EP3118352B1 - Method for galvanically coating of ti-al alloys - Google Patents
Method for galvanically coating of ti-al alloys Download PDFInfo
- Publication number
- EP3118352B1 EP3118352B1 EP16170326.9A EP16170326A EP3118352B1 EP 3118352 B1 EP3118352 B1 EP 3118352B1 EP 16170326 A EP16170326 A EP 16170326A EP 3118352 B1 EP3118352 B1 EP 3118352B1
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- Prior art keywords
- alloy
- layer
- carried out
- tial alloy
- processing
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- 238000000034 method Methods 0.000 title claims description 31
- 238000000576 coating method Methods 0.000 title claims description 20
- 239000011248 coating agent Substances 0.000 title claims description 15
- 229910000838 Al alloy Inorganic materials 0.000 title description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 36
- 239000000956 alloy Substances 0.000 claims description 36
- 229910010038 TiAl Inorganic materials 0.000 claims description 35
- 238000012545 processing Methods 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 238000004381 surface treatment Methods 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000012993 chemical processing Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000005240 physical vapour deposition Methods 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 238000005476 soldering Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000007751 thermal spraying Methods 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 239000010410 layer Substances 0.000 description 23
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012720 thermal barrier coating Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- WIUHYQBOXHNHLG-UHFFFAOYSA-N acetic acid hydrofluoride Chemical compound F.C(C)(=O)O WIUHYQBOXHNHLG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021325 alpha 2-Ti3Al Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
- C25D5/44—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
Definitions
- the invention relates to a method for coating surfaces of TiAl alloys, in which at least one layer is electrodeposited onto the surface.
- turbomachines such as stationary gas turbines or aircraft engines
- TiAl alloys are increasingly used, which allow due to their low specific weight and high strength at the same time a more efficient operation of the turbomachine.
- environmental conditions prevail in turbomachinery which require the application of additional protective layers such as erosion control layers, oxidation protection layers, thermal barrier coatings, and the like.
- a galvanically deposited metal layer is often provided as the base layer or intermediate layer between the component surface and the coating.
- TiAl alloys Similar to titanium alloys and aluminum alloys, which very rapidly form oxide layers due to their affinity of their main alloying constituents titanium and aluminum for oxygen, TiAl alloys often form very rapidly an oxide layer on the surface due to the main constituents titanium and aluminum, which galvanically deposits a metallic one Layer makes it difficult or impossible.
- Mechanical surface roughening may result in unwanted deformation and damage to the surface area, and other processes, such as chemical processes, often fail to provide the necessary surface adhesion or roughness for subsequent electroplating.
- a TiAl alloy is understood as meaning a material having as main constituents, that is to say constituents with the largest proportions in the alloy titanium and aluminum, both titanium and aluminum being able to represent the largest alloying constituent in the alloy.
- it is a TiAl alloy forming intermetallic phases, such as ⁇ 2 - Ti 3 Al and / or ⁇ - TiAl.
- Such TiAl alloy can contain a variety of different constituents, but their concentration is less than that of titanium and / or aluminum. Accordingly, the present invention can be used in a wide range of different compositions of the TiAl alloys, since the main constituents titanium and aluminum and the structural components formed therefrom, the operation of the present invention is given, even if a variety of -.
- each further chemical element in the alloy is contained by itself in a concentration of less than or equal to 10 at.%, in particular less than or equal to 5 at.%, preferably less than or equal to 3 at.%, while aluminum and titanium make up the rest.
- the present invention can be used in so-called TNM alloys which denote a TiAl alloy containing niobium and / or molybdenum as alloy constituents, in particular in proportions of 0 to 3 at.% For molybdenum and 0 to 5 at.% Of niobium ,
- a surface is formed which is formed from a TiAl alloy.
- the surface of the TiAl alloy is subjected to at least two-stage surface treatment to form a roughened surface, wherein at least one stage comprises electrochemical processing and at least the second stage involves electroless chemical processing.
- Electrochemical processing is understood here to mean the processing of the surface in the presence of a chemically active substance, such as an electrolyte, with simultaneous application of an electrical voltage (potential difference), in which the material to be processed is anodically oxidized and thus dissolved.
- a chemically active substance such as an electrolyte
- an electrical voltage potential difference
- the two-step, different in the steps surface treatment can be a particularly good roughening of the surface for subsequent galvanic coating achieve, which in particular allows a good adhesion of the coating.
- surfaces of a TiAl alloy having an average roughness or an average roughness depth of the order of magnitude of 1 to 20 ⁇ m, in particular 5 to 15 ⁇ m, can be produced with the two-stage surface treatment.
- the electrochemical machining may form the first stage of the treatment, while in the second stage an electroless chemical processing is performed.
- electrochemical surface treatment and a subsequent electroless chemical processing is a particularly effective surface treatment for achieving a roughness, which allows a particularly good adhesion of electrodeposited layers given.
- an acetic acid-hydrofluoric acid solution is used, which may in particular have a composition in which the mass concentration of the acetic acid is 800 to 900 g / l and the mass concentration of the hydrofluoric acid is 100-200 g / l.
