EP1752562A1 - Process for stripping an area of a layer from a component - Google Patents

Process for stripping an area of a layer from a component Download PDF

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Publication number
EP1752562A1
EP1752562A1 EP06020613A EP06020613A EP1752562A1 EP 1752562 A1 EP1752562 A1 EP 1752562A1 EP 06020613 A EP06020613 A EP 06020613A EP 06020613 A EP06020613 A EP 06020613A EP 1752562 A1 EP1752562 A1 EP 1752562A1
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EP
European Patent Office
Prior art keywords
acid
component
bath
salt bath
treatment
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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.)
Granted
Application number
EP06020613A
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German (de)
French (fr)
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EP1752562B1 (en
Inventor
Nigel-Philip Cox
Uta Maier
Michael Dr. Ott
Ralph Reiche
Ronald Zimmer
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Siemens AG
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Siemens AG
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Priority to EP06020613A priority Critical patent/EP1752562B1/en
Publication of EP1752562A1 publication Critical patent/EP1752562A1/en
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/005—Repairing methods or devices
    • 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
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/28—Cleaning or pickling metallic material with solutions or molten salts with molten salts
    • C23G1/32—Heavy metals

Definitions

  • the invention relates to a method for removing a layer region of a component.
  • the ability to increase efficiency and thus reduce operating costs is to increase inlet temperatures of a combustion gas within a gas turbine.
  • thermal barrier coatings were developed, which are applied to thermally stressed components, for example of superalloys, which alone could not withstand the high inlet temperatures in the long term.
  • the ceramic thermal barrier coating offers the advantage of high temperature resistance due to its ceramic properties and the metallic substrate has the advantage of good mechanical properties in this composite or layer system.
  • an adhesion-promoting layer having the composition MCrAlY (main constituents) is applied between the substrate in the ceramic thermal barrier coating, M meaning that a metal from the group of nickel, chromium or iron is used.
  • composition of these MCrAlY layers may vary, but all MCrAlY layers are subject to corrosion due to oxidation, sulfidation, or other chemical and / or mechanical attack, despite the overlying ceramic layer.
  • the MCrAlY layer often degrades to a greater extent than the metallic substrate (for example Ni, Co-based superalloy), ie the lifetime of the composite system of substrate and layer is determined by the lifetime of the MCrAlY layer. After prolonged use, the MCrAlY layer is only conditionally functional, but the substrate can still be fully functional.
  • the metallic substrate for example Ni, Co-based superalloy
  • the EP 759 098 B1 shows a method for cleaning turbine blades, in which potassium hydroxide is used.
  • the object is achieved by a method according to claim 1, wherein prior to an acid treatment, a treatment of the component takes place in a salt bath.
  • FIG. 1 shows a component 1 which is to be treated by the method according to the invention.
  • the surface region 10 consists, for example, of an oxide which has been formed at high temperatures. Likewise, non-degraded areas can be removed by the inventive method.
  • FIG. 2 shows a further component 1 which can be treated by the method according to the invention.
  • the component 1 consists of a substrate 4 (eg nickel-, cobalt-based superalloy) and a layer 7 (eg MCrAlY) which is degraded and is to be removed by the method according to the invention.
  • a substrate 4 eg nickel-, cobalt-based superalloy
  • a layer 7 eg MCrAlY
  • the substrate 4 may also be degraded, with the degraded regions of the substrate 4 then likewise being removed, for example.
  • a first removal of the layer regions 7, 10 to be removed and / or a ceramic thermal barrier coating, which is arranged above the layer 7, can take place by coarse mechanical pre-cleaning, such as sandblasting or flow grinding.
  • coarse mechanical pre-cleaning such as sandblasting or flow grinding.
  • the treatment with sandblasting and / or flow grinding can also take place between or after the individual salt and acid treatments or at the end.
  • the component 1, in particular the layer regions 7, 10 to be removed, is treated in a liquid salt bath (melt) into which at least the regions 7, 10 of the component 1 are immersed.
  • a liquid salt bath (melt) into which at least the regions 7, 10 of the component 1 are immersed.
  • salts is understood, for example, as meaning, inter alia, compounds of metal (metal ion) and acid radical (acid less a hydrogen ion), for example NaHCO 3 , Na 2 CO 3 , CaCO 3 ... And / or base radical.
  • the use of such a compound for the salt bath requires that there be a chemical attack of the salt on the component 1. It can also be the entire component 1, possibly provided with a masking, immersed in the salt bath.
  • the salt bath consists for example of sodium hydroxide (NaOH) or potassium hydroxide (KOH) (ie, for example, a molten bath, ie liquid at higher temperatures than room temperature). Both Salts can also be used together, and then in particular have a mixing ratio of 50 to 50 percent by volume. Further salt baths are conceivable.
  • sodium oxide (NaO 2 ) above salts can be added as an oxygen supplier, which enhances the chemical attack on the areas to be removed.
  • oxygen suppliers are conceivable, such as an oxygen supply, oxides or metal oxides.
  • Treatments of the component 1 in different salt baths can also be carried out in succession.
  • treatment in the salt bath is a washing and / or drying.
  • the temperature differences between the salt bath and the washing medium are used for a thermal shock, which mechanically weakens the layer region to be removed by cracking.
  • an acid treatment is carried out in an at least first acid bath, which consists of an acid or an acid mixture.
  • an acid treatment is carried out, for example, with nitric acid HNO 3 and / or phosphoric acid H 3 PO 4 .
  • Other acids eg sulfuric acid, sulfurous, saponified acid, carbonic acid, hydrofluoric acid, .
  • an at least one treatment with hydrochloric acid HCl takes place as the second acid bath.
  • Other acids for the eventual second acid bath are conceivable, but differ from the acids of the first acid bath.
  • each treatment with acid is a washing and / or drying.
  • the individual treatment steps, in which the component comes into contact with the salt bath or the various acids, as well as the watering and drying can each be repeated several times.
  • FIG. 3 shows a device 22 with which the method according to the invention can be carried out.
  • the device 22 consists of a container 19, in which a liquid salt or salt mixture or an acid is present. In this liquid, the component 1 is immersed.
  • the method can be shortened or improved if an ultrasound probe 16 is present in the bath 13 and is operated.
  • FIG. 4 shows a component 1 which has been treated by the method according to the invention.
  • the component 1 no longer has any corroded areas.
  • the flow grinding (see DE 199 02 422A1 ) is particularly suitable for components 1, in particular for blades of turbines, with interiors in which degraded areas are present in the interior.
  • outside areas are preferably sandblasted, where, for example, corundum is used there.
  • the maximum jet pressure and the particle size of the blasting medium must be adjusted so as not to damage the substrate.
  • a salt from Degussa is used, which is sold under the trade name DUFERRIT RS DGS. Oxides of the component that are exposed to the salt bath transform into oxide-enriched compounds that are more acid-soluble.
  • the expansion coefficients of oxides and metals are generally different.
  • a thermal shock is caused, which generates cracks in the area to be removed (7,11) and this mechanically weakens, for example.
  • This thermal shock is used as an additional cleaning effect.
  • it must be ensured that a certain temperature gradient in the component is not exceeded, so that no cracks are generated in the substrate or component.
  • the complexing agent used is diammonium EDTA.
  • the complexing agent can bind metals, thereby removing them.
  • the treatment with the complexing agent can take place between, before or after the individual salt and acid treatments.
  • an ultrasonic probe 16 may also be used in the bath 13 with the complexing agent to speed up the process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)
  • Cleaning In General (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Detergent Compositions (AREA)

