EP0872575A2 - Protective surface coating for titanium alloys - Google Patents
Protective surface coating for titanium alloys Download PDFInfo
- Publication number
- EP0872575A2 EP0872575A2 EP19980106656 EP98106656A EP0872575A2 EP 0872575 A2 EP0872575 A2 EP 0872575A2 EP 19980106656 EP19980106656 EP 19980106656 EP 98106656 A EP98106656 A EP 98106656A EP 0872575 A2 EP0872575 A2 EP 0872575A2
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- EP
- European Patent Office
- Prior art keywords
- layer
- aluminum
- surface protection
- protective layer
- coating according
- 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.)
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Classifications
-
- 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
- C23C28/04—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 only coatings of inorganic non-metallic material
Definitions
- the invention relates to the field of Protection against oxidation and affects one Surface protective coating for titanium alloy components that have a titanium content of> 50%, especially for Turbine or high thermal and mechanical stress Compressor blades.
- Titanium alloys are subject to complex stresses from creep, fatigue and hot gas corrosion at high temperatures in flight and stationary turbines. Despite the fact that the strength level of the titanium alloys would still allow the use at temperatures above 600 ° C, these titanium alloys are currently only used at temperatures up to 525 ° C, because the alloys oxidize at high temperatures due to the strong oxygen affinity of the titanium the areas of the components near the surface become brittle due to the diffusion of oxygen. This process continues with increasing exposure duration, since the TiO 2 layers formed on the surface do not represent tight diffusion barriers for oxygen.
- Oxidation protection layers for titanium alloys known, in which a Ti-Al layer and an additional one on the titanium alloy thin niobium layer can be applied (DE 37 42 944). Indeed this layer formation process requires temperatures of 800 ° C or 1100 ° C, what modern, complex and therefore high-strength high-temperature titanium alloys, because of which then Softening processes taking place is harmful.
- the invention has for its object a Surface protective coating for titanium alloy components that have a titanium content of> 50 at.%, to develop the can be generated at temperatures below 650 ° C and at Temperature and load changes not flaking off.
- an Al 2 O 3 -based protective layer can be located on the basic protective layer.
- this can also contain ZrO 2 .
- the coating can be designed as a multi-layer composite in the form of several superimposed sequences of the layer combination of basic protective layer and protective layer on an Al 2 O 3 basis.
- the material composition and / or the concentration of the elements contained can be designed differently in the individual basic protective layers of the multilayer layer composite.
- the total layer thickness is expediently the Surface protection coating between 1 and 20 ⁇ m.
- the surface protection coating according to the invention for Titanium alloy components stand out from the known ones Protective layers from the fact that these at temperatures can be generated below 650 ° C and that this at Temperature and load changes not flaking off.
- Coating can easily separate functions into one first layer, which serves as an adhesion promoter, and into an outer Layer that prevents oxidation can be reached.
- the invention is based on exemplary embodiments explained in more detail.
- the elements Al, Ti and Cr are simultaneously deposited with a layer thickness of 4 ⁇ m on turbine blades made of titanium alloy in a PACVD system at a temperature of 650 ° C., in such a way that the deposited layer has a stoichiometry of approximately 65 at.% Al, 25 at.% Ti, 1 at.% O, 1 at.% N and 8 at.% Cr.
- the coated turbine blades are then heat-treated in air at a temperature of 625 ° C. for a period of 10 hours. This heat treatment leads to the formation of a dense Al 2 O 3 cover layer, which protects the titanium alloy from oxidation when the turbine blades are used.
- the component provided with this layer composite shows no further increase in the Al 2 O 3 layer thickness and there are also no layer flaking, ie there is a mechanically stable and oxidation-resistant substrate-layer composite in front. In contrast, an uncoated component would corrode at this temperature due to the formation of titanium oxide.
- the elements Al, Ti, O, N and Zr are simultaneously deposited in a PACVD system at a temperature of 550 ° C. to form a base layer with a layer thickness of 4 ⁇ m, in such a way that the deposited layer is a Stoichiometry of about 25 at.% Al, 25 at.% Ti, 1 at.% O, 44 at.% N and 5 at.% Zr.
- an Al 2 O 3 cover layer with a layer thickness of 3 ⁇ m is produced at a temperature of 590 ° C., which serves as an oxidation protection layer.