- the electroless chemical treatment is carried out by active pickling in a Fluorobortica - Natriumtetrafluoroborat - solution.
- a cleaning step with a compressed air cleaning and / or a washing with water spray can be carried out by means of a water gun, which can preferably be followed by a drying step.
- chemical pickling of the TiAl surface, ie the surface of a TiAl alloy, with an ammonium bifluoride-containing nitric acid may additionally be carried out before the two-stage surface treatment.
- the composition of the ammonium bifluoride-containing nitric acid may be such that the mass concentration of the nitric acid is in the range of 300 to 400 g / L, while the ammonium bifluoride may be present in a mass concentration of 50 to 80 g / L.
- a chemical cleaning step may be performed which may be carried out with an alkaline cleaning solution.
- a chemical activation of the surface of the TiAl alloy with a sulfuric acid solution can be carried out.
- the two-stage surface treatment with on the one hand the electrochemical processing and the electroless chemical processing and the chemical activation of the surface, a rinsing of the TiAl surface can be carried out with demineralized water.
- the galvanic layer which can be deposited after the appropriate preparation of the TiAl surface, can be a nickel or cobalt layer which can be deposited with a layer thickness of at least 1 ⁇ m, preferably at least 5 ⁇ m or in particular at least 10 ⁇ m.
- At least one second layer may be deposited, which may be deposited by various methods, such as electrodeposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), thermal spraying , Welding, soldering and the like.
- PVD physical vapor deposition
- CVD chemical vapor deposition
- thermal spraying welding
- soldering soldering
- a component made of a TNM alloy is subjected to a coating comprising 43 to 45 at.% Aluminum, 0.5 to 3 at.% Molybdenum, 0 to 4.0 at.% Niobium, in total 0 to 5 at % Vanadium, chromium, manganese and iron, in sum with 0 to 0.5 at.% Hafnium and zirconium, 0.1 to 1 at.% Carbon and 0.05 to 0.2 at.% Boron and 0 to 1 At.% Silicon.
- the component which in this case is completely made of TiAl - Material is formed, but may only have a surface area of the TiAl - material, is first subjected to a chemical cleaning with an alkaline cleaning solution with the name TURCO 5948 DPM (protected trade name of Fa. Henkel).
- chemical pickling is carried out in an ammonium bifluoride-containing nitric acid containing 350 g / l nitric acid and 60 g / l ammonium bifuoride.
- the TiAl - containing surface is sprayed to remove the pickling sludge with compressed air or a jet of water from an air / water gun and then dried.
- the surface is rinsed with demineralized water. Purge with demineralized water in addition to the other purification steps described, both after chemical cleaning and after chemical pickling and anodic etching.
- the thus prepared TiAl component can be galvanically coated with a layer of nickel and / or cobalt which has a layer thickness of at least 5 ⁇ m.
- thermal barrier coatings such as thermal barrier coatings, oxidation protection coatings, erosion control coatings, wear protection coatings, dimensional correction coatings can be deposited using a wide variety of processes.
- the individual process steps do not have to be carried out immediately after one another, but after a purification step and a drying step, the process can be interrupted and then continue with the next processing step after a break again.
- FIG. 1 shows a cross - section of a metallograph in a scanning electron micrograph, the lower part of the image showing the TNM base material (dark gray) and the upper part (light gray) the electrodeposited coating. It can be clearly seen that the interface has a rough structure that allows the galvanic coating and good adhesion of the deposited layer due.
- the Figures 2 and 3 show scanning electron micrographs of the surface of the TNM component before the deposition of the galvanic layer. Again, it can be seen that the surface has a pronounced structuring, which allows the subsequent electrodeposition of the layer and improves the adhesion of the galvanic layer.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- ing And Chemical Polishing (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
Description
Die Erfindung betrifft ein Verfahren zum Beschichten von Oberflächen aus TiAl - Legierungen, bei welchem auf die Oberfläche mindestens eine Schicht galvanisch abgeschieden wird.The invention relates to a method for coating surfaces of TiAl alloys, in which at least one layer is electrodeposited onto the surface.
In Strömungsmaschinen, wie stationären Gasturbinen oder Flugzeugtriebwerken, werden zur Steigerung der Effizienz der Strömungsmaschinen vermehrt TiAl - Legierungen eingesetzt, die aufgrund ihres niedrigen spezifischen Gewichts bei gleichzeitig hoher Festigkeit einen effizienteren Betrieb der Strömungsmaschine ermöglichen. Allerdings herrschen in den Strömungsmaschinen Umgebungsbedingungen, die das Aufbringen von zusätzlichen Schutzschichten, wie Erosionsschutzschichten, Oxidationsschutzschichten, Wärmedämmschichten und dergleichen erfordern.In turbomachines, such as stationary gas turbines or aircraft engines, to increase the efficiency of turbomachines TiAl alloys are increasingly used, which allow due to their low specific weight and high strength at the same time a more efficient operation of the turbomachine. However, environmental conditions prevail in turbomachinery which require the application of additional protective layers such as erosion control layers, oxidation protection layers, thermal barrier coatings, and the like.
