EP0601490A1 - Procédé pour la préparation de pièces à travailler ou de substrats avec des revêtements composites - Google Patents

Procédé pour la préparation de pièces à travailler ou de substrats avec des revêtements composites Download PDF

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Publication number
EP0601490A1
EP0601490A1 EP93119486A EP93119486A EP0601490A1 EP 0601490 A1 EP0601490 A1 EP 0601490A1 EP 93119486 A EP93119486 A EP 93119486A EP 93119486 A EP93119486 A EP 93119486A EP 0601490 A1 EP0601490 A1 EP 0601490A1
Authority
EP
European Patent Office
Prior art keywords
fibers
felts
mats
fabrics
water
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.)
Granted
Application number
EP93119486A
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German (de)
English (en)
Other versions
EP0601490B1 (fr
Inventor
Wolfgang Schassberger
Monika Dr. Manier
Martin Dr. Thoma
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MTU Aero Engines GmbH
Original Assignee
MTU Motoren und Turbinen Union Muenchen 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 Motoren und Turbinen Union Muenchen GmbH filed Critical MTU Motoren und Turbinen Union Muenchen GmbH
Publication of EP0601490A1 publication Critical patent/EP0601490A1/fr
Application granted granted Critical
Publication of EP0601490B1 publication Critical patent/EP0601490B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/04—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic
    • B24D3/14—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic ceramic, i.e. vitrified bondings
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

