• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a method of manufacturing a ceramic material, the method comprising the following step: - formation of a ceramic material by carrying out a first chemical reaction at least between a first powder of an intermetallic compound and a reactive gas phase, a liquid phase being present around the grains of the first powder during the first chemical reaction, said liquid phase being obtained from a second powder of a metal compound by melting the second powder or following a second chemical reaction between at least one element of the first powder and at least one metallic element of the second powder, a sufficiently low working temperature to avoid melting of the first powder being imposed during the formation of the ceramic material.
    公开号:FR3045598A1
    申请号:FR1562929
    申请日:2015-12-21
    公开日:2017-06-23
    发明作者:Laurence Maille；Jerome Roger；Petitcorps Yann Le；Bernard Reignier
    申请人:Centre National de la Recherche Scientifique CNRS；Herakles SA；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION The invention relates to methods of manufacturing ceramic materials as well as products obtainable by carrying out such methods.
    Methods for densifying fibrous preforms by chemical vapor infiltration ("CVI") are known. This type of process consists in infiltrating a gaseous mixture containing all the elements forming the material in a porous preform with a view to its densification. This type of process is for example described in application FR 2 784 695. The chemical vapor infiltration is derived from the technique of chemical vapor deposition ("CVD": "Chemical Vapor Deposition") and has a deposit kinetics constant over time. It is a method conferring good properties to the material. However, to obtain a homogeneous CMC matrix by avoiding premature clogging of the periphery of the preform, it may be necessary to work at low pressure and relatively low temperature (<1100 ° C) in order to slow the growth kinetics. This can lead to a significant manufacturing time of CMC parts and make the process expensive. Machining may be necessary to re-open the periphery porosity and allow access to gases at heart. However, the matrix densification can be stopped when the porosity reaches a value close to 10% to 15% because of the presence of macropores.
    The slip or ceramic or sol-gel route is also known, which consists of impregnating the fibrous preforms with a slip or a soil (mixture of submicron-sized ceramic particles, sintering additions and liquid solvents) and then drying. and sintering the assembly at 1600-1800 ° C under pressure. Such a process is for example described in EP 0675091 and in J. Magnant, L. Maillé, R. Pailler, J-C. Ichard, A. Guette, F. Rebillat, E. Philippe. "Carbon fiber / reaction-bonded Carbide matrix for composite materials -Manufacture and characterization", J. Europ. Ceram. Soc. 32 (16) 2012, p. 4497-4505. However, the development of carbon xerogels can implement CMR-rated products, which can make industrial production difficult.
    The various known routes can either be used independently or combined with one another to form hybrid processes. Some examples of hybrid processes are described below.
    Known hybrid processes slip / CVI combining the slip route (without sintering additions) and the gaseous route. After impregnation of the fibrous preform with the slip, the conventional CVI infiltration of the green composite can then be used to densify the matrix. However, the great compactness of a (sub) micrometer agglomerated powder is a brake on its good infiltration. The heart of the raw material becomes poorly densified because of the premature closure of the porosity on the periphery of the vintage. The reactive species hardly reach the small pores and their concentration decreases very rapidly from the periphery to the heart which slows down strongly and then prevents the growth of the consolidation layer. Tang et al. (SF Tang, JY Deng, SJ Wang, WC Liu, K. Yang "Ablation behaviors of ultra-high temperature ceramic composites" Materials Science and Engineering A 465 (2007) 1-7) nonetheless made composites from compacts raw micron powders of ZRB2, SiC, HfC and TaC consolidated by CVI of pyrocarbon. In this case, the continuous matrix phase is pyrolytic. By replacing the classical CVI by the pulsed CVI, it is possible to consolidate micrometric powders (4-5 μm) forming a raw compact of millimeter thickness (N. K Sugiyama and Y Ohsawa "Consolidation of S13N4 powder-preform by infiltration of BN using the CVI process "Journal of Materials Science Letters 7 (1988) 1221-1224). Bleeding and filling the raw compact periodically lowers the natural concentration gradient of gaseous species between core and periphery. But the feasibility has not been reported for sub-micron powders and the process seems difficult to industrialize.
    A hybrid slip / pre-ceramic resin method makes it possible to develop a matrix from an impregnated powder and a preceramic resin (Peter Greil, Near Net Shape Manufacturing of Polymer Derived Ceramics, J. European Ceram Soc. 1905-1914). The volume increase of the powder makes it possible to partially compensate for the volume shrinkage of the resin during the pyrolysis.
