Process for fabricating composite parts by low melting point impregnation

Abstract

A method of fabricating a composite material part, the method including making a consolidated fiber preform, the fibers of the preform being carbon or ceramic fibers and being coated with an interphase; obtaining a consolidated and partially densified fiber preform, the partial densification comprising using chemical vapor infiltration to form a first matrix phase on the interphase; and continuing densification of the fiber preform by infiltrating an infiltration composition containing at least silicon and at least one other element suitable for lowering the melting temperature of the infiltration composition to a temperature less than or equal to 1150? C.

Claims

1. A method of fabricating a composite material part, the method comprising: making a consolidated fiber preform, wherein fibers of the consolidated fiber preform comprising one of: carbon fibers or ceramic fibers, and wherein the fibers are coated with an interphase; obtaining a consolidated and partially densified fiber preform, wherein the consolidated and partially densified fiber preform is obtained by using chemical vapor infiltration to form a first matrix phase on the interphase of the consolidated fiber preform; and continuing densification of the consolidated and partially densified fiber preform by infiltrating the consolidated and partially densified fiber preform with an infiltration composition containing at least silicon and nickel suitable for lowering the melting temperature of the infiltration composition to a temperature less than or equal to 1150? C., wherein a first proportion by weight of nickel in the infiltration composition is within a first range of 54% to 75%.

2. A method according to claim 1, wherein: the infiltration composition further includes germanium; and a second proportion by weight of germanium in the infiltration composition is in a second range 89% to 98%.

3. A method according to claim 1, wherein the infiltration composition includes less than 10% by weight of at least one: aluminum and boron.

4. A method according to claim 1, wherein the consolidated fiber preform is made of carbon fibers or silicon carbide (SiC) fibers.

5. A method according to claim 1, wherein the consolidated fiber preform is formed as a fiber structure made as a single part by three-dimensional or multilayer weaving or from a plurality of two-dimensional fiber plies.

6. A method according to claim 1, wherein the interphase is formed by at least one layer of any one of the following materials: pyrolytic carbon (PyC), boron-doped carbon (BC), and boron nitride (BN).

7. A method according to claim 6, wherein the first matrix phase comprises at least one layer of a material selected from at least one of the following materials: a self-healing material, silicon nitride (Si.sub.3N.sub.4), and silicon carbide (SiC).

8. A method according to claim 7, wherein the first matrix phase includes at least one layer of self-healing material selected from a ternary SiBC system and boron carbide B.sub.4C.

9. A method according to claim 1, wherein the first matrix phase comprises a plurality of layers of self-healing material alternating with one or more layers of material selected from pyrolytic carbon (PyC), boron-doped carbon (BC), and a ceramic material that does not contain boron.

10. A method according to claim 1, wherein, after partial densification of the consolidated fiber preform and before densification of the consolidated and partially densified fiber preform by infiltration with the infiltration composition, the method further comprises: modifying an array of pores within the consolidated and partially densified fiber preform by one of: dispersing a powder of at least one of the following materials within the consolidated and partially densified fiber preform: silicon carbide (SiC); silicon nitride (Si.sub.3N.sub.4); carbon (C); boron (B); boron carbide (B.sub.4C); and titanium carbide (TiC); introducing a ceramic or a carbon phase within the consolidated and partially densified preform by impregnating the consolidated and partially densified preform with a polymer, and pyrolyzing the polymer; or introducing a carbon or ceramic foam within the consolidated and partially densified preform by impregnating the consolidated and partially densified preform with a polymer, and pyrolyzing the polymer.

11. A method of fabricating a composite material part, the method comprising: making a consolidated fiber preform, wherein fibers of the consolidated fiber preform comprising one of: carbon fibers or ceramic fibers, and wherein the fibers are coated with an interphase; obtaining a consolidated and partially densified fiber preform, wherein the consolidated and partially densified fiber preform is obtained by using chemical vapor infiltration to form a first matrix phase on the interphase of the consolidated fiber preform; and continuing densification of the consolidated and partially densified fiber preform by infiltrating the consolidated and partially densified fiber preform with an infiltration composition containing at least silicon and germanium suitable for lowering the melting temperature of the infiltration composition to a temperature less than or equal to 1150? C., wherein a first proportion by weight of germanium in the infiltration composition is within a first range of 89% to 98%.

