EP2610371B1 - Procédé de préparation de rhénium - alliages de nickel - Google Patents
Procédé de préparation de rhénium - alliages de nickel Download PDFInfo
- Publication number
- EP2610371B1 EP2610371B1 EP12460097.4A EP12460097A EP2610371B1 EP 2610371 B1 EP2610371 B1 EP 2610371B1 EP 12460097 A EP12460097 A EP 12460097A EP 2610371 B1 EP2610371 B1 EP 2610371B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rhenium
- nickel
- cathode
- electrodeposition
- vii
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 22
- UJRJCSCBZXLGKF-UHFFFAOYSA-N nickel rhenium Chemical compound [Ni].[Re] UJRJCSCBZXLGKF-UHFFFAOYSA-N 0.000 title claims description 15
- 229910000990 Ni alloy Inorganic materials 0.000 title claims description 13
- 229910052702 rhenium Inorganic materials 0.000 claims description 17
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000000956 alloy Substances 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000000576 coating method Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- -1 citric acid) Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 229910000601 superalloy Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910000691 Re alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- NLXYLZCLIHHPMA-UHFFFAOYSA-K aluminum;trisulfamate Chemical compound [Al+3].NS([O-])(=O)=O.NS([O-])(=O)=O.NS([O-])(=O)=O NLXYLZCLIHHPMA-UHFFFAOYSA-K 0.000 description 1
- 238000012769 bulk production Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- YZVJHCGMTYDKFR-UHFFFAOYSA-L magnesium;disulfamate Chemical compound [Mg+2].NS([O-])(=O)=O.NS([O-])(=O)=O YZVJHCGMTYDKFR-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
Classifications
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Definitions
- the subject of this invention is a method for producing homogeneous rhenium - nickel alloys by electrodeposition from aqueous solutions.
- Rhenium being a high-melting metal, with a number of unique properties, is gaining on significance as a high quality engineering material. Properties of rhenium promote its application in many areas of technology, such as aviation, space engineering, nuclear engineering, electrical engineering, biomedicine.
- the application of rhenium as a component of superalloys used, for instance, in the manufacture of jet engine turbine blades, is quickly expanding. Addition of 3 to 6% Re to nickel superalloys enables engine operation at higher temperatures, at higher speed, improving thereby both engine performance and fuel economy.
- the two currently applied methods of producing metallic rhenium include powder metallurgy (PM) and chemical vapour deposition (CVD). These processes are expensive, complex and energy-consuming. Electrodeposition of rhenium and its alloys, carried out at low temperatures and in nontoxic aqueous solutions, requiring low energy input, may be an alternative to methods applied hitherto.
- the dense, metallic and uniform cathodic deposits constitute an excellent material for preliminary alloys for creating rhenium-containing special alloys or superalloys.
- a method of forming high temperature resistant rhenium alloy coating films described in patent specification US 7368048 consists in the use of an electrolyte that contains ions of rhenate(VII), alloy metal selected from the group consisting of Ni, Co, Fe and Cr(III), Li and Na, and an organic acid selected from the group consisting of carboxylic acids or aminocarboxylic acids (e.g. citric acid), acting as a complexing agent.
- This method enables obtaining 10 to 30 ⁇ m thick plated films of appropriate quality at a current density of 10 A/dm 2 .
- Patent specification US 3668083 presents a method of electrodeposition of rhenium and its alloys in the form of low-stressed coating films from rhenium bath containing additionally one or more chemical compounds selected from the group consisting of the following salts: magnesium sulphate, magnesium sulphamate, aluminium sulphate and aluminium sulphamate.
- the agents that provided formation of good quality coating films were additives to the electrolyte in the form of conducting salts, complexing compounds, salts that stabilized processes in the near-electrode zones, or sulphamate ions rendering formation of fine-crystalline deposits of high plasticity and low stress.
- These processes relate to the forming of thin coatings, rather than to bulk production of solid rhenium alloys.
- the method of preparing electrolytic rhenium - nickel alloys according to this invention consists in the use of a sulphate nickel electrolyte, comprising nickel(II) sulphate, sodium sulphate and boric acid, supplemented by ammonium rhenate(VII) added in an amount of 2 to 100 g/dm 3 .
- the cathodic process of depositing the rhenium-nickel alloy proceeds on a centrally arranged cathode. Insoluble anodes are placed on both sides of the cathode. The process is conducted under conditions of stabilizing pH in the near-cathode zone.
- the method of preparing rhenium-nickel alloys according to the invention consists in electrodepositing them at temperatures of from 10 to 80°C and at current density ⁇ 5 A/dm 2 and pH of the electrolytic bath of from 1 to 8. Under these conditions the obtained rhenium - nickel alloy deposit has a dense, metallic, smooth, uniform structure, and it is produced at a high current efficiency of ⁇ 95% and low specific power consumption of within 2.0 to 2.5 kWh per kg of alloy.
- the cathodic alloy deposits obtained after 48 hours of the electrodeposition process have a thickness > 1.5 mm and the following content of the main components:
- the advantage of the invention presented is that a dense and uniform deposit of rhenium-nickel alloy is obtained in the form of a solid solution containing up to 80 wt% rhenium.
- the latter can be used for the production of special alloys.
- the method according to the invention is illustrated in the examples below.
