Silicon based substrate with calcium aluminosilicate environmental/thermal barrier layer

Abstract: A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a calcium alumina silicate.

Description: The present invention relates to an article comprising a substrate containing silicon and a barrier layer which functions as a protective environmental/ thermal barrier coating and, more particularly, a barrier layer which inhibits the formation of gaseous species of Si, particularly Si(OH) x when the article is exposed to a high temperature, aqueous (water and/or steam) environment. EP-A-0 211 579 discloses a silicon nitride'sintered member for engine parts comprising a silicon nitride sintered body and a zirconia layer coated onto the surface of the silicon nitride sintered body. The zirconia layer is not more than 100 µm thick and is preferably coated onto the surface of the silicon nitride sintered body through plasma spraying. The zirconia-coated silicon nitride sintered member should have both: high strength at high temperatures and excellent heat insulating property. From US-A-3 523 881 is known a method of producing electrically insulated magnetic silicon steel sheet material which comprises providing on silicon steel sheet material a first coating of a material selected from the group consisting of colloidal silica and colloidal alumina, applying a second coating of calcium hydroxide on said silicon steel sheet material, and heating the thus-coated sheet material at elevated temperature to react said calcium hydroxide with said colloidal material to form a refractory coating consisting essentially of a compound selected from the group consisting of calcium metasilicate and calcium aluminum silicate. The insulating coating is provided on silicon steel sheet by applying a first coating of colloidal silica or colloidal alumina, electro-depositing thereon a coating of calcium hydroxide, and heating the thus coated sheet at elevated temperature to form a final coating of calcium metasilicate or calcium aluminum silicate. Ceramic materials containing silicon and metal alloys containing silicon have been proposed for structures used in high temperature applications as, for example, gas turbine engines, heat exchangers, internal combustion engines, and the like. A particular useful application for these materials is for use in gas turbine engines which operate at high temperatures in aqueous environments. It has been found that these silicon containing substrates can recede and lose mass as a result of a formation volatile Si species, particularly Si(OH) x and SiO when exposed to high temperature, aqueous environments. For example, silicon carbide when exposed to a lean fuel environment of approximately 1 ATM pressure of water vapor at 1200°C will exhibit weight loss and recession at a rate of approximately 6 mils per 1000 hrs. It is believed that the process involves oxidation of the silicon carbide to form silica on the surface of the silicon carbide followed by reaction of the silica with steam to form volatile species of silicon such as Si(OH) x · Naturally it would be highly desirable to provide a external barrier coating for silicon containing substrates which would inhibit the formation of volatile silicon species, Si(OH) x and SiO, and thereby reduce recession and mass loss. Accordingly, it is the principle object of the present invention to provide an article comprising a silicon containing substrate with a barrier layer which inhibits the formation of gaseous species of Si, particularly Si(OH) x, when the article is exposed to a high temperature, equeous environment. A second objective of this invention is to provide an article comprising a substrate with a barrier layer providing thermal protection, such layer closely matching the thermal expansion of the substrate. It is a further object of the present invention to provide a method for producing an article as aforesaid. The problems are solved by the teaching according to the independent claims. Particular developments are given in the dependent claims. The present invention relates to an article comprising a substrate which is a silicon containing ceramic having a calcium aluminosilicate barrier layer on the substrate, wherein the barrier layer functions to both inhibit the formation of undesirable gaseous species of silicon when the article is exposed to a high temperature, aqueous environment and to provide thermal protection. By high temperatures is meant the temperature at which the Si in the substrate forms Si(OH) x and/or SiO in an aqueous environment. By aqueous environment is meant a water and/or steam environment. The external barrier layer is characterized by a coefficient of thermal expansion which is within plus or minus 3.0 ppm per degree centigrade of the coefficient of expansion of the silicon containing substrate. The barrier layer in accordance with the present invention is a calcium aluminosilicate barrier layer. In a preferred embodiment of the present invention the article can include one or more intermediate layers between the silicon based substrate and the barrier layer. The intermediate layer(s) and serve(s) to provide enhanced adherence between the barrier layer and the substrate and/or to prevent reactions between the barrier layer and the substrate. Within the frame of the invention the said intermediate layer is selected from the group consisting of SiO 2 , mullite, mullite-barium strontium aluminosilicate, mullite-yttrium silicate, mullite-calcium aluminosilicate, and silicon metal or of mullite, barium strontium aluminosilicate, mullite-yttrium silicate, calcium aluminosilicate and mixtures thereof; preferably the intermediate layer comprises mullite. It may comprise from 40 to 80 wt.