EP0648283B1 - Bauteil aus intermetallischer verbindung mit aluminiumdiffusionsbeschichtung - Google Patents

Bauteil aus intermetallischer verbindung mit aluminiumdiffusionsbeschichtung Download PDF

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Publication number
EP0648283B1
EP0648283B1 EP93915829A EP93915829A EP0648283B1 EP 0648283 B1 EP0648283 B1 EP 0648283B1 EP 93915829 A EP93915829 A EP 93915829A EP 93915829 A EP93915829 A EP 93915829A EP 0648283 B1 EP0648283 B1 EP 0648283B1
Authority
EP
European Patent Office
Prior art keywords
aluminium
component
coating
intermetallic compound
diffusion coating
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.)
Expired - Lifetime
Application number
EP93915829A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0648283A1 (de
Inventor
Richard Grunke
Lothar Dr. Peichl
Heinrich Walter
Horst Pillhöfer
Frank Brungs
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 AG
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 EP0648283A1 publication Critical patent/EP0648283A1/de
Application granted granted Critical
Publication of EP0648283B1 publication Critical patent/EP0648283B1/de
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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/02—Pretreatment of the material to be coated
    • 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
    • C23C10/06—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases
    • C23C10/08—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases only one element being diffused
    • 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
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
    • C23C10/48—Aluminising
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • Y10T428/12743—Next to refractory [Group IVB, VB, or VIB] metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • Y10T428/12764—Next to Al-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component