Abstract

Removing a layer from a component comprises treating the component in a salt bath, subjecting it to thermal shock and then treating it with acid.

Description

Die Erfindung betrifft ein Verfahren zur Entfernung eines Schichtbereichs eines Bauteils.The invention relates to a method for removing a layer region of a component.

In heutigen modernen Energieerzeugungsanlagen, wie z. B. Gasturbinenanlagen, spielt der Wirkungsgrad eine wichtige Rolle, weil dadurch die Kosten für den Betrieb der Gasturbinenanlagen reduziert werden können.In today's modern power generation plants, such. As gas turbine plants, the efficiency plays an important role, because thereby the cost of the operation of the gas turbine plants can be reduced.

Die Möglichkeit, den Wirkungsgrad zu erhöhen und damit die Betriebskosten zu reduzieren besteht darin, Einlasstemperaturen eines Verbrennungsgases innerhalb einer Gasturbine zu erhöhen.The ability to increase efficiency and thus reduce operating costs is to increase inlet temperatures of a combustion gas within a gas turbine.

Aus diesem Grund wurden keramische Wärmedämmschichten entwickelt, die auf thermisch belasteten Bauteilen, beispielsweise aus Superlegierungen, aufgebracht werden, die alleine den hohen Einlasstemperaturen auf Dauer nicht mehr standhalten könnten.For this reason, ceramic thermal barrier coatings were developed, which are applied to thermally stressed components, for example of superalloys, which alone could not withstand the high inlet temperatures in the long term.

Die keramische Wärmedämmschicht bietet den Vorteil einer hohen Temperaturresistenz aufgrund ihrer keramischen Eigenschaften und das metallische Substrat den Vorteil der guten mechanischen Eigenschaften in diesem Verbund- oder Schichtsystem. Typischerweise ist zwischen dem Substrat in der keramischen Wärmedämmschicht eine Haftvermittlungsschicht mit der Zusammensetzung MCrAlY (Hauptbestandteile) aufgebracht, wobei M bedeutet, dass ein Metall aus der Gruppe Nickel, Chrom oder Eisen verwendet wird.The ceramic thermal barrier coating offers the advantage of high temperature resistance due to its ceramic properties and the metallic substrate has the advantage of good mechanical properties in this composite or layer system. Typically, an adhesion-promoting layer having the composition MCrAlY (main constituents) is applied between the substrate in the ceramic thermal barrier coating, M meaning that a metal from the group of nickel, chromium or iron is used.