% mullite and from 60 to 20 wt.% barium strontium aluminosilicate especially from 40 to 80 wt.% mullite and from 60 to 20 wt.% yttrium silicate or from 40 to 80 wt.% mullite and from 60 to 20 wt.% calcium aluminosilicate. The thickness of the intermediate layer is ≥ 1.27 x 10 -5 m (0.5 mils; 0.0005 inch); preferably the intermediate layer has a thickness of 7.62 x 10 -5 to 76.2 x 10 -5 m (3 to 30 mils), especially 7.62 x 10 -5 to 12.7 x 10 -5 m (3 to 5 mils). Within the frame of the invention is a bond layer between the substrate and the intermediate layer, which may be silicon metal or SiO 2 with a preferred thickness of between 7.62 x 10 -5 to 15.24 x 10 -5 m (3 to 6 mils). The barrier layer of the article according to the invention has a thickness of between 7.62 x 10 -5 to 76.2 x 10 -5 m (3 to 30 mils) , preferably between 7.62 x 10 -5 to 12.7 x 10 -5 m (3 to 5 mils). The invention further relates to a method for producing an article comprising a silicon containing ceramic substrate and a calcium aluminosilicate barrier layer which inhibits the formation of gaseous species of silicon and/or provides thermal protection when the article is exposed to a high temperature, aqueous environment as defined above. A further step of the invention includes grit blasting the substrate prior to applying the barrier layer, preferably the grit blast with alumina particles having a particle size of ≤ 30 microns, especially grit blasting at a velocity between 150 m/sec to 200 m/sec. The method according to the invention also has the step of applying the barrier layer by thermal spraying. Within the frame of this method is the step of preoxidizing the substrate to form a layer of SiO 2 prior to applying the barrier layer. The preoxidizing may comprise heating the substrate at a temperature between 800°C to 1200°C for 15 minutes to 100 hours. After applying the barrier layer the article should be heat treated. The coefficient of thermal expansion of the barrier layer should be within ± 3.0 ppm/°C the coefficient of thermal expansion of the substrate. In another example this coefficient of thermal expansion of the barrier layer is within ± 0.5 ppm/°C the coefficient of thermal expansion of the substrate. The invention shows that the barrier layer preferably comprises greater than 20% by weight CaO, greater than 38% by weight Al 2 O 3 and greater than 30% by weight SiO 2 and more preferably 24% by weight CaO, 40% by weight Al 2 O 3 and 36% by weight SiO 2 . In one mode of this invention the layer is non-stoichiometric calcium aluminosilicate. The said article shall be heat treated over time to a temperature which allows for crystallization of the calcium aluminosilicate without swelling and/or the formation of pores by the barrier layer, including preferably heating the article from room temperature to a temperature between 1275°C to 1300°C over a time period of at least 68 hours. This article is heated in a stepwise manner at a heat rate between 50°C/min and 3°/min and held at at least one intermediate temperature. Within the frame of this invention the said article is heat treated as follows: a) room temperature to 700°C @ 10°C/min, hold 4 hrs.; b) 700°C to 800°C @ 10°C/min, hold 8 hrs.; c) 800°C to 900°C @ 10°C/min, hold 16 hrs.; d) 900°C to 1000°C @ 10°C/min, hold 16 hrs.; e) 1000°C to 1100°C @ 10°C/min, hold 8 hrs.; f) 1100°C to 1200°C @ 10°C/min, hold 8 hrs.; g) 1200°C to 1225°C @ 5°C/min, hold 2 hrs.; h) 1225°C to 1250°C @ 5°C/min, hold 2 hrs.; i) 1250°C to 1275°C @ 5°C/min, hold 2 hrs.; j) 1275°C to 1300°C @ 5°C/min, hold 2 hrs.; and k) furnace cool to room temperature. Further advantages, characteristics and details of the invention are apparent from the following detailed description of preferred embodiments of the invention with reference to the attached drawing. Figure 1 is a graph showing the stability of the barrier layer of the present invention with respect to recession and mass loss; and Figure 2 is a photomicrograph through a sample of the barrier layer of the present invention on a silicon carbide substrate. The present invention relates to an article comprising a ceramic substrate comprising silicon and a calcium aluminosilicate barrier layer, wherein the barrier layer inhibits the formation of gaseous species of silicon when the article is exposed to a high