(19)
(11)EP 2 602 355 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
26.04.2017 Bulletin 2017/17

(21)Application number: 12196365.6

(22)Date of filing:  10.12.2012
(51)Int. Cl.: 
C23C 14/32  (2006.01)
C23C 14/34  (2006.01)

(54)

METHOD FOR CATHODIC ARC COATING PROCESS.

VERFAHREN FÜR EINEN KATHODENBOGEN-BESCHICHTUNGSPROZESS.

PROCÉDÉ DE REVÊTEMENT PAR ARC CATHODIQUE.


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 09.12.2011 US 201113315859

(43)Date of publication of application:
12.06.2013 Bulletin 2013/24

(73)Proprietor: United Technologies Corporation
Farmington, CT 06032 (US)

(72)Inventors:
  • Clemens, Reade R.
    Plainville, CT Connecticut 06062 (US)
  • Ridgeway, Neil B.
    South Windsor, CT Connecticut 06074 (US)

(74)Representative: Hall, Matthew Benjamin 
Dehns St Bride's House 10 Salisbury Square
London EC4Y 8JD
London EC4Y 8JD (GB)


(56)References cited: : 
EP-A2- 2 110 457
US-A1- 2005 042 474
US-B1- 6 233 822
CN-B- 101 310 972
US-A1- 2008 138 529
  
  • JIANG S M ET AL: "Preparation and hot corrosion behaviour of a MCrAlY+AlSiY composite coating", CORROSION SCIENCE, OXFORD, GB, vol. 50, no. 11, 1 November 2008 (2008-11-01), pages 3213-3220, XP025573872, ISSN: 0010-938X, DOI: 10.1016/J.CORSCI.2008.08.018 [retrieved on 2008-08-22]
  • B.A.PINT ET AL: "Deformation and phase transformations during the cyclic oxidation of Ni-Al and Ni-Pt-Al", JOM, vol. 58, no. 1, 1 January 2006 (2006-01-01), pages 47-52, XP002693872, US DOI: DOI: 10.1007/s11837-006-0068-y (dx.doi.org
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description


[0001] A gas turbine engine typically includes an inlet, a compressor, a combustor, a turbine, and an exhaust duct. The compressor draws in ambient air and increases its temperature and pressure. Fuel is added to the compressed air in the combustor, where it is burned to raise gas temperature thereby imparting energy to the gas stream. To increase gas turbine engine efficiency, it is desirable to increase the temperature of the gas entering the turbine stages. This requires the first stage turbine engine components (e.g. vanes and blades) to be able to withstand the thermal and oxidation conditions of the high temperature combustion gas during the course of operation.

[0002] To protect turbine engine components from the extreme conditions, such components typically include metallic coatings (e.g. aluminides and MCrAlY coatings) that provide oxidation and/or corrosion resistance. The metallic coatings may also function as bond coats to adhere thermal barrier coatings to the substrates of the turbine engine components. Existing bond coats are applied to turbine engine components using a variety of deposition techniques (e.g. plasma spraying, cathodic arc plasma deposition, pack cementation, and chemical vapor deposition techniques). The ceramic thermal barrier coatings are then applied over the bond coats to thermally insulate the turbine engine component from the extreme operating conditions. Each bond coat deposition technique offers challenges that, unless resolved, can lead to quality, throughput, and expense issues for the finished product.

[0003] Viewed from a first aspect, the present invention provides a method of forming targets for cathodic arc deposition of alloy bond coats for turbine engine components comprising: melting a base alloy containing aluminum and other metals, wherein the base alloy consists of one of NiCrAlY, CoCrAlY, FeCrAlY, NiCoCrAlY, FeCoCrAlY, and mixtures thereof, or wherein the base alloy consists of NiCrAlYPt, CoCrAlYPt, FeCrAlYPt, NiCoCrAlYPt, FeCoCrAlYPt, and mixtures thereof; adding a grain boundary strengthening alloy addition to the base alloy melt wherein the grain boundary strengthening alloy addition consists of 2 to 50 ppm Ce; casting the combined melt to form an ingot; further processing the ingot to form cathodic arc targets.

[0004] Viewed from a second aspect, the present invention provides a target for cathodic arc deposition of alloy bond coats for turbine engine components comprising: a base alloy containing aluminum and other metals, wherein the base alloy consists of one of NiCrAlY, CoCrAlY, FeCrAlY, NiCoCrAlY, FeCoCrAlY, and mixtures thereof, or wherein the base alloy consists of one of NiCrAlYPt, CoCrAlYPt, FeCrAlYPt, NiCoCrAlYPt, FeCoCrAlYPt, and mixtures thereof; and a grain boundary strengthening alloy addition to the base alloy wherein the grain boundary strengthening alloy addition consists of 2 to 50 ppm Ce.