Die Zusammensetzung dieser MCrAlY-Schichten kann variieren, jedoch unterliegen alle MCrAlY-Schichten trotz der aufliegenden Keramikschicht einer Korrosion durch Oxidation, Sulfidation oder anderen chemischen und/oder mechanischen Angriffen.The composition of these MCrAlY layers may vary, but all MCrAlY layers are subject to corrosion due to oxidation, sulfidation, or other chemical and / or mechanical attack, despite the overlying ceramic layer.

Die MCrAlY-Schicht degradiert dabei häufig in einem stärkeren Maße als das metallische Substrat (bspw. Ni-, Co basierte Superlegierung), d.h. dass die Lebensdauer des Verbundsystems aus Substrat und Schicht bestimmt wird durch die Lebensdauer der MCrAlY-Schicht.
Die MCrAlY-Schicht ist nach längerem Einsatz nur noch bedingt funktionstüchtig, hingegen kann das Substrat noch voll funktionstüchtig sein.The MCrAlY layer often degrades to a greater extent than the metallic substrate (for example Ni, Co-based superalloy), ie the lifetime of the composite system of substrate and layer is determined by the lifetime of the MCrAlY layer.
After prolonged use, the MCrAlY layer is only conditionally functional, but the substrate can still be fully functional.

Es besteht also der Bedarf, die im Einsatz degradierten Bauteile, beispielsweise Turbinenlaufschaufeln oder -leitschaufeln oder Brennkammerteile, aufzuarbeiten, wobei die korrodierten Schichten oder Zonen der MCrAlY-Schicht oder des Substrats abgetragen werden müssen, um eventuell neue MCrAlY-Schichten oder andere Schutzschichten und/oder wiederum eine Wärmedämmschicht aufzubringen. Die Verwendung von vorhandenen, benutzten Substraten führt zu einer Kostenreduzierung beim Betrieb von Gasturbinenanlagen.Thus, there is a need to work up degraded components such as turbine blades or vanes or combustor parts, with the corroded layers or zones of the MCrAlY layer or substrate being removed to remove any new MCrAlY layers or other protective layers and / or or in turn apply a thermal barrier coating. The use of existing, used substrates leads to a cost reduction in the operation of gas turbine plants.

Dabei muss beachtet werden, dass das Design der Turbinenschaufel und der Leitschaufel nicht verändert wird, das heißt, dass ein gleichmäßiger Oberflächenabtrag vom Material erfolgt. Weiterhin dürfen keine Korrosionsprodukte zurückbleiben, die bei einer Neubeschichtung mit einer MCrAlY-Schicht und/oder einer anderen Schutzschicht und/oder einer keramischen Wärmedämmschicht eine Fehlerquelle bilden oder zu einer schlechten Haftung dieser Schichten führen würden.It should be noted that the design of the turbine blade and the vane is not changed, that is, that a uniform surface removal of the material takes place. Furthermore, no corrosion products must remain which, when re-coated with an MCrAlY layer and / or another protective layer and / or a ceramic thermal barrier coating, form a source of error or would lead to poor adhesion of these layers.

Die EP 759 098 B1 zeigt ein Verfahren zur Reinigung von Turbinenschaufelblättern, bei dem Kaliumhydroxid verwendet wird.The EP 759 098 B1 shows a method for cleaning turbine blades, in which potassium hydroxide is used.

Ebenso ist es Stand der Technik, korrodierte Schichten durch Säurestrippen zu entfernen, wie es aus der US-PS 5,944,909 bekannt ist.It is also state of the art to remove corroded layers by acid stripping, as can be seen from the U.S. Patent 5,944,909 is known.

Die bekannten Verfahren führen oft zu keinem oder zu einem ungleichmäßigen Abtrag und sind auch sehr zeitintensiv.The known methods often lead to no or uneven removal and are also very time consuming.

Es ist daher Aufgabe der Erfindung, dieses Problem zu überwinden.It is therefore an object of the invention to overcome this problem.

Die Aufgabe wird gelöst durch ein Verfahren gemäß Anspruch 1, bei dem vor einer Säurebehandlung eine Behandlung des Bauteils in einem Salzbad erfolgt.The object is achieved by a method according to claim 1, wherein prior to an acid treatment, a treatment of the component takes place in a salt bath.

Weitere vorteilhafte Verfahrensschritte sind in den Unteransprüchen aufgelistet.Further advantageous method steps are listed in the subclaims.