Zur Aufbringung von derartigen Schutzschichten wird häufig eine galvanisch abgeschiedene Metallschicht als Grundschicht beziehungsweise Zwischenschicht zwischen der Bauteiloberfläche und der Beschichtung vorgesehen.For the application of such protective layers, a galvanically deposited metal layer is often provided as the base layer or intermediate layer between the component surface and the coating.
Ähnlich wie bei Titanlegierungen und Aluminiumlegierungen, die aufgrund ihrer Affinität ihrer Hauptlegierungsbestandteile Titan und Aluminium zum Sauerstoff sehr schnell Oxidschichten ausbilden, bilden auch TiAl - Legierungen aufgrund der Hauptbestandteile Titan und Aluminium häufig sehr schnell eine Oxidschicht an der Oberfläche aus, die eine galvanische Abscheidung einer metallischen Schicht erschwert oder unmöglich macht.Similar to titanium alloys and aluminum alloys, which very rapidly form oxide layers due to their affinity of their main alloying constituents titanium and aluminum for oxygen, TiAl alloys often form very rapidly an oxide layer on the surface due to the main constituents titanium and aluminum, which galvanically deposits a metallic one Layer makes it difficult or impossible.
Um dennoch eine galvanische Abscheidung einer Metallschicht auf einer Titan- und/oder Aluminium enthaltenden Oberfläche zu ermöglichen, ist es bereits bekannt die Oberfläche aufzurauen, um durch die Ausbildung von an der Oberfläche hervorstehenden Spitzen die galvanische Abscheidung zu erleichtern bzw. zu ermöglichen. Allerdings sind die bekannten Verfahren mit einer mechanischen Aufrauhung oder einem chemischen Ätzen der Oberfläche nicht zufriedenstellend, da entweder die Verfahren aufwändig sind oder zu unbefriedigenden Ergebnissen führen.In order nevertheless to enable a galvanic deposition of a metal layer on a titanium and / or aluminum-containing surface, it is already known to roughen the surface in order to facilitate the galvanic deposition by the formation of protruding on the surface tips. However, the known methods are with a mechanical roughening or a chemical etching of the surface unsatisfactory because either the procedures are laborious or lead to unsatisfactory results.
Bei der mechanischen Oberflächenaufrauhung kann es zu ungewollten Verformungen und Schädigungen des Oberflächenbereichs kommen und andere Verfahren, wie chemische Verfahren, liefern häufig nicht die notwendige Haftfestigkeit bzw. Rauheit der Oberfläche für die nachfolgende galvanische Beschichtung.Mechanical surface roughening may result in unwanted deformation and damage to the surface area, and other processes, such as chemical processes, often fail to provide the necessary surface adhesion or roughness for subsequent electroplating.
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Es ist deshalb Aufgabe der vorliegenden Erfindung ein Verfahren zur Beschichtung von Oberflächen aus TiAl - Legierungen anzugeben, bei welchem auf der Oberfläche eines Bauteils, die aus einer TiAl - Legierung besteht, eine galvanische Abscheidung einer metallischen Schicht ermöglicht wird, die eine ausreichende Haftfestigkeit aufweist. Gleichzeitig soll das Verfahren einfach und zuverlässig durchführbar sein.It is therefore an object of the present invention to provide a method for coating surfaces of TiAl alloys, in which on the surface of a component which consists of a TiAl alloy, a galvanic deposition of a metallic layer is made possible, which has a sufficient adhesive strength. At the same time, the process should be simple and reliable feasible.
Diese Aufgabe wird gelöst durch ein Verfahren zur Beschichtung einer Oberfläche aus einer TiAl - Legierung mit den Merkmalen des Anspruchs 1. Vorteilhafte Ausgestaltungen sind Gegenstand der abhängigen Ansprüche.This object is achieved by a method for coating a surface of a TiAl alloy having the features of claim 1. Advantageous embodiments are the subject matter of the dependent claims.
