• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The invention relates to a method of protection against oxidation of a composite material part comprising carbon, the method comprising the following steps: a) applying, on at least a part of the external surface of the part, a coating composition in the form of an aqueous suspension comprising: - a metal phosphate, - a powder of a compound comprising titanium, and - a B4C powder, and b) heat treatment of the coating composition applied during step a ), a treatment temperature between 330 ° C and 730 ° C being imposed during the heat treatment to obtain on the outer surface of the part a coating comprising a first phase in which the metal phosphate is in crystalline form and a second phase in which the metal phosphate is in amorphous form.
    公开号:FR3019818A1
    申请号:FR1453198
    申请日:2014-04-10
    公开日:2015-10-16
    发明作者:Nathalie Nicolaus；Veronique Fontarnou；Nadia Roussarie；Julien Sniezewski
    申请人:Messier Bugatti Dowty SA；
    IPC主号:
    专利说明:

    [0001] BACKGROUND OF THE INVENTION The invention relates to the protection against oxidation of carbon-containing composite material parts, that is to say of a material comprising a fiber reinforcement densified by a matrix and in wherein the fibrous reinforcement and / or the matrix and / or interphase coating between fibers of the reinforcement and matrix is carbon. A particular field of application of the invention is the protection against oxidation of parts made of carbon / carbon (C / C) composite material, in particular discs of C / C composite brakes, and in particular of brake disks. aircraft, for example airplanes, or land vehicle brake discs. In an oxidizing medium, the ability of such parts to maintain good mechanical properties at elevated temperatures is conditioned by the presence of effective protection against carbon oxidation. Indeed, after its development, the composite material usually has a residual internal porosity that provides the ambient environment access to the heart of the material. In addition, in some applications, the oxidation protection must remain effective in the presence of moisture and / or carbon oxidation catalysts. This is particularly the case for composite aircraft brake discs C / C which may be exposed to moisture on the tracks and come into contact with carbon oxidation catalysts provided for example by potassium acetates or formates present in de-icing products commonly used on runways. Document US 2008/311301 describes a process for the protection against oxidation of porous material parts containing carbon, in particular brake discs made of C / C composite material, which consists in applying a composition in an aqueous medium comprising: a metal phosphate in aqueous solution such as aluminum hydrogen phosphate, or monoaluminum phosphate Al (H2PO4) 3 ("MALP": "Mono-Aluminum-Phosphate"), a boron or boron compound powder, such as B2O3, titanium powder and an alkaline or alkaline-earth carbon oxidation catalyst for forming a PO-Ti-M bond bound by B2O3 boron oxide in the presence of oxygen. trapping the element M. A final heat treatment is carried out at about 350 ° C in air and, optionally, at about 700 ° C under a non-oxidizing atmosphere (N2). Such a composition is effective with respect to the catalytic oxidation of carbon. However, the use of boron powder in an industrial environment may require the implementation of special precautions because of its toxicity. In addition, B2O3 boron oxide has a high sensitivity to moisture and vaporizes at temperatures below 900 ° C. In addition, the composition may be unstable and difficult to use, boron and B2O3 reacting with monoaluminum phosphate. Document US 2007/0026153 also describes a process for the protection of parts made of composite material containing carbon, in particular brake discs made of C / C composite material. In a first step of the process, an internal protection is put in place by impregnation with an aqueous solution of metal phosphate, such as monoaluminum phosphate, and heat treatment at about 700 ° C under nitrogen (N2). Then, a liquid composition containing, in an aqueous medium, colloidal silica SiO 2, a borosilicate glass powder of "Pyrex®" type and TiB 2 titanium diboride powder is applied. In use in an oxidizing medium, TiB2 oxidizes forming B2O3, ensuring the regeneration of B2O3 and the conservation of a borosilicate glass phase having a healing power by passing to the pasty state from 600 ° C. However, the life of the protection is relatively limited during repeated exposures to a humid environment due to the disappearance of B2O3 and the consumption of TiB2. In addition, an improvement of the protection with respect to the catalytic oxidation of carbon could be desirable in particular with respect to potassium formate de-icglers which, because of their surface tension, can have a relatively The object of the invention is to provide a process for improving the anti-oxidation protection of carbon-containing composite material parts, in a humid environment at a high temperature. temperature 5 as well as in the presence of carbon oxidation catalysts, while being easy to implement especially for the manufacture of parts in large series. The object of the invention is also to provide novel processes for processing parts made of composite material containing carbon, making it possible to obtain improved performances when these parts are used for braking vehicles, especially in the aeronautical field. This object is achieved by means of a method of protection against the oxidation of a composite material part comprising carbon, the process comprising the following steps: a) application, on at least a part of the external surface of the part, a coating composition in the form of an aqueous suspension comprising: - a metal phosphate, - a powder of a compound comprising titanium, and a - powder of 134C, and b) heat treatment of the coating composition applied during step a), a treatment temperature between 330 ° C and 730 ° C being imposed during the heat treatment to obtain on the outer surface of the part a coating comprising a first phase in which the metal phosphate is under crystalline form and a second phase in which the metal phosphate is in amorphous form. The detection of the crystalline and amorphous phases of metal phosphate can be carried out by NMR spectroscopy (1D and 2D) of solid