CN116905059A - Preparation method of Cu-based double-layer coating on surface of SOFC (solid oxide fuel cell) metal connector - Google Patents
Preparation method of Cu-based double-layer coating on surface of SOFC (solid oxide fuel cell) metal connector Download PDFInfo
- Publication number
- CN116905059A CN116905059A CN202310895895.9A CN202310895895A CN116905059A CN 116905059 A CN116905059 A CN 116905059A CN 202310895895 A CN202310895895 A CN 202310895895A CN 116905059 A CN116905059 A CN 116905059A
- Authority
- CN
- China
- Prior art keywords
- coating
- electrolyte
- metal connector
- sulfate
- depositing
- 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.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 109
- 238000000576 coating method Methods 0.000 title claims abstract description 109
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000446 fuel Substances 0.000 title abstract description 9
- 239000007787 solid Substances 0.000 title abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 141
- 229910017566 Cu-Mn Inorganic materials 0.000 claims abstract description 101
- 229910017871 Cu—Mn Inorganic materials 0.000 claims abstract description 101
- 238000000151 deposition Methods 0.000 claims abstract description 75
- 239000003792 electrolyte Substances 0.000 claims abstract description 70
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 52
- 239000000956 alloy Substances 0.000 claims abstract description 52
- 238000004070 electrodeposition Methods 0.000 claims abstract description 36
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 32
- 230000002378 acidificating effect Effects 0.000 claims abstract description 31
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 28
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 28
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 28
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004327 boric acid Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 16
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 16
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 16
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000004090 dissolution Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 238000007747 plating Methods 0.000 claims description 65
- 230000008021 deposition Effects 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 description 28
- 238000007254 oxidation reaction Methods 0.000 description 28
- 239000011572 manganese Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 230000004584 weight gain Effects 0.000 description 9
- 235000019786 weight gain Nutrition 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000010965 430 stainless steel Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 230000007774 longterm Effects 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- KVJXEJFFQNSORF-UHFFFAOYSA-L disodium acetic acid diacetate Chemical compound [Na+].[Na+].CC(O)=O.CC(O)=O.CC([O-])=O.CC([O-])=O KVJXEJFFQNSORF-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The application discloses a preparation method of a Cu-based double-layer coating on the surface of an SOFC (solid oxide fuel cell) metal connector, and relates to the technical field of solid oxide fuel cells. The method comprises the following steps: adding copper sulfate pentahydrate, ammonium sulfate, boric acid and sodium dodecyl sulfate into water for dissolution, and adjusting pH to be acidic to obtain a first electrolyte for depositing a Cu coating; dissolving copper sulfate pentahydrate and disodium ethylenediamine tetraacetate in water, standing, adding manganese sulfate monohydrate to dissolve, adding ammonium sulfate, boric acid and sodium dodecyl sulfate, and regulating pH to be acidic to obtain a second electrolyte for depositing a Cu-Mn coating; sequentially carrying out pulse electrodeposition in a first electrolyte and a second electrolyte by taking a metal connector as a cathode and graphite as an anode to obtain a Cu/Cu-Mn alloy coating on the surface of the metal connector; and drying the Cu/Cu-Mn alloy coating, and sintering to obtain the finished Cu/Cu-Mn double-layer coating.
Description
Technical Field
The application relates to the technical field of solid oxide fuel cells, in particular to a preparation method of a Cu-based double-layer coating on the surface of an SOFC metal connector.
Background
Solid oxide fuel cells (Solid Oxide Fuel Cell, SOFC for short) are increasingly attracting attention by many researchers due to their energy efficiency, environmental friendliness, wide fuel sources, and the like. With the development of the medium-temperature SOFC technology, the working temperature of the SOFC has gradually decreased to 650-800 ℃, so that a metal connector with lower cost can replace a ceramic connector, wherein the ferrite stainless steel has been paid attention to because of the advantages of high conductivity, low cost, matching with the thermal expansion coefficients of other components of the SOFC, and the like. However, after the ferritic stainless steel connector is operated at a high temperature for a long period of time, the surface Cr-containing oxide layer is liable to be thickened continuously and the conductivity is liable to be lowered. In order to improve the service performance of the stainless steel connector and prolong the service life of the SOFC, a high-temperature oxidation-resistant coating is required to be prepared on the surface of the connector to inhibit the growth of a Cr-containing layer, so that the problems of high-temperature performance reduction and cracking of the connector caused by migration and diffusion of Cr elements after long-term service of the connector are solved. However, the high-temperature oxidation resistance and conductivity of the existing metal connector surface coating are poor, the compactness of the coating is to be improved, the preparation cost is high, and the industrial production is not facilitated. Therefore, the application provides a preparation method of a Cu-based double-layer coating on the surface of an SOFC metal connector, which aims to solve the technical problems.