Unter einer TiAl - Legierung wird ein Werkstoff verstanden, der als hauptsächliche Bestandteile, also als Bestandteile mit dem größten Anteilen in der Legierung Titan und Aluminium aufweist, wobei sowohl Titan als auch Aluminium den größten Legierungsbestandteil in der Legierung darstellen können. Insbesondere handelt es sich um eine TiAl - Legierung, die intermetallische Phasen ausbildet, wie zum Beispiel α2 - Ti3Al und/oder γ - TiAl. Eine derartige TiAl - Legierung kann eine Vielzahl unterschiedlicher Bestandteile enthalten, die jedoch in ihrer Konzentration in einem geringeren Maß als Titan und/oder Aluminium vorhanden sind. Die vorliegende Erfindung kann entsprechend in einem großen Bereich unterschiedlicher Zusammensetzungen der TiAl - Legierungen eingesetzt werden, da durch die Hauptbestandteile Titan und Aluminium und den daraus gebildeten Gefügebestandteilen die Wirkungsweise der vorliegenden Erfindung gegeben ist, auch wenn eine Vielzahl unter - schiedlicher Legierungsbestandteile in kleineren Konzentrationen vorhanden sind, insbesondere wenn jedes weitere chemische Element in der Legierung für sich in einer Konzentration kleiner oder gleich 10 At.%, insbesondere kleiner oder gleich 5 At.%, vorzugsweise kleiner oder gleich 3 At.% enthalten ist, während Aluminium und Titan den Rest bilden.A TiAl alloy is understood as meaning a material having as main constituents, that is to say constituents with the largest proportions in the alloy titanium and aluminum, both titanium and aluminum being able to represent the largest alloying constituent in the alloy. In particular, it is a TiAl alloy forming intermetallic phases, such as α 2 - Ti 3 Al and / or γ - TiAl. Such TiAl alloy can contain a variety of different constituents, but their concentration is less than that of titanium and / or aluminum. Accordingly, the present invention can be used in a wide range of different compositions of the TiAl alloys, since the main constituents titanium and aluminum and the structural components formed therefrom, the operation of the present invention is given, even if a variety of -. different alloying constituents are present in smaller concentrations, in particular if each further chemical element in the alloy is contained by itself in a concentration of less than or equal to 10 at.%, in particular less than or equal to 5 at.%, preferably less than or equal to 3 at.%, while aluminum and titanium make up the rest.
Insbesondere kann die vorliegende Erfindung bei sogenannten TNM - Legierungen eingesetzt werden, welche eine TiAl - Legierung bezeichnen, die als Legierungsbestandteile Niob und/oder Molybdän, insbesondere in Anteilen von 0 bis 3 At.% für Molybdän und 0 bis 5 At.% Niob enthalten.In particular, the present invention can be used in so-called TNM alloys which denote a TiAl alloy containing niobium and / or molybdenum as alloy constituents, in particular in proportions of 0 to 3 at.% For molybdenum and 0 to 5 at.% Of niobium ,
Gemäß der Erfindung wird eine Oberfläche beschichtet, die aus einer TiAl - Legierung gebildet ist. Dies bedeutet, dass das gesamte Bauteil, das beschichtet werden soll, oder Teile davon aus einer TiAl - Legierung gebildet sein können. Insbesondere kann auch nur ein zu beschichtender Oberflächenbereich aus einer TiAl - Legierung gebildet sein.According to the invention, a surface is formed which is formed from a TiAl alloy. This means that the entire component to be coated or parts thereof may be formed of a TiAl alloy. In particular, only one surface region to be coated can be formed from a TiAl alloy.
Erfindungsgemäß wird die Oberfläche aus der TiAl - Legierung einer mindestens zweistufigen Oberflächenbehandlung zur Ausbildung einer aufgerauten Oberfläche unterzogen, wobei mindestens eine Stufe eine elektrochemische Bearbeitung und mindestens die zweite Stufe eine stromlose chemische Bearbeitung beinhaltet.According to the invention, the surface of the TiAl alloy is subjected to at least two-stage surface treatment to form a roughened surface, wherein at least one stage comprises electrochemical processing and at least the second stage involves electroless chemical processing.
Unter elektrochemischer Bearbeitung wird hierbei die Bearbeitung der Oberfläche unter Anwesenheit einer chemisch aktiven Substanz, wie ein Elektrolyt, bei gleichzeitigem Anlegen einer elektrischen Spannung (Potenzialdifferenz) verstanden, bei der das zu bearbeitende Material anodisch oxidiert und damit aufgelöst wird. Bei einer stromlosen chemischen Bearbeitung liegt lediglich eine chemisch aktive Substanz vor und es wird kein elektrisches Potenzial angelegt.Electrochemical processing is understood here to mean the processing of the surface in the presence of a chemically active substance, such as an electrolyte, with simultaneous application of an electrical voltage (potential difference), in which the material to be processed is anodically oxidized and thus dissolved. In an electroless chemical processing, only a chemically active substance is present and no electrical potential is applied.
Durch die zweistufige, in den Stufen unterschiedliche Oberflächenbehandlung lässt sich eine besonders gute Aufrauhung der Oberfläche für die nachfolgende galvanische Beschichtung erzielen, die insbesondere eine gute Haftfestigkeit der Beschichtung ermöglicht. Insbesondere lassen sich mit der zweistufigen Oberflächenbehandlung Oberflächen aus einer TiAl - Legierung mit einer mittleren Rauheit bzw. einer gemittelte Rautiefe in der Größenordnung von 1 bis 20 µm, insbesondere 5 bis 15 µm erzeugen.The two-step, different in the steps surface treatment can be a particularly good roughening of the surface for subsequent galvanic coating achieve, which in particular allows a good adhesion of the coating. In particular, surfaces of a TiAl alloy having an average roughness or an average roughness depth of the order of magnitude of 1 to 20 μm, in particular 5 to 15 μm, can be produced with the two-stage surface treatment.