12. A method according to claim 11, wherein: the infiltration composition further comprises nickel having a second proportion by weight in the infiltration composition in a second range of 50% to 75%.

13. A method according to claim 11, wherein the infiltration composition further includes less than 10% by weight of at least one of: aluminum and boron.

14. A method according to claim 11, wherein the consolidated fiber preform is made of carbon fibers or silicon carbide (SiC) fibers.

15. A method according to claim 11, wherein the consolidated fiber preform is formed as a fiber structure made as a single part by three-dimensional or multilayer weaving or from a plurality of two-dimensional fiber plies.

16. A method according to claim 11, wherein the interphase is formed by at least one layer of any one of the following materials: pyrolytic carbon (PyC), boron-doped carbon (BC), and boron nitride (BN).

17. A method according to claim 16, wherein: the first matrix phase comprises at least one layer of a material selected from at least one of the following materials: a self-healing material, silicon nitride (Si.sub.3N.sub.4), and silicon carbide (SiC); and the first matrix phase includes at least one layer of self-healing material selected from a ternary SiBC system and boron carbide B.sub.4C.

18. A method according to claim 11, wherein the first matrix phase comprises a plurality of layers of self-healing material alternating with one or more layers of material selected from pyrolytic carbon (PyC), boron-doped carbon (BC), and a ceramic material that does not contain boron.

19. A method according to claim 11, wherein, after partial densification of the consolidated fiber preform and before densification of the consolidated and partially densified fiber preform by infiltration with the infiltration composition, the method further comprises: modifying an array of pores within the consolidated and partially densified fiber preform by one of: dispersing a powder of at least one of the following materials within the consolidated and partially densified fiber preform: silicon carbide (SiC); silicon nitride (Si.sub.3N.sub.4); carbon (C); boron (B); boron carbide (B.sub.4C); and titanium carbide (TiC); introducing a ceramic or a carbon phase within the consolidated and partially densified fiber preform by impregnating the consolidated and partially densified fiber preform with a polymer, and pyrolyzing the polymer; or introducing a carbon or ceramic foam within the consolidated and partially densified fiber preform by impregnating the consolidated and partially densified fiber preform with a polymer, and pyrolyzing the polymer.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) The invention can be better understood on reading the following description given by way of non-limiting indication with reference to the sole FIGURE, which shows successive steps of a method of fabricating a CMC material part in an implementation of the invention.

DETAILED DESCRIPTION OF IMPLEMENTATIONS

(2) The invention proposes a method of fabricating parts made out of composite materials, in particular out of thermostructural ceramic matrix composite (CMC) materials, i.e. materials formed by reinforcement made of carbon or of ceramic fibers and densified by a matrix that is ceramic at least in part, and also made out of thermostructural carbon/carbon (C/C) composite materials, i.e. materials formed by carbon fiber reinforcement densified by a carbon matrix.

(3) The fabrication method of the invention is remarkable in that it uses an infiltration composition that presents a melting temperature that is lower than that of the silicon-based infiltration compositions that are commonly used for densifying fiber preforms. More particularly, the infiltration composition used in the invention makes it possible to infiltrate fiber preforms with a molten composition at a temperature lower than the thermal stability temperature of the fibers (heat stability), i.e. a temperature that is low enough to avoid any degradation of the mechanical properties of the fibers of the preform during infiltration, as applies in particular to first generation SiC fibers. In accordance with the invention, the fiber preform is infiltrated with an infiltration composition that melts at a temperature lower than or equal to 1150? C.