temperature, aqueous environment. The invention also relates to a method for producing the aforesaid article. In addition, it should be appreciated that while the barrier is particularly directed to an environmental barrier layer, the barrier layer also functions as a thermal barrier layer and thus the present invention broadly encompasses the use of environmental/thermal barrier layers on silicon containing substrates. The silicon containing ceramic substrate is for example silicon carbide, silicon nitride, silicon carbon nitride, silicon oxynitride, and silicon aluminum oxynitride. In accordance with a particular embodiment of the present invention, the silicon containing ceramic substrate comprises a silicon containing matrix with reinforcing materials such as fibers, particles and the like and, more particularly, a silicon based matrix which is fiber-reinforced. Particularly suitable ceramic substrates are a silicon carbide coated silicon carbide fiber-reinforced silicon carbide particle and silicon matrix, a carbon fiber-reinforced silicon carbide matrix and a silicon carbide fiber-reinforced silicon nitride matrix. In a particular embodiment, the barrier layer comprises greater than 20% by weight CaO, greater than 38% by weight Al 2 O 3 and greater than 30% by weight SiO 2 . A particularly suitable barrier layer for use on silicon containing ceramic compositions in the article of the present invention comprises 24% by weight CaO, 40% by weight Al 2 O 3 , and 36% by weight SiO 2 . Non-stoichiometric calcium aluminosilicate is preferred. It is an important feature of the present invention to maintain compatibility between the coefficient of thermal expansion of the silicon containing substrate and the barrier layer. In accordance with the present invention it has been found that the coefficient of thermal expansion of the barrier layer should be within ± 3.0 ppm per degrees centigrade, preferably ± 0.5 ppm per degrees centigrade, of the coefficient of thermal expansion of the silicon containing substrate. When using a silicon containing ceramic substrate such as a silicon carbide or a silicon nitride matrix with or without reinforcing fibers as described above in combination with the calcium aluminosilicate barrier layer of the present invention, the desired thermal compatibility with respect to expansion coefficient between the silicon containing substrate and the barrier layer should be ± 2.00 ppm per degrees centigrade. The barrier layer should be present in the article at a thickness of greater than or equal to 1,27 x 10 -5 m (0.5 mils ; 0.0005 inch), preferably between 7,62 x 10 -5 m and 76,2 x 10 -5 m (3 to 30 mils) and ideally between 7,62 x 10 -5 m and 12,7 x 10 -5 m (3 to 5 mils). The barrier layer may be applied to the silicon containing substrate by any suitable manner known in the art, however, it is preferable that the barrier layer be applied by thermal spraying as will be described hereinbelow. In a further embodiment of the article of the present invention, an intermediate layer can be provided between the silicon containing substrate and the barrier layer. The intermediate layer(s) serve(s) to provide enhanced adhesion between the barrier layer and the substrate and/or to prevent reactions between the barrier layer and the substrate. The intermediate layer consists of, for example, SiO 2 , mullite, mullite-barium strontium aluminosilicate, mullite-yttrium silicate, mullite-calcium aluminosilicate, and silicon metal. Mullite has been found to be a particularly useful intermediate layer; however, mullite by itself tends to be cracked as the result of thermal spraying fabrication processing. Accordingly, it is preferred that the barrier layer comprises mullite-barium strontium aluminosilicate, mullite-yttrium silicate, or mullite-calcium aluminosilicate in an amount of between 40 and 80 wt.% mullite and between 20 and 60 wt.% barium strontium aluminosilicate or yttrium silicate or calcium aluminosilicate. The thickness of the intermediate layer is typical to those described above with regard to the barrier layer and the intermediate layer may likewise be disposed in any manner known in the prior art, however, preferably by thermal spraying as described hereinbelow. In addition to the intermediate layer, a bond layer may be provided between the silicon containing substrate and the intermediate layer. A suitable bond layer includes silicon metal in a thickness of 3 to 6 mils. Alternatively, the silicon based substrate may be pre-oxidized to provide a SiO 2 bond layer prior to application of the intermediate layer. The method of the present invention comprises providing a substrate which is a silicon containing ceramic and applying a calcium aluminosilicate barrier layer wherein the barrier layer inhibits the formation of gaseous species of silicon when the article is exposed to a high temperature, aqueous environment. In accordance with the present invention it is preferred that the barrier layer be applied by thermal spraying. It has been found that the