US20070272331A1 - Method for Local Alitation, Siliconization or Chromation of Metal Components - Google Patents

Method for Local Alitation, Siliconization or Chromation of Metal Components Download PDF

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Publication number
US20070272331A1
US20070272331A1 US10/574,731 US57473104A US2007272331A1 US 20070272331 A1 US20070272331 A1 US 20070272331A1 US 57473104 A US57473104 A US 57473104A US 2007272331 A1 US2007272331 A1 US 2007272331A1
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Prior art keywords
diffusion
pack
paste
coated
component
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Abandoned
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US10/574,731
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English (en)
Inventor
Michael Strasser
Heinrich Walter
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MTU Aero Engines AG
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MTU Aero Engines GmbH
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Assigned to MTU AERO ENGINES GMBH reassignment MTU AERO ENGINES GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: STRASSER, MICHAEL, WALTER, HEINRICH
Publication of US20070272331A1 publication Critical patent/US20070272331A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/04—Diffusion into selected surface areas, e.g. using masks

Definitions

  • the invention relates to a method for the production of a locally limited diffusion layer on the surface of a metal component, whereby the diffusion layer is formed by the absorption of Si, Al and/or Cr into the surface of the metal component.
  • Mechanically and thermally highly stressed metal components usually are provided with protective layers which are intended to improve the wear protection properties or even improve thermal insulation properties.
  • protective layers which are intended to improve the wear protection properties or even improve thermal insulation properties.
  • adhesive layers In order to improve bonding of these functional layers, it is common to provide a specially adapted adhesive layer between the component and the functional layer.
  • adhesive layers must have a suitable chemical composition, and suitable roughness and surface topography. In so doing, a rough surface is advantageous in order to enhance the mechanical meshing of the later-applied cover layer, for example, a thermal insulation layer.
  • Suitable thermal insulation layers may be composed of (partially) stabilized ZrO 2 or even of other refractory oxides.
  • the adhesive layers In addition to being rough, the adhesive layers must be oxide-free and resistant to hot gas corrosion in order to be able to cling to the outer protective layers or the thermal insulation layer.
  • the adhesive layers must provide compensation for various thermal expansion coefficients of metal base materials and the thermal insulation layer.
  • diffusion layers containing Al and, optionally, additional transition metals are well-suited as adhesive layers.
  • the coating process for the production of diffusion layers is a powder pack process (Out of Pack Process).
  • the coated surface is brought into contact with powders containing additive elements, hereinafter also referred to as donor pack, and heated to a temperature at which a diffusion of the powder elements into the surface of the component can take place.
  • the formation of the diffusion layers generally referred to as alitation (diffusion of aluminum), siliconization (diffusion of silicon), chromation (diffusion of chromium), etc., corresponds to the absorption of Al, Si or Cr.
  • German Patent Document DE 198 24 792 A1 describes a method for the production of a corrosion-resistant and oxidation-resistant layer, whereby a slurry containing at least one of the elements Cr, Ni or Ce is applied to a component and dried, and then alitated at temperatures between 800° C. and 1200° C.
  • German Patent Document DE 3883 857 T2 a method has been known for the production of a diffusion layer of Al and other ferrite-stabilizing elements for steel. In so doing, a pack of Al or an aluminum alloy and other elements, a halide activator and optionally fillers is produced, and the steel component to be coated is embedded in this pack. Then diffusion coating takes place at temperatures above approximately 1000° C.
  • the described methods have the disadvantage that the formation of the diffusion layers cannot be locally limited. Rather, the entire component is provided with the diffusion layer in a non-specific manner. A sharp transition between the coated region and the uncoated component cannot be achieved. However, frequently a sharp boundary of the coated region is necessary. Therefore, the diffusion layer should be deposited only at locations where it is in fact required as the adhesive layer. Inasmuch as this layer significantly alters the surfaces or material properties, the layer can create significant disruptions of functionality in the remaining regions of the component.
  • the object of the invention is to provide a method for the formation of diffusion layers on metal components, the method ensuring a local limitation of coated and uncoated regions in a simple manner.
  • this object is achieved by a method for the production of a locally limited diffusion layer on a metal component by alitation, siliconization and/or chromation.
  • the diffusion layer is built up by means of a powder pack process, whereby, inside the packed bed reactor, at least one diffusion-blocking powder pack is provided in addition to the donor pack, the diffusion-blocking powder pack preventing the supply of additive elements to the uncoated regions of the metal component.
  • additive elements that are to be supplied by the donor pack are at least selected from Cr, Si and/or Al.
  • the inventive process comprises at least the following steps:
  • the paste or slurry that is required for the first step is essentially composed of additive elements, specifically Cr, Si and/or Al as their pure metals or as their alloys, of activators, binders and additional ballast substances.
  • the additive elements may be pure metals or even alloys. Frequently, it is advantageous to supply several additive elements simultaneously in the form of alloys (co-diffusion). Preferably, Al and Si are supplied simultaneously, with the quantity of Al far outweighing the quantity of Si.
  • Activators that are suitable in accordance with the invention include compounds which, under reaction conditions, may form volatile, specifically molecular, halides with the additive elements.
  • Preferred activators are NH 4 F, NH 4 Cl or AlF 3 . It is also possible that at least part of the fluorides or chlorides are formed due to the decomposition of fluoridated or chlorinated organic binders or ballast substances.