Disclosure of Invention
The application mainly aims to provide a preparation method of a Cu-based double-layer coating on the surface of an SOFC (solid oxide fuel cell) metal connector, and aims to solve the technical problems of poor high-temperature oxidation resistance and poor electrical conductivity of the existing metal connector surface coating.
In order to achieve the above purpose, the application provides a preparation method of a Cu-based double-layer coating on the surface of an SOFC metal connector, which comprises the following steps:
adding copper sulfate pentahydrate, ammonium sulfate, boric acid and sodium dodecyl sulfate into water for dissolution, and adjusting pH to be acidic to obtain a first electrolyte for depositing a Cu coating;
dissolving copper sulfate pentahydrate and disodium ethylenediamine tetraacetate in water, standing, adding manganese sulfate monohydrate to dissolve, adding ammonium sulfate, boric acid and sodium dodecyl sulfate, and regulating pH to be acidic to obtain a second electrolyte for depositing a Cu-Mn coating;
sequentially performing pulse electrodeposition in the first electrolyte and the second electrolyte by taking a metal connector as a cathode and graphite as an anode to obtain a Cu/Cu-Mn alloy coating on the surface of the metal connector;
and drying the Cu/Cu-Mn alloy coating, and sintering to obtain the finished Cu/Cu-Mn double-layer coating.
Optionally, the step of adding copper sulfate pentahydrate, ammonium sulfate, boric acid and sodium dodecyl sulfate to water for dissolution and adjusting the pH to be acidic to obtain a first electrolyte for depositing a Cu plating layer includes:
10g/L-20g/L of copper sulfate pentahydrate, 6g/L-12g/L of ammonium sulfate, 1.2g/L-2.4g/L of boric acid and 0.005g/L-0.01g/L of sodium dodecyl sulfate are added into deionized water for dissolution, and 20% sulfuric acid is added for regulating the pH to be acidic, so that a first electrolyte for depositing a Cu coating is obtained.
Optionally, the step of dissolving the copper sulfate pentahydrate and the disodium ethylenediamine tetraacetate in water, standing, adding the manganese sulfate monohydrate, dissolving, adding the ammonium sulfate, the boric acid and the sodium dodecyl sulfate, and adjusting the pH to be acidic to obtain a second electrolyte for depositing the Cu-Mn plating layer comprises the following steps:
dissolving 2.5g/L-5g/L of copper sulfate pentahydrate and 2.5g/L-12.5g/L of disodium ethylenediamine tetraacetate in deionized water, standing for 50min-70min, adding 16.9g/L-33.8g/L of manganese sulfate monohydrate, dissolving, adding 9g/L-17g/L of ammonium sulfate, 3g/L-9g/L of boric acid and 0.005g/L-0.015g/L of sodium dodecyl sulfate, and adding 20% sulfuric acid to adjust pH to be acidic to obtain a second electrolyte for depositing Cu-Mn plating layers.
Optionally, in the step of performing pulse electrodeposition, the deposition voltage is 120V, and the deposition duty ratio is 20% -80%.
Optionally, the step of sequentially performing pulse electrodeposition in the first electrolyte and the second electrolyte by using the metal connector as a cathode and graphite as an anode to obtain a Cu/Cu-Mn alloy plating layer on the surface of the metal connector comprises the steps of:
performing pulse electrodeposition for 10-30 min in the first electrolyte according to the deposition temperature of 25-45 ℃ to obtain a Cu plating layer with a first thickness on the surface of the metal connector;
and performing pulse electrodeposition for 10-40 min in the second electrolyte according to the deposition temperature of 25-55 ℃ to obtain a Cu-Mn coating with a second thickness on the surface of the Cu coating with the first thickness so as to obtain a Cu/Cu-Mn alloy coating on the surface of the metal connector.
Optionally, the Cu/Cu-Mn alloy plating layer has a thickness of 20 μm.
Optionally, the first thickness is 7 μm and the second thickness is 13 μm.
