisées et la sensibilité à l'arrachement est limitée. It is important that the material according to the invention can be adapted to be subjected to severe aerothermal stress. Also, it is desirable, even essential, to limit the porosity, in particular the large pores which significantly accelerate the erosion of the material and to ensure that the material is as homogeneous and isotropic as possible. Preferably, the cohesion and density of the charcoal (carbon fibers) are maximized and the pullout sensitivity is limited.
Selon un mode de réalisation, la matrice du matériau de l’invention est une résine phénolique. Les résines phénoliques sont essentiellement des résines issues du formaldéhyde et du phénol. According to one embodiment, the matrix of the material of the invention is a phenolic resin. Phenolic resins are essentially resins derived from formaldehyde and phenol.
De préférence, la résine phénolique est choisie parmi les résines novolaques (préparées par catalyse acide) ou résols (préparées par catalyse basique). Préférentiellement, la matrice du matériau selon l’invention est une matrice phénolique de type résole. Preferably, the phenolic resin is chosen from novolac resins (prepared by acid catalysis) or resols (prepared by basic catalysis). Preferably, the matrix of the material according to the invention is a phenolic matrix of the resole type.
Selon un mode de réalisation, la matrice du matériau de l’invention est une résine phénolique (matrice phénolique) et ledit matériau comprend un taux maximal de 60% en masse de fibres courtes de carbone telles que définies ci-dessus par rapport à la masse totale dudit matériau, lesdites fibres courtes de carbone présentant de préférence une porosité inférieure à 15%. According to one embodiment, the matrix of the material of the invention is a phenolic resin (phenolic matrix) and said material comprises a maximum rate of 60% by mass of short carbon fibers as defined above with respect to the mass total of said material, said short carbon fibers preferably exhibiting a porosity of less than 15%.
Selon un mode de réalisation, le matériau comprend au moins 10% en masse de fibres courtes de carbone telles que définies ci-dessus par rapport à la masse totale dudit matériau. According to one embodiment, the material comprises at least 10% by mass of short carbon fibers as defined above relative to the total mass of said material.
De préférence, la matrice du matériau de l’invention est une résine phénolique et ledit matériau comprend de 25% à 40% en masse de fibres courtes de carbone telles que définies ci-dessus par rapport à la masse totale dudit matériau, lesdites fibres courtes de carbone présentant une porosité inférieure à 5%. Preferably, the matrix of the material of the invention is a phenolic resin and said material comprises from 25% to 40% by mass of short carbon fibers. as defined above with respect to the total mass of said material, said short carbon fibers having a porosity of less than 5%.
L’augmentation de la teneur en fibres courtes de carbone permet d’augmenter la conductivité du matériau sans en dégrader les propriétés ablatives, ce qui permet de limiter l’élévation de température en face avant et de limiter la perte de masse sans compromettre les performances isolantes du matériau. The increase in the content of short carbon fibers makes it possible to increase the conductivity of the material without degrading its ablative properties, which makes it possible to limit the rise in temperature on the front face and to limit the loss of mass without compromising performance insulating material.
Un matériau particulièrement préféré selon l’invention comprend une matrice phénolique renforcée à 25% en masse de fibres courtes de carbone telles que définies ci-dessus présentant une porosité faible, notamment inférieure à 5%. De préférence, la taille des pores des fibres de carbone est inférieure à 1 mm. Les caractéristiques fonctionnelles du matériau résultent du compromis entre la conductivité thermique du matériau et sa tenue à l’érosion du jet. A particularly preferred material according to the invention comprises a phenolic matrix reinforced with 25% by mass of short carbon fibers as defined above, having low porosity, in particular less than 5%. Preferably, the pore size of the carbon fibers is less than 1 mm. The functional characteristics of the material result from the compromise between the thermal conductivity of the material and its resistance to jet erosion.
Selon un mode de réalisation, la matrice du matériau de l’invention est une résine époxy. According to one embodiment, the matrix of the material of the invention is an epoxy resin.
Selon un mode de réalisation, le matériau composite ablatif selon l’invention comprend une matrice qui est une résine époxy, et comprend un taux maximal de 60% en masse de fibres courtes de carbone telles que définies ci-dessus par rapport à la masse totale dudit matériau, ledit matériau présentant une porosité inférieure à 15%. According to one embodiment, the ablative composite material according to the invention comprises a matrix which is an epoxy resin, and comprises a maximum rate of 60% by mass of short carbon fibers as defined above relative to the total mass. of said material, said material having a porosity of less than 15%.
Selon un mode de réalisation, le matériau comprend au moins 10% en masse de fibres courtes de carbone telles que définies ci-dessus par rapport à la masse totale dudit matériau. According to one embodiment, the material comprises at least 10% by mass of short carbon fibers as defined above relative to the total mass of said material.