barrier layer should be thermal sprayed at a temperature between 80°C and 1200°C in order to help equilibrate as-sprayed, splat quenched, microstructure and to provide a means to manage stresses which control delamination. The silicon substrate should be cleaned prior to application of the barrier layer to remove substrate fabrication contamination. It is preferred that the silicon based substrate be subjected to a grit blasting step prior to application of the barrier layer. The grit blasting step must be carried out carefully in order to avoid damage to the surface of the silicon-containing. substrate such as silicon carbide fiber reinforced composite. It has been found that the particles used for the grit blasting should be hard enough to remove the undesired contamination but not as hard as the substrate material to prevent erosive removal of the substrate. Further, the particles must be small to prevent impact damage to the substrate. When processing an article comprising a silicon carbide ceramic substrate, it has been found that the grit blasting should be carried out with Al 2 O 3 particles, preferably of a particle size of ≤ 30 microns and, preferably, at a velocity of 150 to 200 m/sec. In addition to the foregoing, it may be particularly useful to preoxidize the silicon based substrate prior to application of the intermediate and/or barrier layer in order to improve adherence. It has been found that bond layers of between 100 nanometers and 2000 nanometers are preferred. SiO 2 bond layers of the desired thickness can be achieved by preoxidizing the silicon-carbide substrate at a temperature between 800°C and 1200°C for 15 minutes to 100 hours. The silicon bond layer may be applied directly to the grit blasted surface by thermal spraying at approximately 870°C to a thickness of 7,62 x 10 -5 m to 15,24 x 10 -5 m, (3 to 6 mils). Intermediate layers may be applied between the substrate and/or bond layer and the barrier layer or between the bond layer and barrier layer by thermal spraying in the same manner described above with respect to the barrier layer. As noted above, the preferred intermediate layers include mullite, mullite-barium strontium aluminosilicate, mullite-yttrium silicate, and mullite-calcium ' aluminosilicate. After application of the desired layers to the silicon-based substrate material, the article is subjected to a heat treatment step in order to provide stress relief to the thermal sprayed structure, and to promote bonding between the sprayed powder particles and between the layers and the substrate. Broadly, the heat treatment step requires a controlled heating of the article over time in a manner which allows for crystallization of the calcium aluminosilicate without swelling and/or formation of pores by the barrier layer. Preferably, the article is heated from room temperature to a temperature between 1275°C and 1300°C at a rate between 50°C/min and 3°C/min and preferably between 10°C/min and 5°C/min and held at intermediate temperatures wherein the total treatment time is greater than or equal to 68 hours. Specifically, for a barrier layer which comprises non-stoichiometric calcium aluminosilicate, the following heat treatment has been found to be particularly useful for obtaining a non-swelled, substantially porous free barrier layer. a) room temperature to 700°C @ 10°C/min, hold 4 hrs. b) 700°C to 800°C @ 10°C/min, hold 8 hrs. c) 800°C to 900°C @ 10°C/min, hold 16 hrs. d) 900°C to 1000°C @ 10°C/min, hold 16 hrs. e) 1000°C to 1100°C @ 10°C/min, hold 8 hrs. f) 1100°C to 1200°C @ 10°C/min, hold 8 hrs. g) 1200°C to 1225C @ 5°C/min, hold 2 hrs. h) 1225°C to 1250°C @ 5°C/min, hold 2 hrs. i) 1250°C to 1275°C @ 5°C/min, hold 2 hrs. j) 1275°C to 1300°C @ 5°C/min, hold 2 hrs. k) furnace cool to room temperature. The advantages of the article of the present invention will become clear from consideration of the following example. Example 1 Hot pressed bulk coupons of non-stoichiometric calcium aluminosilicate (ns-CAS) of composition 24% CaO, 40% Al 2 O 3 and 36% SiO 2 by weight were fabricated via hot pressing in Argon at 1400°C for 2 hours and then submitted for high steam thermal cycle testing at 1200°C for up to 250 thermal cycles in comparison to silicon carbide. The results show that the silicon carbide loses up to 8mg/cm 2 weight during the testing while the ns-CAS does not. See Figure 1. Example 2 Figure 2 is a cross section of a 10,16 x 10 -5 m (4 mil) thick ns-CAS coating on 10,16 x 10 -5 m of mullite on SiC composite. The ns-CAS and mullite were thermal sprayed onto the silicon carbide composite using the following parameters: Prior to coating the substrate was cleaned by grit blasting with 27 micron alumina particles at an impact velocity of 150 to 200 mps. The ns-CAS powder was obtained from Specialty Glass as a free flowing -200 + 400 mesh powder. The mullite was Cerac Mullite (Aluminum Oxide - Silicon Oxide), -150, +325 mesh, Cerac # A-1226. As can be seen from Figure 2, the invention results in an excellent barrier layer structure.