- the underlying layer has an adhesion-promoting function to the surface of the turbine blade.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Structures Of Non-Positive Displacement Pumps (AREA)
Abstract
Description
Die Erfindung bezieht sich auf das Gebiet des Oxidationsschutzes und betrifft eine Oberflächenschutzbeschichtung für Titanlegierungsbauteile, die einen Titangehalt von > 50% besitzen, insbesondere für thermisch und mechanisch hoch beanspruchte Turbinen- oder Kompressorenschaufeln.The invention relates to the field of Protection against oxidation and affects one Surface protective coating for titanium alloy components that have a titanium content of> 50%, especially for Turbine or high thermal and mechanical stress Compressor blades.
Titanlegierungen unterliegen bei hohen Temperaturen in Flug- und stationären Turbinen einer komplexen Beanspruchung aus Kriechen, Ermüdung und Heißgaskorrosion. Trotz der Tatsache, daß das Festigkeitsniveau der Titanlegierungen noch den Einsatz bei Temperaturen von über 600°C erlauben würde, werden diese Titanlegierungen derzeit nur bei Temperaturen bis zu 525°C eingesetzt, da die Legierungen wegen der starken Sauerstoffaffinität des Titans bei höheren Temperaturen oxidieren und die oberflächennahen Bereiche der Bauteile durch eindiffundierenden Sauerstoff verspröden. Dieser Prozeß setzt sich mit zunehmender Expositionsdauer weiter fort, da die auf der Oberfläche gebildeten TiO2-Schichten keine dichten Diffusionsbarrieren für Sauerstoff darstellen.Titanium alloys are subject to complex stresses from creep, fatigue and hot gas corrosion at high temperatures in flight and stationary turbines. Despite the fact that the strength level of the titanium alloys would still allow the use at temperatures above 600 ° C, these titanium alloys are currently only used at temperatures up to 525 ° C, because the alloys oxidize at high temperatures due to the strong oxygen affinity of the titanium the areas of the components near the surface become brittle due to the diffusion of oxygen. This process continues with increasing exposure duration, since the TiO 2 layers formed on the surface do not represent tight diffusion barriers for oxygen.
Es ist auch bereits bekannt, Bauteile aus Titanlegierungen mit einer Oxidationsschutzschicht auf Aluminiumbasis durch Diffusionsbeschichtung (Alitieren) zu versehen. Nachteilig ist dabei jedoch, daß die durch das Alitieren gebildete Ti-Al-Schutzschicht bei höheren Temperaturen an der Oberfläche Al2O3 bildet. Dieses hat zum Substratmaterial nur eine geringe Bindung und platzt bei auftretenden mechanischen Belastungen des Verbundes leicht ab. Derartige Belastungen treten beim Einsatz solcher Bauteile als Turbinenschaufeln infolge thermischer Ausdehnung bei Temperaturwechseln auf, oft zusätzlich verstärkt durch Änderungen in der Umdrehungsgeschwindigkeit der Turbine während des An- und Abfahrprozesses. An den freigelegten Oberflächenstellen kann sich neues Al2O3 bilden, wodurch aber der Al-Gehalt in der Schutzschicht sinkt. Dies beeinträchtigt die Lebensdauer bzw. die Einsatzdauer der Bauteile. Das ständige Abplatzen und Neubilden von Al2O3 führt in nachteiliger Weise auch zu einer Verminderung der Oberflächengüte, was bei aerodynamischen Bauteilen, wie beispielsweise Kompressorenschaufeln, Wirkungsgradverluste zur Folge hat. Nachteilig ist außerdem die infolge der Ausbildung intermetallischer Phasen mit komplexen Gitterstrukturen vorhandene Sprödigkeit der Ti-Al-Schutzschichten.It is also known to provide components made of titanium alloys with an aluminum-based oxidation protection layer by diffusion coating (alitizing). However, it is disadvantageous that the Ti-Al protective layer formed by the alitation forms Al 2 O 3 at the surface at higher temperatures. This has only a low bond to the substrate material and easily breaks off when the composite is subjected to mechanical loads. Such loads occur when such components are used as turbine blades as a result of thermal expansion during temperature changes, often additionally exacerbated by changes in the rotational speed of the turbine during the start-up and shutdown process. New Al 2 O 3 can form on the exposed surface areas, but this reduces the Al content in the protective layer. This affects the service life or the service life of the components. The constant flaking and new formation of Al 2 O 3 also disadvantageously leads to a reduction in the surface quality, which results in losses in efficiency in aerodynamic components, such as, for example, compressor blades. Another disadvantage is the brittleness of the Ti-Al protective layers which is present due to the formation of intermetallic phases with complex lattice structures.