Selon un mode de réalisation, le matériau composite ablatif comprend, à titre de matrice, une résine époxy choisie parmi les résines époxy ignifugées. According to one embodiment, the ablative composite material comprises, as a matrix, an epoxy resin chosen from flame retardant epoxy resins.
A titre de résines époxy ignifugées préférées, on peut citer par exemple les résines époxy riches en carbone, notamment avec un résidu carboné à 1 000°C sous azote compris entre 20% et 80% en masse. As preferred flame-retardant epoxy resins, mention may be made, for example, of epoxy resins rich in carbon, in particular with a carbonaceous residue at 1000 ° C. under nitrogen of between 20% and 80% by mass.
Selon un mode de réalisation préféré, lorsque la matrice est une résine époxy, le matériau de l’invention comprend en outre de la poudre de carbone, de préférence en une teneur massique comprise entre 5% et 20% par rapport à la masse totale dudit matériau. According to a preferred embodiment, when the matrix is an epoxy resin, the material of the invention further comprises carbon powder, preferably in a mass content of between 5% and 20% relative to the total mass of said material.
A titre de poudre de carbone, on peut notamment citer de la poudre de carbone dont la taille des particules est inférieure à 1 mm. La présente invention concerne également un procédé de préparation du matériau composite ablatif tel que défini ci-dessus, comprenant le mélange de la matrice et du renfort tels que définis ci-dessus. As carbon powder, mention may in particular be made of carbon powder, the particle size of which is less than 1 mm. The present invention also relates to a process for preparing the ablative composite material as defined above, comprising the mixing of the matrix and the reinforcement as defined above.
La présente invention concerne également un procédé de préparation d’une pièce de matériau composite ablatif tel que défini ci-dessus. Ce procédé consiste essentiellement à réaliser un moulage par compression (moule/mandrin). Le procédé de préparation et les paramètres associés permettent de piloter la qualité finale et les caractéristiques du matériau obtenu. The present invention also relates to a process for preparing a part of ablative composite material as defined above. This process essentially consists of performing compression molding (mold / mandrel). The preparation process and the associated parameters make it possible to control the final quality and the characteristics of the material obtained.
Selon un mode de réalisation, le procédé de l’invention comprend une étape de mélange de la matrice et du renfort, et une étape de moulage par compression dudit mélange. According to one embodiment, the method of the invention comprises a step of mixing the matrix and the reinforcement, and a step of compression molding said mixture.
Ainsi, la présente invention concerne également un procédé de préparation d’une pièce de matériau composite ablatif tel que défini ci-dessus, comprenant une résine phénolique à titre de matrice. Thus, the present invention also relates to a process for preparing a part of ablative composite material as defined above, comprising a phenolic resin as a matrix.
La présente invention concerne donc également un procédé de préparation d’une pièce de matériau composite ablatif tel que défini ci-dessus, dans lequel la matrice est une résine phénolique, et comprenant de 10% à 60% en masse de fibres courtes de carbone par rapport à la masse totale dudit matériau. The present invention therefore also relates to a process for preparing a part of ablative composite material as defined above, in which the matrix is a phenolic resin, and comprising from 10% to 60% by mass of short carbon fibers by weight. relative to the total mass of said material.
Ledit procédé est constitué de plusieurs étapes permettant la mise en oeuvre de l’invention. Le cycle de fabrication comprend une mise en pression et température du mélange suivant plusieurs cycles différents (couples température / pression) permettant d’obtenir les caractéristiques requises pour le matériau. Said method consists of several steps allowing the implementation of the invention. The manufacturing cycle includes pressurization and temperature of the mixture according to several different cycles (temperature / pressure pairs) to obtain the characteristics required for the material.
Le cycle de mise en oeuvre est adapté à la nature de la résine phénolique utilisée. Le paramètre essentiel à la mise en oeuvre est donc le couplage entre la pression et la température. Une mise en oeuvre par compression est impérative pour obtenir un matériau répondant aux performances souhaitées. Un mélange homogène et une répartition parfaitement des fibres dans le mélange garantissent des performances du premier ordre. The processing cycle is adapted to the nature of the phenolic resin used. The essential parameter for implementation is therefore the coupling between the pressure and the temperature. An implementation by compression is imperative to obtain a material meeting the desired performance. A homogeneous mixture and a perfect distribution of fibers in the mixture guarantee first-class performance.
