Stock material or miscellaneous articles – All metal or with adjacent metals – Composite; i.e. – plural – adjacent – spatially distinct metal...
Reexamination Certificate
2001-10-01
2004-01-06
Koehler, Robert R. (Department: 1775)
Stock material or miscellaneous articles
All metal or with adjacent metals
Composite; i.e., plural, adjacent, spatially distinct metal...
C148S527000, C427S383700, C427S446000, C428S610000, C428S636000, C428S637000, C428S650000, C428S652000, C428S656000, C428S666000, C428S667000, C428S668000, C428S678000, C428S679000, C428S680000, C428S681000, C428S685000, C428S686000, C428S925000, C428S926000, C428S935000, C428S936000, C428S937000
Reexamination Certificate
active
06673467
ABSTRACT:
FIELD OF THE INVENTION
The invention pertains to metallic components with a coating that is resistant to high temperature steam oxidation and/or corrosion and to a method of applying the coating to the metallic component.
BACKGROUND OF THE INVENTION
It is well known that metallic components exposed to high temperature steam can oxidize and/or corrode and sustain damage when surface oxide layers spall off. Such damage due to high temperature steam oxidation is observed for example on components in steam power plants. These components are exposed to steam of temperatures higher than 550° C. as such steam temperatures are necessary to increase the power plant efficiency.
Oxide layers on components of steam power plants can cause various problems. For example, on heated components such as boiler tubes the growth of oxide layers reduces the thermal conductivity from the outside or fireside to the inside or steam side of the tube walls. This results in an increase of the wall temperature, which in turn can cause creep failure under the internal pressure loading. From heated as well as not heated components exposed to high temperature steam the oxide layers can spall off, which can result in the formation of hard oxide particles. Such particles can cause erosion on other parts of the power plant such as boiler parts, turbine blades and vanes, the rotor, piping, or housing components. They can also impair the function of devices, for example by blocking valve components. As a result, the lifetime of the components is severely reduced.
Steels with a modified composition, for example with additional chromium or cobalt, show a greater oxidation resistance and greatly improve component durability and lifetime. However, the advantage of good oxidation resistance is countered by high cost and, in the case of chromium addition, by a reduction in creep strength, which is necessary in high temperature applications.
The oxidation resistance of components is also improved by the application of protective coatings. The components may be manufactured using relatively low cost materials and coated with very thin layers at only a modest cost. Various coatings are known for the application to components of steam power plants.
U.S. Pat. No. 5,595,831 discloses turbine components plated with nickel metal and coated with a protective layer against corrosion consisting essentially of nickel and zinc. In order to prevent the zinc from diffusing into the component material the component surface is plated with a nickel metal prior to the application of the nickel/zinc coating.
DE 19728054 discloses a tube used for example for the superheating of steam in a boiler of a steam power plant. The tube comprises on its inner surface a coating consisting of a nickel-phosphorus alloy. The coating provides a high oxidation and temperature resistance.
WO 00/70190 discloses a metallic component comprising a coating essentially consisting of aluminum and applied to the component surface by diffusion. The coating provides a resistance to high temperature steam oxidation.
Tests have shown that coatings of these types described above generally suffer from cracking either during application or during exposure of the component to high temperature steam. The cracking eventually allows steam to reach through the coating to the component surface and for oxidation to occur. Even in the case when the coating material is diffused into the substrate material cracks have been observed beyond the diffusion depth and to cause oxidation in the component base material.
SUMMARY OF THE INVENTION
In view of the problems disclosed in connection with the development of metallic components resistant to high temperature steam oxidation it is the object of the invention to provide a metallic component that is resistant to high temperature steam oxidation over a long period of time. In particular, the metallic component shall not develop cracks as observed in components of the state of the art that allow oxidation to occur of the base material of the component after a certain time of exposure. The component shall furthermore be resistant to mechanical loading as for example by impingement of hard solid particles resulting from oxidation and spalling of oxide particles. Furthermore, the metallic component shall have the aforementioned characteristics even when it has a complex shape. Finally, the component shall be relatively low in cost compared to the disclosed components of the state of the art.
It is a further object of the invention to provide a method to manufacture and apply the coating to the surface of the metallic component.
A metallic component exposed to high temperature steam is equipped with a coating that protects the surface of the metallic component from oxidation and/or corrosion. According to the invention the coating on the surface of the metallic component comprises one or more thin, oxidation resistant primer layers that have a high ductility and are free of cracks and pores. Furthermore, the coating comprises one or more oxidation resistant and lower ductility overlay layers deposited on top of the one or more primer layers that protect the primer layers from mechanical damage and have greater thickness than the primer layers.
The one or more primer layers deposited immediately on the surface of the base material of the metallic component consist of an oxidation resistant material and are highly ductile. The high ductility of the material yields a layer that is dense and remains free of any defects such as cracks, pores, or cavities over a long period of exposure to high temperature steam. The crack-free primer layer allows no oxidizing steam to reach the base material of the component and hence provides a very high oxidation resistance.
Such crack-free materials are typically very costly; hence the primer layer is deposited as a thin layer so as to minimize the amount of material necessary. However, a thin layer is more prone to mechanical damage such as from particle impingement than is a thick layer. For this reason an oxidation resistant overlay layer of greater thickness is applied on top of the primer layer in order to provide mechanical protection. As the greater thickness of the overlay layer requires more material a less costly material is chosen for it so that the overall component cost remains low. Low cost material layers tend to be more brittle and form cracks after a certain time of exposure to high temperature steam. Such cracks allow oxidizing steam to penetrate through the overlay layer. However, the crack-free primer layer prevents it from reaching the surface of the base material of the component as the primer layer mainly provides the oxidation resistance.
The combination of primer layer and overlay layer according to the invention provides the necessary oxidation resistance over a long exposure time as well as resistance to mechanical damage. Furthermore, the choice of materials and their thicknesses yields a relatively low-cost protective coating.
In a first embodiment of the invention the one or more primer layers comprise a superalloy such as for example a nickel or cobalt based alloy or a stellite alloy.
In a preferred embodiment the superalloy consists of MCrAlY where the M signifies a metal such as Ni, Co, or Fe.
In a further embodiment of the invention the primer layer is applied in a layer with a thickness equal to or less than 30 microns.
In a preferred embodiment of the invention the thickness of the primer layer is approximately 5 microns.
In a further embodiment of the invention the overlay layer comprises a Ni—P alloy, an Al or Al—Si alloy, or Cr alloy.
These are low-cost materials known for their oxidation resistance. They are easily applied in larger thicknesses. However, due to their brittle characteristic they form cracks that can reach through the entire layer down to the surface of the primer layer.
In a particular embodiment of the invention the thickness of the overlay layer is in the range from 30 to 100 microns. This thickness assures the protection of the primer layer from mecha
Knödler Reinhard
Scarlin Richard Brendon
Alstom (Switzerland Ltd
Burns Doane Swecker & Mathis L.L.P.
Koehler Robert R.
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