EP0663964A1

EP0663964A1 - PROTECTION OF CHROMIUM-STEEL SUBSTRATES AGAINST CORROSIVE AND EROSIVE ATTACK AT TEMPERATURES UP TO ABOUT 500 oC.

Info

Publication number: EP0663964A1
Application number: EP93920767A
Authority: EP
Inventors: Friedhelm Schmitz
Original assignee: Siemens AG
Current assignee: Siemens AG
Priority date: 1992-10-05
Filing date: 1993-09-17
Publication date: 1995-07-26
Anticipated expiration: 2013-09-17
Also published as: DE59304920D1; KR950703669A; EP0663964B1; RU95110753A; CZ77395A3; ES2096943T3; JPH08501831A; US5547769A; WO1994008071A1

Abstract

The invention concerns a method of protecting chromium-steel substrates against corrosion and erosion at temperatures up to about 500 °C. A protective layer containing aluminium is formed on the substrate. The invention calls for this to be done by first depositing a metallic layer containing aluminium and then hardening or annealing at least the surface of the protective layer. The invention enables highly effective protection to be provided, using simple techniques, against corrosion and erosion, particularly for turbine blades, and in particular turbocompressor blades.

Description

Protection against corrosive and erosive attacks at temperatures up to about 500 ^* C for a substrate made of chrome steel.

The invention relates to protection against corrosive and erosive attack at temperatures up to about 500 ^* C for an existing chromium steel substrate by means of a Schutz¬ layer, which contains aluminum.

The invention relates to substrates on components for all types of turbomachinery, in particular turbocompressors regardless of the type of their drive, and on gas and steam turbines, with particular reference being made to components of such turbomachinery which are to be operated at temperatures of up to about 500 ^° C. . A particularly important field of application of the invention is the protection of compressor blades and other components loaded in this way in the turbocompressors of gas turbines.

Possibilities for protecting a substrate on a component of a turbomachine against corrosive and erosive attacks at temperatures up to 450 ^* C emerge from EP 0 379 699 AI. According to this document, blades for turbomachines, which mainly consist of ferritic and / or ferritic-martensitic base materials, are included

Protective layers made of aluminum alloys, in particular of aluminum alloys with 6 to 15% by weight of silicon, are provided. Such aluminum alloys are to be applied to the blades using a high-speed spraying process.

The phenomenon of vibration corrosion on coated compressor blades for turbomachinery is in the article "Vibration crack corrosion of coated compressor blade materials" by H. Hoffmann, W. Magin, M. Schemmer and F. Schmitz, Zeitschrift für Werkstofftechnik r7 (1986) 413, explained in detail. The compressor blades mentioned in this article have protective layers made of aluminum pigments dispersed in chromate / phosphate binders on substrates made of chromium steels. Protective layers made of nickel or nickel-cadmium alloys are also mentioned.

The problem of erosive attacks, to which compressor blades and the like are exposed, is explained in detail in the article "Investigation of the radiation wear resistance of materials and coatings with the aid of a fluidized bed test method" by KG Schmitt-Thomas, T. Happle and P. Steppe, Materials and Corrosion A (1990) 623. This article also deals with the interaction of erosion and corrosion on blades for turbomachinery, since erosion of a protective layer finally exposes the substrate of a blade, the material of which is usually essentially ¬ chen is only optimized for mechanical properties and does not have sufficient resistance to erosion and corrosion. The mechanisms of erosion, which in particular depend on the angles at which eroding particles strike a component, are explained in detail; the dependence of the effect of erosion on the type of material exposed to erosion is also explained. Erosion and corrosion problems of compressor blades, in particular of compressor blades with inorganically bound blades, are described in detail

Aluminum pigment coatings, which may have inorganic or organic top layers. Also from the book "Praxis der Kraftwerk-Chemie", published by Hans-Günter Heitmann, Vulkan-Verlag, Essen, 1986, in particular the article contained therein "Gasturbinen-Anlagen" by F. Schmitz, pp. 57A ff essential information on the problem of corrosive and erosive attacks in the compressors of gas turbine systems. Details on the erosive and corrosive attacks, in particular on vibration crack corrosion, and on the problems that occur when using conventional high-temperature lacquer protective layers are also explained.