Vorzugsweise kann bei der zweistufigen Oberflächenbehandlung die elektrochemische Bearbeitung die erste Stufe der Behandlung bilden, während in der zweiten Stufe eine stromlose chemische Bearbeitung erfolgt. Durch eine Kombination der elektrochemischen Oberflächenbearbeitung und einer nachfolgenden stromlosen chemischen Bearbeitung ist eine besonders effektive Oberflächenbearbeitung zur Erzielung einer Rauheit, die eine besonders gute Haftfestigkeit galvanisch abgeschiedener Schichten ermöglicht, gegeben.Preferably, in the two-stage surface treatment, the electrochemical machining may form the first stage of the treatment, while in the second stage an electroless chemical processing is performed. Through a combination of electrochemical surface treatment and a subsequent electroless chemical processing is a particularly effective surface treatment for achieving a roughness, which allows a particularly good adhesion of electrodeposited layers given.
Für die elektrochemische Bearbeitung durch anodisches Ätzen wird eine Essigsäure - Flusssäure - Lösung eingesetzt, welche insbesondere eine Zusammensetzung aufweisen kann, in der die Massenkonzentration der Essigsäure 800 bis 900 g/l und die Massenkonzentration der Flusssäure 100 - 200 g/l beträgt.For the electrochemical machining by anodic etching, an acetic acid-hydrofluoric acid solution is used, which may in particular have a composition in which the mass concentration of the acetic acid is 800 to 900 g / l and the mass concentration of the hydrofluoric acid is 100-200 g / l.
Die stromlose chemische Bearbeitung erfolgt durch Aktivbeizen in einer Fluoroborsäure - Natriumtetrafluoroborat - Lösung. Zwischen dem Bearbeitungsschritten mit der elektrochemischen Bearbeitung und der stromlosen chemischen Bearbeitung und/oder vor der elektrochemischen Bearbeitung kann ein Reinigungsschritt mit einer Druckluft - Reinigung und/oder einer Reinigung mit Spritzwasser mittels einer Wasserpistole durchgeführt werden, der vorzugsweise von einem Trocknungsschritt gefolgt werden kann.The electroless chemical treatment is carried out by active pickling in a Fluoroborsäure - Natriumtetrafluoroborat - solution. Between the processing steps with the electrochemical processing and the electroless chemical processing and / or before the electrochemical processing, a cleaning step with a compressed air cleaning and / or a washing with water spray can be carried out by means of a water gun, which can preferably be followed by a drying step.
Zusätzlich zu der zweistufigen Oberflächenbehandlung mit einer elektrochemischen Bearbeitung und einer stromlosen chemischen Bearbeitung kann zusätzlich vor der zweistufigen Oberflächenbehandlung ein chemisches Beizen der TiAl - Oberfläche, das heißt der Oberfläche aus einer TiAl - Legierung, mit einer ammoniumbifluoridhaltigen Salpetersäure erfolgen. Die Zusammensetzung der ammoniumbifluoridhaltigen Salpetersäure kann derart sein, dass die Massenkonzentration der Salpetersäure im Bereich von 300 bis 400 g/l liegt, während das Ammoniumbifluorid in einer Massenkonzentration von 50 bis 80 g/l vorliegen kann.In addition to the two-stage surface treatment with an electrochemical machining and an electroless chemical treatment, chemical pickling of the TiAl surface, ie the surface of a TiAl alloy, with an ammonium bifluoride-containing nitric acid may additionally be carried out before the two-stage surface treatment. The composition of the ammonium bifluoride-containing nitric acid may be such that the mass concentration of the nitric acid is in the range of 300 to 400 g / L, while the ammonium bifluoride may be present in a mass concentration of 50 to 80 g / L.
Vor der zweistufigen Oberflächenbehandlung oder vor dem chemischen Beizen der Oberfläche einer TiAl - Legierung kann ein chemischer Reinigungsschritt durchgeführt werden, der mit einer alkalischen Reinigungslösung durchgeführt werden kann.Prior to the two-stage surface treatment or before the chemical pickling of the surface of a TiAl alloy, a chemical cleaning step may be performed which may be carried out with an alkaline cleaning solution.
Nach der zweistufigen Oberflächenbehandlung kann eine chemische Aktivierung der Oberfläche aus der TiAl - Legierung mit einer Schwefelsäure - Lösung durchgeführt werden. Zwischen und/oder nach den einzelnen Bearbeitungsschritten, d.h. dem chemischen Beizen mit einer ammoniumbifluoridhaltigen Salpetersäure, der zweistufigen Oberflächenbehandlung mit einerseits der elektrochemischen Bearbeitung und der stromlosen chemischen Bearbeitung sowie der chemischen Aktivierung der Oberfläche kann jeweils eine Spülung der TiAl - Oberfläche mit demineralisiertem Wasser erfolgen.After the two-stage surface treatment, a chemical activation of the surface of the TiAl alloy with a sulfuric acid solution can be carried out. Between and / or after the individual processing steps, ie the chemical pickling with an ammonium bifluoride-containing nitric acid, the two-stage surface treatment with on the one hand the electrochemical processing and the electroless chemical processing and the chemical activation of the surface, a rinsing of the TiAl surface can be carried out with demineralized water.