    Recent work has been carried out (Liquid-structured nanostructured matrices: application to ceramic matrix composites, Thesis 4323 Université Bordeaux 1, 2011 and L. Maillé, MA Dourges, S. Le Ber, P. Weisbecker, F. Teyssandier, Y Petitcorps, R. Pailler, "Study of the nitridation process of TiSi2 powder", Applied surface science 260 (2012) 29-31) to develop a matrix by volume expansion by reacting a powder, impregnated within the preform, with a gas. The system studied so far is the nitriding of a TiSi 2 powder by normal pressure dinitrogen which allows a higher volume gain of the order of 60%. In this work, the objective was to develop a low-cost matrix using unstable Nicalon® fibers above 1100 ° C and a treatment temperature of 1100 ° C or lower was implemented during nitriding. This work has shown that, under these conditions, the nitriding of the powder is relatively slow and incomplete. The problem is silicon nitriding due to slow conversion kinetics.
    There is therefore a need for new processes for manufacturing low-cost ceramic materials that can be used on an industrial scale and in which a relatively low processing temperature can be implemented.
    In particular, there is a need for new methods of densification of fibrous preforms, usable on an industrial scale and having a relatively low cost and implementation temperature.
    There is also a need for new processes for manufacturing low-cost ceramic materials in which the chemical reaction implemented is complete.
    There is also a need for new processes for producing ceramic materials in which the materials obtained are substantially free of residual free silicon.
    There is still a need for new ceramic materials having satisfactory mechanical properties as well as a homogeneous microstructure.
    OBJECT AND SUMMARY OF THE INVENTION To this end, the invention proposes, according to a first aspect, a method of manufacturing a ceramic material, the method comprising the following step: - formation of a ceramic material by implementation of a first chemical reaction at least between a first powder of a metal disilicide and a reactive gas phase, a liquid phase obtained from a second powder being present around the grains of the first powder during the first chemical reaction, a sufficiently low working temperature to prevent melting of the first powder being imposed during the formation of the ceramic material and one of the following two characteristics being verified: the second powder is a nickel powder and the liquid phase is obtained following a second chemical reaction between at least one element of the first powder and the nickel of the second powder, or o the second powder is a p etdre of an aluminum alloy and silicon and the liquid phase is obtained by melting said alloy of aluminum and silicon.
    A metal disilicide is a compound of chemical formula MS2 wherein M denotes a metallic element. The first powder may, for example, be a TiSi 2 powder, a CrSi 2 powder, a ZrSi 2 powder or a VSi 2 powder.
    In the invention, the second powder promotes the reaction between the reactive gas phase and the first powder. During the first chemical reaction, there is volume expansion of the first powder by formation of one or more new phases (nitrides, oxides, carbides, ...) thus generating the ceramic material. The implementation of a second powder according to the invention making it possible to obtain the liquid phase during the first chemical reaction will advantageously make it possible to accelerate the kinetics of the first chemical reaction by promoting a greater diffusion of the reagents and, by therefore, rapid crystal growth of the reaction products. The use of such a second powder is a trick to accelerate the first chemical reaction despite the implementation of a relatively low working temperature. This advantageously provides a method of manufacturing a ceramic material having a reduced implementation cost while allowing the realization of a relatively fast chemical reaction. The invention may, in addition, advantageously make it possible to form one or more thermally stable phases and to obtain a complete chemical reaction. Furthermore, the ceramic material formed may not have particulate reinforcement dispersed therein.
    In the case where the liquid phase is formed by melting an alloy of aluminum and silicon, said alloy of aluminum and silicon is chosen so as to have a melting temperature sufficiently low to form a liquid phase at the temperature working. For this, once the chemical nature of the first powder, the reactive gas phase and the working temperature chosen, it is sufficient to select an alloy of aluminum and silicon having a melting temperature sufficiently low to obtain a liquid phase during the first chemical reaction. Such an exemplary embodiment corresponds, for example, to the system ZrSi2 / alloy AS 13 detailed below. In the case where the liquid phase is formed by melting an alloy of aluminum and silicon, the melting of said alloy can occur during the treatment of the first powder with the reactive gas phase or during a preliminary heat treatment carried out before the start of the first chemical reaction.
    When the liquid phase is formed following the second chemical reaction, there can be chemical reaction directly between the first powder and the second nickel powder. In this case, a mixture comprising the first powder and the second nickel powder is obtained before the first chemical reaction. Alternatively, the second nickel powder is first melted to form molten nickel and then the first powder is impregnated with the molten nickel so as to perform the second chemical reaction and form the liquid phase.
    When the liquid phase is formed following the second chemical reaction, the liquid phase comprises at least one element of the first powder and nickel. For example, for the system corresponding to a first TiSi 2 powder and a second nickel powder, the liquid phase comprises at least silicon and nickel.
