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WO2008034732A2 - Layered structure and method for producing a layered structure - Google Patents

Layered structure and method for producing a layered structure Download PDF

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Publication number
WO2008034732A2
WO2008034732A2 PCT/EP2007/059467 EP2007059467W WO2008034732A2 WO 2008034732 A2 WO2008034732 A2 WO 2008034732A2 EP 2007059467 W EP2007059467 W EP 2007059467W WO 2008034732 A2 WO2008034732 A2 WO 2008034732A2
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WO
WIPO (PCT)
Prior art keywords
sacrificial anode
structure according
substrate
coating
layer structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2007/059467
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German (de)
French (fr)
Other versions
WO2008034732A3 (en
Inventor
Rene Jabado
Jens Dahl Jensen
Ursus KRÜGER
Daniel Körtvelyessy
Volkmar LÜTHEN
Ralph Reiche
Michael Rindler
Raymond Ullrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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Publication date
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Publication of WO2008034732A2 publication Critical patent/WO2008034732A2/en
Publication of WO2008034732A3 publication Critical patent/WO2008034732A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the present invention relates to a layer structure comprising a substrate made of a substrate material and a corrosion and / or oxidation-inhibiting layer located on the substrate.
  • Corrosion and / or oxidation inhibiting layers and coatings are used where components are exposed to corrosive hot gases.
  • this is binenbau former at Tur ⁇ such as Gasturbinenlauf- or vanes or elements of combustor liners of the case.
  • a typical corrosion and / or oxidation-inhibiting coating is the so-called MCrAlX coating, where M is at least one element of the group consisting of iron (Fe), cobalt (Co), nickel (Ni) and X for an active element, such as yttrium
  • Such alloys are known, for example, from EP 0 486 489 B1, EP 0 786 017 B1, EP 0 412 397 B1 or EP 1 306 454 A1.
  • Such have coatings contain aluminum phases in which the aluminum acts as a sacrificial anode, by, for example, with Feuch ⁇ tmaschinesfilmen on the surface and forms a galvanic cell the material to be protected. This consumes aluminum, which over time reduces the effect of a MCrAlX coating and, after a certain period of use, makes it necessary to remove the coating of components and to re-coat.
  • the object of the present invention is to specify a layer structure which has a corrosion- and / or oxidation-inhibiting layer with a sacrificial anode material and which allows a longer service life in a corrosive and / or oxidative hot gas environment.
  • Another object of the present invention is to provide a method for producing a layered structure which allows a longer operating life of the layered structure in a corrosive and / or oxidative hot gas environment.
  • a layer structure according to the invention has a substrate made of a substrate material and a corrosion and / or oxidation-inhibiting layer on the substrate with an op ⁇ feranodenmaterial. Further, the layer structure of the invention comprises nanoscale Kochanodenteilchen from the sacrificial anode material, which are encapsulated with a ver ⁇ different from the sacrificial anode material encapsulating material.
  • the encapsulated sacrificial anode particles constitute a depot for sacrificial anode material, which in the course of operation of the
  • the sacrificial anode material of the nanoscale sacrificial anode particles can diffuse through the coating and replace used sacrificial anode material.
  • the diffusion of the sacrificial anode particles is slowed down, so that the Agglomerati- onsrea and thus the depletion of coating areas are suppressed. It is therefore available over a long period of time in all areas of the corrosion and / or oxidation-inhibiting coating material replenishment for spent sacrificial ⁇ anode material, especially if a homogeneous distribution of the sacrificial anode particles in the corrosion and / or oxidation-inhibiting layer is present.
  • encapsulation material can be used, for example, the substrate mate ⁇ rial or a component thereof. May be stratmaterial the sub- a super alloy of iron, cobalt or nickel ⁇ as parts especially for turbine ⁇ such as running or vanes of gas turbines is used.
  • the encapsulating material may be, for example, iron, cobalt or nickel.
  • Aluminum can be used in particular as sacrificial nanomaterial.
  • op ⁇ feranodenmaterial materials which emit electrons more easily than the main constituent of the substrate material are suitable as op ⁇ feranodenmaterial.
  • iron, cobalt or nickel-based superalloys these are materials that emit electrons more easily than iron, cobalt or nickel.
  • Suitable materials for such cases would be ⁇ example, chromium (Cr), zinc (Zn), titanium (Ti), vanadium (V), lanthanum (La), magnesium (Mg) or cerium (Ce).
  • the distribution of the sacrificial anode particles in the corrosion and / or oxidation-inhibiting layer can be kept stable for a particularly long time. Since ⁇ through can further counteracted agglomeration and the Operating time until the corrosion and / or oxidation-inhibiting layer must be replaced further extended ⁇ who.
  • an MCrAlX layer As corrosion and / or oxidation-inhibiting layer to ⁇ particular an MCrAlX layer can be used.
  • the substrate may in particular be the main body of a turbine component, for example a guide or moving blade of a gas turbine or an element of a combustion chamber lining.
  • a coating material is applied to a processing substrate comprising nanoscale sacrificial anode part ⁇ surfaces of a sacrificial anode material.
  • the sacrificial anodes ⁇ particles are encapsulated with a different from the sacrificial anode material encapsulation.
  • the encapsulating material is surrounded by a polymer shell.
  • a heat treatment is carried out, whose time and temperature control is selected such that crosslinking of the polymer shells takes place.
  • FIG. 1A shows a schematic representation of a layer structure according to the invention in plan view.
  • FIG. 1B shows the layer structure from FIG. 1A in a cross-sectional view.
