High temperature resistant coating

Abstract: Provided is high temperature equipment, such as gas turbine high temperature portion, usable in high temperature corrosion environment due to corrosive components and in erosion environment due to flying particles. Coating layer (2) in which Cr 3 C 2 is finely dispersed in matrix MCrAlY, where weight ratio of MCrAlY/Cr 3 C 2 is 1/1 to 3/1, is formed on base material (1) as sprayed coating and then diffusion heat treatment is added.

Description: BACKGROUND OF THE INVENTION: Field of the Invention: The present invention relates to a high temperature equipment which is usable in a high temperature corrosion environment due to corrosive components as well as in an erosion environment due to flying particles. Description of the Prior Art: Taking example of a gas turbine, it is a recent tendency that a low quality fuel is going to be used for cost reduction of gas turbine operation. Of the low quality fuel, in a turbine operated by fuel obtained by coal gasification at a pressurized fluidized bed boiler, as compared with natural gas fuel or oil fuel as so far been used, there are produced a severe high temperature corrosion environment due to corrosive components of Na, K, Cl, S, etc. as well as an extremely severe erosion environment due to flying particles. Thus, in order to enhance the corrosion resistance in a high temperature portion of the gas turbine using fuel obtained by coal gasification at the pressurized fluidized bed boiler, especially in a turbine moving/stationary blade used in a severe operation condition, there is employed an element having an aluminum diffusion layer formed thereon by an aluminum diffusion coating, as shown in Fig. 4 (a), or an element having a spray coating of MCrAlY (M: Co, Ni, Co + Ni, Fe) formed thereon, as shown in Fig. 4(b). But, essentially with respect to these coatings, main object thereof is a corrosion resistance and reduction of erosion due to flying particles is a secondary one. Also, as shown in Fig. 4(c), there is often used a spray coating of chromium carbide [75 wt% Cr 3 C 2 - 25 wt% (50 wt% Ni - 50 wt% Cr)] as an erosion resistant coating for steam generator tube and the like which are under an erosion environment. However, while this spray coating of chromium carbide is excellent in the erosion resistance by virtue of the finely dispersed Cr 3 C 2 , quantity of matrix (binding material) contained therein is small and from view point of its ductility and toughness, it is not used for turbine blade which is a rotational element. Another reason for being not used for the turbine blade is that Ni-Cr alloy of the matrix is inferior to the MCrAlY coating in the corrosion resistance and oxidation resistance in a high temperature. Thus, in the prior art gas turbine moving/stationary blade used in such a severe environment, there arises a problem that life of the turbine blade is shortened extremely. It is to be noted that the temperature of damageable portion in such a case is approximately 600 to 800°C. GB-A-2 063 305 discloses a protectively coated superalloy having improved oxidation, corrosion, and wear resistance at elevated temperatures. The protective coating is a MCrAlY type alloy having a carbon content of 0.6 to 11 percent and is characterized in a preferred embodiment by having a carbon bearing matrix containing metal carbides of 1-2 microns mean size and chromium carbides of less than 12 microns. The coating is produced in plasma spraying a mixture of MCrAlY and CR 3 C 2 powders to form a coating having both fine carbides and coarser CR 3 C 2 carbides in a MCrAlY matrix. Heat treatment at 1080°C after coating bonds the substrate and coating and forms further fine carbides. GB-A-2 006 274 discloses a superalloy article having improved oxidation and wear resistance at elevated temperatures, said superalloy article having a protective coating which is a composite layer comprising an MCrAlY-type coating alloy matrix having chromium carbide particles dispersed therein. The composite layer is especially useful as a protective coating on a gas turbine blade tip shroud to provide increased service life. EP-A-0 401 611 discloses a corrosion and wear resistant high-temperature composite material based on an alloy of a MCrAlY type as matrix metal and comprising platinum and/or rhodium as alloying elements in an amount of 5 to 15 wt%. SUMMARY OF THE INVENTION: In view of the problem in the prior art, therefore, it is an object of the present invention to provide a high temperature equipment, such as a gas turbine high temperature portion, which is usable in a high temperature corrosion environment due to corrosive components as well as in an erosion environment due to flying particles. In order to attain said object, the present invention provides a high temperature equipment whose base material 1 has a coating layer formed thereon in which Cr 3 C 2 which is excellent in a high temperature erosion resistance is finely dispersed in a matrix CoNiCrAlY