    In the case where the liquid phase is formed following the second chemical reaction, the nickel constituting the second powder, when associated with at least one other element of the first powder, forms a system whose phase diagram shows the formation of a liquid phase at working temperature. For example, for the system corresponding to a first TiSi 2 powder and a second nickel powder, the binary phase diagram of the Ni-Si system shows the formation of a liquid phase from 956 ° C. (see FIG. 1) and the diagram The ternary phase of the Ni-Ti-Si system at 1100 ° C. also shows the possibility of forming a liquid phase (see FIG. 2). Thus, for example at a working temperature of 1100 ° C., it will be possible to use a second nickel powder with a first TiSi 2 powder and thus obtain the presence of the liquid phase during the first chemical reaction. The phase diagrams also make it possible to identify for each system of interest the relative contents of constituents necessary to obtain the liquid phase when it is formed following the second chemical reaction.
    In the case where the liquid phase is formed following the second chemical reaction, the nickel of the second powder may, when associated with silicon, form a system whose phase diagram shows the formation of a liquid phase at the working temperature .
    In the case where the liquid phase is formed following the second chemical reaction, the nickel of the second powder may, when associated with the metal element of the first powder, form a system whose phase diagram shows the formation of a liquid phase at working temperature.
    Preferably, the first powder may be a TiSi 2 powder and the second powder may be a nickel powder. In this system, the liquid phase is obtained following the implementation of the second chemical reaction.
    Such a system is particularly advantageous because of the existence of a low melting point within the Ni-Si system as explained above. This system can, moreover, advantageously allow to obtain a total conversion and a ceramic material having satisfactory mechanical properties and a homogeneous microstructure. In addition, the reaction of the first powder and of the reactive gas phase is advantageously facilitated by the implementation of a second nickel powder which makes it possible to obtain a silicon-rich liquid phase around the grains helping the diffusion of the species. reactive.
    The reactive gas phase employed in this system may, for example, comprise the element N, for example comprising N 2. This gives a material essentially comprising (ie more than 90% by mass) ΤΊΝ, S13N4 and Ni4Ti4Si7- The volume gain following the first chemical reaction may be greater than or equal to 40%, for example 50 % about. Moreover, the formation of the Ni4Ti4Si7 compound is advantageous insofar as this compound is a refractory and antioxidant compound.
    For example, when using a first TiSi 2 powder and a second nickel powder, it is possible to have before the beginning of the first chemical reaction: a ratio (quantity of material of the first powder) / (quantity of material of the first powder + quantity of material of the second powder) greater than 82.5% and less than 92.5%, and - a ratio (quantity of material of the second powder) / (quantity of material of the first powder + quantity of the second powder) greater than 7.5% and less than 17.5%.
    By "quantity of material", it is necessary to understand the quantity of material measured in mol (mol).
    For example, when using a first TiSi 2 powder and a second nickel powder, the ratio (amount of material of the first powder) / (amount of material of the first powder + amount of material of the second powder) can before the start of the first chemical reaction, be between 85% and 90%.
    For example, when using a first TiSi 2 powder and a second nickel powder, the ratio (amount of material of the second powder) / (amount of material of the first powder + amount of material of the second powder) can before the beginning of the first chemical reaction, be between 10% and 15%.
    Alternatively, the first powder may be a CrS2 powder and the second powder may be a nickel powder. Alternatively, the first powder may be a VSi 2 powder and the second powder may be a nickel powder. In the latter two systems, the liquid phase is obtained following the implementation of the second chemical reaction.
    The reactive gas phase used in the latter two systems may, for example, comprise the element N or the element C, the gas phase may for example comprise N2 or CH4.
    The reactive gas phase employed in the latter system may, for example, comprise the element N, the gas phase may for example comprise N2.
    In an exemplary embodiment, the second powder may be a powder of an alloy AISI13 (aluminum and silicon alloy comprising substantially 13% by weight of silicon).
    Preferably, the first powder may be a ZrSi 2 powder and the second powder may be a powder of an aluminum and silicon alloy, the second powder may, for example, in this case be a powder of an AS13 alloy. (AISÎ13).
    This system may advantageously make it possible to obtain a total conversion and a ceramic material having satisfactory mechanical properties as well as a homogeneous microstructure. In addition, the reaction of the first powder and of the reactive gas phase is advantageously facilitated by the use of the second powder of the AS13 alloy, which makes it possible to obtain the liquid phase around the grains helping to diffuse the reactive species. .
    As mentioned above, in the case where the first powder is a ZrSi2 powder and the second powder is a powder of the AS13 alloy, the liquid phase is formed by melting the AS13 alloy. AS13 has a melting point of 577 ° C.
    The reactive gas phase used in this system may, for example, comprise the element N, for example N2.
    As a variant, the first powder may be a VSi 2 powder and the second powder may be a powder of the AS13 alloy. In the latter case, the liquid phase is also formed by melting the alloy AS13.
    The reactive gas phase used in this system may, for example, comprise the N element or the element C, the gas phase may for example comprise N 2 or CH 4.