[0005] The grain boundary strengthening additions minimize intergranular separation of the targets during cathodic arc deposition.

[0006] Certain preferred embodiments of the present invention will now be described in greater detail, and by way of example only.

[0007] Under conditions of high deposition rates in cathodic arc deposition of alloy bond coats, temperature gradients in the near surface region of the cathodic arc target can generate internal stresses that may result in intergranular separation and ultimate fracture of the target. The invention teaches the addition of grain boundary strengthening alloy additions to the target material to suppress cracking during cathodic arc deposition.

[0008] Cathodic arc deposition involves a source material and a substrate to be coated in an evacuated deposition chamber containing a relatively small amount of gas. The negative lead of a direct current (DC) power supply is attached to the source material (hereinafter referred to as the "cathode") and the positive lead is attached to an anodic member, usually the chamber itself. An arc initiating trigger at or near the source electrical potential of the anode contacts the cathode and moves away from the cathode initiating an arc that extends between the cathode and anodic chamber. The arc, or cathode spot where it contacts the cathode, moves randomly about the surface of the cathode in the absence of a steering mechanism. State of the art cathodic arc deposition equipment has features that both contain and steer the arc for efficient plasma deposition. The energy deposited by the arc at a cathode spot is intense; on the order of 105 to 107 amperes per square centimeter with a duration of a few to several microseconds.

[0009] The intensity of the energy raises the local temperature of the cathode spot to approximately equal that of the boiling point of the cathode material (at the evacuated chamber pressure). As a result, cathode material at the cathode spot vaporizes into a plasma containing atoms, molecules, ions, electrons, and particles. Positively charged ions liberated from the cathode are attracted to any object within the deposition chamber having a negative electrical potential relative to the positively charged ion. Some deposition processes maintain the substrate to be coated at the same electrical potential as the anode. Other processes use a biasing source to lower the potential of the substrate and thereby make the substrate relatively more attractive to the positively charged ions. In either case, the substrate becomes coated with the vaporized material liberated from the cathode.

[0010] As a result of the thermal intensity of the cathode spot during cathodic arc deposition, cathodes are directly or indirectly cooled to maintain reasonable thermal environments in the deposition chamber. Thermal gradients between the evaporating surface at the cathode spot and underlying cathode body and the resulting internal stress gradient may be sufficient to encourage high temperature grain boundary separation in the cathode material. Prolonged exposure to a high temperature tensile stress field may allow grain boundary cracks to reach a critical size resulting in catastrophic fracture of the cathode. High deposition rate coating resulting in higher temperature gradients exacerbates the problem. It is an object of at least the preferred embodiments of the present invention to minimize or eliminate wasteful preliminary fracture of cathodic arc targets during deposition of bond coats on turbine components.

[0011] As noted earlier, bond coats are protective metallic coatings that provide oxidation and/or corrosion resistance to protect components from the extreme operating conditions existing in the hot gas path of a turbine engine. The bond coats supply aluminum to the interface between the superalloy substrate and a ceramic thermal barrier coat that maintains a protective aluminum oxide layer that inhibits oxidation of the substrate and outward diffusion of the alloying elements from the superalloy into the coating.

[0012] Common bond coats are MCrAlY bond coats such as those disclosed in commonly owned U.S. Pat. No. 6,284,390. As used herein, the term "M" in MCrAlY may be nickel, chromium, iron, or mixtures thereof. Examples include NiCrAlY, CoCrAlY, FeCrAlY, NiCoAlY, NiFeAlY, NiCoCrAlY alloys and mixtures thereof.

[0013] Platinum additions to a MCrAlY bond coat are beneficial in that platinum is a slower diffusion species than aluminum and acts to prolong the bond coat and protective aluminum oxide layer lifetime. MCrAlYPt alloy examples include NiCrAlYPt, CoCrAlYPt, FeCrAlYPt, NiCoAlYPt, NiFeAlYPt, NiCoCrAlYPt and mixtures thereof.

[0014] Other additions to MCrAlY and Pt modified MCrAlY bond coat alloys may include hafnium, silicon, tantalum, tungsten, rhenium, zirconium, niobium, titanium, and molybdenum.

[0015] Examples of suitable concentrations for MCrAlY alloys include Cr concentrations from about 4 wt. % to about 25 wt. %, A1 concentrations from about 5 wt. % to about 20 wt. %, Y concentrations from about 0.1 wt. % to about 2 wt. %, and the balance being Ni, Fe, or Co.

[0016] In another embodiment, the bond coat may be a nickel platinum aluminum hafnium bond coat as described in commonly owned U.S. Patent No. 7,214,409.

