RHENIUM-METAL CARBIDE-GRAPHITE ARTICLE AND METHOD

Abstract

A graphite-metal carbide-rhenium article of manufacture is provided, which is suitable for use as a component in the hot zone of a rocket motor at operating temperatures in excess of approximately 3,000 degrees Celsius. One side of the metal carbide is chemically bonded to the surface of the graphite, and the rhenium containing protective coating is mechanically bonded to the other side of the metal carbide. Rhenium forms a solid solution with carbon at elevated temperatures. The metal carbide interlayer serves as a diffusion barrier to prevent carbon from migrating into contact with the rhenium containing protective coating. The metal carbide is formed by a conversion process wherein a refractory metal carbide former is allowed to react with carbon in the surface of the graphite. This structure is lighter and less expensive than corresponding solid rhenium components.

Claims

1-14: (canceled)

15: A method of manufacturing an article comprising: selecting a graphite substrate, said graphite substrate having a predetermined configuration, a surface and a graphite coefficient of thermal expansion; forming a diffusion barrier coating comprising refractory metal carbide chemically bonded to said graphite substrate by allowing a reactive form of said refractory metal to react with carbon in said surface, said diffusion barrier coating having a carbide coefficient of thermal expansion, and a carbon diffusion coefficient of less than approximately 1 times 10.sup.6 centimeters squared per second at a temperature of approximately 2,500 degrees Kelvin; and depositing a protective coating comprising rhenium on said diffusion barrier coating, and allowing said protective coating to mechanically bond to said diffusion barrier coating, said protective coating having a rhenium coefficient of thermal expansion, the largest of said graphite, carbide, and rhenium coefficients of thermal expansion being no more than approximately 30 percent larger than the smallest of said graphite, carbide, and rhenium coefficients of thermal expansion.

16: A method of manufacturing an article of claim 15 comprising carrying out said depositing at a temperature above approximately 600 degrees Celsius.

17: A method of manufacturing an article of claim 15 comprising selecting said graphite substrate, diffusion barrier coating, and protective coating so that the largest of said graphite, carbide, and rhenium coefficients of thermal expansion are no more than approximately 30 percent larger than the smallest of said graphite, carbide, and rhenium coefficients of thermal expansion.

18: A method of manufacturing an article of claim 15 comprising carrying out said forming so that a diffusion barrier coating having a thickness of between approximately 0.3 and 2 mils is achieved.

19: A method of manufacturing an article of claim 15 comprising carrying out said depositing so that a protective coating having a thickness of at least approximately 2 mils is achieved.

20: A method of manufacturing an article of claim 15 comprising configuring said graphite substrate to form mechanical attachment features in said protective coating.

21: A method of manufacturing an article of claim 15 including providing mechanical attachment features in said protective coating.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Further advantages and features of the present invention will become apparent to those skilled in the art with the benefit of the following detailed description of the preferred embodiments and upon reference to the accompanying drawings in which:

[0030] FIG. 1 is a diagrammatic representation of a fragmented cross-sectional view of a rhenium-metal carbide-graphite article according to the present invention;

[0031] FIG. 2 is a diagrammatic representation of certain steps in a method of forming a composite graphite-metal carbide-rhenium article; and

[0032] FIG. 3 is a chart prepared from previously published data, which includes curves that approximately depict the diffusivity of carbon in various refractory carbides at elevated temperatures.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the various embodiments of the claimed subject matter. One skilled in the relevant art will recognize, however, that these embodiments can be practiced without one or more of the specific details, or with a number of other methods or compositions.

[0034] References throughout this specification to one embodiment, certain embodiments, additional embodiments, further embodiments, or an embodiment, or words of similar meaning, means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present claimed subject matter. Thus, the appearances of the phrases in one embodiment or in an embodiment, or phrases of similar meaning, in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0035] Certain physical properties of selected components are set forth in Table 1. The values set forth in this Table 1 are taken from previously published sources. There are other published sources that include different values for these physical properties. The values set forth in Table 1 are believed to be the most accurate that are available.