  • FIG. 2 shows a schematic representation of a production step for a layer structure according to the invention in accordance with a second exemplary embodiment.
  • FIG. 3A shows a schematic representation of a second exemplary embodiment of the layer structure according to the invention in a plan view.
  • FIG. 3B shows the layer structure according to the invention from FIG. 3A in a cross-sectional view.
  • FIGS. 1A and 1B A layer structure according to the invention is shown in highly schematic form in FIGS. 1A and 1B.
  • the figures show a section of the layer structure in plan view (FIG. 1A) and in a cross-sectional view (FIG. 1B).
  • the (IA Fig.) IB FIG.) are views rep ⁇ räsentieren the view of a provided with a corrosion and / or oxidation resistant coating or turbine blade also greatly schemati ⁇ Siert a cross section through the wall of a coated turbine blade.
  • FIG. 1B While the corrosion-resistant and / or oxidation-inhibiting coating 1 and the base body 3 of the turbine blade, which forms the substrate for the coating 1, can be seen in FIG. 1B, only the coating 1 can be seen in FIG. 1A.
  • the coating 1 in the present exemplary embodiment is an MCrAlX coating which comprises an aluminum component. holds.
  • the aluminum serves as a sacrificial anode for corrosion and / or oxidation protection.
  • a thermal barrier coating (TBC, Thermal Barrier Coating) may be present on the MCrAlX coating, which is not shown in the figures.
  • TBC Thermal Barrier Coating
  • Such thermal barrier coatings are at ⁇ play, coatings of zirconium oxide (ZrO 2) whose Git ⁇ ter Jardin is at least partially stabilized by addition of yttrium oxide (Y 2 O 3) or stabili ⁇ Siert.
  • ZrO 2 zirconium oxide
  • Y 2 O 3 yttrium oxide
  • nanoscale aluminum particles 5 are homogenous distributed in the ver ⁇ MCrAlX coating. Their dimensions are less than 1 micrometer and are in the range up to about 100 nanometers, in particular in the range between 30 and 50 nanometers.
  • the aluminum particles 5 in the present embodiment are not to be confused with the aluminum component MCrAlX coating 1, rather they represent a depot of aluminum, is replaced from the spent aluminum of the aluminum component in the MCrAlX coating. In this way, the service life of Le ⁇ MCrAlX coating can be extended. Only when the aluminum of the nanoscale aluminum particles 5 is consumed, the coating must be renewed.
  • the replacement of the aluminum in the aluminum component he follows ⁇ by diffusion of the nanoscale aluminum particles 5 in areas that are depleted of aluminum.
  • the Diffu ⁇ sion of the aluminum particles is delayed as long as is to be replaced in the MCrAlX coating to spent aluminum.
  • the nanoscale aluminum particles are encapsulated with nickel.
  • the encapsulation 7 of the nanoscale particles 5 Aluminum slows the diffusi ⁇ on, whereby the uniform distribution of the aluminum particles is retained longer, which consequently leads to improved corrosion and / or oxidation properties of the coating. 1
  • nickel is selected as the material of the encapsulation 7. This is particularly appropriate when the base material of the base body 3 of the turbine blade is a nickel-based superalloy. Instead of nickel, however, other encapsulating material such as cobalt can be used. The use of cobalt as the encapsulating material is particularly suitable if, instead of the nickel-based superalloy, a cobalt-based superalloy is used.
  • sacrificial anode elements instead of the described MCrAlX coating, it is also possible for other coatings provided with sacrificial anode elements to be provided with encapsulated nanoscale particles made of sacrificial anode material and with corrosion and / or oxidation inhibiting coatings. Also, the sacrificial anode material does not necessarily have to be aluminum. Basically, it is sufficient if the sacrificial anode material, ie the material of the nanoscale particles, emits electrons more easily than the material to be protected by the coating.
  • FIGS. 3A and 3B A second exemplary embodiment of the layer structure according to the invention is shown in FIGS. 3A and 3B.
  • FIGS. 1A and 1B show FIGS. 3A and 3B highly schematic views of sections of a turbine blade.
  • the coating 101 is provided with nanoscale aluminum particles 105, which are surrounded by a nickel encapsulation 107.
  • the encapsulated aluminum particles are still about 109 polymers mitein ⁇ other networked. In this way, a stable lattice ⁇ structure of the encapsulated aluminum particles 105 are generated, which further counteracts premature diffusion of the aluminum particles 105.
  • the lifetime of the coating 101 in a corrosive and / or oxidizing hot gas environment can therefore be further extended compared to the coating 1 of the first embodiment.
  • the coating 101, the nanoscale particles 105 and the enclosure 107 is true with respect to the first exporting ⁇ approximately example performed similarly.
  • a heat-insulating coating may optionally be present on the corrosion-inhibiting and / or oxidation-inhibiting coating 101 in the second exemplary embodiment.
  • the coating 101 with the crosslinked nanoscale aluminum particles 105 can be produced by applying a coating in which the encapsulated nanoscale aluminum particles also have a polymer shell 111 surrounding the encapsulated particles.
  • the polymer shells 111 crosslink with one another, so that as a result the cross-linked structure from FIGS. 3A and 3B is formed.
  • the invention described in the exemplary embodiments shows a way of improving the corrosion and / or oxidation resistance of a layer by maintaining a homogeneous distribution of the sacrificial anode material in the material for a longer time.
  • the diffusion may be delayed wei ⁇ ter, when the particles are interconnected from the sacrificial anode Mate ⁇ rial.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a layered structure comprising a substrate (3) consisting of a substrate material and an anti-corrosion and/or anti-oxidation layer (1) comprising sacrificial anode material on the substrate (3). The anti-corrosion and/or anti-oxidation layer (1) comprises nanoscale sacrificial anode particles (5) consisting of the sacrificial anode material. The sacrificial anode particles (5, 105) are encapsulated in encapsulation material (7) that differs from the sacrificial anode material.

