WO2005035819A1 - Procede de traitement a l'alite, a la silice ou au chrome de composants metalliques - Google Patents

Procede de traitement a l'alite, a la silice ou au chrome de composants metalliques Download PDF

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Publication number
WO2005035819A1
WO2005035819A1 PCT/DE2004/002114 DE2004002114W WO2005035819A1 WO 2005035819 A1 WO2005035819 A1 WO 2005035819A1 DE 2004002114 W DE2004002114 W DE 2004002114W WO 2005035819 A1 WO2005035819 A1 WO 2005035819A1
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WO
WIPO (PCT)
Prior art keywords
diffusion
pack
paste
powder
coated
Prior art date
Application number
PCT/DE2004/002114
Other languages
German (de)
English (en)
Inventor
Michael Strasser
Heinrich Walter
Original Assignee
Mtu Aero Engines Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mtu Aero Engines Gmbh filed Critical Mtu Aero Engines Gmbh
Priority to US10/574,731 priority Critical patent/US20070272331A1/en
Priority to JP2006529616A priority patent/JP2007508449A/ja
Priority to EP04786831A priority patent/EP1670965A1/fr
Publication of WO2005035819A1 publication Critical patent/WO2005035819A1/fr

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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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/04—Diffusion into selected surface areas, e.g. using masks

