Patent Application
20080166589
This application claims priority to German Patent Application Serial No. DE 10 2005 036 162.5, filed Aug. 2, 2005, the entire disclosure of which is incorporated by reference herein.
The present invention relates to a component having a corrosion-resistant and/or oxidation-resistant coating that includes at least one platinum-aluminum substrate area. In addition, the present invention relates to a corrosion-resistant and/or oxidation-resistant coating, and a method for producing such a corrosion-resistant and/or oxidation-resistant coating.
When components, in particular gas turbine components, are operated at high temperatures, their free surfaces are exposed to highly corrosive and/or oxidizing conditions. When employed in gas turbines, such components may be made for example of a super-alloy based on nickel. To protect them against corrosion and/or oxidation, such components are provided with coatings. To provide a corrosion-resistant and/or oxidation-resistant coating on a component, known methods already precipitate aluminum, and platinum if appropriate, on a substrate surface of the component, to provide a coating in the form of an aluminum substrate area or a platinum-aluminum substrate area. Compared to pure aluminum coatings, platinum-aluminum coatings have the advantage of increased resistance to oxidation and to corrosion from hot gases; such platinum-aluminum coatings are brittle, however, and thus have limited thermal-mechanical strength.
EP 0 784 104 B1 describes a component made of a nickel-based alloy with a platinum-aluminum substrate area, platinum first being precipitated onto a substrate surface of the component and then being diffused into the substrate surface to provide the platinum-aluminum substrate area. After that the component coated with platinum is alitized, in order to provide a platinum-aluminum substrate area that has an integrated aluminum content of 18% by weight to 20% by weight, an integrated platinum content of 18% by weight to 45% by weight, and the remainder components of the substrate composition.
The platinum-aluminum substrate area described in EP 0 784 104 B1, or the component described there having such a coating, has relatively low ductility, which results in limited thermal-mechanical strength (TMS), in particular limited HCF strength and LCF strength. Because of the limited thermal mechanical strength of the platinum-aluminum substrate area described there, cracks can form therein, limiting the durability of the coating.
It is also known from EP 0 784 104 B1 to apply a ceramic layer to the platinum-aluminum substrate area. However, the durability of the ceramic layer on the platinum-aluminum substrate area according to EP 0 784 104 B1 is limited.
Another component having a platinum-aluminum substrate area is known from U.S. Pat. No. 6,589,668 B1, the platinum-aluminum substrate area described there having an inner aluminum diffusion zone and an outer platinum-aluminum zone with a single-phase structure. The coating known from this related art also has limited thermal-mechanical strength, and thus limited durability.
U.S. Pat. No. 5,514,482 should also be referenced as related art, which describes a component onto whose substrate surface an aluminum substrate area of aluminum oxide is deposited, a ceramic layer being applied to this aluminum substrate area including an interposed thin aluminum film. This coating of a component also has limited thermal-mechanical strength, and thus limited durability.
Against this background, the object of the present invention is to create an innovative component having a corrosion-resistant and/or oxidation-resistant coating, an innovative corrosion-resistant and/or oxidation-resistant coating, and an innovative method for producing a corrosion-resistant and/or oxidation-resistant coating.
This object is achieved by a component having a corrosion-resistant and/or oxidation-resistant coating. In accordance with an embodiment of the present invention a component having a corrosion-resistant and/or oxidation-resistant coating is provided. The component has a substrate surface and a substrate composition based on nickel. A platinum-aluminum substrate area is formed in the area of the substrate surface of the component by precipitating platinum (Pt) and aluminum (Al) on the substrate surface. The platinum-aluminum substrate area has an inner zone and an outer zone, and the inner zone is located between the substrate surface of the component and the outer zone. The platinum-aluminum substrate area has a two-phase structure or duplex structure in the outer zone, and the two-phase structure or duplex structure includes finely dispersed platinum-aluminum deposits in a nickel-based mixed crystal. The platinum-aluminum substrate area has a single-phase structure of a nickel-based mixed crystal in the inner zone.