  • ammonium halides are of particular interest, because the ammonia formed as a by-product occurs as reducing agent for metals. The undesirable oxidation of metals is thus suppressed.
  • binders used in the preparation of pastes or slurries are used as the binders.
  • compositions of the slurries or pastes in accordance with the invention are intended to simply explain the subject matter of the invention in detail and are by no means to be understood as being restrictive.
  • the stated numerical values are to be understood as being approximate.
  • Solids for Paste for Alitation Powder of Al, AlSi, AlTi, AlCo and/or AlCr: 5-50 wt. % Powder of Al 2 O 3 : 5-50 wt. % Organic binder: 1-15 wt. % Activator of NH 4 F and/or NH 4 Cl: 0.5-2 wt. %
  • Solids for Pastes for Siliconization Powder of Si: 5-50 wt. % Powder of Al 2 O 3 : 5-50 wt. % Organic binder: 1-15 wt. % Activator of NH 4 F and/or NH 4 Cl: 0.5-2 wt. %
  • Solids for Paste for Chromation Powder of Cr: 5-50 wt. % Powder of Al 2 O 3 : 5-50 wt. % Organic binder: 1-15 wt. % Activator of NH 4 F and/or NH 4 Cl: 0.5-2 wt. %
  • the solids are mixed with water and/or alcohols and worked to result in a paste or a slurry.
  • a paste having the consistency of a plastically moldable material is prepared.
  • the organic binders may also be liquid compounds, of course.
  • the paste or slurry is applied to the coated regions and solidified.
  • solidification is achieved by drying in an oven or the like. As a result of this, a firm donor pack adhering to the surface of the metal component is formed.
  • the surfaces of the metal component which later will be in contact with the powder pack or extend into the packed bed reactor, are provided with a separating layer.
  • the separating layer is to facilitate the subsequent detachment of the powder packs after the formation of the diffusion layer.
  • the separating layer is formed by a porous material which is largely inert to the base metal and the additive elements.
  • the separating layer is a thin layer of refractory oxides, specifically Al 2 O 3 .
  • the layer thickness is at approximately 0.02 mm to 3 mm.
  • the separating layer may be applied by conventional coating processes in order to form thick layers.
  • a slurry is applied, for example, by spreading, immersion or spray-depositing.
  • the slurry essentially consists of Al 2 O 3 and binder.
  • the component provided with the packed bed is introduced at least partially in a packed bed reactor.
  • FIG. 1 shows the alitation of damper pockets of a turbine rotor in a packed bed reactor ( 1 ) with the turbine rotor end ( 2 ), whereby its blade footing ( 3 ) extends into the packed bed reactor and is coated with a separating layer ( 4 ) of Al 2 O 3 , and further shows the donor pack ( 5 ) arranged around the damper pockets, and the diffusion-blocking powder pack ( 6 ).
  • the reactor ( 1 ) is a simple device for holding the component and for accommodating the powder fill or the diffusion-blocking powder pack.
  • the reactor may be designed as a metal capsule, into which extends the coated region of the component. Thereafter, the component ( 3 ) having coated and adjacent uncoated regions, as well as the donor pack ( 5 ), are covered with the diffusion-blocking powder pack ( 6 ).
  • the diffusion-blocking powder pack has the inventive effect of retaining or bonding the volatile compounds of the additive elements, so that a coating of the surfaces of the metal component not directly in contact with the donor pack is suppressed or completely avoided.
  • the material responsible for the diffusion-blocking effect of this powder pack is metals which are capable of chemically bonding the additive elements.
  • metals which are capable of chemically bonding the additive elements.
  • Ni, Co and/or Fe alloys are used in conjunction with this.
  • the diffusion-blocking powder pack contains metal powders having a similar or the same composition as the metal component to be coated. As a result of this, the contamination of the metal component with elements of the diffusion-blocking powder pack is avoided. Ni or Ni alloys are particularly preferred.
  • additional components of the diffusion-blocking powder pack are activators.
  • the same or even different activators than those used in the donor pack may be selected. Due to the presence of the activators in the outer powder pack, the activator loss occurring during the diffusion reaction is advantageously reduced in the region of the donor pack.
  • a preferred composition of the diffusion-blocking powder pack consists of a minimum of 50% of metal powder and of an activator content within the range of 0.2 and 5 wt. %. Additional components may be inert substances, such as, for example Al 2 O 3 .
  • the reactor is heated to a temperature above 900° C.
  • the reactor is run with inert or protective gas, whereby Ar and/or H 2 are particularly preferred.
  • Ar and/or H 2 are particularly preferred.
  • step preferably an alitation, siliconization and/or chromation is performed.
  • process temperatures and process times are a function of the selected components, the donor packs and the desired layer consistency.
  • the process temperatures used for alitation are typically in the range of 750° C. to 1200° C. with holding times of 1 h to 20 hrs; for chromation, this is typically between 900° C. and 1200° C. with the same holding time.
  • the metal components may already have metal coatings.
  • the essential features of the inventive method basically remain unchanged.
  • the chemical components required for the surface treatment are formed inside the reactor, i.e., in situ. In so doing, the formation or decomposition of gaseous metal halides plays a substantial part in transporting the metals determined for diffusion from the packed bed to the surface of the metal component.
  • the metal halides are formed in situ by halide-containing activators.
  • the metal halides which reach the areas of the diffusion-blocking powder pack are bound by metal powder and prevented from diffusing into the uncoated regions.
  • the paste had a kneadable consistency.
  • the paste was pressed on the damper pockets and dried at approximately 50° C. in a forced air oven.
  • the thusly conditioned rotor blade was fitted into a metal box, with only the blade end projecting into the packed bed reactor formed in this manner.
  • the penetration site of the blade was sealed with some paste.
  • the reactor was filled with diffusion-blocking cover powder (powder pack) to approximately double the height of the damper pockets.
  • This powder pack was composed of Ni base material powder and 1 wt. % of NH 4 F.

