• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The invention relates to a process for the protection against oxidation of a composite material part comprising carbon, the process comprising at least: the application to an external surface of the part of a first coating composition in the form of aqueous suspension, the first coating composition comprising: - a metal phosphate, - a powder of a component comprising titanium, and - a B4C powder, - a first heat treatment of the first coating composition applied to obtain a first coating on the outer surface of the part, - the application on the first coating of a second coating composition comprising: - an aqueous suspension of colloidal silica, - a borosilicate glass powder, and - a TiB2 powder, and a second heat treatment of the second coating composition applied to obtain a second coating on the first coating.
    公开号:FR3078331A1
    申请号:FR1851604
    申请日:2018-02-23
    公开日:2019-08-30
    发明作者:Julien SNIEZEWSKI；Vincent Caro；Nathalie Nicolaus
    申请人:Safran Landing Systems SAS；
    IPC主号:
    专利说明:

    The invention relates to the protection against oxidation of parts of composite material containing carbon, that is to say of a material comprising a fibrous reinforcement densified by a matrix and in which the fibrous reinforcement and / or the matrix and / or an interphase coating between the fibers of the reinforcement and the matrix is made of carbon. A particular field of application of the invention is the protection against oxidation of parts made of carbon / carbon composite material (C / C), in particular of brake discs made of C / C composite, and in particular of brake discs of aircraft.
    Invention background
    In an oxidizing environment, the ability of parts made of carbon-containing composite material to maintain good mechanical properties at high 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 which provides access to the ambient environment to the heart of the material.
    To give this protection against oxidation, it is known to use internal systems based on metallic phosphate (s) which are put in place by impregnation in the residual porosities of the parts made of composite material with a composition in the form of aqueous solution. In order to extend the protection range to higher temperatures, external coatings can be used.
    By way of example, document US 2007/0026153 describes a process for the protection of parts made of composite material containing carbon, in particular brake discs made of composite material C / C. In a first step of the process, internal protection is put in place by impregnation with an aqueous solution of metallic phosphate, such as mono-aluminum phosphate, and heat treatment at approximately 700 ° C. under nitrogen (N 2 ). Then, an external coating is formed by application of a liquid composition containing, in an aqueous medium, colloidal silica SiO 2 , a borosilicate glass powder of “Pyrex®” type and titanium diboride powder TiB 2 . In service in an oxidizing medium, TiB 2 oxidizes to form 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 lifetime of the protection is relatively limited during repeated exposure to a humid environment due to the disappearance of B 2 O 3 and the consumption of TiB 2 . It would also be desirable to improve the protection provided by the solution according to US 2007/0026153 during stresses at very high temperatures.
    Subject and summary of the invention
    The invention relates, according to a first aspect, to a method of protection against oxidation of a part made of composite material comprising carbon, the method comprising at least:
    the application to an external surface of the part of a first coating composition in the form of an aqueous suspension, the first coating composition comprising:
    - a metal phosphate,
    a powder of a constituent comprising titanium, and
    - a powder of B 4 C,
    a first heat treatment of the first coating composition applied in order to obtain a first coating on the external surface of the part,
    the application to the first coating of a second coating composition comprising:
    - an aqueous suspension of colloidal silica,
    - borosilicate glass powder, and
    - a TiB 2 powder, and
    - A second heat treatment of the second coating composition applied in order to obtain a second coating on the first coating.
    In order to improve the performance of the composition disclosed in document US 2007/0026153, a first solution evaluated by the inventors was to increase the thickness of the coating according to this document. For this, a second layer of the same composition was applied. This increase in thickness has resulted in a decrease in adhesion for the two-layer coating obtained. This solution therefore did not improve the anti-oxidation performance.
    The invention resides in the fact of using the first coating composition described above to produce a first coating constituting the bonding sublayer for the composition disclosed in document US 2007/0026153 which corresponds to the second coating composition described above.
    By specifically choosing to combine the first coating composition with the second coating composition in the order indicated in the invention, a coating of increased thickness is obtained having good adhesion and imparting excellent resistance to oxidation in a humid environment. and at very high temperatures. The anti-oxidation performances obtained are in particular significantly improved compared to those obtained using the solution according to US 2007/0026153 or compared to other coatings having an increased thickness.
    In an exemplary embodiment, the constituent comprising titanium is titanium metal.
    In an exemplary embodiment, the metal phosphate is an aluminum phosphate.