- An electrolytic tank is filled with nickel - rhenium electrolytic bath containing 11.5 g/dm 3 rhenium in the form of ammonium rhenate(VII), 40.0 g/dm 3 nickel in the form of nickel(II) sulphate, 10.0 g/dm 3 boric acid and 80.0 g/dm 3 sodium sulphate.
- the process of rhenium - nickel alloy electrodeposition is conducted without electrolyte flow, making up for evaporation losses and for rhenium and nickel ions consumption caused by deposition of the alloy on the cathode, at the temperature of 55°C, at cathodic current density of 1.2 A/dm 2 and pH of the electrolytic bath of from 1.8 to 4.1.
- the rhenium - nickel alloy deposit obtained on a copper cathode had a thickness of ca. 1.5 mm; it was dense, metallic, lustrous; it adhered tightly to the core, contained 47.9 wt% rhenium (22.5 atomic %) and 51.9 wt% nickel (77.5 atomic %).
- the current efficiency of depositing the alloy of the above composition was 99.0%, with specific power consumption amounting to 2.15 kWh per kg of alloy.
- the process of rhenium - nickel alloy electrodeposition was conducted in a flow electrolyzer, wherein the electrolyte was fed to the bottom of the electrolyzer and was carried away through a weir in the top part of the electrolyzer.
- the flow of electrolyte was laminar, parallel to the surfaces of the cathode and of the anodes, stabilizing thereby pH in the cathode area and carrying excess hydrogen ions away from the electrolyzer.
- the nickel - rhenium electrolyte used contained 13.6 g/dm 3 rhenium in the form of ammonium rhenate(VII), 47.8 g/dm 3 nickel in the form of nickel(II) sulphate, 10.0 g/dm 3 boric acid and 80.0 g/dm 3 sodium sulphate.
- the process was conducted at the temperature of 55°C, at cathodic current density of 1.5 A/dm 2 and pH of the electrolyte of from 2.4 to 3.6.
- Linear flow velocity of the electrolyte was 3.0 cm/min, and the volumetric charge density was 3.0 Ah/dm 3 .
- cathodic rhenium - nickel alloy deposit was lustrous, metallic, fine-crystalline, with no cracks or dendrites; its thickness was ca. 1.5 mm; it contained 46.1 wt% rhenium (21.4 atomic %) and 53.5 wt% nickel (78.6 atomic %).
- the current efficiency of depositing this alloy was 99.9%, with specific power consumption amounting to 2.13 kWh per kg of alloy.
Landscapes
- 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)
- Electrolytic Production Of Metals (AREA)
Claims (1)
- Procédé d'obtention des alliages homogènes de rhénium-nickel en voie d'électroextraction des solutions acqueuses, caractérisé en ce qu'au bain électrolytique de sulfate de nickel utilisé pour la fabrication du nickel cathodique on introduit du rhénium sous forme des ions de rhénium(VII) avantageusement en tant que rhénate(VII) d'ammonium en quantité de 2 à 100 g/dm3 et à température comprise entre 10 et 80°C, avantageusement à température proche de 55°C, on réalise le procédé d'électroextraction de l'alliage de rhénium-nickel sur une cathode placée au centre de la cuve électrolytique, de deux côtés de la cathode il y a des anodes insolubles, avantageusement en titane, revêtues d'oxydes métalliques, la densité cathodique de courant étant fixée à ≤ 5 A/dm2, le pH du bain étant de 1 à 8, étant précisé qu'on assure un flux laminaire de l'électrolyte à vitesse linéaire de 1 à 5 cm/min pour la capacité volumique de la charge électrique de 1 à 5 Ah/dm3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL12460097T PL2610371T3 (pl) | 2011-12-27 | 2012-12-27 | Sposób otrzymywania stopów ren - nikiel |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL397508A PL216443B1 (pl) | 2011-12-27 | 2011-12-27 | Sposób otrzymywania homogenicznych stopów ren-nikiel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2610371A1 EP2610371A1 (fr) | 2013-07-03 |
EP2610371B1 true EP2610371B1 (fr) | 2014-05-14 |
Family
ID=47603183
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12460097.4A Active EP2610371B1 (fr) | 2011-12-27 | 2012-12-27 | Procédé de préparation de rhénium - alliages de nickel |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2610371B1 (fr) |
ES (1) | ES2477328T3 (fr) |
PL (2) | PL216443B1 (fr) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1771763A1 (fr) | 1967-07-03 | |||
FR2770277A1 (fr) * | 1997-10-29 | 1999-04-30 | Framatome Sa | Procede de reparation par chemisage d'un tube et utilisation du procede |
WO2003062501A1 (fr) | 2002-01-18 | 2003-07-31 | Japan Science And Technology Agency | Procede pour former un film de revetement en alliage de re ayant une teneur elevee en re par electroplacage |
-
2011
- 2011-12-27 PL PL397508A patent/PL216443B1/pl unknown
-
2012
- 2012-12-27 PL PL12460097T patent/PL2610371T3/pl unknown
- 2012-12-27 ES ES12460097.4T patent/ES2477328T3/es active Active
- 2012-12-27 EP EP12460097.4A patent/EP2610371B1/fr active Active
Also Published As
Publication number | Publication date |
---|---|
EP2610371A1 (fr) | 2013-07-03 |
PL2610371T3 (pl) | 2014-08-29 |
PL397508A1 (pl) | 2013-03-18 |
PL216443B1 (pl) | 2014-04-30 |
ES2477328T3 (es) | 2014-07-16 |
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