Definitions

  • the invention relates to a method for producing a locally limited diffusion layer of the surface of a metallic component, the diffusion layer being formed by the inclusion of Si, Al and / or Cr in the surface of the metallic component.
  • Adhesive layers of this type must have a suitable chemical composition, roughness and surface topography, among other things. A rough surface to support the mechanical interlocking of the top layer to be applied later, for example thermal insulation layer, is advantageous.
  • Suitable thermal insulation layers can be constructed, for example, from (partially) stabilized Zr0 2 or other refractory oxides.
  • the adhesive layers In addition to the roughness for clinging to the outer protective layers or the heat insulation layer, the adhesive layers must be oxide-free and resistant to hot gas corrosion. Likewise, the adhesive layers must compensate for the different thermal expansion coefficients of the metallic base material and the thermal insulation layer.
  • Diffusion layers which contain Al and optionally further transition metals are particularly suitable as adhesive layers.
  • additional elements to be incorporated into the diffusion layer naturally depends heavily on the base material.
  • a powder pack process (out of pack process) is typically used as the coating process for producing the diffusion layers.
  • the surface to be coated with powders containing the additional elements is also derpackung called, brought into contact and heated to a temperature at which a diffusion of the elements of the powder can take place in the surface of the component.
  • the formation of the diffusion layers is generally referred to as alitizing, siliconizing, chromating, etc., corresponding to the absorption of Al, Si or Cr.
  • DE 198 24 792 A1 describes a method for producing a corrosion and oxidation-resistant layer, in which a slip containing at least one of the elements Cr, Ni or Ce is applied to a component and dried, and then at Temperatures between 800 ° C and 1200 ° C is alitated.
  • DE 3883 857 T2 discloses a method for producing a diffusion layer of Al and other ferrite-stabilizing elements for steels.
  • a package made of aluminum or aluminum alloy, as well as the other elements, a halide activator and optionally fillers is produced and the steel component to be coated is embedded in this package.
  • the diffusion coating is then carried out at temperatures above approx. 1000 ° C.
  • the methods shown have the disadvantage that the formation of the diffusion layers cannot be limited locally. Rather, the entire component is provided with the diffusion layer unspecifically. A sharp transition between the coated area and the uncoated component cannot be realized. Often, however, a sharp delimitation of the coated area is necessary. Therefore, the diffusion layer should only be deposited where it is actually needed as an adhesive layer. Because this layer changes the surface or material properties considerably, it can lead to considerable functional disturbances in the other areas of the component.
  • the object is achieved according to the invention by a method for producing a locally limited diffusion layer on a metallic component by alitizing, siliconizing and / or chroming with the features of the characterizing part of claim 1, and by a use according to claim 8.
  • Advantageous developments of the invention are the subject of the dependent claims.
  • the invention it is thus provided to build up the diffusion layer by means of a powder packing process, wherein in addition to the dispenser packing, at least one diffusion-blocking powder packing is arranged in the packing bed reactor, which prevents the supply of the additional elements to the areas of the metallic component that are not to be coated.
  • at least Cr, Si and / or Al are selected as additional elements which are to be supplied via the dispenser pack.
  • the process according to the invention comprises at least the following essential steps:
  • the paste or slip required for the first step is essentially formed by the additional elements to be applied, in particular Cr, Si and / or Al, as pure metals or their alloys, activators, binders and other additives.
  • the additional elements can be formed by the pure metals or alloys. It is often advantageous to add several additional elements at the same time via the form of alloys (co-diffusion). Al and Si are preferably fed in at the same time, the amount of Al and the amount of Si predominating by far.
  • the activators suitable according to the invention include compounds which can form volatile, in particular molecular, halides with the additional elements under the reaction conditions.
  • Preferred activators are NH F, NH 4 CI or AIF 3 .
  • ammonium halides are of particular interest as activators, since the ammonia formed as a by-product occurs as a reducing agent for the metals. This suppresses the undesirable oxidation of the metals.
  • the binders used are essentially the organic binders customary in the production of pastes or slip.
  • Powder made of AI, AlSi, AlTi, AICo and / or AlCr 5- 50% by weight
  • Al 2 0 3 powder 5-50% by weight
  • Organic binder 1-15 wt
  • Solids for siliconizing paste Si powder: 5-50% by weight Al 2 0 3 powder: 5-50% by weight Organic binder: 1-15% by weight
  • Al 2 0 3 powder 5-50% by weight
  • Organic binder 1-15% by weight
  • the solids are typically mixed with water and / or alcohols and further processed into a paste or a slip.
  • a paste is particularly preferably produced which has the consistency of a plastically moldable mass.
  • the organic binders can of course also be liquid compounds.
  • the paste or slip is applied to the areas to be coated and solidified. Solidification is typically accomplished by drying in an oven or the like.
  • the metallic component is provided with a separating layer, at least on the surfaces which are later in contact with the powder pack or which protrude into the pack bed reactor.
  • the separating layer should facilitate the subsequent detachment of the powder packs after the formation of the diffusion layer.
  • the separating layer is formed by porous material which is largely inert towards the base metal and additional elements.
  • the separating layer is preferably a thin layer of refractory oxides, in particular Al 2 O 3 .
  • the layer thickness is generally about 0.02 to 3 mm.
  • the separating layer can be applied by common coating processes to form thick layers.
  • a slip is applied, for example by brushing, dipping or spraying.
  • the slip is essentially formed by Al 2 0 3 and binder.
  • the component provided with the packing bed is at least partially introduced into a packing bed reactor.
  • Fig. 1 shows the alitation of damper pockets of a turbine blade in a packed bed reactor (1) with a turbine blade poor (2), whose blade root (3) protrudes into the packed bed reactor and which is coated with a separating layer (4) made of Al 2 0 3 , and the dispenser pack (5) arranged around the damper pockets and the diffusion-blocking powder pack (6).
  • the reactor (1) is preferably a simple device for holding the component and for receiving the powder filling or the diffusion-blocking powder pack.
  • the reactor can be formed, for example, by a metal capsule into which the component with the areas to be coated protrude.
  • the component (3) with coated and adjacent uncoated areas and the dispenser pack (5) with the diffusion-blocking powder pack (6) are then overlaid.
  • the diffusion-blocking powder pack has the effect according to the invention of retaining or binding the volatile compounds of the additional elements, so that coating of the surfaces of the metallic component which are not directly connected to the dispenser pack is suppressed or avoided entirely.
  • the material of this powder pack which is responsible for the diffusion-blocking effect, is a metal that can chemically bind the additional elements. Ni, Co and / or Fe alloys are typically used here.
  • the diffusion-blocking powder pack preferably has metal powder with a similar or the same composition as that coating metallic components. This prevents contamination of the metallic component by elements from the diffusion-blocking powder pack. Ni or Ni alloys are particularly preferred.
  • activators are contained as a further component of the diffusion-blocking powder pack.
  • the same or different activators as in the dispenser package can be selected.
  • the activators present in this outer powder pack advantageously reduce the loss of activator in the area of the donor pack during the diffusion reaction.
  • a preferred composition of the diffusion-blocking powder pack has at least 50% metal powder and an activator content in the range from 0.2 to 5% by weight , Inert substances, for example Al 2 O 3 , can be present as further components.
  • the reactor is heated to a temperature above 900 ° C.
  • the reactor is preferably operated under an inert or protective gas, Ar and / or H 2 being particularly preferred here.
  • the reducing conditions under H 2 prevent or at least partially reverse oxide formation.
  • an alitation, siliconization and / or chrome plating is preferably carried out.
  • process temperatures and times depends on the selected components, dispenser packs and the desired layer consistency.
  • the process temperatures for alitation are typically in the range of 750 to 1200 ° C, with holding times of 1 to 20 h; when chroming typically 900 to 1200 ° C are selected with the same holding time.
  • the metallic components can also already have metallic coatings. This may require a slight adjustment of the process parameters compared to the uncoated components. In principle, however, the essential features of the method according to the invention remain unchanged.
  • the chemical components necessary for the surface treatment are formed in situ within the reactor.
  • education and Settlement of gaseous metal halides play an essential role in transporting the metals intended for diffusion from the packing bed to the surface of the metallic component.
  • the metal halides are formed in situ by the halide-containing activators.
  • the gaseous metal halides entering the area of the diffusion-blocking powder pack are bound by the metal powders and prevented from diffusing into the uncoated areas.
  • the paste then had a modeling clay-like consistency.
  • the paste was pressed onto the damper pockets and dried in a convection oven at approx. 50 ° C.
  • the rotor blade thus prepared was fitted into a metal box, only the end of the blade, according to the schematic FIG. 1, protruding into the packed bed reactor formed thereby.
  • the passage of the shovel was sealed with some paste.
  • the reactor was then filled up to about twice the height of the damper pockets with diffusion-blocking cover powder (powder pack). This powder pack was formed from Ni base material powder with 1 wt% NH F.
  • the alitation was carried out at a starting temperature of 1080 ° C and a holding level at 1050 ° C with a duration of 4 h. Ar and H2 were flushed as protective gas.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Powder Metallurgy (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une couche de diffusion localement délimitée sur un composant métallique, consistant à appliquer une pâte contenant Cr, Si et/ou Al et des activateurs, sur les zones à revêtir du composant métallique; à durcir la pâte sous forme de masse de distribution; à recouvrir les zones n'étant pas à revêtir, adjacentes à la masse de distribution, d'une masse pulvérulente bloquant la diffusion; et à chauffer au-dessus de 900 DEG C pour la réalisation d'un traitement à l'alite, à la silice ou au chrome. L'invention concerne également l'utilisation dudit procédé pour la fabrication d'ailettes de turbine.
PCT/DE2004/002114 2003-10-11 2004-09-23 Procede de traitement a l'alite, a la silice ou au chrome de composants metalliques WO2005035819A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/574,731 US20070272331A1 (en) 2003-10-11 2004-09-23 Method for Local Alitation, Siliconization or Chromation of Metal Components
JP2006529616A JP2007508449A (ja) 2003-10-11 2004-09-23 金属部品の局所的アルミナイジング、シリコナイジングまたはクロマイジング方法
EP04786831A EP1670965A1 (fr) 2003-10-11 2004-09-23 Procede de traitement a l'alite, a la silice ou au chrome de composants metalliques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10347363.7 2003-10-11
DE10347363A DE10347363A1 (de) 2003-10-11 2003-10-11 Verfahren zur lokalen Alitierung, Silizierung oder Chromierung von metallischen Bauteilen