Definitions

  • the invention relates to a component made of an intermetallic compound made of titanium and aluminum or of alloys of such intermetallic compounds with alloy additives as the base material and with aluminum diffusion coating of the base material.
  • This base material has interesting properties for engine construction. It has comparable mechanical properties to conventional titanium alloys with a low specific weight, but can be used at significantly higher operating temperatures. However, the ductility at room temperature of this base material is lower and must be improved by alloying elements and heat treatment processes, as are known from DE 30 24 645.
  • the object of the invention is to provide a generic component and a method for its production, in which no coating defects occur and which can be used at operating temperatures of 700 ° C.
  • the component between the base material and the aluminum diffusion coating has a closed zone near the surface with a recrystallization structure.
  • the intermetallic compound is TiAl.
  • this base material it was found that crystallites with a high stacking defect density occur in the form of crystallographic twin planes in the crystallite. These crystallites show a plate structure that has never been observed with conventional titanium alloys. With conventional aluminum diffusion coating, the twin layers remained uncoated. Only after a zone near the surface with a recrystallization structure was formed, components made of the base material with a closed aluminum diffusion coating could be produced.
  • a particularly high density of crystalline plate structures shows base materials made of alloys made of the intermetallic compounds with a TiAl content between 50 and 95 vol.% And with a Ti 3 Al content between 5 and 50 vol.%.
  • components made of these critical base materials which have a higher proportion of titanium than TiAl and are therefore more prone to embrittlement, it was advantageously possible to achieve uniformly thick aluminum diffusion coatings from the recrystallization structure near the surface according to the invention.
  • alloy additives made of niobium, molybdenum, tantalum, tungsten or vanadium or mixtures thereof are preferably contained in the component material.
  • the depth of the near-surface closed zone with recrystallization structure is at least 0.1 ⁇ m.
  • a recrystallization structure depth between 1 and 10 ⁇ m has proven to be practical, since it can be prepared inexpensively, preferably by cold working close to the surface. Recrystallization depths between 0.1 and 1 ⁇ m are preferably achieved by near-surface laser melting and recrystallization. With recrystallization structure depths of more than 100 ⁇ m, the risk increases that large-volume crystallites with a plate structure form during recrystallization and hinder a closed aluminum diffusion coating.
  • the tasks of specifying a method for producing the generic components are solved by the following method steps.
  • the component is cold-formed or melted in a zone near the surface and then annealed at recrystallization temperature, and finally an aluminum diffusion coating is applied to the recrystallized zone.
  • This method has the advantage that low-cost process steps suitable for mass production are provided, so that inexpensively improved components can be used in engine construction.
  • shot peening or mechanical processing of the surface regions of the component to be recrystallized is preferably carried out.
  • the surface is blasted with ceramic balls made of Al 2 0 3 , glass balls or steel balls.
  • the crystalline structure of the base material is disturbed and internal stresses are introduced into the surface of the base material.
  • a fine crystalline recrystallization structure is formed on which an aluminum diffusion layer can grow undisturbed.
  • protective measures must be taken by means of covers or screens during shot peening.
  • pressure rollers For mechanical processing and near-surface cold forming, pressure rollers, presses, rollers, impact or pressure grinding tools can be used.
  • the recrystallization structure can preferably also be formed by first scanning the surface of the component in the areas that are finally to be coated with aluminum and melting it in the process. This has the advantage that particularly small depths of the recrystallization structure between 0.1 and 1 .mu.m can be realized and the surface areas can be scanned, melted and recrystallized precisely without additional protective measures.
  • recrystallization and aluminum diffusion coating are carried out by means of a heat cycle, by first heating the surface, which has been cold-formed or melted and solidified on the surface, to the recrystallization temperature in a system for aluminum diffusion coating, and after recrystallization has been carried out, the temperature for aluminum diffusion coating is set and at the same time aluminum-containing Transmitter gas is supplied.
  • This implementation of the method takes full advantage of the technical conditions of a system for aluminum diffusion coating, since in such systems the component can be heated independently of the coating process. Furthermore, the risk of contamination is reduced since there is no need to remove or convert between recrystallization annealing and coating, which at the same time also reduces the process costs.
  • the component is preferably exposed to a reduced pressure or a protective gas atmosphere during the recrystallization, so that the heat cycle takes place under protective gas or reduced pressure until the aluminum-containing donor gas is supplied.
  • the powder packing process is known for the aluminum diffusion coating of components made of iron, nickel or cobalt-based alloy.
  • a wide variety of aluminum donors are also used to generate aluminum donor gases.
  • the powder packing method is used as the preferred method for aluminum diffusion coating and an aluminum donor of the ternary alloy Ti / Al / C is used to generate a donor gas.
  • the carbon content causes the residual oxygen concentrations remaining in the powder pack to be bound or neutralized by carbon monoxide and carbon dioxide formations, while Ti and Al correspond to the base material and therefore promote the growth process of an aluminum diffusion coating on the base material.
  • FIG. 1 shows an aluminum diffusion coating 1 of components made of intermetallic compounds made of titanium and aluminum without a near-surface zone with a recrystallization structure, the base material 2 being solidified in large-volume crystallites 3 to 8.
  • One of the crystallites 3 shows a pronounced plate structure with stacking defects in the form of twin planes 9.
  • the aluminum diffusion coating has trench-shaped defects at the penetration lines 10 of these defects along the surface. A flawless coating is only found on crystallites 4, 5 and 8, which have no plate structure.
  • the sketched section A was examined with a metallographic cut. The result is shown in FIG. 2.
  • FIG. 2 shows the photo of a metallurgical micrograph through a material according to FIG. 1 in the area of section A.
  • a rotor blade of a TiAl engine was coated in a powder packer with the ternary alloy of Ti / Al / C as an aluminum donor on its airfoil surface.
  • the aluminum diffusion coating 1 shows significant defects in the area of crystallite 3 with a pronounced plate structure.
  • the base material 2 shows large-volume crystallites 12 to 14 with 12 and without a plate structure 13 to 15. In the vicinity of the surface, the base material 2 has a closed zone 11 with a recrystallization structure, which is evenly covered by a closed layer of aluminum without defects.
  • the sketched section B was examined with a metallographic cut.
  • FIG. 4 shows the photo of a metallurgical micrograph through a material according to FIG. 3 in the area of the section B.
  • a guide vane of an engine made of 60% by volume TiAl and 40% by volume Ti 3 Al was first surface to a depth of 5 ⁇ m cold-formed by shot peening and then recrystallized in an aluminum powder packaging plant and finally provided with a 5 ⁇ m thick aluminum diffusion coating 1.
  • a completely uniform aluminum coating 1 has grown on the base material 2 even over the crystallite 12 with an originally extremely pronounced plate structure in the aluminum diffusion process in the aluminum powder packaging system.

Landscapes

  • 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)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
EP93915829A 1992-07-07 1993-07-07 Bauteil aus intermetallischer verbindung mit aluminiumdiffusionsbeschichtung Expired - Lifetime EP0648283B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4222211 1992-07-07
DE4222211A DE4222211C1 (enrdf_load_stackoverflow) 1992-07-07 1992-07-07
PCT/EP1993/001765 WO1994001594A1 (de) 1992-07-07 1993-07-07 Bauteil aus intermetallischer verbindung mit aluminiumdiffusionsbeschichtung

Publications (2)

Publication Number Publication Date
EP0648283A1 EP0648283A1 (de) 1995-04-19
EP0648283B1 true EP0648283B1 (de) 1996-10-09

Family

ID=6462622

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93915829A Expired - Lifetime EP0648283B1 (de) 1992-07-07 1993-07-07 Bauteil aus intermetallischer verbindung mit aluminiumdiffusionsbeschichtung