nuclei such as 31P and 27AI. The invention relies, on the one hand, on the choice of new coating compositions and, on the other hand, on the application of a particular temperature once the coating composition has been applied. During the heat treatment, a sufficiently high temperature is imposed in order to obtain in the coating a combination of at least one crystalline metal phosphate phase and at least one amorphous metal phosphate phase. However, the temperature imposed during step b) remains low enough to avoid crystallizing the entire metal phosphate and, therefore, maintain an amorphous metal phosphate phase in the coating formed. The metal phosphate present in the coating makes it possible both to provide a binder function, a protection function with respect to the catalytic oxidation of carbon and a self-healing function. These advantageous properties result from the joint presence in the coating of amorphous metal phosphate and crystalline metal phosphate. Indeed, the amorphous metal phosphate ensures by its ability to lay in the amorphous state the self-healing function by filling the pores and / or cracks present on the surface of the workpiece to the temperatures of use thereof in order to to prevent oxidizing species from entering the room (protection against thermal oxidation). The amorphous phase also ensures good cohesion between the coating and the underlying part, which may have been protected beforehand by an internal protective layer as will be detailed below. The crystalline metal phosphate makes it possible to confer protection against the catalytic oxidation of carbon by trapping carbon oxidation catalysts, the latter being for example derived from track or road de-icer products, detergents or products. defrosting. Thus, thanks to the combination of amorphous metal phosphate and crystalline metal phosphate in the coating formed, the present invention advantageously makes it possible to give carbon substrates very good protection against oxidation in the presence of catalysts. oxidation over a wide temperature range.
    [0002] As a source of boron capable of generating B2O3, boron carbide B4C is relatively inexpensive, more commercially available and easier to use than boron B. The presence of B4C also makes it possible to obtain a coating which imparts better protection against oxidation at high temperature compared to the use of B or ZrB2 in particular. In addition, unlike B and B2O3, B4C reacts very little with the metal phosphate, which makes it possible to maintain a stable coating composition and B4C has a lower oxidation kinetics than that of B and makes it possible to constitute a source of boron sustainable despite the elimination of B2O3 in the presence of water.
    [0003] When the coating composition comprises compounds comprising non-oxidized titanium, the latter may advantageously be oxidized by the oxygen of the ambient medium and, consequently, reduce the amount of oxygen available for oxidation of the carbon. Once in an oxidized form, the compound comprising titanium can integrate into the vitreous phase ensuring the protection of the workpiece at high temperature, and in doing so can adjust its softening temperature so that it is as close as possible to the temperature of use of the room. This advantageously allows the vitreous phase to have an ideal softening temperature to ensure optimum protection at the temperature of use of the workpiece. In particular, during the heat treatment, the treatment temperature may preferably be imposed for a period greater than or equal to 1 hour, for example between 1 hour and 15 hours.
    [0004] The heat treatment can be carried out under an oxidizing atmosphere, for example under air. Alternatively, the heat treatment can be carried out under an inert atmosphere, for example under nitrogen. The proportion of amorphous metal phosphate obtained in the coating after step b) may depend on the treatment temperature and the duration of application thereof. For example, an increase in the duration of application of the treatment temperature can lead to a lowering of the proportion of amorphous metal phosphate in the coating. Preferably, after step b), the coating obtained can be such as the ratio (mass of amorphous metal phosphate in the coating) / (mass of amorphous metal phosphate in the coating + mass of metal phosphate under crystalline form in the coating) is greater than or equal to 0.1, preferably 0.2. In particular, this ratio may be between 0.1 and 0.7, preferably between 0.2 and 0.5. Advantageously, the coating composition may further comprise an organic dispersing agent. The organic dispersing agent is advantageously sufficiently wetting to give the coating formed a very good adhesion to the underlying part. The organic dispersing agent may be a water-soluble and non-ionic organic dispersant, of the oxyethylenated fatty acid, oxyethylenated fatty alcohol, oxyethylenated alkylphenol or higher polyol ester type. The organic dispersing agent may also be an alkoxylated acetylenic polyol sold, for example, under the name "SurfynolC" by the company of the United States of America: Air Products Chemicals, Inc. It is also possible to use as organic dispersing agent products sold under the name "Levenol®" by the company KAO Corporation or "Marlophen NP9" by the company Sasol Gmbh. In an exemplary embodiment, the compound comprising titanium may be chosen from: titanium metal (Ti), titanium diboride (TiB2), titanium carbide (TiC), titanium dioxide (TiO2) and mixtures thereof . Preferably, the coating composition may comprise a metal titanium powder and / or a titanium diboride powder. The coating composition may further comprise a refractory filler. This charge may be present in the coating composition before step a) at a mass content of less than or equal to 5%. This charge may comprise one or more refractory oxides, nitrides or carbides (other than B4C). Furthermore, with regard to the metal phosphate used, the coating composition may comprise an aluminum phosphate, for example aluminum hydrogen phosphate AI (H 2 PO 4) 3 according to one embodiment of the process. the coating composition may comprise, before step a): the metal phosphate in a mass content of between 27% and 36%, the B4C powder in a mass content of between 11.5% and 21%, and the powder of the compound comprising titanium at a content by weight of between 8% and 18%.