Description

Beschreibungdescription

Schichtstruktur und Verfahren zur Herstellung einer SchichtstrukturLayer structure and method for producing a layer structure

Die vorliegende Erfindung betrifft eine Schichtstruktur mit einem Substrat aus einem Substratmaterial und einer auf dem Substrat befindlichen korrosions- und/oder oxidationshemmen- den Schicht .The present invention relates to a layer structure comprising a substrate made of a substrate material and a corrosion and / or oxidation-inhibiting layer located on the substrate.

Korrosions- und/oder oxidationshemmende Schichten und Be- schichtungen kommen dort zur Anwendung, wo Bauteile korrosiven Heißgasen ausgesetzt sind. Insbesondere ist dies bei Tur¬ binenbauteilen wie etwa Gasturbinenlauf- oder Leitschaufeln oder Elementen von Brennkammerauskleidungen der Fall.Corrosion and / or oxidation inhibiting layers and coatings are used where components are exposed to corrosive hot gases. In particular, this is binenbauteilen at Tur ¬ such as Gasturbinenlauf- or vanes or elements of combustor liners of the case.

Eine typische korrosions- und/oder oxidationshemmende Be- schichtung ist die so genannte MCrAlX-Beschichtung, wobei M zumindest für ein Element der Gruppe aus Eisen (Fe) , Kobalt (Co) , Nickel (Ni) und X für ein Aktivelement, etwa YttriumA typical corrosion and / or oxidation-inhibiting coating is the so-called MCrAlX coating, where M is at least one element of the group consisting of iron (Fe), cobalt (Co), nickel (Ni) and X for an active element, such as yttrium

(Y) und/oder Silizium und/oder zumindest ein Element der seltenen Erden oder Hafnium (Hf) stehen. Solche Legierungen sind beispielsweise aus EP 0 486 489 Bl, EP 0 786 017 Bl, EP 0 412 397 Bl oder EP 1 306 454 Al bekannt. Derartige Be- Schichtungen enthalten Aluminiumphasen, in denen das Aluminium als Opferanode wirkt, indem es beispielsweise mit Feuch¬ tigkeitsfilmen auf der Oberfläche und dem zu schützenden Material eine galvanische Zelle bildet . Dabei wird Aluminium verbraucht, was im Laufe der Zeit die Wirkung einer MCrAlX- Beschichtung vermindert und nach einer gewissen Betriebsdauer das Entfernen der Beschichtung von Bauteilen und ein Neubeschichten notwendig macht. Aufgabe der vorliegenden Erfindung ist es, eine Schichtstruktur anzugeben, welche eine korrosions- und/oder oxidations- hemmende Schicht mit einem Opferanodenmaterial aufweist und die eine längere Betriebsdauer in einer korrosiven und/oder oxidativen Heißgasumgebung ermöglicht. Eine weitere Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zum Herstellen einer Schichtstruktur, welche eine längere Betriebsdauer der Schichtstruktur in einer korrosiven und/oder oxidativen Heißgasumgebung ermöglicht, zur Verfügung zu stellen.(Y) and / or silicon and / or at least one rare earth element or hafnium (Hf). Such alloys are known, for example, from EP 0 486 489 B1, EP 0 786 017 B1, EP 0 412 397 B1 or EP 1 306 454 A1. Such have coatings contain aluminum phases in which the aluminum acts as a sacrificial anode, by, for example, with Feuch ¬ tigkeitsfilmen on the surface and forms a galvanic cell the material to be protected. This consumes aluminum, which over time reduces the effect of a MCrAlX coating and, after a certain period of use, makes it necessary to remove the coating of components and to re-coat. The object of the present invention is to specify a layer structure which has a corrosion- and / or oxidation-inhibiting layer with a sacrificial anode material and which allows a longer service life in a corrosive and / or oxidative hot gas environment. Another object of the present invention is to provide a method for producing a layered structure which allows a longer operating life of the layered structure in a corrosive and / or oxidative hot gas environment.

Diese Aufgaben werden durch eine Schichtstruktur nach Anspruch 1 bzw. ein Verfahren zum Herstellen einer Schichtstruktur nach Anspruch 10 gelöst. Die abhängigen Ansprüche enthalten vorteilhafte Ausgestaltungen der Erfindung.These objects are achieved by a layer structure according to claim 1 and a method for producing a layer structure according to claim 10. The dependent claims contain advantageous embodiments of the invention.

Eine erfindungsgemäße Schichtstruktur weist ein Substrat aus einem Substratmaterial und eine auf dem Substrat befindliche korrosions- und/oder oxidationshemmende Schicht mit einem Op¬ feranodenmaterial auf. Weiterhin umfasst die erfindungsgemäße Schichtstruktur nanoskalige Opferanodenteilchen aus dem Opferanodenmaterial, die mit einem vom Opferanodenmaterial ver¬ schiedenen Kapselungsmaterial gekapselt sind.A layer structure according to the invention has a substrate made of a substrate material and a corrosion and / or oxidation-inhibiting layer on the substrate with an op ¬ feranodenmaterial. Further, the layer structure of the invention comprises nanoscale Opferanodenteilchen from the sacrificial anode material, which are encapsulated with a ver ¬ different from the sacrificial anode material encapsulating material.