TABLE-US-00001 TABLE 1 Coefficient Of Approximate Thermal Diffusion Expansion In Coefficient for parts per million Carbon In per degree Melting Point In Component In Component Kelvin (CTE) Degrees Kelvin cm.sup.2/sec. Graphite 7.7 Above 3900 K Not applicable ZXF-5Q Graphite 8.6 Above 3900 K Not applicable ACF-10Q Graphite 8.4 Above 3900 K Not applicable AXF-5Q Graphite 7.8 Above 3900 K Not applicable AXZ-5Q Graphite 8.6 Above 3900 K Not applicable AXF-5QC Graphite 8.2 Above 3900 K Not applicable AXM-5Q JP-1091 6.1 Above 3900 K Not applicable ISO-88 6.5 Above 3900 K Not applicable Rhenium 6.9 3450 K Forms solid solution at approximately 1773 K Niobium 6.9 3890 K 1 10.sup.7 at Carbide approximately 2800 K Zirconium 7.3 3690 K 1 10.sup.7 at Carbide approximately 3100 K Tantalum 6.6 4260 K 1 10.sup.7 at Carbide approximately 2800 K Titanium 7.9 3340 K 1 10.sup.7 at Carbide approximately 2300 K Hafnium 6.8 4220 K 1 10.sup.7 at Carbide approximately 2900 K Molybdenum 6.0 2965 K 1 10.sup.7 at Carbide approximately 2300 K

[0036] Referring particularly to the drawings for purposes of illustration, and not limitation, a broken cross-section of an embodiment of and article is depicted generally at 10. Article 10 includes a graphite substrate 12, a diffusion barrier coating 14 comprised of metal carbide, and a protective coating 20 comprised of rhenium. Diffusion barrier coating 14 is a conversion coating that is chemically bonded to graphite substrate 12. At the junction between graphite substrate 12 and diffusion barrier coating 14 the metal carbide grades into the graphite through graded region 16. Graded region 16 is shown somewhat thickened for the purposes of illustration. It is generally thinner than illustrated relative to the rest of diffusion barrier coating 14. In graded region 16 there is a mixture of carbon and metallic carbide. Exposed surface 18 of protective coating 20 is adapted, for example, to being exposed to hot exhaust gases in a rocket engine assembly.

[0037] FIG. 2 is a flow chart that diagrammatically depicts a method of forming articles according to the present invention. A graphite substrate is selected and configured. The shaping may be performed by molding a powdered mass of graphite particles under pressure and sintering conditions to form a net or near net shape article with a massive form. In further embodiments, a solid mass of graphite is machined to a desired configuration. The graphite in certain embodiments is in a massive form rather than in filaments or fine particles. The configuration of the graphite substrate determines the configuration of the finished article. Such articles are useful in extremely high temperature applications such as those encountered in the hot sections of liquid or solid propellant rocket engines (for example, throats, nozzles, and combustion chambers), in heat shielding, and the like. The graphite substrate serves as a graphite workpiece for the diffusion barrier coating forming step. According to certain embodiments, graphite substrates also serve as the cores of sandwich structures. In such structures protective coatings (facesheets comprising rhenium), and diffusion barrier coating interlayers (consisting essentially of refractory metal carbide) are formed on each of the opposed sides of a graphite substrate, so there is a diffusion barrier coating between each face sheet and the graphite substrate. The respective metal carbide interlayers have the same or different dimensions, physical, and chemical properties, depending on the requirements of a specific application. The respective facesheets also have the same or different dimensions and properties depending on the requirements of a specific application.

[0038] A reactive form of a carbide forming refractory metal is provided for carrying out a conversion reaction with carbon in the surface of the graphite. Such metal carbide precursors and carbide forming reactions are conventional and well known in the art, and include, for example, the use of refractory metal halides as metal carbide precursors. The metal halides are introduced in the vapor phase and are reduced by hydrogen to provide a source of refractory metal that reacts with carbon at elevated temperatures. Such reactions are conventionally carried out at elevated temperatures above approximately 1000 degrees Celsius. The carbide forming reaction takes place within the surface of the graphite substrate. As the carbide coating thickens the rate of formation slows down because the reactants must penetrate through the carbide coating that has already formed to react with the carbon. A diffusion barrier coating is formed when the conversion reaction is carried out to the extent that a coating having a uniform thickness of at least about 0.3 mils, or, in further embodiments, about 0.5, or 1, or 2, or 3, or 4 to 5 mils is formed. At a thickness of 0.3 mils the coating serves as an effective barrier against the diffusion of carbon from the graphite through this metal carbide coating. The amount of carbon that diffuses through the diffusion barrier coating at operating temperatures above 2,000 or 2,500 degrees Celsius is further reduced as this coating increases in thickness to about 0.5, or 1, or even about 2 mils in certain embodiments. Further thickening tends to be counterproductive in many embodiments, because of an increased incidence of cracking of the coating.

[0039] Metallic carbide coatings withstand the stress of coefficients of thermal expansion mismatches better when they are thin. For example, the temperature gradient across a thin coating of 1 mil thickness will be less during start-up than across a coating with a thickness of 5 mils.