    [0005] By "the coating composition comprising ... the powder of the compound having titanium in a mass content of between 8% and 18%", it is to be understood when the coating composition comprises a plurality of compounds having different titanium that the sum of the mass contents of the various compounds comprising titanium is between 8% and 18%. According to one embodiment of the process, the coating composition may comprise, before step a): aluminum phosphate in a mass content of between 27% and 36%, and B4C powder in a content of the weight of the compound comprising titanium in a mass content of between 8% and 18%, an alkoxylated acetylenic polyol in a mass content of between 0.1% and 1%, 5%, water in a mass content of between 33% and 50%, and optionally a refractory filler in a mass content of less than or equal to 5%. In particular, the coating composition may, before step a) consist of: - aluminum phosphate in a mass content of between 27% and 36%, a 134C powder in a mass content of between 11, 5% and 21%, a powder of at least one compound comprising titanium in a mass content of between 8% and 18%, and an alkoxylated acetylenic polyol in a content by weight of between 0.1% and 1.5%. %, - water in a mass content between 33% and 50 ° h, and - optionally a refractory filler in a mass content less than or equal to 5%.
    [0006] In an exemplary embodiment, the coating composition may further comprise a self-healing vitreous compound. In an exemplary embodiment, at least one inner protective layer may be formed, before step a), by impregnating at least part of the composite material part with an impregnating composition comprising a metal phosphate. The impregnating composition may be an aqueous solution. The impregnating composition may comprise an aluminum phosphate, for example aluminum hydrogen phosphate. The present invention is also directed to a coating composition in the form of an aqueous suspension comprising: - a metal phosphate, - a powder of a compound comprising titanium, and - a B4C powder. The coating composition according to the invention may be intended to be used for carrying out a process as described above. In an exemplary embodiment, the composition may comprise: metal phosphate in a mass content of between 27% and 36%, and B4C powder in a mass content of between 11.5% and 21%, and powder of the compound comprising titanium in a mass content of between 8% and 18%. In one exemplary embodiment, the composition may comprise: aluminum phosphate in a mass content of between 27% and 36%, and B4C powder in a mass content of between 11.5% and 21%; the powder of the compound comprising titanium in a mass content of between 8% and 18%, an alkoxylated acetylenic polyol in a mass content of between 0.1% and 1.5%, and 3019% of water in a mass content of between 33% and 50%. In particular, the composition may consist of: aluminum phosphate in a mass content of between 27% and 36%, a powder of 134C in a mass content of between 11.5% and 21%, powder of at least one compound comprising titanium in a mass content of between 8% and 18%; an alkoxylated acetylenic polyol in a mass content of between 0.1% and 1.5%; a mass content of between 33% and 50%, and optionally a refractory filler with a content by mass of less than or equal to 5%. More generally, the characteristics of the coating composition described above in the context of the process according to the invention apply to this aspect of the invention. Preferably, dry titanium may be used to form the titanium-containing compound present in the coating composition according to the invention. The use of dry titanium is economically advantageous because dry titanium is available in industrial quantities at a relatively low price. BRIEF DESCRIPTION OF THE DRAWINGS Other features and advantages of the method will become apparent on reading the following description, given by way of non-limiting indication, with reference to the appended drawings, in which: FIG. 1 shows successive steps of FIG. an example of a process according to the invention; FIG. 2 shows curves illustrating the variation in mass as a function of oxidation times for C / C composite material samples provided with protection against oxidation by a process according to the invention; FIGS. 3A and 3B show curves illustrating the variation in mass as a function of oxidation times for C / C composite material samples protected against oxidation by implementing processes according to the invention and exposed to a catalyst carbon oxidation; FIG. 4 shows the performances in terms of protection against oxidation of coating compositions incorporating various boron compounds; Figure 5 shows the performance in terms of protection against oxidation of coating compositions incorporating different compounds comprising titanium; FIG. 6 shows, in particular, the performances in terms of protection against oxidation of a coating composition comprising a vitreous compound of borosilicate type; FIG. 7 shows the performances in terms of protection against oxidation conferred by various processes according to the invention; and FIG. 8 compares the performances in terms of protection against oxidation conferred, on the one hand, by a method according to the invention and, on the other hand, by a method known from the state of the art. DETAILED DESCRIPTION OF EMBODIMENTS In the following description, protection against oxidation of C / C composite material parts, more particularly brake discs, is contemplated. More generally, the invention is applicable to the protection against oxidation of all parts made of composite material containing carbon. According to the particular embodiment of the method of FIG. 1, a first phase 10 consists in forming within the accessible porosity of the part, or part of the part to be protected, an internal protection comprising at least a metal phosphate capable in particular to provide protection against the catalytic oxidation of carbon. It is possible to proceed as described in US Pat. No. 5,853,821. A first step 12 consists in depositing a wetting agent within the accessible porosity of the composite material. An aqueous solution of a wetting agent such as, for example, the product marketed by the German company Sasol GmbH under the name "Marlophen NP9" is used for this