Definitions

  • the invention relates to a method for the production of components or substrates with composite coatings by means of galvanic or electroless deposition of metals and its application.
  • the particle size of the substances to be installed is limited to less than 20 ⁇ m and the installation rate cannot be increased above 25% by volume. Because of the risk of short-circuit for the electrolyte, no electrically conductive substances can be installed. Single-layer or monolayer layers that do not contain the material to be installed several times above one another cannot be produced with this method. With complex component geometries, there are fluctuations in the installation rate that cannot be fully compensated for by component and bath movements. Bath care and maintenance is difficult and costly.
  • the object of the invention is to provide a generic method that does not have the above disadvantages and is universally applicable.
  • the process is intended to enable monolayer composite layers and not to restrict the shape or size of the particles of the substances to be stored, so that even fibers can be incorporated.
  • the substances to be installed are not suspended in the electrolyte, but are fixed on the component or substrate surface by means of reaction melting of water-soluble powdered salts or acids before the galvanic or electroless deposition of the matrix material.
  • the salts or acids on the component or substrate surface melt, with the salts or Convert acids to an amorphous water-soluble substance.
  • This water-soluble substance fixes the substances to be incorporated in the form of disperse particles, fibers, felts, mats or fabrics.
  • This substance dissolves again in the electrolytic or electroless plating bath and becomes part of the electrolyte, while at the same time the deposited matrix material first fixes the substances to be installed in a predetermined position and fully integrates them into the matrix as the deposition proceeds.
  • An advantage of this method is that the installation rate can be set by appropriate assignment and is independent of the absorption capacity of the electrolyte of insoluble substances. Electrically conductive substances such as metals can be safely incorporated into the composite coating.
  • single-layer composite coatings are advantageously produced, since the outer layers, provided they are not cross-linked or linked with the first layer, are rinsed off when the amorphous substance is dissolved.
  • the particle shape and size to be incorporated into the composite coating are also not subject to any restrictions.
  • Another advantage of the method is the short dwell time of the substances to be installed in the galvanic or electroless plating bath compared to the previous method, so that ceramic and metallic particles can also be built into the composite coating, which were etched or dissolved in the electrolyte in the previous method.
  • the process can be carried out with all commercially available electrolytes.
  • the component or substrate surface is heated to a temperature for reaction melting of the salt or the acid to a water-soluble substance during or before coating.
  • a temperature for reaction melting of the salt or the acid to a water-soluble substance during or before coating.
  • complex component surfaces can be covered without any problems because, for example, the hot component can be immersed in the mixture of powdered salts or acids and disperse particles or short fibers and can then be removed from the mixture on all sides.
  • Complex designed hot component surfaces can also be moved under a scattering or blasting device of the mixture for covering on all sides.
  • the volume ratio of the mixture between salt or acid powder and the disperse particles, fibers, felts, mats or fabrics is preferably set from 10: 1 to 1:20. This has the advantage that the installation rate can be selected over a wide range and the volume fraction of the substances to be installed can be increased to 95% by volume. The maximum installation rate is thus increased by more than three times compared to the previous method.
  • the salt or acid powder an average grain size of 0.5 to 100 ⁇ m in the mixture of the coating has proven itself.
  • the substances to be installed can have an average grain size of up to 2 mm, without any difficulties in covering and installing.
  • Long fibers or continuous fibers can also be introduced into a composite coating, preferably after winding onto a component surface to cover the component surface with a mixture of long fibers and salt or acid powder.
  • the powdered salt or acid is sprinkled on after a single or multi-layer covering with a long fiber.
  • the long or continuous fiber is fixed by reaction melting of the salt or acid powder and then installed in a matrix by means of galvanic or currentless deposition.
  • the same method is preferably used with felts, mats or fabrics with which the component or substrate surface is first covered and then water-soluble salt or acid.
  • the embedding materials such as felts, mats or fabrics can preferably be covered with a solution coated with salt or acid powder and water, rolled or soaked or immersed in such a solution. The water is then evaporated by drying the intercalation substances with adhering salt or acid solution, so that a mixture of felt, mat or fabric with dried salt or acid powder is present, with which the component or substrate surface is covered.
  • the disperse particles, fibers, felts, mats or fabrics are completely enveloped by the melting substance during reaction melting.