Die gekapselten Opferanodenteilchen stellen ein Depot für Op- feranodenmaterial dar, welches im Laufe des Betriebs derThe encapsulated sacrificial anode particles constitute a depot for sacrificial anode material, which in the course of operation of the

Schichtstruktur in einer korrosiven und/oder oxidativen Heißgasumgebung verbrauchtes Opferanodenmaterial nachliefert. Das Opferanodenmaterial der nanoskaligen Opferanodenteilchen kann hierzu durch die Beschichtung diffundieren und verbrauchtes Opferanodenmaterial ersetzen. Hierbei ist jedoch darauf zu achten, dass die Diffusion nicht zu früh erfolgt, da dies le¬ diglich zur Agglomeration von nanoskaligen Opferanodenteilchen in manchen Bereichen der Beschichtung führen würde, wodurch andere Bereiche der Beschichtung an nanoskaligen Opfer- anodenteilchen verarmen würden. Um eine vorzeitige Diffusion der Opferanodenteilchen zu unterdrücken, sind diese daher gekapselt. Aufgrund des Kapselungsmaterials ist die Diffusion der Opferanodenteilchen verlangsamt, so dass der Agglomerati- onsprozess und damit die Verarmung von Beschichtungsbereichen unterdrückt sind. Es steht daher über einen langen Zeitraum in allen Bereichen des korrosions- und/oder oxidationshemmen- den Beschichtungsmaterials Nachschub für verbrauchtes Opfer¬ anodenmaterial zur Verfügung, insbesondere wenn eine homogene Verteilung der Opferanodenteilchen in der korrosions- und/oder oxidationshemmenden Schicht vorliegt.Layer structure supplied in a corrosive and / or oxidative hot gas environment sacrificed sacrificial anode material. For this purpose, the sacrificial anode material of the nanoscale sacrificial anode particles can diffuse through the coating and replace used sacrificial anode material. However, it must be ensured that the diffusion does not take place too early, as this le ¬ diglich agglomeration of nanoscale Opferanodenteilchen in some areas of the coating would lead, making other areas of the coating of nanoscale victim impoverished anode particles. In order to suppress premature diffusion of the sacrificial anode particles, these are therefore encapsulated. Due to the encapsulating material, the diffusion of the sacrificial anode particles is slowed down, so that the Agglomerati- onsprozess and thus the depletion of coating areas are suppressed. It is therefore available over a long period of time in all areas of the corrosion and / or oxidation-inhibiting coating material replenishment for spent sacrificial ¬ anode material, especially if a homogeneous distribution of the sacrificial anode particles in the corrosion and / or oxidation-inhibiting layer is present.

Als Kapselungsmaterial kann beispielsweise das Substratmate¬ rial oder eine Komponente davon Verwendung finden. Das Sub- stratmaterial kann eine Superlegierung aus Eisen-, Kobalt¬ oder Nickelbasis sein, wie sie insbesondere für Turbinenbau¬ teile, wie etwa Lauf- oder Leitschaufeln von Gasturbinen Verwendung findet. In diesem Fall kann das Kapselungsmaterial beispielsweise Eisen, Kobalt oder Nickel sein. Als Opferano- denmaterial kann insbesondere Aluminium Verwendung finden.As encapsulation material can be used, for example, the substrate mate ¬ rial or a component thereof. May be stratmaterial the sub- a super alloy of iron, cobalt or nickel ¬ as parts especially for turbine ¬ such as running or vanes of gas turbines is used. In this case, the encapsulating material may be, for example, iron, cobalt or nickel. Aluminum can be used in particular as sacrificial nanomaterial.

Aber auch andere Materialien, die leichter Elektronen abgeben als der Hauptbestandteil des Substratmaterials, sind als Op¬ feranodenmaterial geeignet. Im Falle von Superlegierungen auf Eisen-, Kobalt- oder Nickelbasis sind dies also Materialien, die leichter Elektronen abgeben als Eisen, Kobalt oder Nickel. Geeignete Materialien für diese Fälle wären beispiels¬ weise Chrom (Cr) , Zink (Zn) , Titan (Ti) , Vanadium (V) , Lanthan (La) , Magnesium (Mg) oder Cer (Ce) .However, other materials which emit electrons more easily than the main constituent of the substrate material are suitable as op ¬ feranodenmaterial. In the case of iron, cobalt or nickel-based superalloys, these are materials that emit electrons more easily than iron, cobalt or nickel. Suitable materials for such cases would be ¬ example, chromium (Cr), zinc (Zn), titanium (Ti), vanadium (V), lanthanum (La), magnesium (Mg) or cerium (Ce).

Wenn die gekapselten Opferanodenteilchen außerdem über Polymere miteinander vernetzt werden, kann die Verteilung der Opferanodenteilchen in der korrosions- und/oder oxidationshemmenden Schicht besonders lange stabil gehalten werden. Da¬ durch kann einer Agglomeration weiter entgegengewirkt und die Betriebsdauer, bis die korrosions- und/oder oxidationshemmen- de Schicht ausgetauscht werden muss, weiter verlängert wer¬ den .In addition, when the encapsulated sacrificial anode particles are crosslinked with each other via polymers, the distribution of the sacrificial anode particles in the corrosion and / or oxidation-inhibiting layer can be kept stable for a particularly long time. Since ¬ through can further counteracted agglomeration and the Operating time until the corrosion and / or oxidation-inhibiting layer must be replaced further extended ¬ who.

Als korrosions- und/oder oxidationshemmende Schicht kann ins¬ besondere eine MCrAlX-Schicht Verwendung finden.As corrosion and / or oxidation-inhibiting layer to ¬ particular an MCrAlX layer can be used.