purpose. After impregnation of the composite material with this wetting agent solution and drying (step 14), a first impregnating composition in the form of an aqueous solution containing a metal phosphate is applied to the entire outer surface of the piece or , selectively, on a part of the outer surface of the workpiece, for example by brushing or by spraying (ie spraying with a spray gun) (step 16). For example, an aqueous solution of aluminum hydrogen phosphate Al (H 2 PO 4) 3 is used. The metal phosphate may also be a zinc phosphate, for example having the following chemical formula: Zn 3 (PO 4) 2 × H 2 O, a manganese phosphate, for example having the following chemical formula: Mn (H 2 PO 4) 2.2H 2 O or a phosphate magnesium having for example the following chemical formula: Mg3 (PO4) 2.8H2O. The wetting agent present on the surface of the accessible pores of the composite material facilitates penetration of the impregnating composition within the accessible porosity of the composite material. Drying and heat treatment (step 18) are then carried out in order to limit the accessibility of the pore surface by means of an internal metal phosphate protection. The heat treatment is carried out by raising the temperature to a plateau of one or more hours at a temperature of between 200 ° C. and 750 ° C., for example about 700 ° C. under a non-oxidizing atmosphere, for example under nitrogen (N 2 ).
    [0007] A second phase of the process consists in forming a covering and covering outer protective coating. For this purpose, it is possible to use a second composition (also called a coating composition) consisting essentially of, that is to say at least 90% by weight, at least one metal phosphate, a boron carbide B4C powder, a titanium powder, at least one dispersing agent and water. The metal phosphate may be aluminum hydrogen phosphate Al (H 2 PO 4) 3. Such a compound is commercially available in aqueous solution at 48% -50% by weight. In the same way as above, a zinc, manganese or magnesium phosphate can be used. Boron carbide B4C may preferably be in the form of particles having a size of less than or equal to 30, for example less than or equal to 7.5 .mu.m. Unless otherwise stated, "size" refers to the size given by the statistical size distribution at half of the population, called D50. The powdered titanium used is preferably in the form of dry titanium particles (not suspended in water) having a size preferably of less than 150 μm. Refractory fillers other than B4C may be added in a proportion preferably of less than 10% by weight, for example one or more ceramic powders of the oxide, nitride or carbide type. The organic dispersing agent may be as mentioned above and, in particular, be an alkoxylated acetylenic polyol marketed under the name "Surfynol®", in particular "Surfynol® 440". As mentioned above, this organic dispersing agent can be sufficiently wetting to ensure a very good cohesion between the coating and the underlying part. The organic dispersing agent can indeed allow the metal phosphate of the second composition to penetrate the residual porosity to create strong chemical and mechanical anchoring points with the internal phosphate metal undercoat layer. The additional refractory fillers, for example one or more ceramics of the oxide, nitride or carbide type, may be in the form of particles preferably having a size of less than 150 μm. The second composition is applied for example by brushing or spraying (step 22) on the outer surface of the workpiece or a portion of that outer surface, preferably at the same locations as the first composition. In the case of carbon-based composite brake discs, the application of the first composition and the second composition may be limited to the non-friction outer surface portions, the frictional annular surface of an end disc a set of stator disks and rotors or opposite friction surfaces of the disks located between the end disks then being non-impregnated to avoid tampering with the tribological properties. Then, a final heat treatment is carried out (step 24) by raising the temperature gradually to a value between 330 ° C and 730 ° C, with a step of one or more hours at this temperature. The relatively moderate temperature of the heat treatment makes it possible to maintain a metal phosphate phase in the amorphous state, thus preserving its layability. The heat treatment of step 24 is not necessarily carried out under a non-oxidizing atmosphere. This heat treatment can be carried out under air or nitrogen. In particular, this heat treatment can be carried out under air up to 350 ° C. or under nitrogen above 350 ° C. The amount of second composition applied can be chosen to obtain during step b) a coating on the outer surface of the workpiece having an average thickness (arithmetic average) of between 20 μm and 150 μm. The invention advantageously provides a very good protection against oxidation with a coating having a significantly lower thickness than the known coatings of the prior art. The thickness of the coating is measured perpendicular to the outer surface of the coated part. Example 1 Aircraft brake disc C / C composite parts having a density of about 1.65 g / cm3 to about 1.9 g / cm3 and a residual volume porosity of about 6% to about 18% have been provided with an antioxidant protection as follows: - impregnation with a first composition formed of an aqueous solution of "Marlophen NP 9" and drying, - application of an aqueous solution of monoaluminum phosphate to 50% by weight of water by brush or by spraying (ie spraying with a spray gun) robotized, - heat treatment under a nitrogen atmosphere (N2) by progressive elevation of the temperature up to 700 ° C. and maintenance at this temperature for 1 hour. minimum hour, - brushing or spraying the second composition comprising in bulk: - 67% aqueous solution of monoaluminum phosphate to 50% by weight of water - 16.3% powder 134C at 2% at the most impurities, the grains of the powders re having a size less than 7.5 pm - 11% dry titanium powder of particle size up to 150 pm (grain size: about 90 pm) or, lower, up to 50 pm (grain size Approximately 20pm) - 4.7% water - 1% "Surfynol® 440" - heat treatment in air by gradually raising the temperature to 350 ° C and maintaining at this temperature for 10 hours.