Es zeigen

Figur 1
ein Bauteil,
Figur 2
ein Schichtsystem,
Figur 3
eine Vorrichtung, um das erfindungsgemässe Verfahren durchzuführen, und
Figur 4
ein mit dem erfindungsgemäßen Verfahren behandeltes Bauteil.
Show it
FIG. 1
a component,
FIG. 2
a layer system,
FIG. 3
a device to perform the inventive method, and
FIG. 4
a treated with the inventive method component.

Figur 1 zeigt ein Bauteil 1, das mit dem erfindungsgemässen Verfahren behandelt werden soll.FIG. 1 shows a component 1 which is to be treated by the method according to the invention.

Das Bauteil 1, das bspw. aus Metall oder einer Metalllegierung besteht, weist einen Oberflächenbereich 10 auf, der bspw. durch Korrosion, Oxidation oder in sonstiger Art und Weise degradiert ist und entfernt werden soll.
Der Oberflächenbereich 10 besteht bspw. aus einem Oxid, das bei hohen Temperaturen entstanden ist.
Ebenso können auch nicht degradierte Bereiche durch das erfindungsgemässe Verfahren entfernt werden.The component 1, which, for example, consists of metal or a metal alloy, has a surface region 10 which, for example, is degraded by corrosion, oxidation or in any other way and is to be removed.
The surface region 10 consists, for example, of an oxide which has been formed at high temperatures.
Likewise, non-degraded areas can be removed by the inventive method.

Figur 2 zeigt ein weiteres Bauteil 1, das mit dem erfindungsgemäßen Verfahren behandelt werden kann.FIG. 2 shows a further component 1 which can be treated by the method according to the invention.

Das Bauteil 1 besteht aus einem Substrat 4 (z. B. Nickel-, Kobalt-basierte Superlegierung) und einer Schicht 7 (z. B. MCrAlY), die degradiert ist und mit dem erfindungsgemäßen Verfahren entfernt werden soll.
Ebenso kann auch das Substrat 4 degradiert sein, wobei die degradierten Bereiche des Substrats 4 dann bspw. ebenfalls mit entfernt werden.The component 1 consists of a substrate 4 (eg nickel-, cobalt-based superalloy) and a layer 7 (eg MCrAlY) which is degraded and is to be removed by the method according to the invention.
Likewise, the substrate 4 may also be degraded, with the degraded regions of the substrate 4 then likewise being removed, for example.

Bspw. in einem ersten Verfahrensschritt kann durch grobes mechanisches Vorreinigen, wie z.B. Sandstrahlen oder Strömungsschleifen ein erster Abtrag der zu entfernenden Schichtbereiche 7, 10 und/oder auch einer keramischen Wärmedämmschicht, die über der Schicht 7 angeordnet ist, erfolgen.
Die Behandlung mit Sandstrahlen und/oder Strömungsschleifen kann auch zwischen oder nach den einzelnen Salz- und Säurebehandlungen oder am Ende erfolgen.For example. In a first process step, a first removal of the layer regions 7, 10 to be removed and / or a ceramic thermal barrier coating, which is arranged above the layer 7, can take place by coarse mechanical pre-cleaning, such as sandblasting or flow grinding.
The treatment with sandblasting and / or flow grinding can also take place between or after the individual salt and acid treatments or at the end.

Dann erfolgt eine Behandlung des Bauteils 1, insbesondere der zu entfernenden Schichtbereiche 7, 10 in einem flüssigen Salzbad (Schmelze), in das zumindest die Bereiche 7, 10 des Bauteils 1 eingetaucht werden.
Unter dem Begriff Salze werden bspw. u.a. Verbindungen aus Metall (Metallion) und Säurerest (Säure weniger ein Wasserstoffion) also bspw. NaHCO3, Na2CO3, CaCO3 .. und/oder Basenrest verstanden.
Die Verwendung einer solchen Verbindung für das Salzbad setzt voraus, dass es zu einem chemischen Angriff des Salzes auf das Bauteil 1 kommt.
Es kann auch das gesamte Bauteil 1, eventuell mit einer Maskierung versehen, in das Salzbad eingetaucht werden.Then, the component 1, in particular the layer regions 7, 10 to be removed, is treated in a liquid salt bath (melt) into which at least the regions 7, 10 of the component 1 are immersed.
The term "salts" is understood, for example, as meaning, inter alia, compounds of metal (metal ion) and acid radical (acid less a hydrogen ion), for example NaHCO 3 , Na 2 CO 3 , CaCO 3 ... And / or base radical.
The use of such a compound for the salt bath requires that there be a chemical attack of the salt on the component 1.
It can also be the entire component 1, possibly provided with a masking, immersed in the salt bath.