Claims: An article comprising: a substrate which is a silicon containing ceramic; and a calcium aluminosilicate barrier layer, wherein the barrier layer inhibits the formation of gaseous species of Si when the article is exposed to a high temperature, aqueous environment. An article according to claim 1 wherein the silicon containing ceramic is selected from the group consisting of silicon carbide, silicon nitride, silicon oxynitride, and silicon aluminium oxynitride. An article according to claim 1 wherein the substrate is a composite comprising a silicon based matrix and a reinforcing particle. An article according to claim 3 wherein said substrate is selected from the group consisting of silicon carbide fiber-reinforced silicon carbide matrix, carbon fiber-reinforced silicon carbide matrix and silicon carbide fiber-reinforced silicon nitride. An article according to one of the claims 1 to 4 wherein the barrier layer comprises greater than 20% by weight CaO, greater than 38% by weight Al 2 O 3 and greater than 30% by weight SiO 2 . An article according to one of the claims 1 to 5 wherein the barrier layer comprises 24% by weight CaO, 40% by weight Al 2 O 3 and 36% by weight SiO 2 . An article according to one of the claims 1 to 6 wherein the coefficient of thermal expansion of the barrier layer is within ± 3.0 ppm/°C the coefficient of thermal expansion of the substrate or wherein the coefficient of thermal expansion of the barrier layer is within ± 0.5 ppm/°C the coefficient of thermal expansion of the substrate. An article according to one of the claims 1 to 7 wherein the barrier layer has thickness of ≥ 1.27 x 10 -5 m (0.5 mils; 0.0005 inch), preferably 7.62 x 10 -5 m to 12.7 x 10 -5 m(3-5 mils). An article according to one of the claims 1 to 8 including an intermediate layer between the substrate an the barrier layer. An article according to claim 9 wherein said intermediate layer is selected from the group consisting of SiO 2 , mullite, mullite-barium strontium aluminosilicate, mullite-yttrium silicate, mullite-calcium aluminosilicate, and silicon metal or wherein said intermediate layer is selected from the group consisting of mullite, barium strontium aluminosilicate, mullite-yttrium silicate, calcium aluminosilicate and mixtures thereof. An article according to claim 9 wherein said intermediate layer comprises mullite. An article according to one of the claims 9 to 11 wherein said intermediate layer comprises from 40 to 80 wt.% mullite and from 60 to 20 wt.% barium strontium aluminosilicate or wherein said intermediate layer comprises from 40 to 80 wt.% mullite and from 60 to 20 wt.% yttrium silicate. an article according to one of the claims 9 to 11 wherein said intermediate layer comprises from 40 to 80 wt.% mullite and from 60 to 20 wt.% calcium aluminosilicate. An article according to one of the claims 9 to 13 wherein the intermediate layer has a thickness of ≥ 1.27 x 10 -5 m (0.5 mils; 0.0005 inch). An article according to one of the claims 9 to 14 wherein the intermediate layer has a thickness of 7.62 x 10 -5 m to 76.2 x 10 -5 m (3 to 30 mils), wherein preferably the intermediate layer has a thickness of 7.62 x 10 -5 m to 12.7 x 10 -5 m (3 to 5 mils). An article according to one of the claims 9 to 15 including a bond layer between the substrate and the intermediate layer, wherein preferably the bond layer is silicon metal or SiO 2 . An article according to claim 16 wherein the bond layer has a thickness of 7.62 x 10 -5 m to 15.2 x 10 -5 m (3 to 6 mils). An article according to claim 1 wherein the barrier layer has a thickness of between 7.62 x 10 -5 m to 76.2 x 10 -5 m (3 to 30 mils), wherein preferably the barrier layer has a thickness of between 7.62 x 10 -5 m to 12.7 x 10 -5 m (3 to 5 mils). A method for preparing an article comprising the steps of: providing a substrate which is a silicon containing