In accordance with another embodiment of the present invention, a corrosion-resistant and/or oxidation-resistant coating for a component is provided. The coating includes a platinum-aluminum substrate area formed in the area of a substrate surface of the component by precipitating platinum (Pt) and aluminum (Al) on the substrate surface. The platinum-aluminum substrate area has an inner zone and an outer zone, and the inner zone is located between the substrate surface of the component and the outer zone. The platinum-aluminum substrate area has a two-phase structure or duplex structure in the outer zone, and the two-phase structure or duplex structure includes finely dispersed platinum-aluminum deposits in a nickel-based mixed crystal. The platinum-aluminum substrate area has a single-phase structure of a nickel-based mixed crystal in the inner zone.
In accordance with another embodiment of the present invention, a method for producing a corrosion-resistant and/or oxidation-resistant coating is provided, comprising the steps of precipitating platinum onto a surface of a substrate of a component; then diffusing the platinum into the substrate surface; and then an alitizating the substrate, wherein the alitizating further comprises precipitating aluminum thermochemically in a high-activity gas phase process, and thereafter, diffusing aluminum into the substrate surface, such that a platinum-aluminum substrate area is formed that has a two-phase structure or a duplex structure with finely-dispersed platinum-aluminum deposits in a nickel-based mixed crystal in an outer zone, and a single-phase structure made of a nickel-based mixed crystal is formed in an inner zone located between the substrate surface of the component and the outer zone.
As recited in the present invention, the platinum-aluminum substrate area of the corrosion-resistant and/or oxidation-resistant coating of the component includes at least two zones, namely an outer zone having a two-phase structure or duplex structure with finely dispersed platinum-aluminum deposits in a nickel-based mixed crystal, and an inner zone facing the substrate surface, with a single-phase structure made of a nickel-based mixed crystal. The platinum-aluminum substrate area of the present invention has good thermal-mechanical strength, and thus provides effective and durable oxidation protection and corrosion protection, even at high temperatures and under high mechanical stress. In addition, the platinum-aluminum substrate area of the corrosion-resistant and/or oxidation-resistant coating is suitable for effective bonding of a ceramic heat protection layer to the platinum-aluminum substrate area.
Preferably the outer zone of the platinum-aluminum substrate area, having the two-phase structure or duplex structure, has finely dispersed, globulitic PtAl2 deposits between 0.1 μm and 3.0 μm in size in a mixed crystal of β-NiAl, the proportion of the two-phase structure or duplex structure being between 2.0% by volume and 40.0% by volume, and the aluminum proportion in the mixed crystal being greater than 20.0% by weight. In the inner zone of the platinum-aluminum substrate area, the Al proportion in the nickel-based mixed crystal is a maximum of 15.0% by weight and the Pt proportion in the nickel-based mixed crystal is a maximum of 8.0% by weight.
According to an advantageous refinement of the present invention, a ceramic layer is applied to the platinum-aluminum substrate area, an aluminum oxide intermediate layer being formed between the platinum-aluminum substrate area and the ceramic layer. Preferably, the ceramic layer is in the form of a zirconium oxide layer, the Al2O3 intermediate layer having a proportion of at least 90.0% by volume of alpha Al2O3 with a rhombohedral crystal lattice structure and a proportion of no more than 10.0% by volume of gamma Al2O3 with a cubic crystal lattice structure, and the zirconium oxide layer including a proportion of no more than 8.0% by weight of yttrium oxide.
Exemplary embodiments of the present invention will be explained in greater detail on the basis of the following drawings, but are not limited thereto.
Embodiments of the present invention will be described in greater detail below, with reference to
Outer zone 13, having the two-phase structure or duplex structure, has finely dispersed, globulitic PtAl2 deposits between 0.1 μm and 3.0 μm in size in a mixed crystal of β-NiAl, the proportion of the two-phase structure or duplex structure being between 2.0% by volume and 40.0% by volume, and the aluminum proportion in the mixed crystal being greater than 20.0% by weight. In inner zone 14 the Al proportion in the nickel-based mixed crystal is a maximum of 15.0% by weight and the Pt proportion in the nickel-based mixed crystal is a maximum of 8.0% by weight. Yttrium and/or hafnium may be present both in outer zone 13 and in inner diffusion zone 14 of the platinum-aluminum substrate area, the maximum yttrium proportion being 1.5% by weight and/or the maximum hafnium proportion also being 1.5% by weight in both zones 13 and 14.