    In an exemplary embodiment, the quantity of material of the first powder may, before the beginning of the first chemical reaction, be greater than the quantity of material of the second powder.
    This last characteristic means that, before the beginning of the first chemical reaction, the first powder is implemented in an atomic fraction greater than the atomic fraction of the second powder.
    In an exemplary embodiment, the reactive gas phase may comprise at least one of the following gases: NH 3, N 2, O 2, a hydrocarbon gas, for example CH 4, or tetramethylsilane (Si (CH 3) 4).
    Advantageously, the ceramic material formed may have a residual free silicon mass content of less than or equal to 1%.
    This threshold of 1% corresponds to the threshold below which the residual free silicon can not be detected in the ceramic material by X-ray diffraction (XRD).
    In an exemplary embodiment, the working temperature may be less than or equal to 1100 ° C. The implementation of such temperature values can be advantageous for example when one seeks to form a ceramic matrix by implementing a method according to the invention and the fiber reinforcement comprises SiC fibers, such temperatures avoiding the degradation of these fibers. However, the invention is not limited to the implementation of such working temperature values.
    In an exemplary embodiment, especially when it is desired to form a ceramic matrix by implementing the method according to the invention, the average grain size of each of the first and second powders used may be less than or equal to 1 pm.
    Unless otherwise stated, the term "average size" refers to the dimension given by the statistical size distribution at half of the population, called D50.
    The present invention also relates to a method of manufacturing a piece of ceramic matrix composite material, the method comprising the following step: - formation of a ceramic matrix in the porosity of a fibrous preform, the ceramic matrix being formed by implementation of a method as described above.
    In this case, the implementation of the invention is particularly advantageous insofar as it makes it possible to develop the ceramic matrix at a relatively low temperature (for example less than or equal to 1100 ° C.) and thus to have a a method which does not damage the fibers of the fibrous reinforcement, nor the interphase coating that may be present, while filling the porosity of said fibrous reinforcement by virtue of carrying out an expansive chemical reaction. It is thus advantageously possible to obtain a ceramic matrix composite material having a very low porosity. In addition, when the invention is implemented to form a ceramic matrix, it advantageously makes it possible to develop a dense, homogeneous matrix, for example nitride, carbide, boride or oxide, by implementing a relatively inexpensive method. low.
    In an exemplary embodiment, the fiber preform may comprise a plurality of ceramic fibers and / or carbon fibers.
    The ceramic fibers may comprise nitride type fibers, carbide type fibers, for example silicon carbide fibers, oxide type fibers and mixtures of such fibers.
    In an exemplary embodiment, the fibers of the fiber preform may be coated with an interphase coating.
    The interphase coating may comprise, in particular, PyC, BC or BN. The invention is however not limited to the formation of a ceramic matrix in the porosity of a fibrous preform.
    Indeed, the present invention also relates to a method of manufacturing a part coated on its surface with a ceramic material coating comprising a step of forming said coating on the surface of the part by implementing a method such that described above.
    In this case, the part may be made of a composite material, for example a ceramic matrix composite material.
    The coating thus obtained can form an environmental barrier allowing for example to protect the part against oxidation. The coating may further form a thermal barrier or smoothing coating to smooth the surface of the underlying piece.
    The present invention also relates to a method of manufacturing a block of a ceramic material comprising a step of forming said block by implementing a method as described above. The block thus formed can be of any shape.
    The present invention also relates to a method of manufacturing a turbomachine comprising a step of manufacturing a turbomachine element at least by implementing a method as described above and then a step of assembling said element thus manufactured to one or more other elements to obtain the turbomachine.
    Such a turbomachine can be an integral part of an aircraft engine. The turbomachine element referred to above may, for example, constitute a turbomachine rear body, for example a rear body of an aeronautical engine.
    The present invention also relates to a ceramic material comprising essentially TiN, Si3N4 and Ni4Ti4Si7 and having a residual free silicon mass content of less than or equal to 1%.
    This material can be obtained by implementing a method as described above.
    The present invention also provides a piece of ceramic matrix composite material comprising: - a fibrous reinforcement, and - a matrix present in the porosity of the fibrous reinforcement, the matrix comprising a ceramic material as defined above.
    The present invention also relates to a turbomachine comprising such a ceramic material and / or such a piece of ceramic matrix composite material.
    The present invention also relates to an aeronautical engine comprising such a ceramic material and / or such a piece of ceramic matrix composite material.
