EP2839059B1 - Procédé de fabrication d'un bain électrolytique pour la réalisation d'une sous-couche métallique à base de platine sur un substrat métallique. - Google Patents

Procédé de fabrication d'un bain électrolytique pour la réalisation d'une sous-couche métallique à base de platine sur un substrat métallique. Download PDF

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Publication number
EP2839059B1
EP2839059B1 EP13722499.4A EP13722499A EP2839059B1 EP 2839059 B1 EP2839059 B1 EP 2839059B1 EP 13722499 A EP13722499 A EP 13722499A EP 2839059 B1 EP2839059 B1 EP 2839059B1
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Prior art keywords
solution
platinum
bath
salt
hpo
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EP13722499.4A
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German (de)
English (en)
French (fr)
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EP2839059A1 (fr
Inventor
Juliette Hugot
Frédéric Lagrange
Hervé MOLET
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Safran Aircraft Engines SAS
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SNECMA SAS
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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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
    • 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated

Definitions

  • the invention relates to a method of manufacturing an electrolytic bath for producing a platinum-based metal underlayer on a metal substrate.
  • Such metal sub-layers belong in particular to a coating on a substrate consisting of a metal part called to withstand high mechanical and thermal stresses in operation, in particular a superalloy substrate.
  • a thermomechanical part constitutes in particular an aeronautical or terrestrial turbine engine part. Said part may for example be a blade or a turbomachine turbine distributor and in particular in a high-pressure turbojet or turboprop turboprop turbine.
  • the limit temperature of use of the superalloys is of the order of 1100 ° C, the temperature of the gases at the outlet of the combustion chamber or turbine inlet up to 1600 ° C.
  • thermal barriers in aircraft engines has become widespread over the last thirty years and makes it possible to increase the inlet temperature of the gases in the turbines, to reduce the cooling air flow and thus improve the efficiency of the engines.
  • this insulating coating makes it possible to create on a cooled part, in steady state of operation, a thermal gradient across the coating, whose total amplitude can exceed 100 ° C for a coating of about 150 to 200 microns thick. having a conductivity of 1.1 Wm -1 .K -1 .
  • the operating temperature of the underlying metal forming the substrate for the coating is reduced by the same gradient, which results in significant gains in the necessary cooling air volume, the service life of the part and the specific consumption of the material. turbine engine.
  • a thermal barrier comprising a yttria-stabilized zirconia-based ceramic layer, namely a yttria-containing zirconia comprising a molar content of yttrium oxide between 4 and 12% (especially between 6 and 8%), which has a coefficient of expansion different from the superalloy constituting the substrate and a relatively low thermal conductivity.
  • zirconia-based ceramic layer partially stabilized with yttrium oxide for example Zr 0.92 Y 0.08 O 1.96 .
  • a metal underlayer with a coefficient of expansion ideally close to the substrate, is generally interposed between the substrate of the part and the ceramic layer.
  • the metal sub-layer firstly makes it possible to reduce the stresses due to the difference between the thermal expansion coefficients of the ceramic layer and the superalloy forming the substrate.
  • This underlayer also provides adhesion between the substrate of the part and the ceramic layer, knowing that the adhesion between the underlayer and the substrate of the part is by inter-diffusion, and that the adhesion between the underlayer and the ceramic layer is made by mechanical anchoring and by the propensity of the underlayer to be developed at high temperature, at the ceramic / underlayer interface, a thin oxide layer which ensures the chemical contact with ceramics.
  • this metal sub-layer ensures the protection of the superalloy of the part against corrosion and oxidation phenomena (the ceramic layer is permeable to oxygen).
  • a sublayer consisting of a nickel aluminide comprising a metal selected from platinum, chromium, palladium, ruthenium, iridium, osmium, rhodium, or mixture of these metals and / or a reactive element selected from zirconium (Zr), cerium (Ce), lanthanum (La), titanium (Ti), tantalum (Ta), hafnium (Hf), silicon (Si) and yttrium (Y).
  • Zr zirconium
  • Ce cerium
  • La lanthanum
  • Ti titanium
  • Ta tantalum
  • Hf hafnium
  • Si silicon
  • Y yttrium
  • a (Ni, Pt) Al type coating is used in which the platinum is inserted into the nickel network of the ⁇ -NiAl intermetallic compounds.
  • platinum When developing thermal barriers, platinum has a dual role: it is a diffusion barrier to prevent the diffusion of aluminum from the layer to the substrate.