Das Salzbad besteht beispielsweise aus Natriumhydroxid (NaOH) oder Kaliumhydroxid (KOH) (also bspw. ein Schmelzbad, d.h. flüssig bei höheren Temperaturen als Raumtemperatur). Beide Salze können auch zusammen verwendet werden und weisen dann insbesondere ein Mischungsverhältnis von 50 zu 50 Volumenprozent auf.
Weitere Salzbäder sind denkbar.The salt bath consists for example of sodium hydroxide (NaOH) or potassium hydroxide (KOH) (ie, for example, a molten bath, ie liquid at higher temperatures than room temperature). Both Salts can also be used together, and then in particular have a mixing ratio of 50 to 50 percent by volume.
Further salt baths are conceivable.

Ebenso kann bspw. auch Natriumoxid (NaO2) obigen Salzen als Sauerstofflieferant hinzugefügt werden, das den chemischen Angriff auf die zu entfernenden Bereiche verstärkt.
Weitere Sauerstofflieferanten sind denkbar, wie z.B. eine Sauerstoffzufuhr, Oxide oder Metalloxide.Similarly, for example, sodium oxide (NaO 2 ) above salts can be added as an oxygen supplier, which enhances the chemical attack on the areas to be removed.
Other oxygen suppliers are conceivable, such as an oxygen supply, oxides or metal oxides.

Es können auch Behandlungen des Bauteils 1 in verschiedenen Salzbädern hintereinander vorgenommen werden.Treatments of the component 1 in different salt baths can also be carried out in succession.

Beispielsweise nach einer, bspw. nach jeder, Behandlung im Salzbad erfolgt eine Wässerung und/oder Trocknung.
Hierbei werden bspw. die Temperaturunterschiede zwischen Salzbad und dem Wässerungsmedium für einen Thermoschock verwendet, der den zu entfernenden Schichtbereich durch Rissbildung mechanisch schwächt.For example, after one, for example, after each, treatment in the salt bath is a washing and / or drying.
In this case, for example, the temperature differences between the salt bath and the washing medium are used for a thermal shock, which mechanically weakens the layer region to be removed by cracking.

Nach der zumindest einen Salzbadbehandlung erfolgt eine Säurebehandlung in einem zumindest ersten Säurebad, das aus einer Säure oder einem Säuregemisch besteht.After the at least one salt bath treatment, an acid treatment is carried out in an at least first acid bath, which consists of an acid or an acid mixture.

Dabei wird in einem ersten Schritt eine Säurebehandlung beispielsweise mit Salpetersäure HN03 und/oder Phosphorsäure H3PO4 durchgeführt.
Weitere Säuren (z.B. Schwefelsäure, schweflige, sapeltrige Säure, Kohlensäure, Flußsäure,....) und/oder Säuregemische sind denkbar und sind auf das jeweilige Salzbad abgestimmt. Nach einer möglichen weiteren Wässerung und Trocknung erfolgt bspw. noch eine zumindest einmalige Behandlung mit Salzsäure HCl als zweites Säurebad.
Weitere Säuren für das eventuelle zweite Säurebad sind denkbar, jedoch unterscheiden die sich von den Säuren des ersten Säurebads.In this case, in a first step, an acid treatment is carried out, for example, with nitric acid HNO 3 and / or phosphoric acid H 3 PO 4 .
Other acids (eg sulfuric acid, sulfurous, saponified acid, carbonic acid, hydrofluoric acid, ....) and / or acid mixtures are conceivable and are adapted to the particular salt bath. After a possible further washing and drying, for example, an at least one treatment with hydrochloric acid HCl takes place as the second acid bath.
Other acids for the eventual second acid bath are conceivable, but differ from the acids of the first acid bath.

Beispielsweise nach einer, bspw. nach jeder, Behandlung mit Säure erfolgt eine Wässerung und/oder Trocknung.For example, after one, for example, after each treatment with acid is a washing and / or drying.

Die einzelnen Behandlungsschritte, bei dem das Bauteil mit dem Salzbad oder den verschiedenen Säuren in Kontakt kommt, sowie das Wässern und Trocknen können jeweils für sich mehrfach wiederholt werden.The individual treatment steps, in which the component comes into contact with the salt bath or the various acids, as well as the watering and drying can each be repeated several times.

Figur 3 zeigt eine Vorrichtung 22, mit dem das erfindungsgemäße Verfahren durchgeführt werden kann.
Die Vorrichtung 22 besteht aus einem Behälter 19, in dem ein flüssiges Salz bzw. Salzgemisch oder eine Säure vorhanden ist.
In diese Flüssigkeit wird das Bauteil 1 eingetaucht.
Das Verfahren kann verkürzt bzw. verbessert werden, wenn eine Ultraschallsonde 16 in dem Bad 13 vorhanden ist und betrieben wird.FIG. 3 shows a device 22 with which the method according to the invention can be carried out.
The device 22 consists of a container 19, in which a liquid salt or salt mixture or an acid is present.
In this liquid, the component 1 is immersed.
The method can be shortened or improved if an ultrasound probe 16 is present in the bath 13 and is operated.