    [0008] According to the parts, the layer of coating composition (layer of second composition) had before heat treatment a mass per unit area ranging between 16 and 22 mg / cm 2. According to the parts, the coating obtained after the heat treatment had a thickness varying from 40 μm to 70 μm.
    [0009] Two similar additional tests were carried out in which: the final heat treatment was carried out under air by progressive elevation of the temperature to 350 ° C. and maintained at this temperature for 5 hours, and the final heat treatment was carried out under air by gradually raising the temperature to 450 ° C and maintaining at this temperature for 8 hours. The 1D / 2D NMR spectroscopic analysis of the solid nuclei 31P and 27AI made it possible to quantify the mass proportions of the crystalline and amorphous phases of metal phosphate in the coating obtained. The results obtained are shown in Table 1 below. Sample Proportion phosphate Proportion amorphous metal crystalline metal phosphate Example 1 76% 24% 350 ° C, 5 hours, air Example 1 89% 11% 450 ° C, 8 hours, air Table 1 For this example of second composition, the temperature at From which a coating comprising both amorphous monoaluminum phosphate and crystalline monoaluminum phosphate is begun to be obtained at about 330 ° C. Parts with oxidation protection were subjected to the following oxidation protocols: - P650: exposure at 650 ° C under air for 4 h, repeated 6 times with room temperature return after each exposure, - P850: exposure at 850 ° C under air for 30 min, repeated 6 times with return to ambient temperature after each exposure, - P1200: exposure at 650 ° C for 4 h, return to ambient temperature, then exposure to 1200 ° C for 15 h min, return to room temperature, then twice to 650 ° C for 4 h with intermediate return at room temperature, - P1200 H2O: same protocol as P1200 by adding 24 h in water at room temperature after the flash at 1200 ° C and before the two final exposures at 650 ° C, P650AcK: exposure under air at 650 ° C for 4 h, then pollution with potassium acetate at room temperature, then two exposures in air at 650 ° C for 4 hours with return intermediate at room temperature, P1200AcK: same protocol as P650AcK by adding an exposure under air at 1200 ° C for 15 minutes after the first exposure under air at 650 ° C, the pollution AcK being carried out after the flash at 1200 ° vs.
    [0010] FIG. 2 shows, for different parts, the relative mass loss in% measured during the oxidation protocols without potassium acetate pollution, the protection having been carried out with a second composition containing titanium powder with a particle size of less than or equal to at 150 pm. There is a very good resistance to oxidation including high temperature and in the presence of water since the mass loss is less than 5%. For comparison, for an oxidation protocol similar to protocol P1200H2O above, the mass loss observed with parts protected according to the method of US 2007/0026153 is about 7%. FIG. 3A shows the relative mass loss in ° A) measured during the oxidation protocols with the potassium acetate pollution, the protection having been carried out with a second composition containing titanium powder with a particle size of less than 50 pm. FIG. 3B also shows the performances obtained after carrying out a process similar to that described above and treatment with a second composition having the following mass composition: following 27.7% of monoaluminum phosphate, 13.5% B4C powder, 9% titanium powder, 0.8% Surfynol®, 49% water. As illustrated in FIG. 3B, such a composition provides the implementation of a P1200 AcK protocol with excellent protection against catalytic oxidation.
    [0011] Example 2: Technical effect produced by the use of a B4C powder In this example, the performances in terms of the oxidation resistance of three compositions were compared. The three compositions tested differ according to the chemical nature of the boron compound present.
    [0012] More specifically, parts made of C / C composite material of aircraft brake discs having a density of between 1.65 g / cm3 and 1.9 g / cm3 approximately and a residual porosity ranging from 6% to 18% approximately have been provided with an antioxidant protection as follows: - impregnation with a first composition formed of an aqueous solution of "Marlophen NP 9" and drying, - brushing with an aqueous solution of monoaluminum phosphate at 50% by weight of water, - heat treatment under a nitrogen atmosphere (N2) by gradual raising of the temperature to 700 ° C. and keeping at this temperature for at least 1 hour, - brushing of the second composition following comprising by mass: - 34% of mono-aluminum phosphate, - 16% of boron compound (B, ZrB2 or B4C according to the tested composition), - 11.2% of titanium powder, - 38.8% of water, - heat treatment under air by progressive rise in temperature up to at 350 ° C and maintained at this temperature for 10 h. FIG. 4 shows the performances in terms of protection against oxidation of the various compositions according to the nature of the boron compound present (protocol used: P1200 AcK).