In der erfindungsgemäßen Schichtstruktur kann das Substrat insbesondere der Grundkörper eines Turbinenbauteils, bei- spielsweise einer Leit- oder Laufschaufel einer Gasturbine oder ein Element einer Brennkammerauskleidung sein.In the layer structure according to the invention, the substrate may in particular be the main body of a turbine component, for example a guide or moving blade of a gas turbine or an element of a combustion chamber lining.

Im erfindungsgemäßen Verfahren zum Herstellen einer Schichtstruktur mit über Polymere miteinander vernetzten nanoskali- gen Opferanodenteilchen wird auf ein Substrat ein Beschich- tungsmaterial aufgebracht, das nanoskalige Opferanodenteil¬ chen aus einem Opferanodenmaterial umfasst. Die Opferanoden¬ teilchen sind mit einem vom Opferanodenmaterial verschiedenen Kapselungsmaterial gekapselt . Außerdem ist das Kapselungsma- terial von einer Polymerhülle umgeben. Nach dem Aufbringen des Beschichtungsmaterials erfolgt eine Wärmebehandlung, de¬ ren Zeit- und Temperatursteuerung so gewählt ist, dass eine Vernetzung der Polymerhüllen erfolgt. Das Verfahren ermöglich insbesondere das Herstellen von erfindungsgemäßen Schichtsys- temen, in den einer Diffusion der Opferanodenteilchen besonders wirksam entgegengewirkt ist .In the inventive method for producing a layer structure with polymers interconnected nanoscale gen Opferanodenteilchen a coating material is applied to a processing substrate comprising nanoscale sacrificial anode part ¬ surfaces of a sacrificial anode material. The sacrificial anodes ¬ particles are encapsulated with a different from the sacrificial anode material encapsulation. In addition, the encapsulating material is surrounded by a polymer shell. After application of the coating material, a heat treatment is carried out, whose time and temperature control is selected such that crosslinking of the polymer shells takes place. The method makes it possible, in particular, to produce coating systems according to the invention in which diffusion of the sacrificial anode particles is counteracted particularly effectively.

Weitere Merkmale, Eigenschaften und Vorteile der vorliegenden Erfindung ergeben sich aus der nachfolgenden Beschreibung von Ausführungsbeispielen unter Bezugnahme auf die beiliegenden Figuren .Further features, properties and advantages of the present invention will become apparent from the following description of embodiments with reference to the accompanying figures.

Fig. IA zeigt in einer schematischen Darstellung eine erfindungsgemäße Schichtstruktur in Aufsicht. Fig. IB zeigt die Schichtstruktur aus Fig. IA in einer Querschnittsansicht .FIG. 1A shows a schematic representation of a layer structure according to the invention in plan view. FIG. 1B shows the layer structure from FIG. 1A in a cross-sectional view.

Fig. 2 zeigt in einer schematischen Darstellung einen Herstellungsschritt für eine erfindungsgemäße Schichtstruktur gemäß einem zweiten Ausführungsbeispiel .2 shows a schematic representation of a production step for a layer structure according to the invention in accordance with a second exemplary embodiment.

Fig. 3A zeigt in einer schematischen Darstellung ein zweites Ausführungsbeispiel für die erfindungsgemäße Schichtstruktur in einer Aufsicht.3A shows a schematic representation of a second exemplary embodiment of the layer structure according to the invention in a plan view.

Fig. 3B zeigt die erfindungsgemäße Schichtstruktur aus Fig. 3A in einer Querschnittsansicht.FIG. 3B shows the layer structure according to the invention from FIG. 3A in a cross-sectional view.

Eine erfindungsgemäße Schichtstruktur ist stark schematisiert in den Figuren IA und IB dargestellt . Die Figuren zeigen einen Ausschnitt aus der Schichtstruktur in Aufsicht (Fig. IA) und in einer Querschnittansicht (Fig. IB) . Die Ansichten rep¬ räsentieren die Aufsicht auf eine mit einer korrosions- und/ oder oxidationshemmenden Beschichtung versehene Turbinenschaufel (Fig. IA) beziehungsweise ebenfalls stark schemati¬ siert einen Querschnitt durch die Wand einer beschichteten Turbinenschaufel (Fig. IB) .A layer structure according to the invention is shown in highly schematic form in FIGS. 1A and 1B. The figures show a section of the layer structure in plan view (FIG. 1A) and in a cross-sectional view (FIG. 1B). The (IA Fig.) (IB FIG.) Are views rep ¬ räsentieren the view of a provided with a corrosion and / or oxidation resistant coating or turbine blade also greatly schemati ¬ Siert a cross section through the wall of a coated turbine blade.

Während in Fig. IB die korrosions- und/oder oxidationshemmen- de Beschichtung 1 sowie der Grundkörper 3 der Turbinenschaufel, welcher das Substrat für die Beschichtung 1 bildet, zu erkennen sind, ist in Fig. IA lediglich die Beschichtung 1 zu erkennen .While the corrosion-resistant and / or oxidation-inhibiting coating 1 and the base body 3 of the turbine blade, which forms the substrate for the coating 1, can be seen in FIG. 1B, only the coating 1 can be seen in FIG. 1A.