Die galvanische Schicht, die nach der entsprechenden Vorbereitung der TiAl - Oberfläche abgeschieden werden kann, kann eine Nickel - oder Kobaltschicht sein, die mit einer Schichtdicke von mindestens 1 µm, vorzugsweise mindestens 5 µm oder insbesondere mindestens 10 µm abgeschieden werden kann.The galvanic layer, which can be deposited after the appropriate preparation of the TiAl surface, can be a nickel or cobalt layer which can be deposited with a layer thickness of at least 1 μm, preferably at least 5 μm or in particular at least 10 μm.
Nach der Abscheidung der galvanischen Schicht kann mindestens eine zweite Schicht abgeschieden werden, die durch verschiedene Verfahren aufgebracht werden kann, wie beispielsweise wiederum durch galvanische Abscheidung, durch physikalische Dampfphasenabscheidung (PVD physical vapour deposition), chemische Dampfphasenabscheidung (CVD chemical vapour deposition), thermisches Spritzen, Schweißen, Löten und dergleichen.After deposition of the electroplated layer, at least one second layer may be deposited, which may be deposited by various methods, such as electrodeposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), thermal spraying , Welding, soldering and the like.
Die beigefügten Abbildungen zeigen in
- Fig. 1
- eine rasterelektronmikroskopische Aufnahme eines Querschliffs durch eine galvanisch abgeschiedene Beschichtung auf einer TNM - Legierung ,
- Fig. 2
- eine rasterelektronmikroskopische Aufnahme der Oberfläche der TNM - Legierung vor dem galvanischen Beschichten und in
- Fig. 3
- die Oberfläche aus
Figur 2 , die in einem größeren Maßstab und mit dem Sekundärelektronen - Detektor des Rasterelektronmikroskops aufgenommen worden.
- Fig. 1
- a scanning electron micrograph of a cross section through an electrodeposited coating on a TNM alloy,
- Fig. 2
- a scanning electron micrograph of the surface of the TNM alloy before the galvanic coating and in
- Fig. 3
- the surface off
FIG. 2 , which were taken on a larger scale and with the secondary electron detector of the scanning electron microscope.
Weitere Vorteile, Kennzeichen und Merkmale der vorliegenden Erfindung werden bei der nachfolgenden detaillierten Beschreibung eines Ausführungsbeispiels deutlich, wobei die Erfindung nicht auf dieses Ausführungsbeispiel beschränkt ist.Further advantages, characteristics and features of the present invention will become apparent in the following detailed description of an embodiment wherein the invention is not limited to this embodiment.
Bei dem Ausführungsbeispiel wird ein Bauteil aus einer TNM - Legierung einer Beschichtung unterzogen, die 43 bis 45 At.% Aluminium, 0,5 bis 3 At.% Molybdän, 0 bis 4,0 At.% Niob, in Summe 0 bis 5 At.% Vanadium, Chrom, Mangan und Eisen, in Summe mit 0 bis 0,5 At.% Hafnium und Zirkon, 0,1 bis 1 At.% Kohlenstoff und 0,05 bis 0,2 At.% Bor sowie 0 bis 1 At.% Silizium aufweist. Das Bauteil, das in dem vorliegenden Fall komplett aus dem TiAl - Werkstoff gebildet ist, aber lediglich auch nur einen Oberflächenbereich aus dem TiAl - Werkstoff aufweisen kann, wird zunächst einer chemischen Reinigung mit einer alkalischen Reinigungslösung mit der Bezeichnung TURCO 5948 DPM (geschützte Handelsbezeichnung der Fa. Henkel) unterzogen.In the exemplary embodiment, a component made of a TNM alloy is subjected to a coating comprising 43 to 45 at.% Aluminum, 0.5 to 3 at.% Molybdenum, 0 to 4.0 at.% Niobium, in total 0 to 5 at % Vanadium, chromium, manganese and iron, in sum with 0 to 0.5 at.% Hafnium and zirconium, 0.1 to 1 at.% Carbon and 0.05 to 0.2 at.% Boron and 0 to 1 At.% Silicon. The component, which in this case is completely made of TiAl - Material is formed, but may only have a surface area of the TiAl - material, is first subjected to a chemical cleaning with an alkaline cleaning solution with the name TURCO 5948 DPM (protected trade name of Fa. Henkel).
Nach der chemischen Reinigung erfolgt ein chemisches Beizen in einer ammoniumbifluoridhaltigen Salpetersäure mit 350 g/l Salpetersäure und 60 g/l Ammoniumbifuorid. Nach dem Beizen mit der ammoniumbifluoridhaltigen Salpetersäurelösung wird die TiAl - enthaltende Oberfläche zur Entfernung des Beizschlamms mit Druckluft oder einem Wasserstrahl aus einer Luft-/Wasserpistole bespritzt und anschließend getrocknet.After chemical cleaning, chemical pickling is carried out in an ammonium bifluoride-containing nitric acid containing 350 g / l nitric acid and 60 g / l ammonium bifuoride. After pickling with the Ammoniumbifluoridhaltigen nitric acid solution, the TiAl - containing surface is sprayed to remove the pickling sludge with compressed air or a jet of water from an air / water gun and then dried.