    [0013] Incorporation in the coating compositions according to the invention of a B4C powder gives significantly higher results in terms of protection against oxidation compared to the use of other boron powders, such as powders of boron or ZrB2.
    [0014] Example 3: Tests by varying the chemical nature of the compound comprising titanium In this test, the performance in terms of oxidation resistance conferred by different coating compositions according to the invention were evaluated. Each of these coating compositions incorporates a compound having different titanium.
    [0015] Aircraft brake disc C / C composite parts having a density of about 1.65 g / cm3 to about 1.9 g / cm3 and a residual volume porosity of about 6% to about 18% have been provided. an anti-oxidation protection as follows: - impregnation with a first composition formed of an aqueous solution of "Marlophen NP 9" and drying, - brushing with a 50% aqueous solution of mono-aluminum phosphate in mass of water, - heat treatment under a nitrogen atmosphere (N2) by gradual raising of the temperature to 700 ° C. and keeping at this temperature for at least 1 hour, - brushing of the second composition, - heat treatment in air by gradually raising the temperature to 350 ° C and maintaining at this temperature for 10 hours. The mass formulations of the second compositions used are given below: Composition "Ti" (the corresponding curve is designated "Ti" in the drawings): 34% of mono-aluminum phosphate, 20-16% of B4C powder, - 11.2% titanium powder, - 38.8% water, - "TiB2" composition (the corresponding curve is designated "TiB2" in the drawings): 25 - 34.4% monoaluminum phosphate, - 14.2% B4C powder, - 16% TiB2 powder, - 1% Surfynol®, - 34.4% water, - "TiC" composition (the corresponding curve is designated as "TiC" in the drawings): - 36% monoaluminum phosphate, - 12.2% B4C powder, - 14.7% TiC powder, 35-1% Surfynol®, 1 9 8 1 8 19 - 36% water, - Composition "TiO2" (the corresponding curve is designated "TiO2" in the drawings): - 34.75% mono-aluminum phosphate, 5 - 11.8% of B4C powder, - 17.8% of TiO 2 powder, - 1% of Surfynol®, - 34.75 % of water. As illustrated in FIG. 5, the use of various compounds comprising titanium makes it possible to obtain a very good resistance to oxidation, even at high temperature and in the presence of water, since the mass loss is less than 5%. . Example 4: Composition comprising a self-healing vitreous compound A composite C / C aircraft brake disc component having a density of from about 1.65 g / cm3 to about 1.9 g / cm3 and a residual volume porosity of from about 6% to about 18% was provided with an antioxidant protection as follows: - impregnation with a first composition formed of an aqueous solution of "Marlophen NP 9" and drying, - brushing with an aqueous solution of monoaluminum phosphate containing 50% by weight of water, - heat treatment under a nitrogen atmosphere (N 2) by gradual raising of the temperature to 700 ° C. and keeping at this temperature for at least 1 hour - Brush application of the second composition comprising in bulk: - 30% of mono-aluminum phosphate, - 14.5% of B4C powder, 30 - 9.8% of titanium powder, - 1% of Surfynol® , - 34% water, - 10.7% "Pyrex®" glass powder - heat treatment under air by gradually raising the temperature to 350 ° C and maintaining at this temperature for 10 hours.
    [0016] The corresponding curve is designated "Pyrex®" in the drawings. The composition of Pyrex is substantially the following (in percentages by weight): SiO 2: 80.60% B 2 O 3: 12.60% Na 2 O 3: 4.2% Al 2 O 3: 2.25% - Cl: 0.1% CaO: 0.1 % MgO: 0.05% - Fe2O3: 0.05% It is found that such a coating composition provides excellent protection against oxidation (see Figure 6). For the record, the "TiC" and "TiO2" curves introduced above are present in FIG. 6. EXAMPLE 5 Influence of the Temperature of the Heat Treatment Performed in Step b) In this example, a piece of material C / C composite aircraft brake disk having a density of about 1.65 g / cm3 to about 1.9 g / cm3 and a residual volume porosity of about 6% to about 18% has been provided with anti-oxidation as follows: - impregnation with a first composition formed of an aqueous solution of "Marlophen NP 9" and drying, - brushing with an aqueous solution of monoaluminum phosphate at 50% by weight water, - heat treatment under a nitrogen atmosphere (N2) by gradual raising of the temperature to 700 ° C. and keeping at this temperature for at least 1 hour, - brushing of the second composition comprising, by weight: - 33.5% of monoaluminum phosphate ue, 35 - 16.3% of B4C powder, 11% of titanium powder, 1% of Surfynol®, 38.2% of water, heat treatment in air by progressive rise in temperature up to at 650 ° C and hold at this temperature for at least 1 hour. The corresponding curve is designated "Example 5" in the drawings. Figure 7 shows that after thermal treatment at 650 ° C good oxidation resistance properties are obtained. Figure 7 also includes the curves "Ti" and "Pyrex" described above. The 1D / 2D NMR spectroscopic analysis of the solid nuclei 31P and 27AI made it possible to quantify the mass proportions of the crystalline and amorphous phases of metal phosphate in the coating obtained. The results obtained are shown in Table 2 below. Sample Proportion phosphate Proportion amorphous metal crystalline metal phosphate Example 5 59% 41% 650 ° C, 1 hour, N2 Table 2 Figure 8 compares the performance in terms of protection against oxidation (P1200 H2O protocol) of a coating constituted a completely crystalline metal phosphate composition (designated in FIG. 8 by "fully crystalline metal phosphate") and a coating obtained after treatment according to example 5 according to the invention. FIG. 8 shows that the protective coating obtained after implementation of a process according to the invention gives a very good resistance to oxidation in comparison with the known methods of the prior art.