La présente invention concerne également un procédé de préparation d’une pièce de matériau composite ablatif tel que défini ci-dessus, comprenant une résine époxy à titre de matrice. La présente invention concerne donc également un procédé de préparation d’une pièce de matériau composite ablatif tel que défini ci-dessus, dans lequel la matrice est une résine époxy, et comprenant entre 10% et 60% en masse de fibres courtes de carbone par rapport à la masse totale dudit matériau. Ledit procédé est constitué de plusieurs étapes permettant la mise en oeuvre de l’invention. Le cycle de fabrication comprend une mise en pression et température du mélange suivant plusieurs cycles différents (couples température / pression) permettant d’obtenir les caractéristiques requises pour le matériau. The present invention also relates to a process for preparing a part of ablative composite material as defined above, comprising an epoxy resin as a matrix. The present invention therefore also relates to a process for preparing a part of ablative composite material as defined above, in which the matrix is an epoxy resin, and comprising between 10% and 60% by mass of short carbon fibers by weight. relative to the total mass of said material. Said method consists of several steps allowing the implementation of the invention. The manufacturing cycle includes pressurization and temperature of the mixture according to several different cycles (temperature / pressure couples) making it possible to obtain the characteristics required for the material.
Le cycle de mise en oeuvre est adapté à la nature de la résine époxy utilisée. Le paramètre essentiel à la mise en oeuvre est donc le couplage entre la pression et la température. Une mise en oeuvre par compression est impérative pour obtenir un matériau répondant aux performances souhaitées. Un mélange homogène et une répartition parfaitement des fibres dans le mélange garantissent des performances du premier ordre. The processing cycle is adapted to the nature of the epoxy resin used. The essential parameter for implementation is therefore the coupling between the pressure and the temperature. An implementation by compression is imperative to obtain a material meeting the desired performance. A homogeneous mixture and a perfect distribution of fibers in the mixture guarantee first-class performance.
La présente invention concerne également une pièce de matériau composite ablatif, ledit matériau étant tel que défini ci-dessus. De préférence, la présente invention concerne une pièce de matériau composite ablatif obtenue par le procédé susmentionné. The present invention also relates to a part of ablative composite material, said material being as defined above. Preferably, the present invention relates to a part of ablative composite material obtained by the aforementioned method.
La présente invention concerne également un procédé de protection thermique de la surface d’un lanceur de munition propulsée par un carburant, comprenant l’application d’une pièce telle que définie ci-dessus sur ladite surface. The present invention also relates to a method of thermal protection of the surface of a fuel-propelled munition launcher, comprising the application of a part as defined above to said surface.
De préférence, le procédé de protection thermique de l’invention est destiné à protéger l’environnement de tir vis à vis des départs de munitions, notamment celles propulsées par carburant solide. Preferably, the thermal protection method of the invention is intended to protect the firing environment against the releases of ammunition, in particular those propelled by solid fuel.
Parmi les équipements permettant le lancement de munition propulsée par un carburant, on peut citer par exemple les lanceurs verticaux, inclinables ou inclinés de missiles. Among the equipment allowing the launching of ammunition propelled by a fuel, mention may be made, for example, of vertical, tilting or tilted missile launchers.
La présente invention concerne donc également les lanceurs de munitions propulsées par un carburant, comprenant au moins une pièce de matériau composite ablatif telle que définie ci-dessus. EXEMPLES The present invention therefore also relates to fuel-propelled munitions launchers, comprising at least one piece of ablative composite material as defined above. EXAMPLES
Exemple 1 : Préparation d’une pièce de matériau ablatif comprenant une résine phénolique Example 1: Preparation of a piece of ablative material comprising a phenolic resin
Une pièce de matériau comprenant une résine phénolique selon l’invention est préparée selon le procédé décrit dans le tableau 1 ci-dessous. A piece of material comprising a phenolic resin according to the invention is prepared according to the method described in Table 1 below.
Tableau 1 Table 1
Exemple 2 : Préparation d’une pièce de matériau ablatif comprenant une résine époxy Example 2: Preparation of a piece of ablative material comprising an epoxy resin
Une pièce de matériau comprenant une résine époxy selon l’invention est préparée selon le procédé décrit dans le tableau 2 ci-dessous. A piece of material comprising an epoxy resin according to the invention is prepared according to the method described in Table 2 below.
Tableau 2 Table 2
Exemple 3 : Propriétés ablatives des matériaux Example 3: Ablative properties of materials
Les inventions basées sur les résines phénoliques et époxy présentent une répartition homogène des fibres de carbone sans orientation préférentielle. Inventions based on phenolic and epoxy resins exhibit a homogeneous distribution of carbon fibers without preferential orientation.
Les principales caractéristiques thermo-physiques sont reportées dans le tableau ci-dessous. The main thermo-physical characteristics are shown in the table below.
Tableau 3 Table 3
Lors de la dégradation, le matériau doit se dégrader de manière sure et linéaire. Cela signifie que l’érosion doit être progressive et contrôlée avec une bonne linéarité de la cratérisation lors de l’augmentation du temps d’exposition. Lors de la dégradation, le charbon issu de la dégradation doit rester confiné en partie supérieure de la plaque et l’affectation thermique ne doit pas engendrer de dégradation en profondeur de la protection thermique. During degradation, the material must degrade in a safe and linear manner. This means that the erosion must be gradual and controlled with good linearity of craterization as the exposure time increases. During degradation, the carbon resulting from the degradation must remain confined to the upper part of the plate and the thermal affectation must not lead to in-depth degradation of the thermal protection.