(4) For this purpose, in addition to silicon, the infiltration composition contains at least one other element suitable for lowering the melting point or temperature of the composition to a temperature that is less than or equal to 1150? C. This lowering of the melting point of the infiltration composition may be obtained in particular by adding nickel (Ni) or germanium (Ge) to the silicon. More precisely, when adding nickel, the infiltration composition contains 50% to 75% (percentages by weight) of nickel, thus making it possible to obtain a melting point that lies in the range 1000? C. (infiltration composition containing 50% Si and 50% Ni) to 1150? C. (infiltration composition containing 25% Si and 75% Ni). When adding germanium, the infiltration composition contains 89% to 98% germanium, thus making it possible to obtain a melting point lying in the range 1000? C. (infiltration composition containing 2% Si and 98% Ge) and 1150? C. (infiltration composition containing 11% Si and 89% Ge). Thus, by adding a nickel content lying in the range 50% to 75% or at least 89% germanium to the silicon, a silicon alloy is obtained that presents a melting temperature that is less than or equal to 1150? C., which is a temperature lower than the thermal stability temperature of fibers made of silicon carbide (SiC) (referred to below as SiC fibers), such as for example first generation Nicalon?, Tyranno Lox-M?, or Tyranno ZMI? type SiC fibers.

(5) In addition to a lower melting point, the infiltration composition presents all of the other properties required for enabling a composite material of good quality to be fabricated. Specifically, the infiltration composition is chemically compatible with the elements present in the preform for infiltrating. The infiltration composition also presents good resistance to oxidizing or corrosive environments, and excellent long-term behavior.

(6) The infiltration composition may also include less than 10% (percentage by weight) of at least one of the following elements: aluminum and boron. Adding at least one of these ingredients serves to improve the deoxidizing and/or the wettability of the infiltration composition on the substrate for treatment, thereby imparting special properties to the treated material, such as improved ability to withstanding oxidation and corrosion.

(7) A first implementation of a method of fabricating a CMC material in accordance with the invention is described below with reference to the sole FIGURE.

(8) A first step 10 consists in making a fiber structure from which a fiber preform of shape close to that of the part that is to be fabricated is to be made. Such a fiber structure may be obtained by multilayer or three-dimensional weaving using yarns or tows. It is also possible to start from two-dimensional fiber textures such as woven fabrics or sheets of yarns or tows in order to form plies that are subsequently draped over a shaper and possibly bonded together, e.g. by stitching or by implanting yarns.

(9) The fibers constituting the fiber structure are preferably ceramic fibers, e.g. fibers made essentially of silicon carbide SiC (referred to below as SiC fibers), or of silicon nitride Si.sub.3N.sub.4. It is also possible to use the SiC fibers as sold under the names Tyranno ZMI, Tyranno Lox-M, and Tyranno SA3 by the Japanese supplier Ube Industries, Limited, or Nicalon, Hi-Nicalon, and Hi-Nicalon(S), sold by the Japanese supplier Nippon Carbon. In a variant, it is also possible to use carbon fibers.

(10) In known manner, with ceramic fibers, and in particular SiC fibers, it is preferable to perform surface treatment (step 20) on the fibers prior to forming an interphase coating in order to eliminate both the sizing and a surface oxide layer such as silica SiO.sub.2 present on the fibers.

(11) Step 30 consists in shaping the fiber structure with tooling in order to obtain a preform having a shape close to that of the part to be fabricated.

(12) With the preform held in its shaping tooling, e.g. made of graphite, an embrittlement-relief interphase is formed by CVI on the fibers of the preform, this interphase being constituted in particular by pyrolytic carbon (PyC) or by boron nitride (EN), or by boron-doped carbon (BC), having 5 at % to 20 at % boron, the balance being carbon (step 40). The thickness of the PyC or BC interphase preferably lies in the range 10 nm to 1000 nm.

(13) Thereafter (step 50), a first matrix phase is formed by CVI, the matrix possibly containing at least one layer of self-healing material. It is possible to select a self-healing material containing boron, e.g. a ternary SiBC system or boron carbide B.sub.4C that is capable, in the presence of oxygen, of forming a borosilicate type glass having self-healing properties. The thickness of the first matrix phase is not less than 500 nm, and preferably lies in the range 1 micrometer (?m) to 30 ?m.