  • the substances to be installed are advantageously protected during intermediate storage and, in the case of large-scale production, intermediate storage enables a favorable lot size for the galvanic or electroless plating bath.
  • a further preferred embodiment of the invention provides that the disperse particles, fibers, felts, mats or fabrics are fixed during the reaction melting by the melting substance in such a way that their distance from the surface becomes less than 30 ⁇ m.
  • This short distance advantageously ensures that any desired packing density of substances to be incorporated can be fixed on the surface of a component or substrate with a minimum of melt substance.
  • This distance also ensures a smooth transition from fixation by the water-soluble substance to fixation by the deposition process of matrix material. A punctual or complete contact between the substances to be installed and the component surface is not excluded.
  • the salt or acid powder used is preferably crystalline ortho-boric acid H 3 B0 3 , which is converted into water-soluble meta-boric acid HB0 2 with the release of water of crystallization during reaction melting at a reaction temperature of 170 ° C. due to the high temperature gradient that occurs between boric acid and component surface when crystal water is released, it is transformed into a glassy melt.
  • This glassy melt solidifies on cooling to a water-soluble substance that fixes the substances to be installed on the component surface.
  • the crystalline ortho-boric acid H 3 B0 3 is transformed into the crystalline meta-boric acid HB0 2 with the release of water of crystallization
  • the crystalline meta-boric acid HB0 2 becomes wide rer heat supply with release of water converted into a glassy melt, some of which contains boron trioxide B 2 0 3 When it cools down, the glassy melt solidifies into a water-soluble substance.
  • the water-soluble substance is dissolved in the electrolyte as boric acid.
  • This conversion and dissolution process takes place relatively slowly, so that a safe transition of the fixation of the substances to be installed from the dissolving water-soluble substance to the deposition matrix that is formed is ensured.
  • the boric acid that is formed does not interfere with the deposition process in any way and is in many cases advantageously a desired buffer substance in the electrolyte.
  • water-soluble phosphates or phosphites can preferably be used as the salt or acid powder.
  • These have the advantage that their metallic components can be matched to the matrix material, so that they simultaneously form a buffer for these substances.
  • chromium orthophosphate CrP0 4 .2H 2 0 can advantageously be used for a chromium matrix and Ni (HP0 2 ) 3 .6H 2 0 for a nickel matrix.
  • Cu, Co, Ni, Cr or alloys thereof are preferably deposited as the matrix material.
  • These coating materials have the advantage that they are resistant to corrosion and oxidation or are particularly suitable for anchoring hard material particles as substances to be incorporated in the composite coating in monolayers.
  • the method steps are preferably carried out several times in succession.
  • This has the advantage that the composition can be varied in any position both in particle size, in particle form, in the particle material and in the particle incorporation rate and in the matrix material.
  • the composite coating can thus be technically tailored to a specific requirement profile.
  • the lowermost fiber layer of the felts, mats or fabrics is preferably fixed by the water-soluble substance. This has the advantage that relatively small amounts of salt or acid powder are to be used, since the entire cross-linked felt or cross-linked mat or cross-linked fabric is already anchored on the component surface with the lowest fiber layer.
  • Diamond, oxides, borides, carbides, silicides, nitrides or brittle metals or metal alloys are preferably used as disperse particles or short fibers in order to advantageously achieve an abrasive effect of the composite coating.
  • Corundum or chromium oxide are preferably used as oxides.
  • Iron boride particles are preferred borides.
  • silicon carbide particles are preferably used as hard materials to be incorporated.
  • silicides titanium silicide is preferably used in composite coatings.
  • the cubic boron nitride is preferably used as the hard material particle and MCrAIY is preferably used as the hard material as the brittle metal or metal alloy.
  • the composite coating is subjected to a heat treatment after the deposition of the matrix material. This has the advantage that better adhesion or compaction or diffusion welding of the coating can be achieved.
  • a preferred metal composite coating is achieved in that initially disperse CoCrAIY particles are fixed on a component surface by means of reaction melts and then an Ni matrix is deposited. After the deposition, there is preferably a heat treatment step in which an extremely corrosion-resistant coating with CoNiCrAIY phases is formed by diffusion processes between the nickel matrix and CoCrAlY particles.
  • Plastics are also preferably used as disperse particles, fibers, felts, mats or fabrics. This advantageously enables fiber-reinforced coatings or coatings with emergency running properties to be produced.
  • Polyimide or polytetrafluoroethylene are preferably used as plastics. These materials to be installed are characterized by an increased softening temperature compared to other plastics.
  • hexagonal boron nitride or hexagonal spheroidal graphite is preferably added to the salts or acids to cover a component surface, for example to cover a bearing shell.