    In an exemplary embodiment, the first coating composition comprises before its application:
    - metallic phosphate in a mass content of between 27% and 36%,
    the powder of the constituent comprising titanium in a mass content of between 8% and 18%, and
    - B 4 C powder in a mass content of between 11.5% and 21%.
    In an exemplary embodiment, a first treatment temperature between 330 ° C and 740 ° C is imposed during the first heat treatment.
    In an exemplary embodiment, the aqueous suspension of colloidal silica is basic.
    The fact of using a basic suspension advantageously makes it possible to further improve the adhesion of the second coating to the first coating based on metallic phosphate which has an acidic character.
    In an exemplary embodiment, the second coating composition comprises before its application:
    the aqueous suspension of colloidal silica in a mass content of between 25% and 50%, with a mass content of silica in this suspension of between 20% and 50%,
    - borosilicate glass powder in a mass content of between 5% and 20%, and
    - TiB 2 powder in a mass content of between 30% and 60%, and
    - the possible complement being water.
    In an exemplary embodiment, a second treatment temperature between 600 ° C and 800 ° C is imposed during the second heat treatment. The second treatment temperature can for example be between 650 ° C. and 740 ° C.
    In an exemplary embodiment, at least one internal protective layer is formed, before application of the first coating composition, by impregnation of at least part of the part made of composite material with an impregnation composition comprising a metal phosphate.
    In an exemplary embodiment, the part is a friction part. In particular, the friction part can be made of a carbon / carbon composite material.
    Brief description of the drawings
    Other characteristics and advantages of the invention will emerge from the following description, given without limitation, with reference to the appended drawings, in which:
    FIG. 1 is a flowchart showing different successive stages of an example of a method according to the invention, and
    FIGS. 2 to 5 show curves illustrating the variation in mass as a function of oxidation times for samples of C / C composite material provided with different protections against oxidation.
    Detailed description of embodiments
    In the following description, protection against oxidation of parts made of C / C composite material, more particularly brake discs, such as aeronautical brake discs, is envisaged. 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 consists in forming, within the accessible porosity of the part, or of a part of the part to be protected, an internal protection comprising at least one phosphate. metallic suitable in particular for providing protection against carbon oxidation.
    One can proceed as described in document US Pat. No. 5,853,821. A first step consists in depositing a wetting agent within the accessible porosity of the composite material. An aqueous solution of a wetting agent is used for this purpose, such as for example the product sold by the German company Sasol Gmbh under the name Marlophen NP9. After impregnation of the composite material with this solution of wetting agent and drying, an impregnation composition in the form of an aqueous solution containing a metal phosphate is applied to the entire external surface of the part or, selectively, on a part of the external surface of the part, for example with a brush or by projection (ie spraying with a spray gun) (step 10). An aqueous solution of aluminum hydrogen phosphate AI (H 2 PO4) 3 is used, for example. The metal phosphate can also be a zinc phosphate, for example having the following chemical formula: Zn 3 (PO4) 2.xH 2 O, a manganese phosphate, having for example the following chemical formula: Mn (H 2 PO4) 2 .2H 2 O or a magnesium phosphate having for example the following chemical formula: Mg 3 (PO4) 2 .8H 2 O.
    The wetting agent present on the surface of the accessible pores of the composite material facilitates the penetration of the impregnation composition into the accessible porosity of the composite material.
    Drying and then a preliminary heat treatment (step 20) are then carried out in order to limit the access of oxygen from the air to the surface of the pores thanks to an internal protection in metallic phosphate.
    The preliminary heat treatment is carried out by raising the temperature to a temperature between 200 ° C and 740 ° C, for example between 650 ° C and 740 ° C, for example about 700 ° C. This temperature can be imposed for one or more hours.
    The preliminary heat treatment can be carried out under a non-oxidizing atmosphere, for example under nitrogen (N 2 ).
    The first and second coatings are then formed on the surface of the part made of composite material. The formation of these coatings will be described below.
    The first coating is first formed from the first coating composition.
    The first coating composition is applied for example by brush or by spraying onto the external surface of the part or onto a part of this external surface, preferably at the same locations as the impregnation composition (step 30).
    In the case of brake discs made of carbon-based composite material, the application of the impregnating composition and of the first coating composition can be limited to the parts of the non-rubbing outer surface, the annular rubbing surface of a disc end of a set of stator and rotor discs or the opposing friction surfaces of the discs located between the end discs then being non-impregnated to avoid deterioration of the tribological properties.