    [0017] The expression "comprising / containing / including a" should be understood as "containing / containing / including at least one". The expression "understood between ... and ..." or "from ... to ... 5" must be understood as including the boundaries.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. A method of protecting against oxidation of a composite material part comprising carbon, the process comprising the following 5 steps: a) applying, on at least a part of the external surface of the part, a coating composition under aqueous suspension form comprising: - a metal phosphate, - a powder of a compound comprising titanium, and - a powder of 134C, and b) heat treatment of the coating composition applied in step a), a a treatment temperature between 330 ° C and 730 ° C being imposed during the heat treatment to obtain on the outer surface of the part a coating comprising a first phase in which the metal phosphate is in crystalline form and a second phase in which metal phosphate is in amorphous form.
    [0002]
    2. The process according to claim 1, characterized in that the coating composition further comprises a dispersing organic agent.
    [0003]
    3. Process according to claim 2, characterized in that the organic dispersing agent is an alkoxylated acetylenic polyol.
    [0004]
    4. Process according to any one of Claims 1 to 3, characterized in that the compound comprising titanium is chosen from: metal titanium, titanium diboride, titanium carbide, titanium dioxide and their mixtures.
    [0005]
    5. Process according to claim 4, characterized in that the coating composition comprises a titanium metal powder and / or a titanium diboride powder.
    [0006]
    6. Method according to any one of claims 1 to 5, characterized in that the coating composition comprises an aluminum phosphate. 3019 818 24
    [0007]
    7. Method according to any one of claims 1 to 6, characterized in that the coating composition further comprises a vitreous self-healing compound.
    [0008]
    8. Method according to any one of claims 1 to 7, characterized in that the coating composition comprises before step a): - the metal phosphate in a mass content of between 27% and 36%, - the powder B4C in a mass content of between 11.5 10 ° A) and 21%, and the powder of the compound comprising titanium in a mass content of between 8% and 18%.
    [0009]
    9. A process according to claim 8, characterized in that the coating composition comprises, before step a): aluminum phosphate in a mass content of between 27% and 36%, the B4C powder in one a mass content of between 11.5 ° and 21%; - the powder of the compound comprising titanium in a content by weight of between 8% and 18%; and an alkoxylated acetylenic polyol in a mass content of between 0.1% and 1.5%, and - water in a mass content of between 33% and 50%. 25
    [0010]
    10. Method according to any one of claims 1 to 9, characterized in that at least one inner protective layer is formed, before step a), by impregnation of at least a portion of the composite material part by an impregnating composition comprising a metal phosphate. 30
    [0011]
    11. The method of claim 10, characterized in that the impregnating composition comprises an aluminum phosphate.
    [0012]
    12. Method according to any one of claims 1 to 11, characterized in that the treatment temperature is imposed during the heat treatment for a period greater than or equal to 1 hour.
    [0013]
    13. Coating composition in the form of an aqueous suspension comprising: - a metal phosphate, - a powder of a compound comprising titanium, and - a B4C powder.
    [0014]
    14. Composition according to claim 13, characterized in that it comprises: the metal phosphate in a mass content of between 27% and 36%, the B4C powder in a mass content of between 11.5 ° and 21 °. And the powder of the compound comprising titanium in a mass content of between 8% and 18%.