In this regard, reference should be made to corrosion phenomena that start from pores in the protective layers and can damage the base materials under protective layers that appear more or less intact.

The article "Corrosion behavior of anodically oxidized aluminum materials" by W. Paatsch, metal surface A5 (1991) 8, provides information on corrosion phenomena on aluminum surfaces that have been anodically oxidized. The anodic oxidation of aluminum is known in many fields of technology, but not in connection with turbo machines, for the formation of robust, decorative surfaces. The article is silent on the problem of erosion and the resilience of an aluminum surface at elevated temperatures.

In respect of the problems of the previously temperatures to form a protection against corrosive and erosive attack at Tempera¬ to about 500 ^* C provided for a component of a turbomachine protective layers, the invention is the Auf¬ based on the object, a considerably improved protection for an existing chromium steel substrate to achieve, the cost of achieving protection also being kept low, possibly even reduced, shall be. According to the invention, methods for the formation of such protection, protective layers which ensure such protection, substrates which are provided with such protection and methods for producing such substrates are to be specified.

The inventive method for achieving protection against a corrosive and / or erosive attack at a temperature up to about 500 ^* C for a chrome steel existing of the substrate, forming said ge on the substrate, a protective layer, includes that aluminum, is characterized ge ¬ indicates that an aluminum-containing metal layer is applied to the substrate and is hardened or cured at least on its surface to form the protective layer.

The invention is based on the knowledge that the hardenability or hardenability of the aluminum itself or of the aluminum base materials can advantageously be used to form a protection of the type mentioned. The metal layer containing aluminum can be hardened, for example, chemically, in particular by oxidation, or mechanically, in particular by rolling. Curing is understood to mean, for example, a structural change in the metal layer caused by heat treatment, in particular precipitation hardening. The hardening or hardening need not necessarily cover the entire metal layer; it may be advantageous to restrict the hardening or hardening to a part near the surface and thus a so-called "duplex

The hard layer formed according to the invention advantageously has a Vickers hardness HV 0.025 of more than about 200, considerably more than HV 0.025 of a conventional high-temperature lacquer layer, where HV 0.025 is usually at most 120. The metal layer to be applied to the substrate to be protected advantageously consists mainly of aluminum and is accordingly in particular an aluminum-based alloy, for example with the addition of at least one of the elements magnesium, copper and zinc. Silicon, manganese and titanium can also be used as additives.

The hardening or hardening of the metal layer takes place with particular advantage in such a way that the metal layer is converted at least on its surface into a hard layer. As already indicated, the hard layer can be produced by numerous different methods that may be combined with one another, in particular mechanical strengthening, chemical or thermal treatment. It is particularly favorable if a part of the metal layer remains under the hard layer, so that the protective layer is a duplex layer which comprises the metal layer and the hard layer. In view of the erosion attack which is dependent on the orientation of the attacked areas of the substrate in relation to the direction of flight of eroding particles, a duplex layer, which comprises a rather hard layer on the one hand and a rather ductile metal layer on the other hand, is particularly favorable since hard layers and ductile layers each withstand different types of erosion: hard layers are suitable as protection against erosion attack by particles which strike grazing to approximately at an angle, ductile metal layers are advantageous for protection against erosion through at large angles, in particular at an angle to approximately vertical, impacting particles. The duplex layer can therefore provide protection against eroding particles regardless of their angle of incidence, although removal of the hard layer must initially be expected in areas of the component where the particles meet approximately vertically until which is exposed to erosion resistant to large impact angles, ductile metal layer.