Optionally, before the step of drying the Cu/Cu-Mn alloy plating layer, cleaning the Cu/Cu-Mn alloy plating layer to remove the acidic electrolyte on the surface of the Cu/Cu-Mn alloy plating layer.
Optionally, in the step of drying the Cu/Cu-Mn alloy plating layer, the drying temperature is 60-80 ℃ and the drying time is 8-12 h.
Optionally, in the step of sintering, the sintering temperature is 700-900 ℃ and the sintering time is 2-4 h.
The application adopts a pulse electrodeposition method, firstly, the electrolyte for depositing the Cu plating layer is prepared by using the copper sulfate pentahydrate, and then the electrolyte for depositing the Cu-Mn plating layer is prepared by using the copper sulfate pentahydrate and the manganese sulfate monohydrate, and because the co-deposition of metal salts generally needs two element deposition potentials to be as similar as possible, but Cu is prepared by adopting the method 2+ The Cu standard potential is 0.337V H ，Mn 2+ The Mn standard potential is-1.180V H Therefore, the deposition potentials of Cu and Mn are greatly different, and only a very small amount of positive potential salt is contained in the solution to realize co-deposition, so the complexing agent disodium ethylenediamine tetraacetate is adopted to complex Cu 2+ And Mn of 2+ The deposition potential of Cu and Mn is pulled up to realize the co-deposition of the Cu and Mn, so that the problem that the Cu and Mn are difficult to co-deposit due to large deposition potential difference is solved, then a Cu/Cu-Mn alloy plating layer is obtained on the surface of a metal connector through pulse electrodeposition, and then the Cu/Cu-Mn alloy plating layer is dried and sinteredAnd then obtaining the Cu/Cu-Mn double-layer coating. The Cu/Cu-Mn double-layer coating has better high-temperature conductivity and oxidation resistance, and can be converted into CuO/CuMn after being oxidized at 800 ℃ in the long-term service process of the metal connector 2 O 4 Double-layer coating, cuO/CuMn 2 O 4 The double-layer coating still has good high-temperature conductivity, can effectively improve the high-temperature performance of the metal connector, inhibit the migration and volatilization of Cr in the metal connector, prolong the high-temperature service life of the metal connector, can reduce the manufacturing cost by adopting an electrodeposition method, has higher compactness of the obtained coating, and has important significance for industrially preparing the high-performance antioxidant coating on the surface of the metal connector in batches.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing comparison of oxidation weight gain curves of coating samples according to experimental examples of the present application.
The achievement of the objects, functional features and advantages of the present application will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The ferrite stainless steel connector is easy to cause the problems of continuous thickening of the surface Cr-containing oxide layer, reduced conductivity and the like after running at high temperature for a long time. In order to improve the service performance of the stainless steel connector and prolong the service life of the SOFC, a high-temperature oxidation-resistant coating is required to be prepared on the surface of the connector to inhibit the growth of a Cr-containing layer, so that the problems of high-temperature performance reduction and cracking of the connector caused by migration and diffusion of Cr elements after long-term service of the connector are solved. However, the high-temperature oxidation resistance and conductivity of the existing metal connector surface coating are poor, the compactness of the coating is to be improved, the preparation cost is high, and the industrial production is not facilitated.
Aiming at the technical problems of the prior metal connector surface coating, the embodiment of the application provides a preparation method of a Cu-based double-layer coating on the surface of an SOFC metal connector, which comprises the following steps:
adding copper sulfate pentahydrate, ammonium sulfate, boric acid and sodium dodecyl sulfate into water for dissolution, and adjusting pH to be acidic to obtain a first electrolyte for depositing a Cu coating;
dissolving copper sulfate pentahydrate and disodium ethylenediamine tetraacetate in water, standing, adding manganese sulfate monohydrate to dissolve, adding ammonium sulfate, boric acid and sodium dodecyl sulfate, and regulating pH to be acidic to obtain a second electrolyte for depositing a Cu-Mn coating;
sequentially performing pulse electrodeposition in the first electrolyte and the second electrolyte by taking a metal connector as a cathode and graphite as an anode to obtain a Cu/Cu-Mn alloy coating on the surface of the metal connector;
and drying the Cu/Cu-Mn alloy coating, and sintering to obtain the finished Cu/Cu-Mn double-layer coating.