which is excellent in a corrosion resistance and oxidation resistance, as shown in a schematic cross sectional view of Fig. 1, so that life of a high temperature portion of turbine blade, steam generator tube and the like may be elongated, wherein a weight ratio of CoNiCrAlY/Cr 3 C 2 in said coating layer 2 is 1/1 to 3/1. A representative of CoNiCrAlY is shown in Table 1 together with chemical composition. Co Ni Fe Cr Al Y CoNiCrAlY Remainder 32 0 22 8 0.5 Mixing ratio of CoNiCrAlY to Cr 3 C 2 is (50 - 75):(50 - 25) in weight ratio, that is, CoNiCrAlY/Cr 3 C 2 = 1/1 - 3/1. This is for the reason that if ratio of Cr 3 C 2 is less than 25%, effect of the erosion resistance becomes low and if ratio of Cr 3 C 2 is beyond 50%, toughness of the coating, when used for a rotational element, becomes low to crack easily. In working the coating layer of the present invention, like in the case of conventional MCrAlY, there can be used various spraying methods, such as a low pressure plasma spraying (LPPS), an atmospheric pressure plasma spraying (APS), a high speed flame spraying (HVOF) and the like. Spray powder is made such that CoNiCrAlY powder is mixed with Cr 3 C 2 powder sufficiently at a ball mill and then is classified to each particle size distribution which is appropriate for the kind of spraying work. The powder particle size distribution is classified according to the particle size distribution generally specified by the respective spraying apparatus manufactures. That is, the particle size distribution of 45 µm or less is used for LPPS, that of 45 to 106 µm is used for APS and that of 16 53 µm is used for HVOF. BRIEF DESCRIPTION OF THE DRAWINGS: Fig. 1 is a cross sectional view showing structure of a high temperature equipment of one embodiment according to the present invention. Fig. 2 is a photograph showing a cross sectional microstructure of a coating in the high temperature equipment of Fig. 1, wherein Fig. 2(a) is of a 100 multiple and Fig. 2(b) is of a 500 multiple. Fig. 3 is an explanatory view showing an erosion test apparatus used for evaluation of erosion characteristic of the high temperature equipment. Fig. 4 is an explanatory view showing cross sectional structures of the high temperature equipment in the prior art, wherein Fig. 4(a) shows a structure having diffusion layer of Al, Fig. 4(b) shows that having coating layer of CoNiCrAlY and Fig. 4(c) shows that having coating layer of chromium carbide. DESCRIPTION OF THE PREFERRED EMBODIMENTS: Herebelow, description will be made concretely on a high temperature equipment of an embodiment according to the present invention. As shown in Fig. 1, a base material 1 (X-45: Tradename: Co radial alloy, Co-11Ni-25.5 Cr-7W-2Fe-0.25C) has a coating layer 2 formed thereon, said coating layer being formed so as to have both a corrosion/oxidation resistance and an erosion resistance. As a coating material, used is CoNiCrAlY (Co-32Ni-21Cr-8Al-0.5Y), which is mixed with Cr 3 C 2 in a ratio of 50 wt% : 50 wt% and 75 wt% : 25 wt%, respectively. It is to be noted that the coating powder is made of CoNiCrAlY powder mixed with Cr 3 C 2 powder sufficiently at a ball mill and is classified to the particle size distribution of 45 µm or less which is appropriate for LPPS. Firstly, the base material X-45 is applied to its surface by a grid blast treatment using Al 2 O 3 grains so that the surface of the base material is made in an appropriate state for plasma spraying. Then, CoNiCrAlY + Cr 3 C 2 as sample No. 1 is sprayed by the LPPS method. Thickness of the coating is 0.2 mm. Also, as sample No. 2, chromium carbide coating [75 wt% Cr 3 C 2 - 25 wt% (50 wt% Ni - 50 wt% Cr)] is sprayed by the APS method, said chromium carbide coating being often used in the prior art as a high temperature erosion resistant coating for steam generator tube and the like. Particle size distribution of the spray powder is classified to the particle size distribution of 45 to 106 µm which is appropriate for APS. Thickness of the coating is 0.2 mm. Further, as sample No. 3, CoNiCrAlY coating is sprayed by the LPPS method, said CoNiCrAlY coating being used in the prior art as a corrosion resistant and oxidation resistant coating. Particle size distribution of the spray powder is classified to the particle size distribution of 44 µm or less which is appropriate for LPPS. Thickness of the coating is 0.2 mm. Structures of these samples No. 1 to No. 3 are shown in Table 2. Sample Nos. Base material Coating material Coating thickness (mm) 1 (Invented coating) X-45 50%Cr 3 C 2 +50%CoNiCrAlY 0.2 25%Cr 3 C 2 +75%CoNiCrAlY 0.2 2 (Prior art coating) X-45 75%Cr 3 C 2 +25%NiCr 0.2 3 (Prior art coating) X-45 CoNiCrAlY 0.2 Finally, in order to enhance a bonding strength of the corrosion resistant and erosion resistant coating, a vacuum heat treatment (10 -3 - 10 -4 Torr) of heating temperature of 1,000°C and heating time of 2 hours as a diffusion heat treatment is applied to the respective test pieces. A representative photograph of the