Preferably, the size of the PtAl2 deposits is between 0.1 μm and 1.0 μm in outer zone 13 of platinum-aluminum substrate area 12, the proportion of the two-phase structure or duplex structure is between 2.0% by volume and 20.0% by volume, and the proportion of aluminum in the mixed crystal is greater than 25% by weight. In inner diffusion zone 14 the maximum proportion of aluminum is preferably 10.0% by weight and the maximum proportion of platinum is 1.0% by weight, while in an especially preferred embodiment the maximum proportion of platinum in inner diffusion zone 14 of platinum-aluminum substrate area 12 is 0.1% by weight.
To produce component 10 shown in
Component 10 may be for example a rotor blade of a gas turbine made of a monocrystalline nickel-based alloy of type SC 2000, which includes over 5.0% by weight of cobalt, 10.0% by weight of chromium, 5.0% by weight of aluminum, 1.5% by weight of titanium, 12.0% by weight of tantalum, 4.0% by weight of tungsten, and a remainder of nickel.
In a second step prepared component 10 is then cleaned in the area of substrate surface 11, preferably by abrasive blasting with an aluminum oxide abrasive which has a particle size between 5 μm and 150 μm, preferably between 45 μm and 75 μm. The abrasive blasting takes place preferably in a multiple-jet blasting facility at a pressure of between 2 bar and 5 bar, preferably at a pressure of 3 bar, where a degree of overlap of the abrasive blasting is between 400% and 1000%, preferably 800%. In this process a layer thickness between 5 μm and 10 μm is removed from substrate surface 11 by abrasion.
Following the abrasive blasting or cleaning of substrate surface 11 of component 10, platinum is precipitated onto the cleaned substrate surface 11 of component 10, a platinum layer thickness between 1 μm and 10 μm, preferably between 2 μm and 4 μm, forming here.
Following precipitation of the platinum onto substrate surface 11 of component 10, the platinum is diffused into the substrate surface, the diffusing preferably being carried out as diffusing annealing at a temperature between 960° C. and 1,160° C., preferably at a temperature between 1000° C. and 1,100° C. The holding period of the diffusion annealing to diffuse the platinum into substrate surface 11 is relatively short, i.e., between 5 minutes and 60 minutes, preferably between 5 minutes and 15 minutes.
In an additional step of the method according to the present invention, aluminum is then precipitated onto platinum-coated substrate surface 11. Aluminum is precipitated thermochemically in a high-activity gas phase process in an atmosphere of aluminum monohalogenides, the proportion of aluminum monohalogenides in the atmosphere being at least 15% by volume, the pressure during precipitation being 10 mbar to 800 mbar above normal pressure or ambient pressure, and the temperature being between 950° C. and 1,140° C.
Following the precipitation of the aluminum, the aluminum is diffused at an activity level of at least 50 atom percent in relation to pure nickel, the diffusing taking place at a temperature that is at least 10° C. lower than the annealing temperature of the platinum, and the holding period for diffusing the aluminum being between 180 minutes and 360 minutes, preferably between 210 minutes and 330 minutes. Platinum-aluminum substrate area 12 is formed, with a thickness of approximately 60 μm.
Using the above method, platinum-aluminum substrate area 12 shown in
Aluminum oxide intermediate layer 16, which adjoins outer zone 13 of platinum-aluminum substrate area 12, is implemented as an Al2O3 intermediate layer, and has a proportion of at least 90.0% by volume of alpha Al2O3 with a rhombohedral crystal lattice structure and a proportion of no more than 10.0% by volume of gamma Al2O3 with a cubic crystal lattice structure, the crystal lattice structures having similar lattice sizes. The maximum deviation of the lattice sizes of the crystal lattice structure is approximately 2%.