    BRIEF DESCRIPTION OF THE DRAWINGS Other features and advantages of the invention will emerge from the following description, with reference to the accompanying drawings, in which: FIG. 1 represents the binary phase diagram of the Ni-Si system, FIG. the ternary phase diagram at 1100.degree. C. of the Ni-Si-Ti system; FIGS. 3A to 3C are photographs of a ceramic material obtained after implementation of a process according to the invention; FIG. a DRX diagram of a ceramic material obtained after implementation of a method according to the invention, - Figures 5A to 5C are photographs showing, after implementation of a method according to the invention for forming a ceramic matrix , the fibers of a fiber preform, the interphase and the matrix formed, - Figures 6A and 6B are photographs of a ceramic material obtained after implementation of a method according to the invention, - Figures 7A and 7B are photographers ies of a ceramic material obtained after implementation of a method outside the invention, and - Figure 8 shows thermogravimetric analysis measurements comparing the results obtained between processes according to the invention and methods outside the invention.
    Examples
    Example 1 (invention)
    Figures 3A to 3C are photographs showing the material obtained after conversion of a sample of initial composition 90% at. TiSi2 + 10% at. Neither under normal pressure treatment of N2 at 1100 ° C for 40 hours. The phases present at the end of the treatment are TiN, S13N4 and Ni4Ti4Si7 (see FIG. 4). It should be noted the absence of residual TiSi2 and free silicon at the end of the treatment. This reaction is accompanied by a volume gain of the order of 50%.
    FIGS. 5B and 5C are photographs showing in particular a matrix obtained by conversion of an infiltrated powder (d50 = 300 nm) of initial 90% at composition. TiSi2 + 10% at. Neither treated under normal pressure of N2 at 1100 ° C for 40 hours in a fibrous preform. The phases formed are identical to those presented above (TiN, Si3N4 and Ni4Ti4Si7). No reaction is observed between the powder and the Nicalon® fibers coated with a PyC / SiC interphase.
    Similarly, FIG. 5A also shows the absence of reaction between the powder and the interphase-coated fibers when a carbon fiber preform coated with a PyC interphase is treated under the same operating conditions. The lack of reactivity, in particular the liquid phase, is attributable to the nitrogen atmosphere which tends to favor nitriding. A piece is thus obtained in which the fibers as well as the interphase are not degraded by nitriding as well as a dense and rigid matrix having a homogeneous microstructure. There is also good interphase / matrix adhesion.
    Figures 6A and 6B show photographs of the ceramic matrices obtained after implementation of another example of the method according to the invention implementing an initial atomic content of nickel in the mixture of 12.5%. A hard, dense and homogeneous material containing only TiN, Si3N4 and Ni4Ti4Si7 is obtained. In this example, the Ni4Ti4Si7 is present in a molar content equal to 2%, a mass content equal to 14%, and a volume content equal to 10%.
    The results obtained using a TiSi 2 + Ni system at 1100 ° C./40 h / N 2 at various nickel contents are listed in Table 1 below.
    Table 1
    These exemplary embodiments lead to a complete reaction with the formation of TiN + S13N4 + Ni1 Si2. Note also the absence of impurities such as free silicon, TiSi2 or NiSi / NiSi2-
    Example 2 (comparative)
    The results obtained by a process according to the invention were compared with those obtained by a process outside the invention in which the second powder is not used. The non-invention process for obtaining the composite material used in this comparative example is detailed below: impregnation of the TiSi 2 powder within a fibrous preform, heat treatment under nitrogen: nitriding reaction to form TiN and S13N4.
    In order to avoid the degradation of the SiC fibers (Nicalon®) of the preform, the treatment temperature is limited to 1100 ° C. The results obtained for the test outside the invention at a reaction temperature of 1100 ° C. are given in FIGS. 7A and 7B. The inventors have observed that at this temperature, the nitriding reaction was slow and incomplete because the formation of Si 3 N 4 can be relatively difficult at temperatures of less than or equal to 1100 ° C. A lower volume gain is obtained and the presence of mechanically and chemically undesirable metal silicon is noted.
    Figure 8 shows thermogravimetric analysis (TGA) measurements obtained after treatment at 1100 ° C with N2: of a mixture (100-x) TiSi2 + x% at. Neither with x = 10; 12.5 and 15% at. nickel (invention), or TiSi2 alone: without implementation of a second powder or formation of a liquid phase (outside the invention).
    It can be seen that the examples according to the invention make it possible to promote the nitriding of silicon at a relatively low temperature of 1100.degree. The nitriding of silicon is facilitated by the presence of the second nickel powder which makes it possible to obtain a silicon-rich liquid phase around the grains. The addition of nickel alters and greatly increases the transformation over nickel free systems.
    Example 3 (comparative)
    The process outside the invention used in this comparative example corresponds to a nitriding process in which the nickel powder that can be used in the context of the invention is replaced by a Ni3Al powder. More specifically, the present comparative test evaluates the influence of a Ni3AI addition at 1% by volume as taught in the publication Zhang et al. ("Influence of 1 vol% N13AI addition on sintering and mechanical properties of reaction-bonded S / 3N4", Journal of the European Ceramic Society (1995) 1065-1070) on the silicon nitriding reaction.