Die Beschichtung 1 ist im vorliegenden Ausführungsbeispiel eine MCrAlX-Beschichtung, die eine Aluminiumkomponente ent- hält. Das Aluminium dient als Opferanode zum Korrosions- und/oder Oxidationsschutz . Auf der MCrAlX-Beschichtung kann optional noch eine wärmedämmende Beschichtung (TBC, Thermal Barrier Coating) vorhanden sein, die in den Figuren nicht dargestellt ist. Derartige Wärmedämmbeschichtungen sind bei¬ spielsweise Beschichtungen aus Zirkonoxid (ZrO2), dessen Git¬ terstruktur durch die Zugabe von Yttriumoxid (Y2O3) stabili¬ siert oder wenigstens teilstabilisiert ist. Selbstverständ¬ lich können statt der MCrAlX-Beschichtung auch andere korro- sions- und/oder oxidationshemmende Beschichtungen 1 zur Anwendung kommen. Andere optionale Wärmedämmschichten als die beschriebene sind ebenfalls möglich.The coating 1 in the present exemplary embodiment is an MCrAlX coating which comprises an aluminum component. holds. The aluminum serves as a sacrificial anode for corrosion and / or oxidation protection. Optionally, a thermal barrier coating (TBC, Thermal Barrier Coating) may be present on the MCrAlX coating, which is not shown in the figures. Such thermal barrier coatings are at ¬ play, coatings of zirconium oxide (ZrO 2) whose Git ¬ terstruktur is at least partially stabilized by addition of yttrium oxide (Y 2 O 3) or stabili ¬ Siert. Selbstverständ ¬ Lich can sions- other corrosion and / or oxidation resistant coatings 1 instead of the MCrAlX coating are used. Other optional thermal barrier coatings than those described are also possible.

Im vorliegenden Ausführungsbeispiel sind in der MCrAlX- Beschichtung 1 nanoskalige Aluminiumpartikel 5 homogen ver¬ teilt. Ihre Abmessungen betragen weniger als 1 Mikrometer und liegen im Bereich bis etwa 100 Nanometer, insbesondere im Bereich zwischen 30 und 50 Nanometer. Die Aluminiumpartikel 5 im vorliegenden Ausführungsbeispiel sind nicht zu verwechseln mit der Aluminiumkomponente MCrAlX-Beschichtung 1, vielmehr stellen sie ein Depot an Aluminium dar, aus dem heraus verbrauchtes Aluminium der Aluminiumkomponente in der MCrAlX- Beschichtung ersetzt wird. Auf diese Weise lässt sich die Le¬ bensdauer der MCrAlX-Beschichtung verlängern. Erst wenn auch das Aluminium der nanoskaligen Aluminiumpartikel 5 verbraucht ist, muss die Beschichtung erneuert werden.In the present embodiment 1 nanoscale aluminum particles 5 are homogenous distributed in the ver ¬ MCrAlX coating. Their dimensions are less than 1 micrometer and are in the range up to about 100 nanometers, in particular in the range between 30 and 50 nanometers. The aluminum particles 5 in the present embodiment are not to be confused with the aluminum component MCrAlX coating 1, rather they represent a depot of aluminum, is replaced from the spent aluminum of the aluminum component in the MCrAlX coating. In this way, the service life of Le ¬ MCrAlX coating can be extended. Only when the aluminum of the nanoscale aluminum particles 5 is consumed, the coating must be renewed.

Das Ersetzen des Aluminiums in der Aluminiumkomponente er¬ folgt durch Diffusion der nanoskaligen Aluminiumpartikel 5 in Bereiche, die an Aluminium verarmt sind. Dabei ist jedoch darauf zu achten, dass sich aufgrund der Diffusionsprozesse keine Agglomerate oder nur sehr kleine Agglomerate von Alumi¬ niumpartikeln 5 bilden, da durch die Agglomeration die homogene Verteilung der nanoskaligen Aluminiumpartikel 5 beein- trächtigt wird. Außerdem ist es vorteilhaft, wenn die Diffu¬ sion der Aluminiumteilchen solange verzögert wird, bis verbrauchtes Aluminium in der MCrAlX-Beschichtung zu ersetzen ist. Im vorliegenden Ausführungsbeispiel sind die nanoskali- gen Aluminiumpartikel mit Nickel gekapselt. Die Kapselung 7 der nanoskaligen Aluminiumpartikel 5 verlangsamt die Diffusi¬ on, wodurch die homogene Verteilung der Aluminiumpartikel länger erhalten bleibt, was in der Folge zur verbesserten Korrosions- und/oder Oxidationseigenschaften der Beschichtung 1 führt.The replacement of the aluminum in the aluminum component he follows ¬ by diffusion of the nanoscale aluminum particles 5 in areas that are depleted of aluminum. However, it is important to ensure that form as affect by the agglomeration, the homogeneous distribution of the nanoscale alumina particles 5 due to the diffusion processes no agglomerates or only very small agglomerates of Alumi ¬ niumpartikeln 5 is pregnant. Moreover, it is advantageous if the Diffu ¬ sion of the aluminum particles is delayed as long as is to be replaced in the MCrAlX coating to spent aluminum. In the present embodiment, the nanoscale aluminum particles are encapsulated with nickel. The encapsulation 7 of the nanoscale particles 5 Aluminum slows the diffusi ¬ on, whereby the uniform distribution of the aluminum particles is retained longer, which consequently leads to improved corrosion and / or oxidation properties of the coating. 1

Im vorliegenden Ausführungsbeispiel ist Nickel als Material der Kapselung 7 gewählt. Dies bietet sich insbesondere dann an, wenn das Basismaterial des Grundkörpers 3 der Turbinen- schaufei eine auf Nickel basierende Superlegierung ist. Statt Nickel kann jedoch auch anderes Kapselungsmaterial wie etwa Kobalt Verwendung finden. Die Verwendung von Kobalt, als Kapselungsmaterial bietet sich insbesondere dann an, wenn statt der auf Nickel basierenden Superlegierung eine auf Kobalt ba- sierende Superlegierung Verwendung findet.In the present embodiment, nickel is selected as the material of the encapsulation 7. This is particularly appropriate when the base material of the base body 3 of the turbine blade is a nickel-based superalloy. Instead of nickel, however, other encapsulating material such as cobalt can be used. The use of cobalt as the encapsulating material is particularly suitable if, instead of the nickel-based superalloy, a cobalt-based superalloy is used.