cross sectional microstructure of the sample No. 1 after heat treated is shown in Fig. 2, from which it is found that Cr 3 C 2 of white color of particle size of 2 - 11 µm is finely dispersed in the CoNiCrAlY matrix. Using the mentioned test pieces, oxidation test, corrosion test and erosion test have been done for evaluation. For the oxidation test, heating (700°C × 1000 Hr) in a furnace in the atmosphere is done and after the test, cross sectional microstructure is observed for evaluation of oxidation state of the coating layer and coating thickness still remaining. For the corrosion test, molten salt (80% Na 2 SO 4 + 20% NaCl) spreading method is employed and where one cycle is 700°C × 20 Hr, 10 cycles thereof are repeated. After the test, cross sectional microstructure is observed for evaluation of corrosion state of the coating layer and coating thickness still remaining. For the erosion test, in order to evaluate erosion characteristic due to particles, rotary type erosion test apparatus is employed, as shown in Fig. 3, and the test pieces are rotated in a tank where alumina of particle size of 1±0.1 mm is filled, wherein the test is done in the atmosphere, test temperature is 700°C, speed of rotation is 10 rpm and test time is 8 hours. After the test, depth of the coating thinned by the erosion test is measured for evaluation of erosion resistance. Results of the above-mentioned tests are shown in Table 3. Sample Nos. Coating material Oxidation test results (Thinned depth) Corrosion test results (Thinned depth) Erosion test results (Thinned depth) 1 (Invented coating) 50%Cr 3 C 2 +50%CoNiCrAlY 1.0 1.0 1.0 25%Cr 3 C 2 +75%CoNiCrAlY 0.9 1.0 1.8 2 (Prior art coating) 75%Cr 3 C 2 +25%NiCr 3.8 9.5 0.9 3 (Prior art coating) CoNiCrAlY 0.9 0.9 11.2 Thinned depth is relative value where the value of invented coating is 1. From Table 3, the element having the corrosion resistant and erosion resistant coating layer of the present invention formed thereon is excellent apparently in the corrosion resistance and erosion resistance and the effect of the element having the corrosion resistant and erosion resistant coating layer of the present invention formed thereon has been proved. It is to be noted that while the LPPS method is employed for the spraying in the sample No. 1, it is clear that same effect can be obtained even if the spraying of the APS method or the HVOF method is employed. As described above, the present invention provides a high temperature equipment having a coating layer formed thereon in which Cr 3 C 2 is finely dispersed in MCrAlY. In the prior art, for example, turbine moving/stationary blade of a gas turbine using fuel from a fluidized bed boiler has no such a coating as having both the corrosion/oxidation resistance and the erosion resistance but either one of said resistances is sacrificed and the turbine blade is of a short life. On the other hand, the high temperature equipment of the present invention has the corrosion resistant and erosion resistant coating formed thereon in which Cr 3 C 2 which is excellent in the erosion resistance is finely dispersed in the MCrAlY layer which is excellent in the corrosion/oxidation resistance, as mentioned above, so that both the corrosion/oxidation resistance and the erosion resistance are exhibited effectively at the same time. Thus, the equipment having the corrosion resistant and erosion resistant coating layer of the present invention is applied to a gas turbine and the like, for example to a gas turbine operated by fuel from a pressurized fluidized bed boiler, thereby a high temperature portion (turbine moving/stationary blade, combustor, etc.) which stands a long time use in a very severe environment where both corrosion and erosion exist can be provided. It is understood that the invention is not limited to the particular construction and arrangement herein described and illustrated but embraces such modified forms thereof as come within the scope of the appended claims.

Claims: A high temperature equipment having a corrosion resistant and erosion resistant coating formed thereon, characterized in that said coating is formed by a coating layer (2) in which Cr 3 C 2 is finely dispersed in CoNiCrAlY, wherein a weight ratio of CoNiCrAlY/Cr 3 C 2 in said coating layer (2) is 1/1 to 3/1. A high temperature equipment as claimed in claim 1, characterized in that said coating layer (2) is a sprayed coating.

Inventors: ABE KATSUHIKO, KAWAI HISATAKA, NISHIURA YUKIKO, TAKAHASHI KOJI, TORIGOE TAIJI, ABE, KATSUHIKO, KAWAI, HISATAKA, NISHIURA, YUKIKO, TAKAHASHI, KOJI, TORIGOE, TAIJI, Abe, Katsuhiko, c/o Takasago Machinery Works of, Kawai, Hisataka, c/o Takasago Machinery Works of, Nishiura, Yukiko, c/o Takasago Machinery Works of, Takahashi, Koji, c/o Takasago Machinery Works of, Torigoe, Taiji, c/o Takasago R &amp; D Center of
Applicants: MITSUBISHI HEAVY IND LTD, MITSUBISHI HEAVY INDUSTRIES, LTD.
Application year: 1999
Main classification: F02C7
IPC codes: C23C4, F02C7, F01D5, F01D25