    Examples of first coating compositions which can be used in the context of the present invention are described in document US 2015/0291805.
    As indicated above, the first coating composition comprises:
    - a metal phosphate,
    a powder of a constituent comprising titanium, and
    - a powder of B 4 C.
    The metal phosphate of the first coating composition can comprise an aluminum phosphate, for example aluminum hydrogen phosphate AI (H 2 PO4) 3. Such a compound is commercially available in an aqueous solution at 48% -50% by mass. As above, zinc, manganese or magnesium phosphate can be used as the metal phosphate of the first coating composition.
    The constituent comprising titanium can be chosen from: titanium metal (Ti), titanium diboride (TiB 2 ), titanium carbide (TiC), titanium dioxide (TiO 2 ), and mixtures thereof.
    In particular, the first coating composition may comprise a titanium metal powder and / or a titanium diboride powder. In particular, the constituent comprising titanium can be titanium metal.
    The powder of the constituent comprising titanium may be in the form of particles having an average size less than or equal to 150 μm. Unless otherwise stated, “average size” denotes the dimension given by the statistical particle size distribution to half the population, called D50.
    The powder of boron carbide B 4 C may be in the form of particles having an average size less than or equal to 30 μm, for example less than or equal to 7.5 μm.
    The first coating composition can, in addition, comprise an organic dispersing agent. The organic dispersing agent advantageously makes it possible to further improve the adhesion of the first coating to the underlying part.
    The organic dispersing agent can be an organic dispersing agent, soluble in water and nonionic, of oxyethylenated fatty acid, oxyethylenated fatty alcohol, oxyethylenated alkyl-phenol or higher poly-ol ester type. The organic dispersing agent can also be an alkoxylated acetylenic polyol, for example sold under the name "Surfolnol®" by the United States of America company Evonik. 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.
    The first coating composition may further include a refractory filler. The refractory filler can be present, in the first coating composition before its application, in a mass content of less than or equal to 5%.
    The refractory charge may comprise one or more oxides, nitrides or refractory carbides (other than B 4 C). The refractory charge may include one or more ceramic compounds. The refractory charge can be in the form of particles having an average size less than or equal to 150 μm.
    According to one example, the first coating composition may comprise before its application:
    - metallic phosphate in a mass content of between 27% and 36%,
    - B 4 C powder in a mass content of between
    11.5% and 21%,
    - the powder of the constituent comprising titanium in a mass content of between 8% and 18%,
    the organic dispersing agent, such as an alkoxylated acetylene polyol, in a mass content of between 0.1% and 1.5%,
    - water in a mass content of between 33% and 50%, and
    - optionally the refractory charge in a mass content less than or equal to 5%.
    According to one example, the first coating composition can, before its application, consist essentially of, that is to say for at least 90% by mass, at least one metal phosphate, a powder of titanium metal, a powder of carbide of boron B 4 C, an organic dispersing agent and water.
    Once the first coating composition has been applied, a first heat treatment is then carried out in order to obtain the first coating (step 40). A first treatment temperature is imposed during the first heat treatment.
    During the first heat treatment, the first treatment temperature may be high enough to obtain in the first coating a combination of at least one phase of crystalline metal phosphate and at least one phase of amorphous metal phosphate. The first treatment temperature can remain sufficiently low to avoid crystallizing all of the metal phosphate and, consequently, to keep an amorphous metal phosphate phase in the first coating formed.
    The proportion of metallic phosphate in amorphous form obtained in the first coating may depend on the first treatment temperature and the duration of application thereof. For example, an increase in the duration of application of the first treatment temperature can lead to a reduction in the proportion of metallic phosphate in amorphous form in the first coating.
    The first coating obtained can be such that the ratio [mass of metallic phosphate in amorphous form in the first coating] / [mass of metallic phosphate in amorphous form in the first coating + mass of metallic phosphate in crystalline form in the first coating] or greater than or equal to 0.1, for example 0.2. In particular, this ratio can be between 0.1 and 0.7, for example between 0.2 and 0.5.
    The detection of the crystalline and amorphous phases of metallic phosphate can be carried out by NMR spectroscopy (1D and 2D) of solid nuclei such as 31P and 27AI.).
    The first treatment temperature can be between 330 ° C and 740 ° C, for example between 650 ° C and 740 ° C. Such temperature values make it possible in particular to obtain a first 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.
    During the first heat treatment, the first treatment temperature can be imposed for a duration greater than or equal to 1 hour, for example between 1 hour and 15 hours.