    A pellet comprising a mixture of a silicon powder and Ni3Al present in a proportion of 1% by volume was obtained. This pellet had a diameter of 10 mm and a thickness of 3 mm. This pellet was treated with N 2 by imposing a temperature of 1100 ° C as in Examples 1 and 2 above. The following results were obtained after 30 hours of treatment: - mass content of residual silicon: 86.8%, - mass content of Si3N4a: 11.6%, and - mass content of Si3N4p: 1.6%.
    Mass contents were determined by X-ray diffraction.
    It can be seen that by implementing Ni3AI in proportions as taught in the publication Zhang et al. cited above and imposing a relatively low working temperature of 1100 ° C, the degree of progress of the nitriding reaction is significantly lower than that obtained by adding a nickel powder according to Example 1 according to 'invention.
    Example 4
    ZrSi 2 pellets were nitrided for 40 hours under normal pressure of dinitrogen at a temperature of 1100 ° C.
    When 10% at. of nickel are added to the mixture, the majority phases are, after 40 hours of nitriding, ZrN and Si3N4. The presence of ZrSi2, ZrNi2Si and NiZr is observed in a minority. The presence of free silicon has not been demonstrated.
    Without addition of nickel (except invention), the majority phases are ZrN and ZrSÎ2 after 40 hours of nitriding. S13N4 is detected but is a minority phase. Free silicon is also detected. The addition of nickel thus facilitates the nitriding of the ZrSi 2 metal disilicide even at a relatively low working temperature of 1100 ° C.
    Example 5
    ZrSi 2 pellets were nitrided for 40 hours under normal pressure of dinitrogen at a temperature of 1100 ° C.
    When a powder of an AS13 alloy is added at a rate of 10 at%, the majority phases are, after 40 hours of nitriding, ZrN, S13N4 and ZrSi2. The presence of free silicon in a minimal amount is observed.
    Without adding this AS13 powder, the majority phases are, after 40 hours of nitriding, ZrN and ZrSi2, Si3N4 is observed in a minority. Free silicon is also detected. The addition of an alloy of aluminum and silicon thus facilitates the nitriding of ZrSi2 metal disilicide even at a relatively low working temperature of 1100 ° C.
    Example 6
    VS12 pellets were nitrided for 40 hours under normal pressure of dinitrogen at a temperature of 1100 ° C.
    When a powder of an AS13 alloy is added at a rate of 10 at%, the majority phases are, after 40 hours of nitriding, VS12, VN and S13N4. The presence of V4,75Si3No, 58 is also observed in a minimal amount.
    Without adding this AS13 powder, the majority phase is, after 40 hours of nitriding, VSi2. VN, Si3N4 and V4, 75Si3No, 58 are minor. The addition of an aluminum and silicon alloy thus facilitates the nitriding of the VS12 metal disilicide even at a relatively low working temperature of 1100 ° C. ly
    Example 7
    The possibility of carrying out the carburation of a mixture Tis 2 + 10% at. Neither at 1100 ° C under normal pressure of methane was evaluated by simulation by the ThermoCalc software. The simulation results showed the formation of SiC, Ti3SiC2 and Ni4Ti4Si7 and the absence of residual silicon or TiSi2. The expression "understood between ... and ..." must be understood as including boundaries.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    1. A method of manufacturing a ceramic material, the method comprising the following step: formation of a ceramic material by carrying out a first chemical reaction at least between a first powder of a metal disilicide and a gaseous phase reactive, a liquid phase obtained from a second powder being present around the grains of the first powder during the first chemical reaction, a sufficiently low working temperature to prevent the melting of the first powder being imposed during the formation of the ceramic material and one of the following two characteristics being verified: the second powder is a nickel powder and the liquid phase is obtained following a second chemical reaction between at least one element of the first powder and the nickel of the second powder, or the second powder is a powder of an alloy of aluminum and silicon and the liquid phase is obtained by melting said alumina binding of aluminum and silicon.
    [2" id="c-fr-0002]
    2. Method according to claim 1, characterized in that the first powder is a TiSi2 powder, a CrS2 powder, a ZrSi2 powder or a VSI2 powder.
    [3" id="c-fr-0003]
    3. Method according to claim 2, characterized in that the first powder is a TiSi2 powder and the second powder is a nickel powder.
    [4" id="c-fr-0004]
    4. Method according to claim 2, characterized in that the first powder is a ZrSi2 powder and the second powder is a powder of an aluminum alloy and silicon.
    [5" id="c-fr-0005]
    5. Method according to any one of claims 1, 2 and 4, characterized in that the second powder is a powder of an alloy AISÎ13.
    [6" id="c-fr-0006]
    6. Method according to any one of claims 1 to 5, characterized in that, before the beginning of the first chemical reaction, the amount of material of the first powder is greater than the amount of material of the second powder.