  • platinum aluminide increases the corrosion resistance at high temperature and the adhesion of protective layers.
  • platinum aluminide coatings rapidly degrade at 1100 ° C: there are phase transformations related to the inter-diffusion of the elements of the coating and the substrates.
  • this metal sub-layer may consist of a NiPtAl platinum-modified nickel aluminide, according to a process comprising the following steps: the preparation of the surface of the part by chemical etching and sanding; depositing on the part, by electrolysis, a platinum coating (Pt); the possible heat treatment of the assembly to diffuse Pt in the room; aluminum deposition (Al) by chemical vapor deposition (CVD) or physical vapor deposition (PVD); the possible heat treatment of the assembly to diffuse Pt and Al in the room; the preparation of the surface of the formed metallic underlayer; and electron beam evaporation (EB-PVD) deposition of a ceramic coating.
  • Pt platinum coating
  • Al aluminum deposition
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • EB-PVD electron beam evaporation
  • the platinum is deposited electrolytically before the thermochemical treatment of aluminization in the vapor phase.
  • electroplating reduces a complexed metal entity initially present in the solution by passing an electric current over a conductive part (the cathode). between an anode (electrode seat of an oxidation reaction) and a cathode on which deposition takes place (and on which other reduction reactions can take place simultaneously).
  • the pH of these solutions can be basic, acidic or neutral.
  • the compounds obtained after the extraction of platinum are ammonium hexachloroplatinate (IV): (NH 4 ) 2 PtCl 6 or potassium hexachloroplatinate (IV): K 2 PtCl 6 .
  • the main platinum compounds present in the casting baths are derived from the transformation of these compounds.
  • electroplating baths for depositing platinum have been proposed to date and include a number of chemical species in aqueous solution, giving the bath its properties.
  • the present invention aims to provide an electrolytic bath for the deposition of platinum on a metal substrate, which electrolytic bath has an improvement in technical performance, including identical or almost identical parameters and deposition conditions regardless of the geometry of the piece, an identical or almost identical deposition rate regardless of the current density applied, a deposition quality in accordance with the specifications, and an improved service life.
  • a complex resulting from the bond between an amino ligand and a platinum metal salt is preferred.
  • a ligand without carbon chain and a single amine function NH 3 (ammonia) or a salt xNH 4 + or an X-NH 2 ammonium) or X is chosen either as inert molecule, spectator of the main reaction is as an interacting molecule in formulation reactions.
  • the metal salt of the third system is chosen from platinum salts of oxidation state IV.
  • This solution also has the additional advantage of allowing, in addition, to use platinum salts of oxidation degree IV, much more stable than platinum salts of oxidation state II.
  • the first system, the second system and the fourth system are grouped into a single solution forming a first solution B.
  • the third system forms a second solution A consisting of an aqueous solution with platinum, comprising sodium hydroxide (NaOH) and at least one platinum salt of degree of oxidation IV.
  • a second solution A consisting of an aqueous solution with platinum, comprising sodium hydroxide (NaOH) and at least one platinum salt of degree of oxidation IV.
  • the molar ratio between the amount of sodium hydroxide NaOH and the amount of platinum salt of oxidation degree IV is 2.
  • a step f) is carried out during which said electrolytic bath is heated at a temperature of between 80 ° C. and 97 ° C. for at least two hours. then a step g) is carried out during which electroplating of a platinum deposit on a metal substrate is carried out with said electrolytic bath.
  • the second solution A is added to the first solution B.
  • the first solution B is brought to a temperature of 60 ° C.
  • said oxidation state platinum salt IV is diammonium hexachloroplatinate of formula (NH 4 ) 2 PtCl 6 .
  • said amine compound x p - (NH 4 ) + p comprises diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 and / or ammonium dihydrogen phosphate NH 4 H 2 PO 4 .
  • the first system comprises diammonium hydrogenophosphate (NH 4 ) 2 HPO 4 and ammonium dihydrogen phosphate NH 4 H 2 PO 4 with a molar ratio of 2 between the amount of ammonium dihydrogen phosphate NH 4 H 2 PO 4 and the amount of diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 .
  • said platinum salt of oxidation state IV is diammonium hexachloroplatinate of formula (NH 4 ) 2 PtCl 6 .
  • the molar ratio between the amount of sodium hydroxide NaOH and the amount of platinum salt of oxidation degree IV is 2.
  • said amine compound x p- (NH 4 ) + p comprises diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 and / or ammonium dihydrogen phosphate NH 4 H 2 PO 4 .