  • fibers, felts, mats or fabrics made of quartz glass, glass, carbon or graphite are built into the metallic matrix.
  • glass, carbon or graphite fiber reinforced metal alloy layers of increased tensile strength are produced inexpensively, which is particularly advantageous for a brittle metal matrix made of intermetallic phases.
  • Titanium fibers and, as matrix material, intermetallic titanium compounds are preferably used instead of glass, carbon or graphite in engine construction, as a result of which hard composite coatings, which are tensile through the titanium fibers, are created.
  • a preferred application of the method is the production of run-in or run-in coatings, preferably of nickel matrix with dispersed particles of cubic boron nitride.
  • Such inlet or run-up pads grind uneven blade tips of a rotor down to a minimal gap seal.
  • the softer nickel matrix forms an advantageous embedding for the hard cubic boron nitride particles.
  • sealing tips are preferably produced on turbine blades, on labyrinth seals or on shroud segments of engine blades using the method according to the invention.
  • a matrix material made of copper, cobalt or nickel or alloys thereof is used and aluminum oxide is incorporated as a hard material particle.
  • Another preferred application of the method relates to the production of abrasive layers, preferably for the production of grinding wheels.
  • the production of diamond-tipped saw blades for cutting widths below 100 ⁇ m for hard and brittle single crystals or single-crystal components can be produced extremely precisely and inexpensively using this process.
  • a glass fiber mat of 0.3 mm thickness made of glass fibers with a diameter of 40 ⁇ m is coated with a viscous solution which is mixed from powdered ortho-boric acid (H3 B03) and water in a volume ratio of 3: 1. After the water has evaporated, a mixture of powdered water-soluble ortho-boric acid and glass fiber mat has formed. An iron sheet heated to 180 ° C. is coated with this mixture as a substrate. At this temperature, when the coating is coated, the crystalline ortho-boric acid melts with the release of water of crystallization to give meta-boric acid (HB0 2 ), or when the water of crystal is further released into a glassy melt on the substrate surface due to the high temperature gradient between the surface of the substrate and the coating. When the melt cools, the glass fiber mat is fixed on the substrate surface with this process step.
  • the boric acid that has fixed the glass mat goes into solution and the fixation is taken over by the depositing nickel until the glass fiber mat is completely installed in a nickel matrix.
  • the adhesion of the composite layer on the iron sheet substrate can be improved by heating at 150 to 500 ° C for 1 to 10 hours.
  • a metal powder made of CoCrAIY with an average grain size of 100 ⁇ m in a volume ratio of 3: 1 is mixed with ortho-boric acid powder with an average particle size of 30 ⁇ m and the blade surface of a turbine blade made of a Ni-based alloy is coated with this mixture at 180 to 190 ° C.
  • Reaction melting of the crystalline ortho-boric acid begins, so that the ortho-boric acid is converted to meta-boric acid with the release of water of crystallization or to a glassy melt when water of crystal is further released.
  • the melt cools, the CoCrAIY particles are fixed on the surface of the airfoil.
  • this composite coating is heat treated at 1000 to 1150 ° C for 5 hours. This creates a corrosion-resistant coating with a high proportion of CoNiCrAIY- Phases out.
  • a compressor blade made of a titanium alloy is first completely covered with a mask except for the end face of the blade tip.
  • the blade is then heated to 180 to 200 ° C. and coated with a mixture of ortho-boric acid powder with an average grain size of 30 ⁇ m and cubic boron nitride particles with an average grain size of 250 ⁇ m.
  • a reaction melt forms on the hot component surface, so that when the glassy melt cools, a monolayer of boron nitride particles is fixed on the blade tip.
  • the boron nitride particles are enclosed in a nickel matrix only up to 2/3 of their length, they form a tooth-like abrasive blade armor at the tip of the blade.
  • the protective covering made of, for example, thermoplastic or wax is finally removed from the covered surface areas of the blade.
  • a rubbing segment of a casing ring of an engine is coated with a mixture of powdered phosphites and graphite particles (spheroidal graphite, diameter 80 ⁇ m). After the stripping segment has been heated to 180 to 200 ° C., the graphite particles are fixed on the surface of the stripping segment by the water-soluble substance that forms.
  • the graphite particles After immersion for 5 hours in a lead / indium electrolyte at a current of 4 A per dm 2, the graphite particles are enclosed as a monolayer by a lead / indium matrix. After the composite coating has dried, the coated component is coated again and a second monolayer of spheroidal graphite with a diameter of 40 ⁇ m is galvanically embedded in a lead / indium matrix. This is followed by the production of a third monolayer with a spherical graphite diameter of only 20 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemically Coating (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP93119486A 1992-12-09 1993-12-03 Procédé pour la préparation de pièces à travailler ou de substrats avec des revêtements composites Expired - Lifetime EP0601490B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4241420 1992-12-09
DE4241420A DE4241420C1 (de) 1992-12-09 1992-12-09 Verfahren zur Herstellung von Bauteilen oder Substraten mit Verbundbeschichtungen und dessen Anwendung