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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)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Powder Metallurgy (AREA)
US10/574,731 2003-10-11 2004-09-23 Method for Local Alitation, Siliconization or Chromation of Metal Components Abandoned US20070272331A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE103-47-363.7 2003-10-11
DE10347363A DE10347363A1 (de) 2003-10-11 2003-10-11 Verfahren zur lokalen Alitierung, Silizierung oder Chromierung von metallischen Bauteilen
PCT/DE2004/002114 WO2005035819A1 (de) 2003-10-11 2004-09-23 Verfahren zu lokalen alitierung, silizierung oder chromierung von metallischen bauteilen

Publications (1)

Publication Number Publication Date
US20070272331A1 true US20070272331A1 (en) 2007-11-29

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US10/574,731 Abandoned US20070272331A1 (en) 2003-10-11 2004-09-23 Method for Local Alitation, Siliconization or Chromation of Metal Components

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US (1) US20070272331A1 (de)
EP (1) EP1670965A1 (de)
JP (1) JP2007508449A (de)
DE (1) DE10347363A1 (de)
WO (1) WO2005035819A1 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090214773A1 (en) * 2008-02-27 2009-08-27 General Electric Company Diffusion Coating Systems with Binders that Enhance Coating Gas
US20100330271A1 (en) * 2006-06-20 2010-12-30 Daeubler Manfred A Method of repairing run-in coatings
US20110058951A1 (en) * 2009-09-08 2011-03-10 Mtu Aero Engines Gmbh Turbine blade of a gas turbine and method for coating a turbine blade of a gas turbine
US20130189429A1 (en) * 2011-07-28 2013-07-25 Mtu Aero Engines Gmbh Method for Producing a Locally Limited Diffusion Coat and Reactor for it
US20150197842A1 (en) * 2014-01-14 2015-07-16 Zhihong Tang Modified slurry compositions for forming improved chromium diffusion coatings
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
EP2631325A3 (de) * 2012-02-21 2017-08-09 Howmet Corporation Beschichtung und Beschichtungsverfahren für Gasturbinenkomponente
US20210292882A1 (en) * 2018-08-07 2021-09-23 Commissariat A L'energie Atomique Et Aux Energies Alternatives Coating for refractory alloy part