In any case, it is particularly favorable to form a hard layer by at least partially oxidizing the metal layer; the oxidizing is preferably an anodizing, in particular anodizing. Following an anodizing, the hard layer obtained can be additionally compacted by treating it with boiling water or a boiling, aqueous salt solution. Details of this are known in the field of anodic oxidation of aluminum and do not require any further explanation at this point. Any oxidation of an aluminum-containing layer produces a surface layer which has aluminum oxide or corundum, one of the hardest minerals, as an essential component. In order to achieve a particularly thick, dense and hard layer, anodic oxidation is particularly suitable. It should be noted that not only layers of essentially pure aluminum can be used for anodic oxidation, but in particular also layers of aluminum-magnesium alloys. In particular, aluminum-based alloys with the addition of magnesium in a proportion by weight of between 0.5% and 5%, in particular between 1% and A%, possibly with further small proportions of silicon, iron, copper, chromium, zinc and / or titanium in the usual framework.

An alternative method of forming a hard layer on a metal layer is to use a hardenable alloy to form the metal layer followed by hardening. The hardening can be limited to a region of the metal layer near the surface are achieved by curing, for example, by irradiation with laser light; it can also cover the entire metal layer, for which the component provided with the metal layer can be heat-treated in a conventional manner in an oven. An aluminum-based alloy with additions of magnesium and copper or zinc is particularly suitable as the hardenable alloy. Advantageously, an aluminum-based alloy is used with a weight proportion of magnesium between 0, A and 2% and copper between 3.5 and 5%, with usual impurities and possibly further admixtures, as mentioned above. Also possible is an aluminum-based alloy with a weight proportion of zinc between 1% and 5%, in particular between A% and 5%, and magnesium up to 2%, in particular between 1% and 1.5%, also with usual impurities and any other admixtures.

Generally, it is advantageous to about 500 ^* C apply to the formation of the protection against corrosive and erosive attack at temperatures on the substrate a metal layer having a thickness which microns between 15 and 200 μ, vor¬ preferably between AO microns and 100 μ is, .

The metal layer is applied electrochemically, in particular by electroplating, as part of any configuration of the method. Electroplating produces a particularly uniform and dense layer with extremely low porosity, in which the occurrence of pitting corrosion is accordingly suppressed. Pitting corrosion occurs when an electrically conductive liquid, for example a water drop with salt or ash parts, enters a pore of the protective layer and with the protective layer and the Substrate forms a galvanic element. The decomposition processes occurring in such an element can, starting from the pore, spread into the boundary layer between the protective layer and the substrate and destroy the substrate under the externally intact protective layer. For this reason, the electrochemical application of the metal layer is particularly preferred since it avoids pores.

It is particularly advantageous to apply the protective layer of any configuration directly to the substrate, that is to say without inserting any intermediate layers. As a result, the outlay associated with achieving protection is kept low.

According to the invention, a protective layer is provided on a substrate made of chrome steel, which protective layer provides protection against corrosive and erosive attack at Tem¬ temperatures up to about 500 ^* C has and by at least superficial hardening or curing a coating applied to the substrate, aluminum-containing metal layer by the method according to the invention was formed.

The invention also relates to a substrate which is provided with a protective layer according to the invention as protection against corrosive and / or erosive attack at a temperature of up to about 500 ^° C. Such a substrate can in particular belong to a blade of a turbomachine such as a turbocompressor, be it a rotor blade or a guide blade. The blade can have a foot part for fastening the component and a blade part which is the effective part in the thermodynamic process in the turbomachine, and at least one of which is a gas, in particular air, gas turbine exhaust gas or steam, exposed sheet part has a substrate protected according to the invention.

The substrate preferably consists of a chromium steel with the following proportions, the proportions being given in percentages by weight: 0.1 to 0.3% carbon 11 to 17% chromium 0 to 6% nickel 0 to 1.5 X molybdenum 0 to 1 % Vanadium 0 to 1% silicon 0 to 1% manganese balance iron with manufacturing-related impurities.