    The first heat treatment can be carried out in an oxidizing atmosphere, for example in air. As a variant, the first heat treatment can be carried out under an inert atmosphere, for example under nitrogen.
    The amount of first coating composition applied can be chosen to obtain a first coating having a thickness of between 40 µm and 80 µm. It is typically possible to apply a quantity of first coating composition, measured before the first heat treatment, of between 16 mg / cm 2 and 23 mg / cm 2 .
    We have just described the formation of the first coating on the surface of the part made of composite material. A second coating is then produced on this first coating.
    The second coating is formed from the second coating composition, as will now be described.
    The second coating composition is applied for example by brush or by spraying onto the first coating previously formed (step 50). The second coating composition is applied in contact with the first coating.
    Examples of second coating compositions which can be used in the context of the present invention are described in document US 2007/0026153.
    As indicated above, the second coating composition comprises:
    - an aqueous suspension of colloidal silica,
    - a borosilicate glass powder, and
    - a TiB 2 powder.
    The powders of borosilicate glass and of TiB 2 are dispersed in the aqueous suspension of colloidal silica.
    The average size of silica particles in the suspension is less than or equal to 200 nm, for example between 5 nm and 100 nm, for example still between 5 nm and 40 nm.
    Borosilicate glass comprises silica and a boron oxide B 2 O 3 . The sum of the mass content of silica and the mass content of boron oxide B 2 O 3 in borosilicate glass may be greater than or equal to 80%, for example 90%.
    As an example of borosilicate glass, one can use a glass powder "Pyrex®", from the company of the United States of America Corning or supplied by the British company Barloword Scientific (formerly Bibby Sterilin) which glass has substantially the following composition (in percentages by mass):
    - SiO 2 : 80.60%,
    - B 2 O 3 : 12.60%,
    - Na 2 O 3 : 4.2%,
    - AI 2 O 3 : 2.25%,
    - Cl: 0.1%,
    - CaO: 0.1%,
    - MgO: 0.05%,
    - Fe 2 O 3 : 0.05%.
    Other glasses can be used such as borosilicate glasses of reference 823-01 to -05 from the company of the United States of America Ferro, or the glasses sold by the German company Schott AG under the name "Duran" (by example under the reference "8330"), "Suprax" or "Borofloat 40".
    The aqueous suspension of colloidal silica can be basic. The basic character can be imparted by an additive, advantageously a stabilizer of the colloidal suspension such as ammonia NH 3 or sodium oxide Na 2 O.
    The second coating composition may comprise before its application:
    the aqueous suspension of colloidal silica in a mass content of between 25% and 50%, with a mass content of silica in this suspension of between 20% and 50%,
    - borosilicate glass powder in a mass content of between 5% and 20%,
    - TiB 2 powder in a mass content of between 30% and 60%, and
    - the possible complement being water.
    In particular, the aqueous suspension of colloidal silica can be present in the second coating composition before its application in a mass content of between 30% and 40%.
    In particular, the borosilicate glass powder may be present in the second coating composition before its application in a mass content of between 10% and 15%.
    In particular, the TiB 2 powder may be present in the second coating composition before its application in a mass content of between 35% and 50%.
    Once the second coating composition has been applied, a second heat treatment is then carried out in order to obtain the second coating on the first coating (step 60). The second coating formed is in contact with the first coating. A second treatment temperature is imposed during the second heat treatment.
    The second treatment temperature imposed during the second heat treatment can be between 600 ° C and 800 ° C, for example between 650 ° C and 740 ° C.
    During the second heat treatment, the second treatment temperature can be imposed for a duration greater than or equal to 3 hours, for example between 3 hours and 4 hours. As a variant, the second treatment temperature can be imposed for a duration less than or equal to 10 minutes, for example between 1 minute and 10 minutes.
    The second heat treatment can be carried out under an inert atmosphere, for example under nitrogen.
    The amount of second coating composition applied can be chosen to obtain a second coating having a thickness between 30 µm and 70 µm. A quantity of second coating composition, measured before the second heat treatment, can typically be applied between 14 mg / cm 2 and 21 mg / cm 2 .
    Example
    Tests have been carried out by the inventors in order to demonstrate the advantage conferred by the invention in terms of protection against oxidation.
    During these tests, parts made of C / C composite material having a density of between 1.65 g / cm 3 and 1.9 g / cm 3 approximately and a residual volume porosity ranging from 6 to 18% approximately were used. These parts have been fitted with various anti-oxidation protections.