[0017] Cathodic arc deposition targets may be formed by pressing metal powder, in particular hot isostatic pressing of powder, casting and other processes known in the art. In an embodiment, a preferred method is casting, in particular vacuum induction melting (VIM) during which the MCrAlY alloy is melted in a vacuum and then cast into a, preferably, cylindrical mold. Following casting, the ingot may be optionally hot isostatically pressed (HIP) at a temperature of about 1200°C.

[0018] Techniques for applying metallic bond coats by cathodic arc plasma vapor deposition are discussed in U.S. Pat. Nos. 5,932,078; 5,972,185; 6,036,825; and 6,224,726.

[0019] Production lots of cathodic arc target alloy material are in the form of cast bars. Due to the inherent hardness of cast MCrAlY, puck shaped targets are wire saw cut from the bars and installed in cathodic arc deposition equipment. During MCrAlY bond coat deposition, the surface temperature of the target will exceed the melting point even with cooling systems operating.

[0020] In platinum modified MCrAlY deposition, platinum can be introduced to the target in a number of ways. First, platinum can be introduced to the melt before casting. This results in homogeneous platinum distribution in the deposited coating. In other ways, platinum can be added to the top surface of an MCrAlY target as a coating. The platinum coating may be formed on the target surface using a variety of techniques such as electroplating processes and physical vapor deposition techniques. Examples of suitable platinum coating thicknesses include thicknesses ranging from about 1 micron to about 20 microns. Following deposition of the platinum layer, the target is then heat treated to at least partially diffuse the platinum into the MCrAlY alloy. Examples of suitable temperatures for the high temperature diffusion anneal process include temperatures ranging from about 930°C to about 1100°C. Suitable heat treat durations include at least about 1 hour to about 4 hours. It is desirable to perform the diffusion anneal in a reduced pressure inert environment or vacuum. Adding platinum via a diffusion anneal results in a sharper concentration gradient with higher platinum at the surface and decreasing with depth below the surface of the target. US 2005/042474 A1 discloses a NiCrAlYBMg alloy It is the purpose of the present invention to strengthen the grain boundaries of MCrAlY bond coat targets during high temperature cathodic arc deposition. With the present invention alloying elements are added to the cathodic targets to strengthen grain boundaries in the target. Examination of fracture surfaces of broken MCrAlY targets indicated a number of features. The fracture surface morphology always included grain boundary facets as well as transgranular fracture. It is suggested that, at the temperatures existing near the target surface during deposition, some grain boundaries separated due to the thermally induced stress field in the target. The grain boundary cracks then grew under the stress field until a point was reached where the stress concentration at the crack tip exceeded the critical stress intensity factor (i.e. the fracture toughness) and the fracture proceeded in a catastrophic transgranular fashion. The fracture origin is presumably related to low grain boundary strength in the near surface regions of the target during deposition.

[0021] An alloying element that can perform this function is cerium. In particular, additions of about 2 ppm Ce to about 50 ppm Ce.

[0022] With the above alloying additions, high temperature grain boundary separation and eventual fracture of expensive MCrAlY and other alloy cathodic arc targets is delayed or prevented resulting in increased product throughput.

[0023] While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention, which is defined by the claims. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.


Claims

1. A method of forming targets for cathodic arc deposition of alloy bond coats for turbine engine components comprising:

melting a base alloy containing aluminum and other metals, wherein the base alloy consists of one of NiCrAlY, CoCrAlY, FeCrAlY, NiCoCrAlY, FeCoCrAlY, and mixtures thereof, or wherein the base alloy consists of NiCrAlYPt, CoCrAlYPt, FeCrAlYPt, NiCoCrAlYPt, FeCoCrAlYPt, and mixtures thereof;

adding a grain boundary strengthening alloy addition to the base alloy melt wherein the grain boundary strengthening alloy addition consists of 2 to 50 ppm Ce;

casting the combined melt to form an ingot;

further processing the ingot to form cathodic arc targets.


 
2. The method of claim 1, wherein melting comprises vacuum induction melting, or vacuum arc melting.
 
3. The method of any preceding claim, wherein casting comprises forming a cylindrical ingot.
 
4. The method of any preceding claim, wherein further processing the ingot comprises hot isostatic pressing the ingot.
 
5. A target for cathodic arc deposition of alloy bond coats for turbine engine components comprising:

a base alloy containing aluminum and other metals, wherein the base alloy consists of one of NiCrAlY, CoCrAlY, FeCrAlY, NiCoCrAlY, FeCoCrAlY, and mixtures thereof, or wherein the base alloy consists of one of NiCrAlYPt, CoCrAlYPt, FeCrAlYPt, NiCoCrAlYPt, FeCoCrAlYPt, and mixtures thereof; and

a grain boundary strengthening alloy addition to the base alloy wherein the grain boundary strengthening alloy addition consists of 2 to 50 ppm Ce.