Es ist auch bereits ein Verfahren zum Erzeugen von Oxidationsschutzschichten für Titanlegierungen bekannt, bei dem auf die Titanlegierung eine Ti-Al-Schicht und zusätzlich eine dünne Niobschicht aufgebracht werden (DE 37 42 944). Allerdings benötigt dieser Schichtbildungsprozeß Temperaturen von 800°C bzw. 1100°C, was für moderne, komplex aufgebaute und damit hochfeste Hochtemperatur-Titanlegierungen, wegen der dann im Gefüge stattfindenden Erweichungsvorgänge schädlich ist.It is also already a process for generating Oxidation protection layers for titanium alloys known, in which a Ti-Al layer and an additional one on the titanium alloy thin niobium layer can be applied (DE 37 42 944). Indeed this layer formation process requires temperatures of 800 ° C or 1100 ° C, what modern, complex and therefore high-strength high-temperature titanium alloys, because of which then Softening processes taking place is harmful.
Der Erfindung liegt die Aufgabe zugrunde, eine Oberflächenschutzbeschichtung für Titanlegierungsbauteile, die einen Titangehalt von > 50 At.% besitzen, zu entwickeln, die bei Temperaturen unterhalb 650°C erzeugt werden kann und bei Temperatur- und Belastungswechseln nicht abplatzt.The invention has for its object a Surface protective coating for titanium alloy components that have a titanium content of> 50 at.%, to develop the can be generated at temperatures below 650 ° C and at Temperature and load changes not flaking off.
Diese Aufgabe ist mit der in den Patentansprüchen beschriebenen Beschichtung gelöst. This task is with that described in the claims Coating released.
Die erfindungsgemäße Oberflächenschutzbeschichtung besteht aus einer auf die Oberfläche des Titanlegierungsbauteils aufgebrachten Grundschicht der Zusammensetzung
- Ti
- 25 bis 50 At.%
- Al
- 25 bis 75 At.%
- X
- 1 bis 21 At.%
- O
- 1 bis 25 At.%
- N
- 1 bis 50 At.%,
- Ti
- 25 to 50 at.%
- Al
- 25 to 75 at.%
- X
- 1 to 21 at.%
- O
- 1 to 25 at.%
- N
- 1 to 50 at.%,
Erfindungsgemäß kann sich auf der Grundschutzschicht eine Deckschutzschicht auf Al2O3-Basis befinden. In dieser kann neben Al2O3 auch ZrO2 enthalten sein.According to the invention, an Al 2 O 3 -based protective layer can be located on the basic protective layer. In addition to Al 2 O 3 , this can also contain ZrO 2 .
Gemäß einer vorteilhaften Ausgestaltung der Erfindung kann die Beschichtung als Multilagen-Schichtverbund in Form mehrerer übereinander angeordneter Folgen der Schichtkombination von Grundschutzschicht und Deckschutzschicht auf Al2O3-Basis ausgeführt sein. Dabei kann erfindungsgemäß in den einzelnen Grundschutzschichten des Multilagen-Schichtverbundes die stoffliche Zusammensetzung und/oder die Konzentration der enthaltenen Elemente unterschiedlich ausgeführt sein.According to an advantageous embodiment of the invention, the coating can be designed as a multi-layer composite in the form of several superimposed sequences of the layer combination of basic protective layer and protective layer on an Al 2 O 3 basis. According to the invention, the material composition and / or the concentration of the elements contained can be designed differently in the individual basic protective layers of the multilayer layer composite.
Zweckmäßigerweise liegt die Gesamtschichtdicke der Oberflächenschutzbeschichtung zwischen 1 und 20 µm.The total layer thickness is expediently the Surface protection coating between 1 and 20 µm.
Die erfindungsgemäße Oberflächenschutzbeschichtung für Titanlegierungsbauteile zeichnet sich gegenüber den bekannten Schutzschichten dadurch aus, daß diese bei Temperaturen unterhalb 650°C erzeugt werden kann und daß diese bei Temperatur- und Belastungswechseln nicht abplatzt. Durch die erfindungsgemäß vorgesehene Multilagenausbildung der Beschichtung kann leicht eine Trennung der Funktionen in eine erste Schicht, die als Haftvermittler dient, und in eine äußere Schicht, welche die Oxidation verhindert, erreicht werden. The surface protection coating according to the invention for Titanium alloy components stand out from the known ones Protective layers from the fact that these at temperatures can be generated below 650 ° C and that this at Temperature and load changes not flaking off. Through the multilayer training of the invention Coating can easily separate functions into one first layer, which serves as an adhesion promoter, and into an outer Layer that prevents oxidation can be reached.