Danach erfolgt ein anodisches Ätzen in konzentrierter Essigsäure/ Flusssäure - Lösung mit einer Zusammensetzung von 850 g/l Essigsäure und 150 g/l Flusssäure. Auch nach dem anodischen Ätzen wird die Oberfläche durch Abspritzen mit Druckluft und/oder einem Wasserstrahl aus einer Luft-/Wasserpistole gereinigt.This is followed by anodic etching in concentrated acetic acid / hydrofluoric acid solution having a composition of 850 g / l of acetic acid and 150 g / l of hydrofluoric acid. Even after the anodic etching, the surface is cleaned by spraying with compressed air and / or a jet of water from an air / water gun.
Danach erfolgt das chemische aktiv Beizen mit einer Fluoroborsäure - Natriumtetrafluoroborat - Lösung.Thereafter, the active chemical pickling is carried out with a Fluoroborsäure - sodium tetrafluoroborate - solution.
Nach diesem Bearbeitungsschritt wird die Oberfläche mit demineralisiertem Wasser gespült. Das Spülen mit demineralisierten Wasser kann zusätzlich zu den anderen beschriebenen Reinigungsschritten sowohl nach dem chemischen Reinigen als auch nach dem chemischen Beizen und dem anodischen Ätzen erfolgen.After this processing step, the surface is rinsed with demineralized water. Purge with demineralized water in addition to the other purification steps described, both after chemical cleaning and after chemical pickling and anodic etching.
Zum Abschluss der Vorbereitung der TiAl - haltigen Oberfläche für die nachfolgende galvanische Beschichtung erfolgt ein chemisches Aktivieren der Oberfläche in einer Schwefelsäure - Lösung.At the end of the preparation of the TiAl - containing surface for the subsequent galvanic coating, a chemical activation of the surface in a sulfuric acid solution takes place.
Nach dem Spülen mit demineralisiertem Wasser kann das so vorbereitete TiAl - Bauteil galvanisch mit einer Schicht aus Nickel und/oder Kobalt überzogen werden, die eine Schichtdicke von mindestens 5 µm aufweist.After rinsing with demineralized water, the thus prepared TiAl component can be galvanically coated with a layer of nickel and / or cobalt which has a layer thickness of at least 5 μm.
Anschließend lassen sich verschiedenste Beschichtungen, wie Wärmedämmschichten, Oxidationsschutzschichten, Erosionsschutzschichten, Verschleißschutzschichten, Maßkorrekturschichten mit unterschiedlichsten Verfahren abscheiden.Subsequently, a wide variety of coatings, such as thermal barrier coatings, oxidation protection coatings, erosion control coatings, wear protection coatings, dimensional correction coatings can be deposited using a wide variety of processes.
Die einzelnen Verfahrensschritte müssen nicht unmittelbar nacheinander durchgeführt werden, sondern nach einem Reinigungsschritt und einem Trocknungsschritt kann das Verfahren auch unterbrochen werden und anschließend mit dem nächsten Bearbeitungsschritt nach einer Pause wieder fortgesetzt werden.The individual process steps do not have to be carried out immediately after one another, but after a purification step and a drying step, the process can be interrupted and then continue with the next processing step after a break again.
Die
Obwohl die vorliegende Erfindung anhand des Ausführungsbeispiels deutlich beschrieben worden ist, ist für den Fachmann selbstverständlich, dass die Erfindung nicht auf dieses Ausführungsbeispiel beschränkt ist, sondern dass vielmehr Abweichungen in der Weise möglich sind, dass einzelne Merkmale weggelassen werden können oder andere Kombinationen von Merkmalen verwirklicht werden können, wobei der Umfang der vorliegenden Erfindung in den nachfolgenden Ansprüchen definiert wird. Die vorliegende Offenbarung schließt sämtliche Kombinationen der vorgestellten Einzelmerkmale mit ein.Although the present invention has been clearly described with reference to the embodiment, it will be understood by those skilled in the art that the invention is not limited to this embodiment, but rather deviations in the manner that individual features can be omitted or other combinations of features realized The scope of the present invention is defined in the following claims. The present disclosure includes all combinations of the features presented.
Claims (12)
- Method for coating a surface which is made of a TiAl alloy, the TiAl alloy being a material that comprises titanium and aluminum as the main constituents having the largest proportions in the alloy and comprises intermetallic phases, at least one layer being applied to the surface made of the TiAl alloy by electrodeposition in the method, the surface made of the TiAl alloy being subjected to an at least two-step surface treatment process in order to form an abraded surface, in which treatment process at least one electrochemical processing procedure and at least one electroless chemical processing procedure is carried out, characterized in that the electrochemical processing is carried out by anodic etching in an acetic acid/hydrofluoric acid solution and the electroless chemical processing is carried out by pickling in a fluoroboric acid/sodium tetrafluoroborate solution.