(14) The first matrix phase may comprise a single layer of self-healing material or a plurality of layers of different self-healing materials. It is also possible to form the first matrix layer out of a plurality of layers of self-healing material alternating with layers of PyC or of BC or of ceramic material not containing boron, such as for example SiC or silicon nitride Si.sub.3N.sub.4.

(15) A layer of ceramic material that does not contain boron, e.g. SiC or Si.sub.3N.sub.4, is formed on the layer of self-healing material when the first matrix phase comprises only one layer of self-healing material, or on the last layer of self-healing material when the first matrix phase comprises a plurality of layers of self-healing material, in order to constitute a reaction barrier between the self-healing material and the molten silicon or silicon-based liquid composition that is introduced subsequently.

(16) The thickness of this layer of ceramic material forming a reaction barrier may be at least 500 nm, and typically lies in the range one to a several micrometers. Ceramic materials that do not contain boron and other than SiC or Si.sub.3N.sub.4 may be used to form the reaction barrier, for example refractory carbides such as ZrC or HfC.

(17) The total thickness of the interphase together with the first matrix phase is selected to be sufficient to consolidate the fiber preform, i.e. to bind together the fibers of the preform sufficiently to allow the preform to be handled while conserving its shape without the assistance of support tooling. This thickness may be at least 500 nm. After consolidation, the preform remains porous, and for example its initial pores may be filled in to a minority extent only by the interphase and the first matrix phase.

(18) It is known to use CVI to deposit PyC, BC, B.sub.4C, SiBC, Si.sub.3N.sub.4, BN, and SiC. Reference may be made in particular to the following documents: U.S. Pat. No. 5,246,736, U.S. Pat. No. 5,738,951, U.S. Pat. No. 5,965,266, U.S. Pat. No. 6,068,930, and U.S. Pat. No. 6,284,358.

(19) It may be observed that the interphase may be formed by CVI on the fibers of the fiber structure before the structure is shaped, providing the interphase is thin enough to avoid affecting the desired ability of the fiber structure to deform.

(20) The porous consolidated preform is removed from its shaping tooling in order to continue densification by an MI type process comprising modifying the array of pores and infiltrating the preform with an infiltration composition.

(21) The array of pores in the preform is modified (step 60) by means of one of the following treatments: dispersing a powder of at least one of the following materials within the preform: silicon carbide (SiC); silicon nitride (Si.sub.3N.sub.4); carbon (C); boron (B); boron carbide (B.sub.4C); and titanium carbide (TiC); introducing a ceramic or a carbon phase within the preform by impregnating said preform with a polymer, and pyrolyzing said polymer; or introducing a carbon or ceramic foam within the preform by impregnating said preform with a polymer, and pyrolyzing said polymer.

(22) In the presently-described example, the array of pores within the preform is modified by using an impregnation composition to disperse a powder. The impregnation composition may be a slip containing the powder in suspension in a liquid vehicle, e.g. water. The powder may be retained in the preform by filtering or by settling, possibly with the help of suction. It is preferable to use a powder made of particles having a mean size of less than 5 ?m.

(23) After drying, a consolidated preform is obtained having a carbon and/or ceramic powder dispersed within its pores.

(24) Densification is continued (step 70) by infiltrating the preform with an infiltration composition, specifically in this example a composition containing 46% (percentage by weight) silicon and 54% (percentage by weight) of nickel, the composition being melted at a temperature of about 1000? C. Infiltration is performed under a non-oxidizing atmosphere, and preferably under reduced pressure.

(25) When the previously introduced powder is made of carbon or if the material contains an accessible carbon phase, and when in the presence of a carbon residue of a resin used for impregnating the consolidated preform, the silicon reacts therewith to form silicon carbide SiC. When the previously introduced powder is made of ceramic, in particular a carbide, nitride, or silicide, and when in the presence of a ceramic residue of a resin used for impregnating the consolidated preform, a matrix that is made in part out of silicon is obtained binding the ceramic powder. Under all circumstances, the majority of the matrix is ceramic.