    In the following tests, the application of all the anti-oxidation protections was preceded by the following preliminary steps:
    - impregnation with an aqueous solution of Marlophen NP 9 or Levenol C201-B and drying,
    - robotic application of an aqueous solution of monoaluminous phosphate at 50% by mass of water with a brush or by spraying (i.e. spraying with a spray gun),
    - heat treatment under nitrogen (N 2 ) atmosphere by gradually raising the temperature to 700 ° C and maintaining this temperature for at least 1 hour.
    In order to assess the anti-oxidation performance of the protections tested, various oxidation protocols have been implemented which are detailed below:
    - P650 +: exposure to 650 ° C in air for 4 h, repeated 6 times with return to room temperature after each exposure, then leaching in water for 24 hours at 20 ° C, then exposure to 650 ° C in air for 4 p.m.,
    - P850 +: exposure to 850 ° C in air for 30 min, repeated 6 times with return to room temperature after each exposure, then leaching in water for 24 hours at 20 ° C, then exposure to 850 ° C in air for 3h,
    - P1200 +: exposure to 650 ° C for 4 h, return to room temperature, then exposure to 1,200 ° C for 15 min, return to room temperature, then two exposures to 650 ° C for 4 h with intermediate return to room temperature, return to ambient temperature, then exposure to 1200 ° C. for 15 min, return to ambient temperature, then exposure to 650 ° C. for 8 h,
    - P1400 +: exposure to 650 ° C for 4 h, return to ambient temperature, then exposure to 1400 ° C for 10 min, return to ambient temperature, then twice to 650 ° C for 4 h with intermediate return to ambient temperature, return at room temperature, then exposure to 1,400 ° C for 10 min, return to room temperature, then exposure to 650 ° C for 8 h.
    The leaching in water implemented consisted of the following sequence of steps:
    - immersion of the coated parts in demineralized water at 20 ° C for 24 h, and
    - drying of test pieces at 90 ° C for 4 h.
    Reference protection 1 (outside the invention)
    A first reference protection ("reference protection 1") was carried out by applying to the C / C composite part an aqueous suspension comprising:
    - an aqueous solution at 50% by mass of aluminum monophosphate in a mass content equal to 67%,
    - a titanium metal powder in a mass content equal to 11%,
    - a powder of B 4 C in a mass content equal to 16.3%,
    - water in a mass content equal to 4.7%, and
    - 1% of Surfynol®.
    A heat treatment of the applied composition was carried out at a temperature of 660 ° C for a period of 1 hour under a nitrogen atmosphere in order to obtain the coating.
    A single layer of the composition was applied to constitute the reference protection 1.
    The amounts of composition deposited for the reference protection 1 before and after the heat treatment are indicated in table 1 below for each of the test protocols carried out. These amounts of composition are indicated per unit area.
    Reference protection 1 "·" Test protocols Quantity of liquid composition deposited before heat treatment Quantity of composition deposited after heat treatment P650 + 22.7mg / cm 2 12.25mg / cm 2 P850 + 17.2mg / cm 2 9.3mg / cm 2 P1200 + 21.7mg / cm 2 11.7mg / cm 2 P1400 + 19.7mg / cm 2 10.6mg / cm 2
    Table 1
    The coatings obtained for the reference protection 1 had a thickness of approximately 60 μm.
    Reference protection 2 (outside the invention)
    A second reference protection ("reference protection 2") was carried out by applying the following composition to a C / C composite part comprising:
    an aqueous suspension of colloidal silica in a mass content equal to 38%, the mass content of silica in this suspension was 30%,
    - a borosilicate glass powder "Pyrex®" in a mass content equal to 13%, and
    - a TiB 2 powder in a mass content equal to 49%.
    The “Pyrex®” glass used was supplied by the American company Corning and had substantially the following composition (in percentages by mass):
    - SiO 2 : 80.60%,
    - B 2 O 3 : 12.60%,
    - Na 2 O 3 : 4.2%,
    - AI 2 O 3 : 2.25%,
    - Cl: 0.1%,
    - CaO: 0.1%,
    - MgO: 0.05%,
    - Fe 2 O 3 : 0.05%.
    A heat treatment of the applied composition was carried out at a temperature of 700 ° C for a period of 3 hours under a nitrogen atmosphere in order to obtain the coating.
    A single layer of the composition was applied to constitute the reference protection 2.