Publications (1)

Publication Number Publication Date
WO2005035819A1 true WO2005035819A1 (fr) 2005-04-21

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PCT/DE2004/002114 WO2005035819A1 (fr) 2003-10-11 2004-09-23 Procede de traitement a l'alite, a la silice ou au chrome de composants metalliques

Country Status (5)

Country Link
US (1) US20070272331A1 (fr)
EP (1) EP1670965A1 (fr)
JP (1) JP2007508449A (fr)
DE (1) DE10347363A1 (fr)
WO (1) WO2005035819A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007056979A2 (fr) * 2005-11-19 2007-05-24 Mtu Aero Engines Gmbh Procede de production d'une garniture de rodage
WO2007147387A2 (fr) * 2006-06-20 2007-12-27 Mtu Aero Engines Gmbh Procédé de réparation de garnitures de rodage
WO2010091667A1 (fr) * 2009-02-11 2010-08-19 Mtu Aero Engines Gmbh Revêtement et procédé de revêtement d'une pièce
EP2960431A1 (fr) * 2014-05-09 2015-12-30 United Technologies Corporation Systèmes et procédés de réparation d'une surface de composants métalliques endommagés
DE102016224546A1 (de) 2016-12-09 2018-06-14 MTU Aero Engines AG HEIßGASKORROSIONS - UND OXIDATIONSSCHUTZSCHICHT FÜR TIAL-LEGIERUNGEN
EP2441855B1 (fr) * 2010-10-13 2019-11-27 Walbar Inc. Procédé de formation d'un revêtement d'aluminure à diffusion sur une surface d'un composant de turbine et pâte homogène pour le revêtement de telles surfaces
EP3620548A1 (fr) * 2018-09-10 2020-03-11 MTU Aero Engines GmbH Procédé de fabrication d'un composant résistant à l'oxydation à partir d'un alliage à base de molybdène