Figur 4 zeigt ein Bauteil 1, das nach dem erfindungsgemäßen Verfahren behandelt worden ist.
Das Bauteil 1 weist keine korrodierten Bereiche mehr auf.FIG. 4 shows a component 1 which has been treated by the method according to the invention.
The component 1 no longer has any corroded areas.

Im Folgenden sind beispielhafte Behandlungsabfolgen aufgelistet:

  • 1. Strömungsschleifen
  • 2. Salzbad oder Salzgemischbad für 1,0 Stunde,
  • 3. Phosphorsäurebad für 1,0 Stunde,
  • 4. Sandstrahlen
  • 5. Salzsäurebad für 1,5 Stunden,
  • 6. Wässerung und/oder Trocknung
  • 7. Salzsäurebad für 1,5 Stunden,
  • 8. Ultraschallreinigung mit Komplexbildner
  1. 1. Sandstrahlen
  2. 2. Salzbad für 1,0 Stunde,
  3. 3. Phosphorsäurebad für 1,0 Stunde,
  4. 4. Strömungsschleifen
  5. 5. Salzsäurebad für 2,0 Stunden,
  6. 6. Wässerung und/oder Trocknung
  7. 7. Salzsäurebad für 2,0 Stunden,
  8. 8. Ultraschallreinigung mit Komplexbildner
  • 1. Sandstrahlen
  • 2. Salzbad für 1,0 Stunde,
  • 3. Phosphorsäurebad für 1,0 Stunde,
  • 4. Strömungsschleifen
  • 5. Ultraschallreinigung mit Komplexbildner
  • 6. Salzsäurebad für 2,0 Stunden,
  • 9. Wässerung und/oder Trocknung
  • 7. Salzsäurebad für 2,0 Stunden
  1. 1. Salzbad für 1,0 Stunde,
  2. 2. Phosphorsäurebad für 1,0 Stunde,
  1. 1. Salzbad
  2. 2. Phosphorsäurebad
  3. 3. Wässerung
  4. 4. Phosphorsäurebad
  1. 1. Sandstrahlen
  2. 2. Salzbad für 1,0 Stunde,
  3. 3. Phosphor/Salpetersäurebad für 1,0 Stunde
  1. 1. Sandstrahlen
  2. 2. Salzbad für 1,0 Stunde,
  3. 3. Phosphor/Salpetersäurebad für 1,0 Stunde
  4. 4. Salzsäurebad
  1. 1. Sandstrahlen
  2. 2. Salzbad für 1,0 Stunde,
  3. 3. Phosphorsäurebad für 1,0 Stunde
  4. 4. Salzsäurebad
  1. 1. Sandstrahlen
  2. 2. Salzbad für 1,0 Stunde,
  3. 3.Salpetersäurebad für 1,0 Stunde
  4. 4. Salzsäurebad
The following are examples of treatment sequences:
  • 1. flow loops
  • 2. salt bath or salt mixed bath for 1.0 hour,
  • 3. phosphoric acid bath for 1.0 hour,
  • 4. Sandblasting
  • 5. hydrochloric acid bath for 1.5 hours,
  • 6. Watering and / or drying
  • 7. hydrochloric acid bath for 1.5 hours,
  • 8. Ultrasonic cleaning with complexing agent
  1. 1. Sandblasting
  2. 2nd salt bath for 1.0 hour,
  3. 3. phosphoric acid bath for 1.0 hour,
  4. 4. Flow grinding
  5. 5. hydrochloric acid bath for 2.0 hours,
  6. 6. Watering and / or drying
  7. 7. hydrochloric acid bath for 2.0 hours,
  8. 8. Ultrasonic cleaning with complexing agent
  • 1. Sandblasting
  • 2nd salt bath for 1.0 hour,
  • 3. phosphoric acid bath for 1.0 hour,
  • 4. Flow grinding
  • 5. Ultrasonic cleaning with complexing agent
  • 6. hydrochloric acid bath for 2.0 hours,
  • 9. Watering and / or drying
  • 7. hydrochloric acid bath for 2.0 hours
  1. 1. salt bath for 1.0 hour,
  2. 2. phosphoric acid bath for 1.0 hour,
  1. 1st salt bath
  2. 2. phosphoric acid bath
  3. 3. Watering
  4. 4. Phosphoric acid bath
  1. 1. Sandblasting
  2. 2nd salt bath for 1.0 hour,
  3. 3. Phosphoric / nitric acid bath for 1.0 hour
  1. 1. Sandblasting
  2. 2nd salt bath for 1.0 hour,
  3. 3. Phosphoric / nitric acid bath for 1.0 hour
  4. 4. hydrochloric acid bath
  1. 1. Sandblasting
  2. 2nd salt bath for 1.0 hour,
  3. 3. Phosphoric acid bath for 1.0 hour
  4. 4. hydrochloric acid bath
  1. 1. Sandblasting
  2. 2nd salt bath for 1.0 hour,
  3. 3.Saltic acid bath for 1.0 hour
  4. 4. hydrochloric acid bath