    The amounts of composition deposited for the reference protection 2 before and after the heat treatment are indicated in table 2 below for each of the test protocols carried out. These amounts of composition are indicated per unit area.
    Reference protection 2 “♦” Test protocols Quantity of liquid composition deposited before heat treatment Quantity of composition deposited after heat treatment P650 + 20.2mq / cm 2 13.5mg / cm 2 P850 + 18.7mg / cm 2 12.5mg / cm 2 P1200 + 18.7mg / cm 2 12.5mg / cm 2 P1400 + 19.7mg / cm 2 13.2mg / cm 2
    Table 2
    The coatings obtained for reference protection 2 were approximately 60 µm thick.
    Reference protection 3 (outside the invention)
    A third reference protection ("reference protection 3") was carried out by applying an aqueous suspension comprising:
    - an aqueous solution at 50% by mass of aluminum monophosphate in a mass content equal to 67%,
    - a titanium metal powder in a mass content equal to 11%,
    - a powder of B 4 C in a mass content equal to 16.3%,
    - water in a mass content equal to 4.7%, and
    - 1% of Surfynol®.
    A first layer of this composition was applied and then a first heat treatment was carried out at a temperature of 660 ° C for a period of 1 hour under a nitrogen atmosphere.
    A second layer of this composition was then applied to the coating thus obtained. Then a second heat treatment was carried out at a temperature of 660 ° C for a period of 1 hour under a nitrogen atmosphere.
    A two-layer coating was thus obtained from the composition described above.
    The amounts of composition deposited for the reference protection 3 are indicated in Table 3 below for each of the test protocols carried out. These amounts of composition are indicated per unit area.
    Reference protection 3 ""Test protocols Quantity of liquid composition deposited before heat treatment (layer 1) Quantity of composition deposited after heat treatment (layer 1) Quantity of liquid composition deposited before heat treatment (layer 2) Quantity of composition deposited after heat treatment (layer 2) Total coating composition P650 + 16.7mg / cm 2 9mg / cm 2 17.2mg / cm 2 11.5mg / cm 2 20.5m g / cm 2 P850 + 18.7mg / cm 2 10mg / cm 2 17.7mg / cm 2 11.8mg / cm 2 21.8mg / cm 2 P1200 + 18.2mg / cm 2 9.8mg / cm 2 18.7mg / cm 2 12.5mg / cm 2 22.3mg / cm 2 P1400 + 19.2mg / cm 2 10.5mg / cm 2 17.7mg / cm 2 11.8mg / cm 2 22.3mg / cm 2
    Table 3
    The coatings obtained for the reference protection 3 had a thickness of approximately 100 μm.
    Protection according to the invention
    An example of protection according to the invention (“protection according to the invention”) was carried out by applying a first coating composition in the form of an aqueous suspension to a C / C composite part, the first coating composition comprising:
    - an aqueous solution at 50% by mass of aluminum monophosphate in a mass content equal to 67%,
    - a titanium metal powder in a mass content equal to 11%,
    - a powder of B 4 C in a mass content equal to 16.3%,
    - water in a mass content equal to 4.7%, and
    - 1% of Surfÿnol®.
    A first layer of this first coating composition was applied and then a first heat treatment was carried out at a temperature of 660 ° C. for a period of 1 hour under a nitrogen atmosphere. A first coating was thus obtained.
    A second coating composition was then applied to the first coating thus formed, which included:
    an aqueous suspension of colloidal silica in a mass content equal to 38%, the mass content of silica in this suspension was 30%,
    - a borosilicate glass powder "Pyrex®" in a mass content equal to 13%, and
    - a TiB 2 powder in a mass content equal to 49%.
    A second heat treatment was then carried out at a temperature of 700 ° C. for a period of 3 hours under an inert atmosphere. A second coating was thus obtained on the first coating.
    The amounts of composition deposited for the protection according to the invention are indicated in table 4 below for each of the test protocols carried out. These amounts of composition are indicated per unit area.
    Protection according to invention "A"Test protocols Quantity of liquid composition deposited before heat treatment (layer 1) Quantity of composition deposited after heat treatment (layer 1) Quantity of liquid composition deposited before heat treatment (layer 2) Quantity of composition deposited after heat treatment (layer 2) Total coating composition P650 + 15.3mg / cm 2 8.2mg / cm 2 15.8mg / cm 2 10.6mg / cm 2 18.8mg / cm 2 P850 + 17.2mq / cm 2 9.3mg / cm 2 20.2mg / cm 2 13.5mg / cm 2 22.8mg / cm 2 P1200 + 17.7mg / cm 2 9.5mg / cm 2 17.2mg / cm 2 11.5mg / cm 2 21 mg / cm z P1400 + 16.7mg / cm 2 9mg / cm 2 20.2mg / cm 2 13.5mg / cm 2 22.5mg / cm 2
    Table 4
    The coatings obtained for the protection according to the invention had a thickness of approximately 100 μm.