    [0015]
    15. Composition according to claim 14, characterized in that it comprises: - aluminum phosphate in a mass content of between 27% and 36%, - B4C powder in a mass content between 11.5 ° h and 21%, the powder of the compound comprising titanium in a mass content of between 8% and 18%, an alkoxylated acetylenic polyol in a mass content of between 0.1% and 1.5%, and water in a mass content of between 33% and 50%. 35
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    同族专利:
    公开号 | 公开日
    FR3019818B1|2016-05-06|
    US20150291805A1|2015-10-15|
    EP2930162B1|2016-12-21|
    US9758678B2|2017-09-12|
    EP2930162A1|2015-10-14|
    CN104973886A|2015-10-14|
    CN104973886B|2019-03-19|
    US20170369714A1|2017-12-28|
    MY168965A|2019-01-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2893939A1|2005-11-29|2007-06-01|Snecma Propulsion Solide Sa|Oxidation protection of a porous composite material containing carbon by aqueous impregnation with a compound containing phosphorus, titanium and boron, notably applicable for aeronautical disc brakes |
    CA2136373A1|1993-11-29|1995-05-30|Steven W. Medina|Ethoxylated acetylenic glycols having low dynamic surface tension|
    FR2726554B1|1994-11-04|1997-01-31|Europ Propulsion|PROCESS FOR THE PROTECTION AGAINST OXIDATION OF PARTS OF COMPOSITE CARBON-CONTAINING MATERIAL|
    FR2858318B1|2003-07-31|2007-03-02|Snecma Propulsion Solide|PROTECTION AGAINST OXIDATION OF COMPOSITE MATERIALS CONTAINING CARBON AND PARTS THUS PROTECTED|
    GB2426756A|2005-06-03|2006-12-06|Huntercombe Consultancy Ltd|Porous body containing within its pores a chemically bonded phosphate ceramic|
    FR2889186B1|2005-08-01|2008-01-04|Messier Bugatti Sa|ANTI-OXIDATION PROCESS OF PARTS IN A COMPOSITE MATERIAL CONTAINING CARBON|
    US20070154712A1|2005-12-22|2007-07-05|Mazany Anthony M|Oxidation inhibition of carbon-carbon composites|
    FR2966455B1|2010-10-25|2013-05-17|Commissariat Energie Atomique|METHOD FOR COATING A PART OF A COATING AGAINST OXIDATION|
    CN102249705A|2011-04-29|2011-11-23|孙振光|Electrode antioxidant coating|US9526846B2|2009-08-19|2016-12-27|Safety Syringes, Inc.|Patient-contact activated needle stick safety device|
    JP6107952B2|2014-01-10|2017-04-05|Ｊｆｅスチール株式会社|Method for suppressing backside oxidation of carbon-containing refractory, lining structure, and carbon-containing refractory|
    US10087101B2|2015-03-27|2018-10-02|Goodrich Corporation|Formulations for oxidation protection of composite articles|
    US10377675B2|2016-05-31|2019-08-13|Goodrich Corporation|High temperature oxidation protection for composites|
    US10465285B2|2016-05-31|2019-11-05|Goodrich Corporation|High temperature oxidation protection for composites|
    US10508206B2|2016-06-27|2019-12-17|Goodrich Corporation|High temperature oxidation protection for composites|
    US10767059B2|2016-08-11|2020-09-08|Goodrich Corporation|High temperature oxidation protection for composites|
    CN106518166B|2016-09-22|2021-09-28|北京优材百慕航空器材有限公司|Carbon/carbon composite material anti-oxidation coating and heat treatment method|
    US10526253B2|2016-12-15|2020-01-07|Goodrich Corporation|High temperature oxidation protection for composites|
    US20190233324A1|2018-02-01|2019-08-01|Goodrich Corporation|High temperature oxidation protection for composites|
    FR3078331B1|2018-02-23|2020-03-13|Safran Landing Systems|METHOD FOR PROTECTING AGAINST THE OXIDATION OF A PART MADE OF COMPOSITE MATERIAL|
    FR3084885B1|2018-08-09|2021-01-15|Safran Ceram|MANUFACTURING PROCESS OF A PART IN COMPOSITE MATERIAL|
    US11046619B2|2018-08-13|2021-06-29|Goodrich Corporation|High temperature oxidation protection for composites|
    法律状态:
    2015-04-27| PLFP| Fee payment|Year of fee payment: 2 |
    2016-04-22| PLFP| Fee payment|Year of fee payment: 3 |
    2017-04-25| PLFP| Fee payment|Year of fee payment: 4 |
    2017-06-23| CD| Change of name or company name|Owner name: MESSIER-BUGATTI-DOWTY, FR Effective date: 20170518 |
    2018-04-23| PLFP| Fee payment|Year of fee payment: 5 |
    2020-03-19| PLFP| Fee payment|Year of fee payment: 7 |
    2021-03-23| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1453198A|FR3019818B1|2014-04-10|2014-04-10|PROTECTION AGAINST THE OXIDATION OF CARBON COMPOSITE MATERIALS|FR1453198A| FR3019818B1|2014-04-10|2014-04-10|PROTECTION AGAINST THE OXIDATION OF CARBON COMPOSITE MATERIALS|
    EP15248016.6A| EP2930162B1|2014-04-10|2015-04-03|Protecting parts made of carbon-containing composite material from oxidation|
    MYPI2015000915A| MY168965A|2014-04-10|2015-04-09|Protecting parts made of carbon-containing composite material from oxidation|
    US14/682,351| US9758678B2|2014-04-10|2015-04-09|Protecting parts made of carbon-containing composite material from oxidation|
    CN201510170819.7A| CN104973886B|2014-04-10|2015-04-10|Protection is anti-oxidant by the component that carbon-containing composite material manufactures|
    US15/699,456| US20170369714A1|2014-04-10|2017-09-08|Protecting parts made of carbon-containing composite material from oxidation|
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