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Publication number Priority date Publication date Assignee Title
DE102005053531A1 (de) * 2005-11-08 2007-05-10 Man Turbo Ag Wärmedämmende Schutzschicht für ein Bauteil innerhalb des Heißgasbereiches einer Gasturbine
DE102005055200A1 (de) * 2005-11-19 2007-05-24 Mtu Aero Engines Gmbh Verfahren zum Herstellen eines Einlaufbelags
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
DE102008057162A1 (de) 2008-11-13 2010-05-20 Mtu Aero Engines Gmbh Verfahren zur Reparatur des Bauteils einer Gasturbine
DE102009008510A1 (de) * 2009-02-11 2010-08-12 Mtu Aero Engines Gmbh Beschichtung und Verfahren zum Beschichten eines Werkstücks
US20120094021A1 (en) * 2010-10-13 2012-04-19 Goodrich Corporation Method of forming a diffusion aluminide coating on a surface of a turbine component and a homogeneous paste for coating such surfaces
US20150321297A1 (en) * 2014-05-09 2015-11-12 United Technologies Corporation Systems and methods for repairing a surface of damaged metal components
US10053779B2 (en) * 2016-06-22 2018-08-21 General Electric Company Coating process for applying a bifurcated coating
DE102016224546A1 (de) 2016-12-09 2018-06-14 MTU Aero Engines AG HEIßGASKORROSIONS - UND OXIDATIONSSCHUTZSCHICHT FÜR TIAL-LEGIERUNGEN
DE102018215313A1 (de) * 2018-09-10 2020-03-12 MTU Aero Engines AG Verfahren zur Herstellung eines oxidationsbeständigen Bauteils aus einer Molybdän-Basislegierung

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US3824122A (en) * 1971-07-02 1974-07-16 G Cook Continuous diffusion coating
US4004047A (en) * 1974-03-01 1977-01-18 General Electric Company Diffusion coating method
US4181758A (en) * 1976-07-30 1980-01-01 Gulf & Western Industries, Inc. Method for preventing the deposition of a coating on a substrate
US4352840A (en) * 1980-11-17 1982-10-05 Turbine Metal Technology, Inc. Interdispersed phase coatings method
US5194219A (en) * 1981-07-08 1993-03-16 Alloy Surfaces Company, Inc. Metal diffusion and after-treatment
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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100330271A1 (en) * 2006-06-20 2010-12-30 Daeubler Manfred A Method of repairing run-in coatings
US9303522B2 (en) 2006-06-20 2016-04-05 Mtu Aero Engines Gmbh Method of repairing run-in coatings
US20090214773A1 (en) * 2008-02-27 2009-08-27 General Electric Company Diffusion Coating Systems with Binders that Enhance Coating Gas
US20110058951A1 (en) * 2009-09-08 2011-03-10 Mtu Aero Engines Gmbh Turbine blade of a gas turbine and method for coating a turbine blade of a gas turbine
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
US20130189429A1 (en) * 2011-07-28 2013-07-25 Mtu Aero Engines Gmbh Method for Producing a Locally Limited Diffusion Coat and Reactor for it
EP2631325A3 (de) * 2012-02-21 2017-08-09 Howmet Corporation Beschichtung und Beschichtungsverfahren für Gasturbinenkomponente
US20150197842A1 (en) * 2014-01-14 2015-07-16 Zhihong Tang Modified slurry compositions for forming improved chromium diffusion coatings
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
JP2017507250A (ja) * 2014-01-14 2017-03-16 プラックセアー エス．ティ．テクノロジー、 インコーポレイテッド 改良されたクロム拡散コーティングを形成するための改質されたスラリー組成物
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US9970094B2 (en) * 2014-01-14 2018-05-15 Praxair S.T. Technology, Inc. Modified slurry compositions for forming improved chromium diffusion coatings
WO2015108764A1 (en) * 2014-01-14 2015-07-23 Praxair S.T. Technology, Inc. Modified slurry compositions for forming improved chromium diffusion coatings
US10156007B2 (en) 2014-01-14 2018-12-18 Praxair S.T. Technology, Inc. Methods of applying chromium diffusion coatings onto selective regions of a component
US20210292882A1 (en) * 2018-08-07 2021-09-23 Commissariat A L'energie Atomique Et Aux Energies Alternatives Coating for refractory alloy part
US11542586B2 (en) * 2018-08-07 2023-01-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Coating for refractory alloy part

Also Published As

Publication number Publication date
WO2005035819A1 (de) 2005-04-21
EP1670965A1 (de) 2006-06-21
JP2007508449A (ja) 2007-04-05
DE10347363A1 (de) 2005-05-12

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