Durch weitere Zwischenschichten, deren chemische Zusammensetzung zueinander stufenweise verändert ist, können die unterschiedlichen mechanischen Eigenschaften aneinandergrenzender Schichten angepaßt und so ein gradierter Multilagen-Schichtverbund mit verbesserter mechanischer Stabilität erzeugt werden. Durch die Möglichkeit, die Beschichtung mittels PACVD bei Temperaturen unterhalb 650°C herzustellen, werden im Titanlegierungsbauteil Gefügeveränderungen, die zu einem Festigkeitsverlust führen würden, ausgeschlossen.Through further intermediate layers, their chemical Composition to each other is gradually changed the different mechanical properties adjoining layers and thus a graded Multi-layer composite with improved mechanical Stability can be generated. By being able to PACVD coating at temperatures below 650 ° C manufacture in the titanium alloy component Structural changes that lead to a loss of strength would be excluded.
Nachstehend ist die Erfindung an Hand von Ausführungsbeispielen näher erläutert.The invention is based on exemplary embodiments explained in more detail.
Auf Turbinenschaufeln aus einer Titanlegierung werden in einer PACVD-Anlage bei einer Temperatur von 650°C gleichzeitig die Elemente Al, Ti und Cr mit einer Schichtdicke von 4 µm abgeschieden, und zwar so, daß die abgeschiedene Schicht eine Stöchiometrie von etwa 65 At.% Al, 25 At.% Ti, 1 At.% O, 1 At.% N und 8 At.% Cr aufweist. Nachfolgend werden die beschichteten Turbinenschaufeln in Luft bei einer Temperatur von 625°C während einer Dauer von 10 h wärmebehandelt. Diese Wärmebehandlung führt zur Ausbildung einer dichten Al2O3-Deckschicht, welche die Titanlegierung beim Einsatz der Turbinenschaufeln vor Oxidation schützt.The elements Al, Ti and Cr are simultaneously deposited with a layer thickness of 4 μm on turbine blades made of titanium alloy in a PACVD system at a temperature of 650 ° C., in such a way that the deposited layer has a stoichiometry of approximately 65 at.% Al, 25 at.% Ti, 1 at.% O, 1 at.% N and 8 at.% Cr. The coated turbine blades are then heat-treated in air at a temperature of 625 ° C. for a period of 10 hours. This heat treatment leads to the formation of a dense Al 2 O 3 cover layer, which protects the titanium alloy from oxidation when the turbine blades are used.
Das mit diesem Schichtverbund versehene Bauteil zeigt nach einer Expositionsdauer von 100 h bei 550°C an Luft keine weitere Erhöhung der Al2O3-Schichtdicke und es treten auch keine Schichtabplatzungen auf, d.h. es liegt ein mechanisch stabiler und oxidationsbeständiger Substrat-Schicht-Verbund vor. Demgegenüber würde ein unbeschichtetes Bauteil bei dieser Temperatur durch Titanoxidbildung korrodieren. After an exposure time of 100 h at 550 ° C in air, the component provided with this layer composite shows no further increase in the Al 2 O 3 layer thickness and there are also no layer flaking, ie there is a mechanically stable and oxidation-resistant substrate-layer composite in front. In contrast, an uncoated component would corrode at this temperature due to the formation of titanium oxide.
Auf Turbinenschaufeln aus einer Titanlegierung werden in einer PACVD-Anlage bei einer Temperatur von 550°C gleichzeitig die Elemente Al, Ti, O, N und Zr zu einer Grundschicht mit einer Schichtdicke von 4 µm abgeschieden, und zwar so, daß die abgeschiedene Schicht eine Stöchiometrie von etwa 25 At.% Al, 25 At.% Ti, 1 At.% O, 44 At.% N und 5 At.% Zr aufweist. Danach wird auf die Grundschicht in einem zweiten Beschichtungsvorgang in der PACVD-Anlage bei einer Temperatur von 590°C eine Al2O3-Deckschicht mit einer Schichtdicke von 3 µm erzeugt, die als Oxidationsschutzschicht dient. Die darunter befindliche Grundschicht hat eine haftvermittelnde Funktion zur Oberfläche der Turbinenschaufel.On turbine blades made of titanium alloy, the elements Al, Ti, O, N and Zr are simultaneously deposited in a PACVD system at a temperature of 550 ° C. to form a base layer with a layer thickness of 4 μm, in such a way that the deposited layer is a Stoichiometry of about 25 at.% Al, 25 at.% Ti, 1 at.% O, 44 at.% N and 5 at.% Zr. Then, in a second coating process in the PACVD system, an Al 2 O 3 cover layer with a layer thickness of 3 μm is produced at a temperature of 590 ° C., which serves as an oxidation protection layer. The underlying layer has an adhesion-promoting function to the surface of the turbine blade.