  • the first solution B comprises diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 and ammonium dihydrogen phosphate NH 4 H 2 PO 4 with a molar ratio of 2 between the amount of ammonium dihydrogenophosphate NH 4 H 2 PO 4 and the amount of diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 .
  • the invention also relates to the electrolytic bath resulting from the manufacturing method according to the invention.
  • Such an electrolytic bath for producing a platinum-based metal underlayer on a superalloying substrate is characterized in that it comprises a platinum amine complex of the wavelength of a Pt-NH bond. 3 or Pt-NH 2 and a buffer solution
  • An electrolytic bath makes it possible to deposit the platinum in a way which is particularly ecological and economical (short time of realization, realization under atmospheric pressure avoiding the equipment of putting under vacuum) compared to techniques of deposition in vapor phase or thermal projection.
  • this deposition method is compatible with pierced parts: the geometry of the current lines preventing significant deposition in the holes, in particular small cooling holes which are thus not obstructed.
  • the bath formulation is made from four ingredients distributed between two separate solutions, A and B, heated and stirred separately to react the ingredients together in each solution, before mixing together the two solutions A and B.
  • the mixture between the two solutions A and B is then itself heated and stirred. Once the heating time of the mixture A + B is respected, the platinum plating bath is ready for use for carrying out the electroplating.
  • solution A comprises, inter alia, the platinum salt (s)
  • solution B is the solution comprising, inter alia, ligands (it is recalled that a ligand is a chemical entity, ionic or molecular, bearing chemical functions allowing it to bind to one or more metallic entities, usually a cation, the association of a metallic entity with one or more ligands forming a soluble edifice in solution called complex).
  • the pH of the mixture of solutions A + B is set between 6 and 10 and preferably between 6 and 7.
  • T ° heating B (° C) Heating time B (h) T ° heater AB (° C) Heating time AB (h) 1 50 ° C 1:30 50 ° C 1 hour 2 50 ° C 4:30 85 ° C 3h 3 50 ° C 8h 95 ° C 8h 4 85 ° C 1:30 85 ° C 8h 5 85 ° C 4:30 95 ° C 1 hour 6 85 ° C 8h 50 ° C 3h 7 95 ° C 1:30 95 ° C 3h 8 95 ° C 4:30 50 ° C 8h 9 95 ° C 8h 85 ° C 1 hour
  • pions are coated with platinum at different intensities. Each pawn is weighed before and after deposit.
  • the bath of test 2 offers the following advantages:
  • the bath of test 2 shows little loss of platinum over time ( Figure 1 C) and that the average efficiency ( Figure 2A ) and speed ( Figure 2B ) of the bath is almost identical after three successive regenerations.
  • Concerning the platinum losses we encounter with the reference bath many platinum losses, mainly in the form of a platinum solid precipitate at the bottom of the tank.
  • the baths according to the invention it is observed for the baths according to the invention that the platinum losses are lower and above all constant in time (constant with the electrolyses).
  • the bath of test 2 is the one with less platinum losses, so the bath of test 2 is more economical from the economic point of view.
  • the manufacture of the electrolytic bath is similar to that of the recipe of Example 1, except for the following points.
  • Solution B comprises ammonium hydrogen sulphate of chemical formula (NH 4 ) 2 SO 4 in an amount of 43.5 g and diammonium sulphate of chemical formula NH 4 S O 4 in an amount of 76 g and water . The whole is brought to 50 ° C during 4:30.
  • the pH of the mixture of solutions A + B is set between 1 and 5.
  • the manufacture of the electrolytic bath is similar to that of the recipe of Example 1, except for the following points.
  • Solution B contains ammonium acetate of chemical formula CH 3 COONH 4 in an amount of 102.4 g and acetic acid of chemical formula CH 3 COOH in an amount of 39.6 g.
  • the whole is brought to 50 ° C during 4:30.
  • the pH of the mixture of solutions A + B is set between 1 and 5.
  • the ligand is chosen from aliphatic polyamines of 3 to 20 carbon atoms with a linear or branched carbon chain.
  • the ligand is chosen from primary polyamines such as diaminopropanes such as 1,3-diaminopropane and 1,2-diaminopropane, diethylenetriamine, 1,4-diaminobutane and 1,6-diaminohexane; secondary polyamines such as N, N 'dimethyl-1,3-propanediamine; and tertiary polyamines such as N, N, N ', N' tetramethylethylenediamine.
  • the ligands preferentially chosen are diaminopropanes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
EP13722499.4A 2012-04-19 2013-04-18 Procédé de fabrication d'un bain électrolytique pour la réalisation d'une sous-couche métallique à base de platine sur un substrat métallique. Active EP2839059B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1253599A FR2989694B1 (fr) 2012-04-19 2012-04-19 Procede de fabrication d'un bain electrolytique pour la realisation d'une sous-couche metallique a base de platine sur un substrat metallique
PCT/FR2013/050855 WO2013156737A1 (fr) 2012-04-19 2013-04-18 Procede de fabrication d'un bain electrolytique pour la realisation d'une sous-couche metallique a base de platine sur un substrat metallique