The substrate protected according to the invention preferably has, at least in part, a ferritic or martensitic structure.

Examples of chromium steels which are suitable for substrates to be protected according to the invention are the chromium steels X20 Cr 13, X20 CrMoV 12 1, X20 CrNiMo 15 5 1, X12 CrNiMo 12. The chromium steel X20 Cr 13 is regarded as particularly preferred.

The method according to the invention for producing a substrate which has protection against a corrosive and / or erosive attack at a temperature of up to about 500 ^° C. is characterized by the use of the method described above for forming the protection.

The invention relates to achieving protection for a substrate, in particular a substrate on a turbine or compressor blade of a turbomachine, against one Corrosive and / or erosive attack at a temperature up to about 500 'C. A protective layer is formed on the substrate, which contains aluminum. According to the invention, a metal layer containing aluminum is first applied and hardened or cured at least on its surface to form the protective layer. Within the scope of the invention, highly effective protection against corrosion and erosion can be obtained with simple means.

Claims

1. A method for achieving protection against a corrosive and / or erosive attack at a temperature up to about 500 ^* C for a substrate made of chromium steel, a protective layer comprising aluminum being formed on the substrate, characterized in that an aluminum-containing metal layer is applied to the substrate and is hardened or cured at least on its surface to form the protective layer.

2. The method according to claim 1, in which a metal layer is applied which consists mainly of aluminum, in particular an aluminum-based alloy, in particular with the addition of at least one of the elements magnesium, copper and zinc.

3. The method according to claim 1 or 2, in which to form the protective layer, the metal layer at least on it

Surface is converted into a hard layer.

A. The method of claim 3, wherein the metal layer is at least partially substantially completely converted into the hard layer.

5. The method according to claim 3 or A, in which at least in places a part of the metal layer remains under the hard layer.

6. The method of claim 3, A or 5, wherein the hard layer is formed by oxidizing the metal layer. 7. The method according to claim 6, wherein the oxidizing is an anodizing, in particular anodizing.

8. The method according to claim 7, in which the hard layer is compressed, in particular by treatment with boiling water or boiling, aqueous salt solutions.

9. The method according to any one of claims 3 to 5, wherein the metal layer is formed from a hardenable alloy and is hardened to form the hard layer.

10. The method according to claim 9, wherein the alloy is an aluminum-based alloy, in particular with additions of magnesium and copper or zinc.

11. The method according to any one of the preceding claims, in which a metal layer is formed with a thickness which is between 15 μm and 200 μm, preferably between AO μm and 100 μm.

12. The method according to any one of the preceding claims, in which the application of the metal layer is carried out electrochemically, in particular by electroplating.

13. The method according to any one of the preceding claims, in which the protective layer is applied directly to the substrate.

1A. Protective layer on a substrate made of chrome steel, which offers protection against corrosive and erosive attacks at temperatures up to about 500 ^* C, produced by a method according to one of the preceding claims. 15. substrate which has a protective layer according to claim 1A as protection against corrosive and erosive attacks at temperatures up to about 500 ^* C.

16. The substrate according to claim 15, which belongs to a blade, in particular a moving blade or a guide blade, for a turbomachine, preferably for a turbocompressor.

17. The substrate of claim 16, wherein the blade is one

Has foot part and a leaf part and wherein the substrate belongs to the leaf part.

18. Substrate according to one of claims 15 to 17, which consists of a chromium steel with the following proportions

(In percentages by weight):

0.1 to 0.3% carbon

11 to 17% chromium

0 to 6% nickel 0 to 1.5 X molybdenum

0 to 1% vanadium

0 to 1% silicon

0 to 1% manganese

Remainder iron with production-related impurities.

19. Substrate according to one of claims 15 to 18, which at least partially has a ferritic or martensitic structure.

20. A method for producing a substrate which has protection against corrosive and erosive attacks at temperatures up to about 500 ^* C, characterized ¬ characterized by the use of the method for forming the protection according to one of claims 1 to 13.