Im Korrosionstest bei 600°C an Luft zeigt dieser Verbundwerkstoff nach 100 h weder eine fortschreitende Oxidation noch Abplatzungen des Schichtsystems.This shows in a corrosion test at 600 ° C in air Composite material after 100 h neither progressive Oxidation still flaking of the layer system.
Claims (6)
- Ti
- 25 bis 50 At.%
- Al
- 25 bis 75 At.%
- X
- 1 bis 21 At.%
- O
- 1 bis 25 At.%
- N
- 1 bis 50 At.%
- Ti
- 25 to 50 at.%
- Al
- 25 to 75 at.%
- X
- 1 to 21 at.%
- O
- 1 to 25 at.%
- N
- 1 to 50 at.%
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19716533 | 1997-04-19 | ||
| DE19716533 | 1997-04-19 | ||
| DE19814613A DE19814613A1 (en) | 1997-04-19 | 1998-04-01 | Surface protective layer for titanium alloy components |
| DE19814613 | 1998-04-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0872575A2 true EP0872575A2 (en) | 1998-10-21 |
Family
ID=26035928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19980106656 Withdrawn EP0872575A2 (en) | 1997-04-19 | 1998-04-11 | Protective surface coating for titanium alloys |
Country Status (1)
| Country | Link |
|---|---|
| EP (1) | EP0872575A2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19920567A1 (en) * | 1999-05-03 | 2000-11-16 | Fraunhofer Ges Forschung | Component consisting of titanium or titanium alloy has a functional intermediate layer made of a group IVb element, alloy or oxide and an oxide ceramic protective layer on the surface of the component |
| EP1316627A1 (en) * | 2001-11-28 | 2003-06-04 | METAPLAS IONON Oberflächenveredelungstechnik GmbH | Hard coating coated parts |
| US6906295B2 (en) * | 2003-02-20 | 2005-06-14 | National Material L.P. | Foodware with multilayer stick resistant ceramic coating and method of making |
| EP1566463A1 (en) * | 2004-02-18 | 2005-08-24 | Jürgen Bach Immobilien und Maschinen KG | Anti-abrasion coating for tools |
| WO2006094481A1 (en) * | 2005-03-10 | 2006-09-14 | Mtu Aero Engines Gmbh | Component, in particular, a gas turbine component |
| US7947363B2 (en) * | 2007-12-14 | 2011-05-24 | Kennametal Inc. | Coated article with nanolayered coating scheme |
| US8021768B2 (en) | 2009-04-07 | 2011-09-20 | National Material, L.P. | Plain copper foodware and metal articles with durable and tarnish free multiplayer ceramic coating and method of making |
-
1998
- 1998-04-11 EP EP19980106656 patent/EP0872575A2/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19920567A1 (en) * | 1999-05-03 | 2000-11-16 | Fraunhofer Ges Forschung | Component consisting of titanium or titanium alloy has a functional intermediate layer made of a group IVb element, alloy or oxide and an oxide ceramic protective layer on the surface of the component |
| DE19920567C2 (en) * | 1999-05-03 | 2001-10-04 | Fraunhofer Ges Forschung | Process for coating a component consisting essentially of titanium or a titanium alloy |
| EP1316627A1 (en) * | 2001-11-28 | 2003-06-04 | METAPLAS IONON Oberflächenveredelungstechnik GmbH | Hard coating coated parts |
| US6794064B2 (en) | 2001-11-28 | 2004-09-21 | Metaplas Ionon Oberflaechenveredelungstechnik Gmbh | Hard coating coated parts |
| US6906295B2 (en) * | 2003-02-20 | 2005-06-14 | National Material L.P. | Foodware with multilayer stick resistant ceramic coating and method of making |
| US7462375B2 (en) | 2003-02-20 | 2008-12-09 | National Material L.P. | Method of making a stick resistant multi-layer ceramic coating |
| EP1566463A1 (en) * | 2004-02-18 | 2005-08-24 | Jürgen Bach Immobilien und Maschinen KG | Anti-abrasion coating for tools |
| WO2006094481A1 (en) * | 2005-03-10 | 2006-09-14 | Mtu Aero Engines Gmbh | Component, in particular, a gas turbine component |
| US7947363B2 (en) * | 2007-12-14 | 2011-05-24 | Kennametal Inc. | Coated article with nanolayered coating scheme |
| US8021768B2 (en) | 2009-04-07 | 2011-09-20 | National Material, L.P. | Plain copper foodware and metal articles with durable and tarnish free multiplayer ceramic coating and method of making |
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