Es sei an dieser Stelle darauf hingewiesen, dass statt der beschriebenen MCrAlX-Beschichtung auch andere mit Opferanodenelementen versehenen korrosions- und/oder oxidationshem- mende Beschichtungen mit gekapselten nanoskaligen Partikeln aus Opferanodenmaterial versehen sein können. Auch muss das Opferanodenmaterial nicht notwendigerweise Aluminium sein. Im Grunde reicht es aus, wenn das Opferanodenmaterial, also das Material der nanoskaligen Partikel, leichter Elektronen ab- gibt als das durch die Beschichtung zu schützende Material.It should be pointed out at this point that, instead of the described MCrAlX coating, it is also possible for other coatings provided with sacrificial anode elements to be provided with encapsulated nanoscale particles made of sacrificial anode material and with corrosion and / or oxidation inhibiting coatings. Also, the sacrificial anode material does not necessarily have to be aluminum. Basically, it is sufficient if the sacrificial anode material, ie the material of the nanoscale particles, emits electrons more easily than the material to be protected by the coating.

Ein zweites Ausführungsbeispiel für die erfindungsgemäße Schichtstruktur ist in den Figuren 3A und 3B dargestellt. Wie die Figuren IA und IB stellen die Figuren 3A und 3B stark schematisiert Ausschnitte aus einer Turbinenschaufel dar.A second exemplary embodiment of the layer structure according to the invention is shown in FIGS. 3A and 3B. As FIGS. 1A and 1B show FIGS. 3A and 3B highly schematic views of sections of a turbine blade.

Wie im ersten Ausführungsbeispiel ist die Beschichtung 101 mit nanoskaligen Aluminiumpartikeln 105 versehen, die von einer Nickel-Kapselung 107 umgeben sind. Zusätzlich sind die gekapselten Aluminiumpartikel noch über Polymere 109 mitein¬ ander vernetzt. Auf diese Weise kann eine stabile Gitter¬ struktur der gekapselten Aluminiumpartikel 105 erzeugt wer- den, die einer vorzeitigen Diffusion der Aluminiumpartikel 105 weiter entgegenwirkt. Die Lebensdauer der Beschichtung 101 in einer korrosiven und/oder oxidierenden Heißgasumgebung kann daher gegenüber der Beschichtung 1 aus dem ersten Ausführungsbeispiel weiter verlängert werden. Im Übrigen und insbesondere im Hinblick auf die Materialien des Grundkörpers 3, der Beschichtung 101, der nanoskaligen Partikel 105 sowie des Kapselung 107 gilt das mit Bezug auf das erste Ausfüh¬ rungsbeispiel ausgeführte analog.As in the first embodiment, the coating 101 is provided with nanoscale aluminum particles 105, which are surrounded by a nickel encapsulation 107. In addition, the encapsulated aluminum particles are still about 109 polymers mitein ¬ other networked. In this way, a stable lattice ¬ structure of the encapsulated aluminum particles 105 are generated, which further counteracts premature diffusion of the aluminum particles 105. The lifetime of the coating 101 in a corrosive and / or oxidizing hot gas environment can therefore be further extended compared to the coating 1 of the first embodiment. Moreover, and particularly with regard to the materials of the base body 3, the coating 101, the nanoscale particles 105 and the enclosure 107 is true with respect to the first exporting ¬ approximately example performed similarly.

Wie im ersten Ausführungsbeispiel kann auch im zweiten Aus¬ führungsbeispiel optional eine wärmedämmende Beschichtung auf der korrosions- und/oder oxidationshemmenden Beschichtung 101 vorhanden sein.As in the first exemplary embodiment, a heat-insulating coating may optionally be present on the corrosion-inhibiting and / or oxidation-inhibiting coating 101 in the second exemplary embodiment.

Das Herstellen der Beschichtung 101 mit den vernetzten nanoskaligen Aluminiumpartikeln 105 kann erfolgen, indem eine Beschichtung aufgebracht wird, in der die gekapselten nanoskaligen Aluminiumpartikel außerdem eine Polymerhülle 111 aufweisen, welche die gekapselten Partikel umgeben. Durch ei- ne Wärmebehandlung mit einer geeigneten Zeit- und Temperatursteuerung kommt es zu einer Vernetzung der Polymerhüllen 111 miteinander, so dass als Resultat die vernetzte Struktur aus Fig. 3A und Fig. 3B entsteht. Die in den Ausführungsbeispielen beschriebene Erfindung zeigt einen Weg, die Korrosions- und/oder Oxidationsresistenz einer Schicht dadurch zu verbessern, dass eine homogene Verteilung des Opferanodenmaterials im Material länger beibehalten wird. Dies wird durch eine Verzögerung der Diffusion von Opferanodenpartikeln erreicht, welche sich durch eine Kapselung der Opferanodenpartikel erzielen lässt. Die Diffusion kann wei¬ ter verzögert werden, wenn die Partikel aus Opferanodenmate¬ rial miteinander vernetzt werden. The coating 101 with the crosslinked nanoscale aluminum particles 105 can be produced by applying a coating in which the encapsulated nanoscale aluminum particles also have a polymer shell 111 surrounding the encapsulated particles. By means of a heat treatment with a suitable time and temperature control, the polymer shells 111 crosslink with one another, so that as a result the cross-linked structure from FIGS. 3A and 3B is formed. The invention described in the exemplary embodiments shows a way of improving the corrosion and / or oxidation resistance of a layer by maintaining a homogeneous distribution of the sacrificial anode material in the material for a longer time. This is achieved by delaying the diffusion of sacrificial anode particles, which can be achieved by encapsulating the sacrificial anode particles. The diffusion may be delayed wei ¬ ter, when the particles are interconnected from the sacrificial anode Mate ¬ rial.