Das Strömungsschleifen (siehe dazu DE 199 02 422A1 ) eignet sich besonders für Bauteile 1, insbesondere für Schaufeln von Turbinen, mit Innenräumen, bei denen degradierte Bereiche im Innenraum vorhanden sind.The flow grinding (see DE 199 02 422A1 ) is particularly suitable for components 1, in particular for blades of turbines, with interiors in which degraded areas are present in the interior.

Außenbereiche werden vorzugsweise sandgestrahlt, wobei dort bspw. Korund verwendet wird.
Dabei muss insbesondere der maximale Strahldruck und die Partikelgröße des Strahlguts eingestellt werden, um das Substrat nicht zu schädigen.Outside areas are preferably sandblasted, where, for example, corundum is used there.
In particular, the maximum jet pressure and the particle size of the blasting medium must be adjusted so as not to damage the substrate.

Für das Salzbad wird vorzugsweise ein Salz der Firma Degussa verwendet, das mit dem Handelsnamen DUFERRIT RS DGS vertrieben wird.
Oxide des Bauteils, die dem Salzbad ausgesetzt werden, transformieren sich in oxidreichere Verbindungen, die besser säurelöslich sind.For the salt bath, preferably a salt from Degussa is used, which is sold under the trade name DUFERRIT RS DGS.
Oxides of the component that are exposed to the salt bath transform into oxide-enriched compounds that are more acid-soluble.

Die Ausdehnungskoeffizienten von Oxiden und Metallen sind i.a. unterschiedlich. Durch die Umsetzung der Bauteile 1 von einem warmen Salzbad in ein Abschreckwasserbad wird ein Thermoschock verursacht, der Risse in dem zu entfernenden Bereich (7,11) erzeugt und diesen mechanisch schwächt bspw. durch Vergrösserung der Angriffsflächen für Salz und/oder Säure.
Dieser Thermoschock wird als zusätzliche Wirkung bei der Reinigung eingesetzt.
Bei der Abschreckbehandlung ist darauf zu achten, dass ein gewisser Temperaturgradient im Bauteil nicht überschritten wird, damit keine Risse im Substrat oder Bauteil erzeugt werden.The expansion coefficients of oxides and metals are generally different. By the implementation of the components 1 of a warm salt bath in a Abschreckwasserbad a thermal shock is caused, which generates cracks in the area to be removed (7,11) and this mechanically weakens, for example. By increasing the attack surfaces for salt and / or acid.
This thermal shock is used as an additional cleaning effect.
During the quenching treatment, it must be ensured that a certain temperature gradient in the component is not exceeded, so that no cracks are generated in the substrate or component.

Als Komplexbildner wird Diammonium EDTA verwendet. Der Komplexbildner kann Metalle binden, wodurch diese entfernt werden. Die Behandlung mit dem Komplexbildner kann zwischen, vor oder nach den einzelnen Salz- und Säurebehandlungen erfolgen.
Auch hier kann ebenso eine Ultraschallsonde 16 in dem Bad 13 mit dem Komplexbildner benutzt werden, um das Verfahren zu beschleunigen.The complexing agent used is diammonium EDTA. The complexing agent can bind metals, thereby removing them. The treatment with the complexing agent can take place between, before or after the individual salt and acid treatments.
Again, an ultrasonic probe 16 may also be used in the bath 13 with the complexing agent to speed up the process.

Claims (14)