Country Status (5)

Country Link
US (1) US5562999A (enrdf_load_stackoverflow)
EP (1) EP0648283B1 (enrdf_load_stackoverflow)
JP (1) JP3188904B2 (enrdf_load_stackoverflow)
DE (1) DE4222211C1 (enrdf_load_stackoverflow)
WO (1) WO1994001594A1 (enrdf_load_stackoverflow)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9302978D0 (en) * 1993-02-15 1993-03-31 Secr Defence Diffusion barrier layers
JP3459138B2 (ja) * 1995-04-24 2003-10-20 日本発条株式会社 ＴｉＡｌ系金属間化合物接合体およびその製造方法
US5695821A (en) * 1995-09-14 1997-12-09 General Electric Company Method for making a coated Ni base superalloy article of improved microstructural stability
CN1149301C (zh) * 1995-11-08 2004-05-12 时至准钟表股份有限公司 表面硬化钛材料和钛材料的表面硬化方法
US5807443A (en) * 1995-11-30 1998-09-15 Hitachi Metals, Ltd. Sputtering titanium target assembly and producing method thereof
FR2775297B1 (fr) 1998-02-25 2000-04-28 Lorraine Laminage Tole dotee d'un revetement d'aluminium resistant a la fissuration
US6267558B1 (en) * 1999-05-26 2001-07-31 General Electric Company Dual intensity peening and aluminum-bronze wear coating surface enhancement
US6805971B2 (en) 2002-05-02 2004-10-19 George E. Talia Method of making coatings comprising an intermetallic compound and coatings made therewith
DE102004034312A1 (de) * 2004-07-15 2006-02-02 Mtu Aero Engines Gmbh Dichtungsanordnung und Verfahren zur Herstellung eines Dichtkörpers für eine Dichtungsanordnung
DE102013209994A1 (de) * 2013-05-29 2014-12-04 MTU Aero Engines AG TiAl-Schaufel mit Oberflächenmodifizierung
DE102016215556A1 (de) * 2016-08-19 2018-02-22 MTU Aero Engines AG HEIßGASKORROSIONS- UND OXIDATIONSSCHUTZSCHICHT FÜR TIAL - LEGIERUNGEN
DE102016224546A1 (de) * 2016-12-09 2018-06-14 MTU Aero Engines AG HEIßGASKORROSIONS - UND OXIDATIONSSCHUTZSCHICHT FÜR TIAL-LEGIERUNGEN
CN111647845B (zh) * 2020-06-15 2021-04-06 燕山大学 一种锆钛基合金包埋渗铝层的制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2903785A (en) * 1957-02-11 1959-09-15 Gen Motors Corp Method of hot working titanium
US2920007A (en) * 1958-01-16 1960-01-05 Gen Electric Elastic fluid blade with a finegrained surface
US3615279A (en) * 1967-12-04 1971-10-26 Reynolds Metals Co Metal composite having an aluminum alloy layer bonded to a titanium alloy layer
US3804679A (en) * 1968-05-21 1974-04-16 Cockerill Method of coating steel products
US4168183A (en) * 1978-06-23 1979-09-18 University Of Delaware Process for improving the fatigue properties of structures or objects
US4824482A (en) * 1979-03-30 1989-04-25 Alloy Surfaces Company, Inc. Pyrophoric iron product and process of making
DE3742721C1 (de) * 1987-12-17 1988-12-22 Mtu Muenchen Gmbh Verfahren zur Aluminium-Diffusionsbeschichtung von Bauteilen aus Titanlegierungen
US5300159A (en) * 1987-12-23 1994-04-05 Mcdonnell Douglas Corporation Method for manufacturing superplastic forming/diffusion bonding tools from titanium
US4830265A (en) * 1988-05-13 1989-05-16 Grumman Aerospace Corporation Method for diffusion of metals and alloys using high energy source
JP2768518B2 (ja) * 1989-12-25 1998-06-25 新日本製鐵株式会社 高純度ＴｉＡ▲ｌ▼基金属間化合物およびその製造方法
JPH03249147A (ja) * 1990-02-27 1991-11-07 Sumitomo Metal Ind Ltd 耐酸化性に優れた金属間化合物ＴｉＡｌ基合金及びその製造方法

Also Published As

Publication number Publication date
JP3188904B2 (ja) 2001-07-16
EP0648283A1 (de) 1995-04-19
WO1994001594A1 (de) 1994-01-20
DE4222211C1 (enrdf_load_stackoverflow) 1993-07-22
US5562999A (en) 1996-10-08
JPH07508561A (ja) 1995-09-21

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