    [7" id="c-fr-0007]
    7. Method according to any one of claims 1 to 6, characterized in that the reactive gas phase comprises at least one of the following gases: NH3, N2, O2, a gaseous hydrocarbon or tetramethylsilane.
    [8" id="c-fr-0008]
    8. A method of manufacturing a block of a ceramic material comprising a step of forming said block by implementing a method according to any one of claims 1 to 7.
    [9" id="c-fr-0009]
    9. A method of manufacturing a part coated on its surface with a coating of ceramic material comprising a step of forming said coating on the surface of the part by implementing a method according to any one of claims 1 to 7.
    [10" id="c-fr-0010]
    10. A method of manufacturing a piece of ceramic matrix composite material, the method comprising the following step: forming a ceramic matrix in the porosity of a fiber preform, the ceramic matrix being formed by implementation of a process according to any one of claims 1 to 7.
    [11" id="c-fr-0011]
    11. A method of manufacturing a turbomachine comprising a step of manufacturing a turbomachine element at least by implementing a method according to any one of claims 1 to 10 and a step of assembling said manufactured element to one or more other elements to obtain the turbomachine.
    [12" id="c-fr-0012]
    12. Ceramic material essentially comprising TiN, S13N4 and Ni4Ti4Si7 and having a residual free silicon mass content of less than or equal to 1%.
    [13" id="c-fr-0013]
    13. Part made of ceramic matrix composite material comprising: a fibrous reinforcement, and a matrix present in the porosity of the fibrous reinforcement, the matrix comprising a ceramic material according to claim 12.
    [14" id="c-fr-0014]
    14. A turbomachine comprising a ceramic material according to claim 12 and / or a part according to claim 13.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP2785665B1|2017-11-22|Cmc material part manufacture method
    EP2986582B1|2017-03-29|Process for manufacturing a carbide matrix composite material
    US20130167374A1|2013-07-04|Process of producing ceramic matrix composites and ceramic matrix composites formed thereby
    EP3394002B1|2019-08-21|Manufacturing process of a ceramic via a chemical reaction between a disilicide and a reactive gaseous phase
    EP2900623B1|2017-09-06|Method for manufacturing a cmc workpiece
    EP3169648B1|2021-06-30|Process for the fabrication of a composite body by high temperature self propagating synthesis
    WO2016001026A1|2016-01-07|Part coated with a surface coating and associated methods
    WO2014135700A1|2014-09-12|Method for preparing a multilayer carbide ceramic coating on, and possibly in, a part made of carbon material using an rmi reactive melt infiltration technique
    EP3024801B1|2019-09-25|Process for fabricating composite parts by low melting point impregnation
    EP3700876B1|2022-01-26|Particulate ceramic composite material, part comprising the same, and method for the production of said part
    FR3053329A1|2018-01-05|METHOD FOR COATING A COMPOSITE MATERIAL PART WITH A CERAMIC MATRIX BY AN ENVIRONMENTAL BARRIER
    WO2019122760A1|2019-06-27|Method for producing a composite part containing a ceramic matrix
    WO2019122758A1|2019-06-27|Method for manufacturing a ceramic matrix composite part
    FR3081475A1|2019-11-29|PROCESS FOR TREATING SILICON CARBIDE FIBERS BY CHEMICAL VAPOR DEPOSITION
    FR3016305A1|2015-07-17|COMBINING MACROPORES OF A FIBROUS SUBSTRATE BY HOMOGENEOUS NUCLEATION
    FR3016306A1|2015-07-17|COMBINING MACROPORES OF A FIBROUS SUBSTRATE WITH A MIXTURE OF PRECURSOR FLUIDS
    同族专利:
    公开号 | 公开日
    US10723658B2|2020-07-28|
    US20180370859A1|2018-12-27|
    RU2018126768A3|2020-05-27|
    RU2018126768A|2020-01-23|
    CA3009448A1|2017-06-29|
    FR3045598B1|2018-01-12|
    BR112018012736A2|2018-12-04|
    JP2019507083A|2019-03-14|
    EP3394002A1|2018-10-31|
    WO2017109373A1|2017-06-29|
    CN108698940A|2018-10-23|
    EP3394002B1|2019-08-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1028977A|1962-02-24|1966-05-11|Eric Campbell Shears|Improvements in or relating to the manufacture of silicon nitride and oxynitride|