Publications (2)

Publication Number Publication Date
EP0601490A1 true EP0601490A1 (fr) 1994-06-15
EP0601490B1 EP0601490B1 (fr) 1996-03-20

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EP93119486A Expired - Lifetime EP0601490B1 (fr) 1992-12-09 1993-12-03 Procédé pour la préparation de pièces à travailler ou de substrats avec des revêtements composites

Country Status (3)

Country Link
US (1) US5385760A (fr)
EP (1) EP0601490B1 (fr)
DE (2) DE4241420C1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT408527B (de) * 1999-04-19 2001-12-27 Boehler Uddeholm Ag Metall-keramischer werkstoff und verfahren zu dessen herstellung

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DE4341216C2 (de) * 1993-12-03 1997-01-16 Mtu Muenchen Gmbh Dichtungsbauteil für Spalt- oder Labyrinthdichtungen und Verfahren zu seiner Herstellung
DE4443440A1 (de) * 1994-01-26 1995-07-27 Forschungskuratorium Maschinen Verschleißschutzschicht und Verfahren zum Auftragen dieser auf Bauteile
DE4432685C1 (de) * 1994-09-14 1995-11-23 Mtu Muenchen Gmbh Anlaufbelaf für das Gehäuse einer Turbomaschine und Verfahren zur Herstellung
US5932356A (en) * 1996-03-21 1999-08-03 United Technologies Corporation Abrasive/abradable gas path seal system
DE19750516A1 (de) * 1997-11-14 1999-05-20 Asea Brown Boveri Abreibbare Dichtung
DE19848103A1 (de) * 1998-10-19 2000-04-20 Asea Brown Boveri Dichtungsanordnung
DE19848104A1 (de) * 1998-10-19 2000-04-20 Asea Brown Boveri Turbinenschaufel
EP1157076A1 (fr) 1998-11-18 2001-11-28 Radiovascular Systems, L.L.C. Solutions de revetement radioactives, procedes et substrats associes
DE19858031A1 (de) * 1998-12-16 2000-06-21 Rolls Royce Deutschland Anstreifdichtung zwischen einem Wandabschnitt und den Schaufelspitzen einer Gasturbine
DE19933445C2 (de) * 1999-07-16 2001-12-13 Mtu Aero Engines Gmbh Dichtring für nicht- hermetische Fluiddichtungen
US20030057101A1 (en) * 2000-02-22 2003-03-27 Ward Close Charles M Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms
US6434876B1 (en) * 2000-09-26 2002-08-20 General Electric Company Method of applying a particle-embedded coating to a substrate
DE102004011818A1 (de) * 2004-03-11 2005-09-29 Daimlerchrysler Ag Gehäuse für ein Turbinenrad
WO2006002351A1 (fr) * 2004-06-23 2006-01-05 Advanced Components & Materials, Inc. Revetement electrolytique composite de joints souples et son procede d'application
US20060141283A1 (en) * 2004-12-29 2006-06-29 Honeywell International, Inc. Low cost inovative diffused MCrAIY coatings
US7140952B1 (en) * 2005-09-22 2006-11-28 Pratt & Whitney Canada Corp. Oxidation protected blade and method of manufacturing
EP2096194B1 (fr) 2008-02-19 2016-06-01 Parker-Hannifin Corporation Revêtement protecteur pour joints métalliques
EP2098606A1 (fr) * 2008-03-04 2009-09-09 Siemens Aktiengesellschaft Micro-alliage, procédés de production d'une couche de micro-alliage et joint en nids d'abeille
TWI484065B (zh) * 2013-10-15 2015-05-11 Univ Nat Cheng Kung 可撓性透明導電膜之製作方法
DE102015210601A1 (de) * 2015-06-10 2016-12-15 Voith Patent Gmbh Laufrad für eine Pumpe oder Turbine
FR3085172B1 (fr) * 2018-08-22 2021-03-05 Safran Aircraft Engines Revetement abradable pour aubes tournantes d'une turbomachine

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Publication number Priority date Publication date Assignee Title
AT408527B (de) * 1999-04-19 2001-12-27 Boehler Uddeholm Ag Metall-keramischer werkstoff und verfahren zu dessen herstellung

Also Published As

Publication number Publication date
DE4241420C1 (de) 1993-11-25
DE59301959D1 (de) 1996-04-25
US5385760A (en) 1995-01-31
EP0601490B1 (fr) 1996-03-20

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