Publications (2)

Publication Number Publication Date
EP2839059A1 EP2839059A1 (fr) 2015-02-25
EP2839059B1 true EP2839059B1 (fr) 2016-04-13

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EP13722499.4A Active EP2839059B1 (fr) 2012-04-19 2013-04-18 Procédé de fabrication d'un bain électrolytique pour la réalisation d'une sous-couche métallique à base de platine sur un substrat métallique.

Country Status (10)

Country Link
US (1) US9752243B2 (hr)
EP (1) EP2839059B1 (hr)
JP (1) JP6290179B2 (hr)
CN (1) CN104271811B (hr)
BR (1) BR112014026033B1 (hr)
CA (1) CA2870760C (hr)
FR (1) FR2989694B1 (hr)
IN (1) IN2014DN08735A (hr)
RU (1) RU2625923C2 (hr)
WO (1) WO2013156737A1 (hr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104975312A (zh) * 2015-07-30 2015-10-14 江苏金曼科技有限责任公司 一种延长镀液使用寿命的电镀方法
FR3058165B1 (fr) 2016-10-27 2018-12-14 Safran Aircraft Engines Procede et dispositif de regeneration de bain de platine
FR3066505B1 (fr) 2017-05-16 2021-04-09 Safran Aircraft Engines Procede et dispositif ameliores de filtration de bain de platine par electrodialyse
CN110894617A (zh) * 2018-09-13 2020-03-20 深圳市永达锐国际科技有限公司 3d铂金电铸工艺方法
CN114214685A (zh) * 2021-09-22 2022-03-22 湘潭大学 高温防护涂层及其制备方法与应用

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NL124423C (hr) * 1963-03-20
US3285839A (en) * 1963-12-16 1966-11-15 American Chem & Refining Co Method and bath for electroplating rhenium
GB1431548A (en) * 1972-09-21 1976-04-07 Engelhard Ind Ltd Electrodeposition of plantinum
US4182724A (en) * 1976-04-06 1980-01-08 Rustenburg Platinum Mines Limited Compositions containing platinum
SU707382A1 (ru) * 1978-05-30 2000-06-20 Р.В. Джагацпанян Электролит платинирования
SU954527A1 (ru) * 1980-12-30 1982-08-30 Предприятие П/Я В-2287 Электролит дл платинировани титана
US4427502A (en) * 1981-11-16 1984-01-24 Bell Telephone Laboratories, Incorporated Platinum and platinum alloy electroplating baths and processes
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IL98550A (en) 1990-06-29 1996-07-23 Electroplating Eng Baths for the investment of platinum and for the production of platinum products by electricity, methods for investing platinum and for the production of platinum products that use them and products produced by them
JP2577832B2 (ja) * 1990-06-29 1997-02-05 日本エレクトロプレイテイング・エンジニヤース株式会社 白金電鋳浴
JPH04333589A (ja) * 1990-06-29 1992-11-20 Electroplating Eng Of Japan Co 高硬度白金材料の製造方法及びその高硬度白金材料
US5788823A (en) * 1996-07-23 1998-08-04 Howmet Research Corporation Platinum modified aluminide diffusion coating and method
GB2351089B (en) * 1999-06-15 2001-04-18 Hong Kong Productivity Council Platinum electroforming/electroplating bath and method

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Publication number Publication date
US9752243B2 (en) 2017-09-05
IN2014DN08735A (hr) 2015-05-22
WO2013156737A1 (fr) 2013-10-24
EP2839059A1 (fr) 2015-02-25
CN104271811A (zh) 2015-01-07
RU2625923C2 (ru) 2017-07-19
CA2870760A1 (fr) 2013-10-24
JP6290179B2 (ja) 2018-03-07
FR2989694B1 (fr) 2015-02-27
CA2870760C (fr) 2021-02-23
US20150075996A1 (en) 2015-03-19
BR112014026033A2 (pt) 2017-06-27
RU2014146284A (ru) 2016-06-10
JP2015514873A (ja) 2015-05-21
CN104271811B (zh) 2016-10-12
BR112014026033B1 (pt) 2020-11-24
FR2989694A1 (fr) 2013-10-25

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