    JPH05330921A|1992-06-02|1993-12-14|Honda Motor Co Ltd|Production of silicon nitride sintered compact|
    FR2988777A1|2012-03-29|2013-10-04|Snecma Propulsion Solide|INTEGRATION OF REAR BODY PARTS OF AERONAUTICAL MOTOR|
    EP0520520B1|1987-04-10|1996-09-11|Hitachi, Ltd.|Ceramic composite and process for production thereof|
    JP2587807B2|1993-02-22|1997-03-05|プラクスエアエスティテクノロジーインコーポレイテッド|Method for forming carbide film and article having the film|
    DE69414689T2|1994-03-29|1999-04-08|Euratom|Composite materials for sliding purposes, processes for their manufacture and use|
    JP3390773B2|1994-03-30|2003-03-31|黒崎播磨株式会社|Conductive antioxidant for graphite electrodes|
    US5882561A|1996-11-22|1999-03-16|Drexel University|Process for making a dense ceramic workpiece|
    FR2784695B1|1998-10-20|2001-11-02|Snecma|DENSIFICATION OF POROUS STRUCTURES BY CHEMICAL STEAM INFILTRATION|
    RU2239613C1|2003-02-10|2004-11-10|Федеральное государственное унитарное предприятие "Обнинское научно-производственное предприятие "Технология"|Method of manufacturing silicon nitride-based products|
    FR2894499B1|2005-12-08|2011-04-01|Snecma|ASSEMBLY BETWEEN A METAL PIECE AND A PIECE OF CERAMIC MATERIAL BASED ON SIC AND / OR C|
    CN100532251C|2007-06-04|2009-08-26|哈尔滨工业大学|Nitride silicon based composite material burning synthesis method|
    RU2382690C1|2008-09-30|2010-02-27|Томский научный центр Сибирского отделения Российской академии наук |Method of receiving of composite ceramic powder on basis of silicium nitride and titanium nitride|
    RU2490232C1|2012-02-17|2013-08-20|Мансур Хузиахметович Зиатдинов|METHOD OF OBTAINING FIRE-PROOF MATERIAL BASED ON SILICON BETA-NITRIDE β-Si3N4|
    FR3008968B1|2013-07-23|2016-12-09|Herakles|PROCESS FOR MANUFACTURING COMPOSITE MATERIAL PARTS BY LOW TEMPERATURE FUSION IMPREGNATION|
    CN106116586B|2016-06-14|2019-01-18|中南大学|A kind of molybdenum alloy MoSi2-ZrO2-Y2O3Coating and its preparation method and application|CN110627507B|2019-09-18|2022-02-25|广东工业大学|Low-temperature silicon carbide ceramic and preparation method and application thereof|
    CN112125675A|2020-08-14|2020-12-25|中国科学院金属研究所|ZrB2-SiC-VSi2Ultrahigh-temperature ceramic composite material and preparation method thereof|
    CN112624766B|2020-12-29|2021-11-16|哈尔滨工业大学|Preparation method of silicon nitride @ silicon carbide @ boron nitride composite fiber felt|
    法律状态:
    2016-12-07| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-23| PLSC| Publication of the preliminary search report|Effective date: 20170623 |
    2017-11-21| PLFP| Fee payment|Year of fee payment: 3 |
    2018-08-17| CD| Change of name or company name|Owner name: SAFRAN CERAMICS, FR Effective date: 20180716 Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, FR Effective date: 20180716 |
    2019-11-20| PLFP| Fee payment|Year of fee payment: 5 |
    2020-11-20| PLFP| Fee payment|Year of fee payment: 6 |
    2021-11-18| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1562929|2015-12-21|
    FR1562929A|FR3045598B1|2015-12-21|2015-12-21|PROCESS FOR PRODUCING A CERAMIC FROM A CHEMICAL REACTION|FR1562929A| FR3045598B1|2015-12-21|2015-12-21|PROCESS FOR PRODUCING A CERAMIC FROM A CHEMICAL REACTION|
    RU2018126768A| RU2018126768A3|2015-12-21|2016-12-20|
    CN201680082251.6A| CN108698940A|2015-12-21|2016-12-20|By the method for chemical reaction production ceramics|
    EP16826121.2A| EP3394002B1|2015-12-21|2016-12-20|Manufacturing process of a ceramic via a chemical reaction between a disilicide and a reactive gaseous phase|
    JP2018532592A| JP2019507083A|2015-12-21|2016-12-20|Process for producing ceramics from chemical reactions|
    CA3009448A| CA3009448A1|2015-12-21|2016-12-20|Method for producing a ceramic from a chemical reaction|
    PCT/FR2016/053563| WO2017109373A1|2015-12-21|2016-12-20|Method for producing a ceramic from a chemical reaction|
    US16/064,544| US10723658B2|2015-12-21|2016-12-20|Method of fabricating a ceramic from a chemical reaction|
    BR112018012736-1A| BR112018012736A2|2015-12-21|2016-12-20|methods for fabricating a ceramic material, a ceramic matrix composite material, a ceramic material block, a coated part and a turbocharger, ceramic material, a ceramic matrix composite material, and a turbomachine|
    [返回顶部]