Claims

REVENDICATIONS
1. Matériau composite ablatif comprenant une matrice et un renfort, caractérisé en ce que : 1. Ablative composite material comprising a matrix and a reinforcement, characterized in that:
la matrice est une résine phénolique ou une résine époxy et the matrix is a phenolic resin or an epoxy resin and
le renfort est formé de fibres courtes de carbone de longueur comprise entre 0,5 mm et 20 mm, et de diamètre compris entre 6 pm et 20 pm et dont la porosité est inférieure à 15%. the reinforcement is formed of short carbon fibers with a length of between 0.5 mm and 20 mm, and of a diameter of between 6 μm and 20 μm and the porosity of which is less than 15%.
2. Matériau composite ablatif selon la revendication 1 , dans lequel la matrice est une résine phénolique, et comprenant au maximum 60% en masse de fibres courtes de carbone par rapport à la masse totale dudit matériau. 2. Ablative composite material according to claim 1, wherein the matrix is a phenolic resin, and comprising at most 60% by mass of short carbon fibers relative to the total mass of said material.
3. Matériau composite ablatif selon la revendication 2, dans lequel la résine phénolique est choisie parmi les résines novolaques ou résols. 3. Ablative composite material according to claim 2, wherein the phenolic resin is chosen from novolac or resol resins.
4. Matériau composite ablatif selon la revendication 1 , dans lequel la matrice est une résine époxy, et comprenant au maximum 60% en masse de fibres courtes de carbone par rapport à la masse totale dudit matériau, lesdites fibres courtes de carbone présentant une porosité inférieure à 15%. 4. Ablative composite material according to claim 1, wherein the matrix is an epoxy resin, and comprising at most 60% by weight of short carbon fibers relative to the total weight of said material, said short carbon fibers having a lower porosity. at 15%.
5. Matériau composite ablatif selon la revendication 4, dans lequel la résine époxy est choisie parmi les résines époxy ignifugées. 5. Ablative composite material according to claim 4, wherein the epoxy resin is chosen from flame retardant epoxy resins.
6. Matériau composite ablatif selon la revendication 4 ou 5, comprenant en outre de la poudre de carbone, de préférence en une teneur massique comprise entre 5% et 20 % par rapport à la masse totale dudit matériau. 6. Ablative composite material according to claim 4 or 5, further comprising carbon powder, preferably in a mass content of between 5% and 20% relative to the total mass of said material.
7. Procédé de préparation du matériau composite ablatif selon l’une quelconque des revendications 1 à 6, comprenant le mélange de la matrice et du renfort. 7. A method of preparing the ablative composite material according to any one of claims 1 to 6, comprising mixing the matrix and the reinforcement.
8. Pièce de matériau composite ablatif selon l’une quelconque des revendications 1 à 6. 8. Part of ablative composite material according to any one of claims 1 to 6.
9. Procédé de protection thermique de la surface d’un lanceur de munition propulsée par un carburant, comprenant l’application d’une pièce selon la revendication 8 sur ladite surface. 9. A method of thermal protection of the surface of a fuel-powered munition launcher, comprising applying a part according to claim 8 to said surface.
10. Lanceur de munition propulsée par un carburant comprenant au moins une pièce de matériau composite ablatif selon la revendication 8. 10. A fuel-propelled munition launcher comprising at least one piece of ablative composite material according to claim 8.
EP20735592.6A 2019-07-03 2020-07-02 New ablative composite material Pending EP3994205A1 (en)

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JPS5424416B1 (en) * 1968-07-02 1979-08-21
JPS548694B1 (en) * 1977-10-28 1979-04-18
FR2684679B1 (en) * 1991-12-05 1995-03-17 Aerospatiale MOLDING MATERIAL CONTAINING REFRACTORY FIBERS, FOR USE IN THE MANUFACTURE OF ABLATABLE PARTS, PROCESS FOR ITS MANUFACTURE AND ITS APPLICATIONS.
FR2707287B1 (en) * 1993-07-05 1995-10-06 Europ Propulsion Method of manufacturing a part made of composite material comprising a fibrous reinforcement consolidated by the liquid route.
FR2959237B1 (en) * 2010-04-22 2014-03-14 Astrium Sas THERMAL PROTECTION MATERIAL
JP2011252238A (en) * 2010-05-31 2011-12-15 Teijin Techno Products Ltd Porous para-type wholly aromatic polyamide fiber
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FR3098220A1 (en) 2021-01-08
WO2021001484A1 (en) 2021-01-07

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