- Method according to claim 1, characterized in that, during the two-step surface treatment, the electrochemical processing is carried out in a first step and the electroless chemical processing is carried out in a second step.
- Method according to either of the preceding claims, characterized in that mass concentrations of 800 to 900 g/l acetic acid and 100 to 200 g/l hydrofluoric acid are selected for the composition of the acetic acid/hydrofluoric acid solution for the electrochemical processing by means of anodic etching.
- Method according to any of the preceding claims, characterized in that a cleaning step using compressed air and/or spray water, in particular followed by a drying step, is carried out between the electrochemical processing and the electroless chemical processing and/or before the electrochemical processing.
- Method according to any of the preceding claims, characterized in that the surface made of the TiAl alloy is chemically pickled using an ammonium bifluoride-containing nitric acid solution before the two-step surface treatment, in particular mass concentrations of 300 to 400 g/l nitric acid and 50 to 80 g/l ammonium bifluoride being selected for the composition.
- Method according to claim 5, characterized in that chemical cleaning using an alkaline cleaning solution takes place before the two-step surface treatment or before the surface made of the TiAl alloy is chemically pickled using an ammonium bifluoride-containing nitric acid solution.
- Method according to any of the preceding claims, characterized in that the surface is chemically activated using a sulfuric acid solution after the two-step surface treatment.
- Method according to any of the preceding claims, characterized in that the surface is rinsed with demineralized water between and/or after the individual processing steps.
- Method according to any of the preceding claims, characterized in that a nickel or cobalt layer is applied as the electrodeposited layer.
- Method according to any of the preceding claims, characterized in that at least one second layer is applied to the layer applied by electrodeposition.
- Method according to claim 10, characterized in that the second layer is applied using a method which is selected from the group comprising electrodeposition, physical vapor deposition, chemical vapor deposition, thermal spraying, welding, and soldering.
- Method according to any of the preceding claims, characterized in that the TiAl alloy is an alloy comprising niobium and/or molybdenum as additional constituents, in particular the niobium content being in the range of 0 to 5 at.% and/or the molybdenum content being in the range of 0 to 3 at.% and/or preferably the Al content being in the range of 40 to 45 at.%, the remainder being Ti and optionally other alloy constituents.
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| US20200032412A1 (en) * | 2018-07-25 | 2020-01-30 | The Boeing Company | Compositions and Methods for Activating Titanium Substrates |
| CN111621841B (en) * | 2020-05-21 | 2022-05-10 | 南京理工大学 | TiAl single crystal EBSD sample-based electrolytic polishing solution and electrolytic method thereof |
| JP7108984B1 (en) | 2021-09-22 | 2022-07-29 | 哲男 原田 | Removal of oxide film on titanium alloy surface |
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| US6670049B1 (en) | 1995-05-05 | 2003-12-30 | General Electric Company | Metal/ceramic composite protective coating and its application |
| US5783315A (en) | 1997-03-10 | 1998-07-21 | General Electric Company | Ti-Cr-Al protective coatings for alloys |
| US6884542B1 (en) * | 2002-05-13 | 2005-04-26 | Zinc Matrix Power, Inc. | Method for treating titanium to electroplating |
| EP1772186B1 (en) * | 2004-05-31 | 2011-08-24 | Japan Science and Technology Agency | Process for producing nanoparticle or nanostructure with use of nanoporous material |
| US20060032757A1 (en) * | 2004-08-16 | 2006-02-16 | Science & Technology Corporation @ Unm | Activation of aluminum for electrodeposition or electroless deposition |
| DE102005055303A1 (en) * | 2005-11-21 | 2007-05-24 | Mtu Aero Engines Gmbh | Multi-stage surface etching process to manufacture high-temperature metal titanium components for gas turbine engine |
| PL211775B1 (en) * | 2008-12-04 | 2012-06-29 | Inst Chemii Fizycznej Polskiej Akademii Nauk | Method of activation of titanium surface under the control of the electrode potential |
| JP5445670B2 (en) | 2010-03-25 | 2014-03-19 | 株式会社Ｉｈｉ | Method for forming oxidation resistant coating layer |
-
2015
- 2015-07-14 DE DE102015213162.9A patent/DE102015213162A1/en not_active Ceased
-
2016
- 2016-05-19 EP EP16170326.9A patent/EP3118352B1/en not_active Not-in-force
- 2016-06-27 US US15/193,688 patent/US10081877B2/en active Active
Non-Patent Citations (1)
| Title |
|---|
| None * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3118352A3 (en) | 2017-04-05 |
| US10081877B2 (en) | 2018-09-25 |
| DE102015213162A1 (en) | 2017-01-19 |
| US20170016132A1 (en) | 2017-01-19 |
| EP3118352A2 (en) | 2017-01-18 |
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