    The results of the tests obtained for the different oxidation protocols are provided in Figures 2 to 5. In each of these figures:
    - the reference protection 1 is marked by the points “·”,
    - the reference protection 2 is marked by the points “♦”,
    - the reference protection 3 is marked by the points “”, and
    - the protection according to the invention is marked by the points “▲”.
    The results of tests P650 + and P850 + (Figures 2 and 3) show that the loss of mass is much lower for the protection according to the invention compared to the reference protections 1 to 3. These tests demonstrate that the protection according to the invention provides better protection against oxidation in a humid environment compared to reference protections 1 to 3.
    The results of tests P1200 + and P1400 + (Figures 4 and 5) show that the loss of mass is much lower for the protection according to the invention compared to the reference protections 1 to 3. These tests demonstrate that the protection according to the invention provides better protection against oxidation at very high temperatures compared to reference protections 1 to 3.
    The inventors have moreover found that a reference protection 4 consisting of two superposed layers of the reference protection 2 does not make it possible to improve the anti-oxidation protection insofar as such a solution leads to a two-layer coating having limited adhesion.
    An adhesion problem was also encountered during tests for a reference protection 5 consisting of a “reverse” bilayer coating with respect to the protection according to the invention. This reference protection 5 had therefore been formed first by application of the second coating composition described above, then by application of the first coating composition described above.
    By specifically choosing to combine the first coating composition with the second coating composition in the order indicated in the invention, a coating of increased thickness is obtained having good adhesion and excellent resistance to oxidation in a humid environment and at very high temperature. This resistance to oxidation is in particular significantly higher than that presented by a coating also having an increased thickness but having a different composition, where two layers of first coating composition have been applied successively (reference protection 3 marked with dots " In Figures 2 to 5). The specific combination of the first and second coating compositions according to the invention therefore provides particularly high anti-oxidation performance in humid conditions and at very high temperatures.
    The expression "included between ... and ..." must be understood as including the limits.
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    1. A method of protection against oxidation of a part made of composite material comprising carbon, the method comprising at least:
    the application to an external surface of the part of a first coating composition in the form of an aqueous suspension, the first coating composition comprising:
    - a metal phosphate,
    a powder of a constituent comprising titanium, and
    - a powder of B 4 C,
    a first heat treatment of the first coating composition applied in order to obtain a first coating on the external surface of the part,
    the application to the first coating of a second coating composition comprising:
    - an aqueous suspension of colloidal silica,
    - a borosilicate glass powder, and
    - a TiB 2 powder, and
    - A second heat treatment of the second coating composition applied in order to obtain a second coating on the first coating.
    [2" id="c-fr-0002]
    2. Method according to claim 1, in which the constituent comprising titanium is titanium metal.
    [3" id="c-fr-0003]
    3. The method of claim 1 or 2, wherein the metal phosphate is an aluminum phosphate.
    [4" id="c-fr-0004]
    4. Method according to any one of claims 1 to 3, in which the first coating composition comprises before its application:
    - metallic phosphate in a mass content of between 27% and 36%,
    the powder of the constituent comprising titanium in a mass content of between 8% and 18%, and
    - B 4 C powder in a mass content of between 11.5% and 21%.
    [5" id="c-fr-0005]
    5. Method according to any one of claims 1 to 4, wherein a first treatment temperature between 330 ° C and 740 ° C is imposed during the first heat treatment.
    [6" id="c-fr-0006]
    6. Method according to any one of claims 1 to 5, wherein the aqueous suspension of colloidal silica is basic.
    [7" id="c-fr-0007]
    7. Method according to any one of claims 1 to 6, in which the second coating composition comprises before its application:
    the aqueous suspension of colloidal silica in a mass content of between 25% and 50%, with a mass content of silica in this suspension of between 20% and 50%,
    - borosilicate glass powder in a mass content of between 5% and 20%, and
    - TiB 2 powder in a mass content between 30% and 60%.