Claims

Patentansprüche claims 1. Schichtstruktur mit einem Substrat (3) aus einem Substrat¬ material und einer auf dem Substrat (3) befindlichen korrosi- ons- und/oder oxidationshemmenden Schicht (1, 101) mit einem Opferanodenmaterial, die nanoskalige Opferanodenteilchen (5, 105) aus dem Opferanodenmaterial umfasst und in dem die Op¬ feranodenteilchen (5, 105) mit einem vom Opferanodenmaterial verschiedenen Kapselungsmaterial (7, 107) gekapselt sind.1. layer structure comprising a substrate (3) made of a substrate ¬ material and a on the substrate (3) located onsorption and / or oxidation-inhibiting layer (1, 101) with a sacrificial anode material, the nanoscale sacrificial anode particles (5, 105) the sacrificial anode material and in which the Op ¬ feranodenteilchen (5, 105) are encapsulated with a different from the sacrificial anode material encapsulation material (7, 107). 2. Schichtstruktur nach Anspruch 1, in der die Opferanodenteilchen (5, 105) homogen in der korrosions- und/oder oxidationshemmenden Schicht (1, 101) verteilt sind.2. Layer structure according to claim 1, in which the sacrificial anode particles (5, 105) are homogeneously distributed in the corrosion and / or oxidation-inhibiting layer (1, 101). 3. Schichtstruktur nach Anspruch 1 oder 2, in der das Kapselungsmaterial (7, 107) das Substratmaterial oder eine Kompo¬ nente davon ist.3rd layer structure according to claim 1 or 2, in which the encapsulation material (7, 107), the substrate material or a compo nent ¬ thereof. 4. Schichtstruktur nach einem der vorangehenden Ansprüche, in der das Opferanodenmaterial Aluminium ist.A laminated structure according to any one of the preceding claims, wherein the sacrificial anode material is aluminum. 5. Schichtstruktur nach einem der vorangehenden Ansprüche, in der das Substratmaterial eine Superlegierung auf Eisen-, Ko¬ balt- oder Nickelbasis ist.5. Layer structure according to one of the preceding claims, in which the substrate material is a superalloy based on iron, Ko ¬ balt or nickel. 6. Schichtstruktur nach Anspruch 5, in der das Kapselungsmaterial Eisen, Kobalt oder Nickel ist.A layered structure according to claim 5, wherein the encapsulating material is iron, cobalt or nickel. 7. Schichtstruktur nach einem der vorangehenden Ansprüche, in der die gekapselten Opferanodenteilchen (105) über PolymereA layered structure according to any one of the preceding claims, in which the encapsulated sacrificial anode particles (105) are polymeric (109) miteinander vernetzt sind. (109) are crosslinked with each other. 8. Schichtstruktur nach einem der vorangehenden Ansprüche, in der die korrosions- und/oder oxidationshemmende Schicht eine MCrAlX-Schicht ist.8. Layer structure according to one of the preceding claims, in which the corrosion and / or oxidation-inhibiting layer is a MCrAlX layer. 9. Schichtstruktur nach einem der vorangehenden Ansprüche, in der das Substrat (3) der Grundkörper eines Turbinenbauteils ist.9. Layer structure according to one of the preceding claims, in which the substrate (3) is the main body of a turbine component. 10. Verfahren zum Herstellen einer Schichtstruktur nach An- spruch 7, in dem auf ein Substrat (3) ein Beschichtungsmaterial aufge¬ bracht wird, das nanoskalige Opferanodenteilchen (105) aus einem Opferanodenmaterial umfasst, wobei die Opfer¬ anodenteilchen (105) mit einem vom Opferanodenmaterial verschiedenen Kapselungsmaterial (107) gekapselt sind und das Kapselungsmaterial (107) von einer Polymerhülle (111) umgeben ist; und nach dem Aufbringen des Beschichtungsmaterials eine Wär¬ mebehandlung durchgeführt wird, deren Zeit- und Tempera- tursteuerung so gewählt ist, dass eine Vernetzung der Po¬ lymerhüllen (111) erfolgt. 10. A method of manufacturing a layered structure according to demanding 7, in which on a substrate (3) a coating material is ¬ introduced, the nanoscale Opferanodenteilchen (105) made of a sacrificial anode material, wherein the sacrificial ¬ anodenteilchen (105) having a from Sacrificial anode material encapsulated encapsulating material (107) and the encapsulating material (107) is surrounded by a polymer shell (111); and after application of the coating material a Wär ¬ mebehandlung is performed, the time and temperature tursteuerung is selected so that cross-linking of the Po ¬ lymerhüllen (111) takes place.
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DE102005062225B3 (en) * 2005-12-21 2007-06-21 Siemens Ag MCrAIX-type alloy product and process for producing a layer of this alloy product

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CN118895509A (en) * 2024-10-08 2024-11-05 山东天厚石油科技有限责任公司 A high temperature resistant sacrificial anode tungsten plated oil pipe and its preparation method

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