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DE102005053531A1 (de) * 2005-11-08 2007-05-10 Man Turbo Ag Wärmedämmende Schutzschicht für ein Bauteil innerhalb des Heißgasbereiches einer Gasturbine
DE102006058677B4 (de) * 2006-12-13 2010-11-04 Mtu Aero Engines Gmbh Verfahren und Vorrichtung zur Verbesserung der Verschleißeigenschaften des Bauteils einer Gasturbine
DE102007003735B4 (de) * 2007-01-25 2010-07-01 Mtu Aero Engines Gmbh Verfahren zum Herstellen einer Schutzbeschichtung sowie Schutzbeschichtung
DE102007004744B8 (de) * 2007-01-31 2014-01-30 MTU Aero Engines AG Verfahren und Vorrichtung zur partiellen Beschichtung von Bauteilen
DE102007027474A1 (de) * 2007-06-14 2008-12-18 Burgmann Industries Gmbh & Co. Kg Verfahren zur Ausbildung einer planen Schicht aus einem Diamantmaterial auf einer Werkstückoberfläche
US20090214773A1 (en) * 2008-02-27 2009-08-27 General Electric Company Diffusion Coating Systems with Binders that Enhance Coating Gas
DE102008057162A1 (de) 2008-11-13 2010-05-20 Mtu Aero Engines Gmbh Verfahren zur Reparatur des Bauteils einer Gasturbine
US10006298B2 (en) * 2009-09-08 2018-06-26 Mtu Aero Engines Gmbh Turbine blade of a gas turbine and method for coating a turbine blade of a gas turbine
DE102011108771B3 (de) * 2011-07-28 2012-09-27 Mtu Aero Engines Gmbh Verfahren zur Herstellung einer lokal begrenzten Diffusionsschicht und Reaktor hierfür
JP6126852B2 (ja) * 2012-02-21 2017-05-10 ハウメット コーポレイションＨｏｗｍｅｔ Ｃｏｒｐｏｒａｔｉｏｎ ガスタービン部品のコーティング及びコーティング方法
US9587302B2 (en) 2014-01-14 2017-03-07 Praxair S.T. Technology, Inc. Methods of applying chromium diffusion coatings onto selective regions of a component
US9970094B2 (en) * 2014-01-14 2018-05-15 Praxair S.T. Technology, Inc. Modified slurry compositions for forming improved chromium diffusion coatings
US10053779B2 (en) * 2016-06-22 2018-08-21 General Electric Company Coating process for applying a bifurcated coating
FR3084891B1 (fr) * 2018-08-07 2022-06-24 Commissariat Energie Atomique Revetement pour piece en alliage refractaire

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US3415672A (en) * 1964-11-12 1968-12-10 Gen Electric Method of co-depositing titanium and aluminum on surfaces of nickel, iron and cobalt
GB1186924A (en) * 1966-06-24 1970-04-08 Onera (Off Nat Aerospatiale) Process for Forming Surface Diffusion Alloys on Refractory Metal Members
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US3824122A (en) * 1971-07-02 1974-07-16 G Cook Continuous diffusion coating
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US5194219A (en) * 1981-07-08 1993-03-16 Alloy Surfaces Company, Inc. Metal diffusion and after-treatment
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007056979A2 (fr) * 2005-11-19 2007-05-24 Mtu Aero Engines Gmbh Procede de production d'une garniture de rodage
WO2007056979A3 (fr) * 2005-11-19 2008-05-15 Mtu Aero Engines Gmbh Procede de production d'une garniture de rodage
WO2007147387A2 (fr) * 2006-06-20 2007-12-27 Mtu Aero Engines Gmbh Procédé de réparation de garnitures de rodage
WO2007147387A3 (fr) * 2006-06-20 2008-04-10 Mtu Aero Engines Gmbh Procédé de réparation de garnitures de rodage
US9303522B2 (en) 2006-06-20 2016-04-05 Mtu Aero Engines Gmbh Method of repairing run-in coatings
WO2010091667A1 (fr) * 2009-02-11 2010-08-19 Mtu Aero Engines Gmbh Revêtement et procédé de revêtement d'une pièce
EP2441855B1 (fr) * 2010-10-13 2019-11-27 Walbar Inc. Procédé de formation d'un revêtement d'aluminure à diffusion sur une surface d'un composant de turbine et pâte homogène pour le revêtement de telles surfaces
EP2960431A1 (fr) * 2014-05-09 2015-12-30 United Technologies Corporation Systèmes et procédés de réparation d'une surface de composants métalliques endommagés
EP2960431B1 (fr) 2014-05-09 2017-03-08 United Technologies Corporation Systèmes et procédés de réparation d'une surface de composants métalliques endommagés
DE102016224546A1 (de) 2016-12-09 2018-06-14 MTU Aero Engines AG HEIßGASKORROSIONS - UND OXIDATIONSSCHUTZSCHICHT FÜR TIAL-LEGIERUNGEN
EP3620548A1 (fr) * 2018-09-10 2020-03-11 MTU Aero Engines GmbH Procédé de fabrication d'un composant résistant à l'oxydation à partir d'un alliage à base de molybdène

Also Published As

Publication number Publication date
US20070272331A1 (en) 2007-11-29
EP1670965A1 (fr) 2006-06-21
JP2007508449A (ja) 2007-04-05
DE10347363A1 (de) 2005-05-12

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