Verfahren zum Entfernen eines Schichtbereichs (7,10) eines Bauteils (1),
bei dem Säure verwendet wird,
dadurch gekennzeichnet,
dass das Bauteil (1) zuerst in zumindest einem Salzbad (13) behandelt wird,
dass nach dem Salzbad das Bauteil (1) eine
Thermoschockbehandlung erfährt,
dass dann in einem weiteren Verfahrensschritt zumindest einmal mit zumindest einer ersten Säure oder zumindest einem ersten Säuregemisch behandelt wird.Method for removing a layer region (7, 10) of a component (1),
in which acid is used,
characterized,
that the component (1) is first treated in at least one salt bath (13),
that after the salt bath, the component (1) a
Undergoes thermal shock treatment,
that is then treated in a further process step at least once with at least a first acid or at least a first acid mixture. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass
für das Salzbad (13) Natriumhydroxid (NaOH) und/oder Kaliumhydroxid (KOH) verwendet wird.Method according to claim 1,
characterized in that
for the salt bath (13) sodium hydroxide (NaOH) and / or potassium hydroxide (KOH) is used. Verfahren nach Anspruch 2,
dadurch gekennzeichnet, dass
für das Salzbad (13) Kaliumhydroxid und Natriumhydroxid in einem Mischungsverhältnis von 1 zu 1 (vol%) verwendet wird.Method according to claim 2,
characterized in that
for the salt bath (13) potassium hydroxide and sodium hydroxide in a mixing ratio of 1 to 1 (vol%) is used. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass
als Säure für das zumindest erste Säurebad (13) Salpetersäure (HNO3) oder Phosphorsäure (H3PO4) oder eine Mischung daraus verwendet wird.Method according to claim 1,
characterized in that
the acid used for the at least first acid bath (13) is nitric acid (HNO 3 ) or phosphoric acid (H 3 PO 4 ) or a mixture thereof. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass
zwei verschiedene Säurebäder (13) verwendet werden.Method according to claim 1,
characterized in that
two different acid baths (13) can be used. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass
als Säure für das zweite Säurebad (13) Salzsäure (HCl) verwendet wird.Method according to claim 1,
characterized in that
as acid for the second acid bath (13) hydrochloric acid (HCl) is used. Verfahren nach Anspruch 5,
dadurch gekennzeichnet, dass
zuerst Salpetersäure (HNO3) oder Phosphorsäure (H3PO4) oder eine Mischung daraus, und
dann Salzsäure (HCl) verwendet wird.Method according to claim 5,
characterized in that
first nitric acid (HNO 3 ) or phosphoric acid (H 3 PO 4 ) or a mixture thereof, and
then hydrochloric acid (HCl) is used. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass
eine Ultraschallsonde (16) in dem Bad (13) verwendet wird, um das Verfahren zu beschleunigen.Method according to claim 1,
characterized in that
an ultrasonic probe (16) is used in the bath (13) to speed up the process. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass
vor der Behandlung des Bauteils (1) im Salzbad (13) und/oder
nach der Behandlung im Salzbad (13) und/oder
nach der ersten Säurebehandlung und/oder
nach einer weiteren Säurebehandlung
das Bauteil (1) mit dem zu entfernenden Schichtbereich (7,10) sandgestrahlt wird oder
ein Strömungsschleifen mit dem Bauteil (1) durchgeführt wird.Method according to claim 1,
characterized in that
before the treatment of the component (1) in the salt bath (13) and / or
after treatment in a salt bath (13) and / or
after the first acid treatment and / or
after another acid treatment
the component (1) is sandblasted with the layer region (7, 10) to be removed, or
a flow grinding with the component (1) is performed. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass
dem Salzbad zumindest ein Sauerstofflieferant hinzugefügt wird.Method according to claim 1,
characterized in that
at least one oxygen supplier is added to the salt bath. Verfahren nach Anspruch 10,
dadurch gekennzeichnet, dass
der zumindest eine Sauerstofflieferant ein Oxid ist.Method according to claim 10,
characterized in that
the at least one oxygen source is an oxide. Verfahren nach Anspruch 10 oder 11,
dadurch gekennzeichnet, dass
der zumindest eine Sauerstofflieferant ein Metalloxid ist.Method according to claim 10 or 11,
characterized in that
the at least one oxygen source is a metal oxide. Verfahren nach Anspruch 12,
dadurch gekennzeichnet, dass
das Metalloxid Natriumoxid (NaO2) ist.Method according to claim 12,
characterized in that
the metal oxide is sodium oxide (NaO 2 ). Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass
in zumindest einem Zwischenschritt eine Wässerung und/oder Trocknung des Bauteils (1) durchgeführt wird.Method according to claim 1,
characterized in that
In at least one intermediate step, a washing and / or drying of the component (1) is carried out.
EP06020613A 2002-10-18 2003-08-20 Process for stripping an area of a layer from a component Expired - Lifetime EP1752562B1 (en)

Priority Applications (1)

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EP02023394A EP1411149A1 (en) 2002-10-18 2002-10-18 Process for stripping coatings from components
EP03809256A EP1552037B1 (en) 2002-10-18 2003-08-20 Method for removing a layer area of a component
EP06020613A EP1752562B1 (en) 2002-10-18 2003-08-20 Process for stripping an area of a layer from a component

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EP03809256.5 Division 2003-08-20

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EP1411149A1 (en) 2004-04-21
ES2372406T3 (en) 2012-01-19
CN100392152C (en) 2008-06-04
EP1552037B1 (en) 2006-11-08
US20060231123A1 (en) 2006-10-19
JP2006503186A (en) 2006-01-26
DE50305651D1 (en) 2006-12-21
WO2004038068A1 (en) 2004-05-06
EP1552037A1 (en) 2005-07-13
CN1688749A (en) 2005-10-26
US20070131255A1 (en) 2007-06-14
EP1752562B1 (en) 2011-10-05

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