ceramic; and applying a calcium aluminosilicate barrier layer to the substrate wherein the barrier layer inhibits the formation of gaseous species of Si when the article is exposed to a high temperature, aqueous environment. A method according to claim 19 further including the step of grit blasting the substrate prior to applying the barrier layer. A method according to claim 20 including grit blast with alumina particles having a particle size of ≤ 30 microns, including preferably grit blasting at a velocity between 150m/sec and 200m/sec. A method according to one of the claims 19 to 21 including applying the barrier layer by thermal spraying, including preferably thermal spraying at a temperature between 800°C and 1200°C. A method according to one of the claims 19 to 22 including the step of preoxidizing the substrate to form a layer of SiO 2 prior to applying the barrier layer. A method according to one of the claism 19 to 23 wherein the preoxidizing comprises heating the substrate at a temperature between 800°C and 1200°C for 15 minutes to 100 hours. A method according to one of the claims 19 to 24 including the step of, after applying the barrier layer, heat treating the article. A method according to one of the claims 19 to 25 wherein the coefficient of thermal expansion of the barrier layer is within ± 3.0 ppm/°C the coefficient of thermal expansion of the substrate or wherein the coefficient of thermal expansion of the barrier layer is within ± 0.5 ppm/°C the coefficient of thermal expansion of the substrate. A method according to one of the claims 19 to 26 wherein the barrier layer comprises greater than about 20% by weight CaO, greater than 38% by weight Al 2 O 3 and greater than 30% by weight SiO 2 , wherein preferably the barrier layer comprises about 24% by weight CaO, about 40% by weight Al 2 O 3 and 36% by weight SiO 2 . A method according to one of the claims 18 to 27 wherein the barrier layer is non-stoichiometric calcium aluminosilicate. A method according to claim 27 or 28 including heat treating said article over time to a temperature which allows for crystallization of the calcium aluminosilicate without swelling and/or the formation of pores by the barrier layer, including preferably heating the article from room temperature to a temperature between 1275°C and about 1300°C over a time period of at least 68 hours A method according to claim 28 wherein the article is heated in a stepwise manner at a heat rate between 50°C/min and 3°C/min and held at at least one intermediate temperature. A method according to claim 29 or 30 wherein said article is heat treated as follows: a) room temperature to 700°C @ 10°C/min, hold 4 hrs.; b) 700°C to 800°C @ 10°C/min, hold 8 hrs.; c) 800°C to 900°C @ 10°C/min, hold 16 hrs.; d) 900°C to 1000°C @ 10°C/min, hold 16 hrs.; e) 1000°C to 1100°C @ 10°C/min, hold 8 hrs.; f) 1100°C to 1200°C @ 10°C/min, hold 8 hrs.; g) 1200°C to 1225°C @ 5°C/min, hold 2 hrs.; h) 1225°C to 1250°C @ 5°C/min, hold 2 hrs.; i) 1250°C to 1275°C @ 5°C/min, hold 2 hrs.; j) 1275°C to 1300°C @ 5°C/min, hold 2 hrs.; and k) furnace cool to room temperature.

Inventors: ALLEN WILLIAM P, EATON HARRY E JR, JACOBSON NATHAN S, LEE KANG N, LUTHRA KRISHAN L, MESCHTER PETER J, MILLER ROBERT A, NAGARAJ BANGALORE A, OPILA ELIZABETH J, SMIALEK JAMES L, WANG HONGYU, ALLEN, WILLIAM P., EATON, HARRY E., JR., JACOBSON, NATHAN S., LEE, KANG N., LUTHRA, KRISHAN L., MESCHTER, PETER J., MILLER, ROBERT A., NAGARAJ, BANGALORE A., OPILA, ELIZABETH J., SMIALEK, JAMES L., WANG, HONGYU
Applicants: GEN ELECTRIC, NASA, UNITED TECHNOLOGIES CORP, GENERAL ELECTRIC COMPANY, THE UNITED STATES OF AMERICA, REPRESENTED BY THE ADMINISTRATOR OF THE NATIONAL AERONAUTICS AND SPACE ADMINISTRATION (NASA), UNITED TECHNOLOGIES CORPORATION
Application year: 2000
Main classification: C04B41
IPC codes: C23C28, C23C4, C04B41, B05D7, F01D5, B32B9, B32B18