Ceramic layer 15, which is in the form of a zirconium oxide layer having a maximum proportion of 8.0% by weight of yttrium oxide, is deposited onto this aluminum oxide intermediate layer 16. Ceramic layer 15 has a columnar structure and a cubic-tetragonal crystal lattice, ceramic layer 15 adhering very well to aluminum oxide intermediate layer 16.
The thickness of aluminum oxide intermediate layer 16 is between 0.02 μm and 0.8 μm, and the thickness of ceramic layer 15 is between 100 μm and 200 μm. Within ceramic layer 15, which has a laminar columnar structure, the minimum ratio of height to width of the columns is 10, the length of the columns being between 0.05 μm and 0.5 μm.
The component according to the present invention as shown in
After such a component 10 is prepared, substrate surface 11 made thereof is cleaned, preferably by abrasive blasting using corundum with a particle size between 20 μm and 100 μm at a pressure of 2.5 bar and a degree of overlap in a multiple-jet blasting facility of preferably 800%±200%. In this process a layer thickness between 3 μm and 10 μm is removed from substrate surface 11 by abrasion.
Following the cleaning of substrate surface 11, platinum with a layer thickness of preferably 2 μm to 4 μm is precipitated onto substrate surface 11, and following the platinum precipitation, platinum is diffused at a temperature of approximately 1,080° C. and at a holding time of approximately 15 minutes.
After this platinum coating of the substrate surface, aluminum is precipitated as in the exemplary embodiment of
After platinum-aluminum substrate area 12 is prepared, platinum-aluminum substrate area 12 is cleaned by abrasive blasting to form aluminum oxide intermediate layer 16, a layer thickness of approximately 2 μm being removed during the mechanical abrasive blasting of outer zone 13 of platinum-aluminum substrate area 12. The thickness of the removed layer here may be between 0.5 μm and 8 μm, preferably between 1 μm and 3 μm. The mechanical abrasive blasting is preferably done using aluminum oxide particles with a particle size between 10 μm and 150 μm, preferably between 10 μm and 50 μm. The blasting pressure is under 3 bar, preferably 2.5 bar, the abrasive blasting being performed with a degree of overlap of between 300% and 1,500%, preferably with a degree of overlap of between 300% and 500%.
To form aluminum oxide intermediate layer 16, the component coated with platinum-aluminum substrate area 12 and cleaned undergoes a thermo-oxidative treatment by heating it under a high vacuum at a pressure of approximately 14 mbar to a temperature of approximately 900° C., and then holding it at a temperature of between 900° C. and 1,100° C. under low vacuum or partial vacuum at a maximum pressure of 5×10−2 for about 10 minutes. During this holding in a low vacuum or partial vacuum of preferably 10−3 mbar, an atmosphere of oxygen and argon or helium prevails, the proportion of oxygen being between 25% by volume and 60% by volume and accordingly the proportion of argon or helium being between 75% by volume and 40% by volume. In this way it is possible to prepare aluminum oxide intermediate layer 16, which is preferably made of pure alpha Al2O3.
Following the formation of aluminum oxide intermediate layer 16, ceramic layer 15 is deposited onto aluminum oxide intermediate layer 16 by precipitating zirconium oxide Zr2O3 with a maximum proportion of 8.0% by weight of yttrium oxide (Y2O3). Ceramic layer 15 is precipitated under thermal oxidizing conditions, a temperature between 900° C. and 1,100° C. being held for a predetermined time of approximately 15 minutes at a low vacuum or partial vacuum. An atmosphere of oxygen and argon and helium prevails, the proportion of oxygen being between 25% by volume and 60% by volume.
The ceramic layer is vapor-deposited with an oscillating and/or wobbling motion of component 11 in a vapor cone of the ceramic material. Ceramic layer 15 may also be precipitated as a sol-gel process or CVD process or PVD process.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2005 036 162.5 | Aug 2005 | DE | national |