 


Ansprüche

1. Verfahren zum Bilden von Zielen zur Kathodenbogenabscheidung von Legierungsbindungsbeschichtungen für Turbinenmotorkomponenten, umfassend:

Schmelzen einer Grundlegierung, die Aluminium und andere Metalle enthält, wobei die Grundlegierung aus einem von NiCrAlY, CoCrAlY, FeCrAlY, NiCoCrAlY, FeCoCrAlY und Gemischen davon besteht, oder wobei die Grundlegierung aus NiCrAlYPt, CoCrAlYPt, FeCrAlYPt, NiCoCrAlYPt, FeCoCrAlYPt und Gemischen davon besteht;

Zusetzen eines Korngrenzenverstärkungslegierungszusatzes zu der Grundlegierungsschmelze, wobei der Korngrenzenverstärkungslegierungszusatz aus 2 bis 50 ppm Ce besteht;

Gießen der kombinierten Schmelze, um einen Gussblock zu bilden;

weiteres Verarbeiten des Gussblocks, um Kathodenbogenziele zu bilden.


 
2. Verfahren nach Anspruch 1, wobei das Schmelzen Vakuuminduktionsschmelzen oder Vakuumbogenschmelzen umfasst.
 
3. Verfahren nach einem der vorangehenden Ansprüche, wobei das Gießen das Bilden eines zylindrischen Gussblocks umfasst.
 
4. Verfahren nach einem der vorangehenden Ansprüche, wobei das weitere Verarbeiten des Gussblocks isostatisches Heißpressen des Gussblocks umfasst.
 
5. Ziel zur Kathodenbogenabscheidung von Legierungsbindungsbeschichtungen für Turbinenmotorkomponenten, umfassend:

eine Grundlegierung, die Aluminium und andere Metalle enthält, wobei die Grundlegierung aus einem von NiCrAlY, CoCrAlY, FeCrAlY, NiCoCrAlY, FeCoCrAlY und Gemischen davon besteht, oder wobei die Grundlegierung aus einem von NiCrAlYPt, CoCrAlYPt, FeCrAlYPt, NiCoCrAlYPt, FeCoCrAlYPt und Gemischen davon besteht; und

einen Korngrenzenverstärkungslegierungszusatz zu der Grundlegierungsschmelze, wobei der Korngrenzenverstärkungslegierungszusatz aus 2 bis 50 ppm Ce besteht.


 


Revendications

1. Procédé de formation de cibles pour le dépôt par arc cathodique de revêtements d'ancrage d'alliages pour les composants de moteur à turbine comprenant :

la fusion d'un alliage de base contenant de l'aluminium et d'autres métaux, dans lequel l'alliage de base est constitué de l'un parmi NiCrAlY, CoCrAlY, FeCrAlY, NiCoCrAlY, FeCoCrAlY, et de mélanges de ceux-ci, ou dans lequel l'alliage de base est constitué de NiCrAlYPt, de CoCrAlYPt, de FeCrAlYPt, de NiCoCrAlYPt, de FeCoCrAlYPt, et de mélanges de ceux-ci ;

l'ajout d'un élément d'alliage renforçant le joint de grain au bain d'alliage de base dans lequel l'élément d'alliage renforçant le joint de grain est constitué de 2 à 50 ppm Ce ;

le moulage de la matière fondue pour former un lingot ;

le traitement ultérieur du lingot pour former des cibles d'arc cathodique.


 
2. Procédé selon la revendication 1, dans lequel la fusion comprend la fusion par induction sous vide, ou la fusion par arc sous vide.
 
3. Procédé selon une quelconque revendication précédente, dans lequel le moulage comprend la formation d'un lingot cylindrique.
 
4. Procédé selon une quelconque revendication précédente, dans lequel le traitement ultérieur du lingot comprend le pressage isostatique à chaud du lingot.
 
5. Cible pour le dépôt par arc cathodique de revêtements d'ancrage d'alliages pour les composants de moteur à turbine comprenant :

un alliage de base contenant de l'aluminium et d'autres métaux, dans lequel l'alliage de base est constitué de l'un parmi NiCrAlY, CoCrAlY, FeCrAlY, NiCoCrAlY, FeCoCrAlY, et de mélanges de ceux-ci, ou dans lequel l'alliage de base est constitué de NiCrAlYPt, de CoCrAlYPt, de FeCrAlYPt, de NiCoCrAlYPt, de FeCoCrAlYPt, et de mélanges de ceux-ci ; et

un élément d'alliage renforçant le joint de grain ajouté à l'alliage de base dans lequel l'élément d'alliage renforçant le joint de grain est constitué de 2 à 50 ppm Ce.


 




REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description