    [8" id="c-fr-0008]
    8. Method according to any one of claims 1 to 7, wherein a second treatment temperature between 600 ° C and 800 ° C is imposed during the second heat treatment.
    [9" id="c-fr-0009]
    9. Method according to any one of claims 1 to 8, in which at least one internal protective layer is formed, before application of the first coating composition, by impregnation of at least part of the part made of composite material by an impregnation composition comprising a metal phosphate.
    [10" id="c-fr-0010]
    10. Method according to any one of claims 1 to 9, wherein the part is a friction part.
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    同族专利:
    公开号 | 公开日
    EP3530637B1|2020-04-22|
    US10899673B2|2021-01-26|
    CN110183249A|2019-08-30|
    EP3530637A1|2019-08-28|
    FR3078331B1|2020-03-13|
    US20190264039A1|2019-08-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2889186A1|2005-08-01|2007-02-02|Messier Bugatti Sa|Provision of an anti-oxidation coating for a composite material containing carbon, notably for aircraft disc brakes|
    EP2930162A1|2014-04-10|2015-10-14|Messier-Bugatti-Dowty|Protecting parts made of carbon-containing composite material from oxidation|
    FR2726554B1|1994-11-04|1997-01-31|Europ Propulsion|PROCESS FOR THE PROTECTION AGAINST OXIDATION OF PARTS OF COMPOSITE CARBON-CONTAINING MATERIAL|
    WO2005047213A2|2003-04-22|2005-05-26|Goodrich Corporation|Oxidation inhibition of carbon-carbon composites|
    FR2858318B1|2003-07-31|2007-03-02|Snecma Propulsion Solide|PROTECTION AGAINST OXIDATION OF COMPOSITE MATERIALS CONTAINING CARBON AND PARTS THUS PROTECTED|
    FR2893939B1|2005-11-29|2008-02-22|Snecma Propulsion Solide Sa|OXIDATION PROTECTION OF COMPOSITE MATERIALS CONTAINING CARBON|
    US20070154712A1|2005-12-22|2007-07-05|Mazany Anthony M|Oxidation inhibition of carbon-carbon composites|
    US20140227511A1|2013-02-13|2014-08-14|Goodrich Corporation|Formulations and methods for oxidation protection of composite articles|US10087101B2|2015-03-27|2018-10-02|Goodrich Corporation|Formulations for oxidation protection of composite articles|
    US10465285B2|2016-05-31|2019-11-05|Goodrich Corporation|High temperature oxidation protection for composites|
    US10377675B2|2016-05-31|2019-08-13|Goodrich Corporation|High temperature oxidation protection for composites|
    US10508206B2|2016-06-27|2019-12-17|Goodrich Corporation|High temperature oxidation protection for composites|
    US10526253B2|2016-12-15|2020-01-07|Goodrich Corporation|High temperature oxidation protection for composites|
    US11046619B2|2018-08-13|2021-06-29|Goodrich Corporation|High temperature oxidation protection for composites|
    US20200148340A1|2018-11-14|2020-05-14|Goodrich Corporation|High temperature oxidation protection for composites|
    US20200270182A1|2019-02-27|2020-08-27|Hamilton Sundstrand Corporation|Oxidation protection of composites|
    US20210198159A1|2019-12-27|2021-07-01|Goodrich Corporation|High temperature oxidation protection for composites|
    法律状态:
    2019-01-23| PLFP| Fee payment|Year of fee payment: 2 |
    2019-08-30| PLSC| Publication of the preliminary search report|Effective date: 20190830 |
    2020-01-22| PLFP| Fee payment|Year of fee payment: 3 |
    2021-01-20| PLFP| Fee payment|Year of fee payment: 4 |
    2022-01-19| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1851604|2018-02-23|
    FR1851604A|FR3078331B1|2018-02-23|2018-02-23|METHOD FOR PROTECTING AGAINST THE OXIDATION OF A PART MADE OF COMPOSITE MATERIAL|FR1851604A| FR3078331B1|2018-02-23|2018-02-23|METHOD FOR PROTECTING AGAINST THE OXIDATION OF A PART MADE OF COMPOSITE MATERIAL|
    EP19156265.1A| EP3530637B1|2018-02-23|2019-02-08|Method for protecting against oxidation of a part made from composite material|
    CN201910123733.7A| CN110183249A|2018-02-23|2019-02-19|A kind of protection composite material component antioxidation method|
    US16/280,707| US10899673B2|2018-02-23|2019-02-20|Method of protecting a composite material part against oxidation|
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