[0040] The conversion reaction of metal carbide precursors with carbon in the surfaces of slightly porous graphite substrates results in the formation of metal carbide coatings that are chemically bonded with the surface of the graphite substrate. The intermediate article of manufacture that is recovered from this conversion reaction is a metal carbide coated graphite substrate in which the configuration, dimension, and texture of the surface of the original graphite substrate have not been significantly altered. That is, the dimensions of this intermediate article are within less than one mil (0.001 inches) of those of the original graphite substrate when the carbide coating. Because the reactive carbon comes from within the surface of the graphite substrate, there is no surface build up such as occurs with overlay or deposited coatings. The metal carbides may be formed using a mixture of different refractory metals so as to achieve certain diffusion coefficients, melting points, and/or coefficients of thermal expansion as may be necessary or desired for particular applications.

[0041] The metal carbide coated graphite substrate serves as a carbide coated workpiece for the step in which a protective coating is formed by the application of a mechanically bonded overlay or deposited coating that comprises rhenium.

[0042] Formation of a rhenium containing protective coating is carried out using conventional procedures. Such conventional procedures include, for example, chemical vapor deposition (CVD), powder metallurgy techniques, and thermal spraying such as, for example, plasma spray. Electroforming procedures at approximately room temperature have also been used, as well as physical vapor deposition procedures (PVD). As those skilled in the art know, inspection of the grain structure and impurity levels of the rhenium comprising protective coating generally reveals the method of formation. The formation of the protective coatings is typically carried out to the extent that the coating is at least approximately 2, and in certain embodiments at least about 4, or 5, or 7, or more mils thick. The thickness of the protective coating selected depending on the intended end use for a particular article of manufacture. For large articles that are expected to repeatedly withstand prolonged exposure to temperatures above 2,500 or 3,000 degrees Celsius, the protective coating in some embodiments may be as much as 0.05, or 0.5, or more inches thick.

[0043] Rhenium is almost impossible to weld. In order to overcome this problem, a deposit of some other refractory metal that is weldable is formed onto the protective coating where welds are desired. For example, niobium may be welded and may be deposited on and bonded to rhenium by chemical vapor deposition. High temperature super alloys (for example, may be welded and may be deposited on and bonded to rhenium by conventional plasma spray techniques. Niobium sleeves were conventionally applied over prior rhenium combustion chambers that were used in prior satellite propulsion systems. This allows for welding attachment of injectors and nozzles. Also, mechanical attachment features may be provided so that grooves, bumps, ridges or other physical mounting features appear in the protective coating (rhenium) surface. Such mechanical attachment features may be provide by shaping the graphite substrate, or by otherwise altering selected dimensions of the surface of the protective coating.

[0044] FIG. 3 is a chart that depicts the diffusion coefficients of various refractory metal carbides against temperature. The diffusion coefficients increase with increasing temperature. Zirconium carbide, hafnium carbide, tantalum carbide, and molybdenum carbide all have diffusion coefficients of less than or about 1 times 10.sup.6 centimeters squared per second (cm.sup.2/sec.) at a temperature of approximately 2,500 degrees Kelvin. Zirconium carbide, hafnium carbide, tantalum carbide, and niobium carbide have diffusion coefficients of less than about 1 times 10.sup.5.5 cm.sup.2/sec. at a temperature of approximately 3,000 degrees Kelvin.

[0045] The present invention finds particular application when applied to pintles (also known as poppets) and throats (also known as seats) of various sizes for use in high performance (high temperature, long range) missile solid rocket motors.

[0046] According to one embodiment, articles according to the present invention are produced by a series of steps. A graphite substrate is machined to the desired size and configuration, taking into account the thickness of rhenium that will be required to survive the thermomechanical loads and thermochemical environment of the application. The configuration of the graphite substrate may also provide for the mechanical attachment of the completed article to a supporting structure. The machined graphite substrate is subjected to a high temperature (greater than 2500 degrees Celsius) heat treatment/outgassing treatment in a chlorine atmosphere to remove metallic impurities and other contaminants from the substrate. A refractory metal carbide diffusion barrier interlayer is formed with the surface of the graphite substrate by allowing a metal halide to react with the graphite surface to form the desired metal carbide conversion coating. A deposit of rhenium metal is formed on the diffusion barrier coating by a chemical vapor deposition operation. This chemical vapor deposition operation is performed via the thermal decomposition of rhenium chloride in the temperature range of 1000-1400 degrees Celsius. The chemical vapor deposition operation is carried out until the deposit reaches the required thickness. The exterior surface of the rhenium layer may be ground or otherwise machined to the desired final dimensions, if necessary.

[0047] While the detailed description of the claimed subject matter has been described with reference to multiple embodiments, it should be understood by those skilled in the art that various changes and modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the claimed subject matter. Therefore, the claimed subject matter is not limited to the various disclosed embodiments including the best mode contemplated for carrying out the claimed subject matter, but instead includes all possible embodiments that fall under the subject matter to be claimed.