The application adopts a pulse electrodeposition method, firstly, the electrolyte for depositing the Cu plating layer is prepared by using the copper sulfate pentahydrate, and then the electrolyte for depositing the Cu-Mn plating layer is prepared by using the copper sulfate pentahydrate and the manganese sulfate monohydrate, and because the co-deposition of metal salts generally needs two element deposition potentials to be as similar as possible, but Cu is prepared by adopting the method 2+ The Cu standard potential is 0.337V H ，Mn 2+ The Mn standard potential is-1.180V H Therefore, the deposition potentials of Cu and Mn are greatly different, and only a very small amount of positive potential salt is contained in the solution to realize co-deposition, so the complexing agent ethylenediamine is adopted in the applicationComplexing of Cu with disodium tetraacetate 2+ And Mn of 2+ And the deposition potential of Cu and Mn is pulled up to realize the co-deposition of the Cu and Mn, so that the problem that the Cu and Mn are difficult to co-deposit due to large difference of the deposition potential is solved, then a Cu/Cu-Mn alloy coating is obtained on the surface of a metal connector through pulse electrodeposition, and then the Cu/Cu-Mn alloy coating is dried and sintered to obtain the Cu/Cu-Mn double-layer coating. The Cu/Cu-Mn double-layer coating has better high-temperature conductivity and oxidation resistance, and can be converted into CuO/CuMn after being oxidized at 800 ℃ in the long-term service process of the metal connector 2 O 4 Double-layer coating, cuO/CuMn 2 O 4 The double-layer coating still has good high-temperature conductivity, can effectively improve the high-temperature performance of the metal connector, inhibit the migration and volatilization of Cr in the metal connector, prolong the high-temperature service life of the metal connector, can reduce the manufacturing cost by adopting an electrodeposition method, has higher compactness of the obtained coating, and has important significance for industrially preparing the high-performance antioxidant coating on the surface of the metal connector in batches.
As an embodiment of the present application, the step of dissolving copper sulfate pentahydrate, ammonium sulfate, boric acid and sodium dodecyl sulfate in water and adjusting pH to be acidic to obtain a first electrolyte for depositing Cu plating layer includes:
10g/L-20g/L of copper sulfate pentahydrate, 6g/L-12g/L of ammonium sulfate, 1.2g/L-2.4g/L of boric acid and 0.005g/L-0.01g/L of sodium dodecyl sulfate are added into deionized water for dissolution, and 20% sulfuric acid is added for regulating the pH to be acidic, so that a first electrolyte for depositing a Cu coating is obtained.
To obtain a first electrolyte for depositing a Cu plating layer, the application determines the mass fractions of the pentahydrate copper sulfate, the ammonium sulfate, the boric acid and the sodium dodecyl sulfate, and adds dilute sulfuric acid to adjust the pH of the electrolyte to be acidic so as to prepare the first electrolyte for depositing the Cu plating layer.
As an embodiment of the present application, the step of dissolving copper sulfate pentahydrate and disodium ethylenediamine tetraacetate in water, standing, adding manganese sulfate monohydrate to dissolve, adding ammonium sulfate, boric acid and sodium dodecyl sulfate, and adjusting pH to acidity to obtain a second electrolyte for depositing Cu-Mn plating layer, comprises:
dissolving 2.5g/L-5g/L of copper sulfate pentahydrate and 2.5g/L-12.5g/L of disodium ethylenediamine tetraacetate in deionized water, standing for 50min-70min, adding 16.9g/L-33.8g/L of manganese sulfate monohydrate, dissolving, adding 9g/L-17g/L of ammonium sulfate, 3g/L-9g/L of boric acid and 0.005g/L-0.015g/L of sodium dodecyl sulfate, and adding 20% sulfuric acid to adjust pH to be acidic to obtain a second electrolyte for depositing Cu-Mn plating layers.
The application is to obtain a second electrolyte for depositing Cu-Mn plating layer, firstly, mixing and dissolving copper sulfate pentahydrate and disodium ethylenediamine tetraacetate, then adding manganese sulfate monohydrate, and using disodium ethylenediamine tetraacetate as complexing agent to make Cu 2+ And Mn of 2+ Complexing, pulling up the deposition potential of the two, adding ammonium sulfate, boric acid and sodium dodecyl sulfate, and adding dilute sulfuric acid to adjust the pH to be acidic, thus obtaining a second electrolyte capable of depositing the Cu-Mn plating layer.
As an embodiment of the present application, in the step of performing pulse electrodeposition, the deposition voltage is 120V, and the deposition duty ratio is 20% -80%.
As an embodiment of the present application, the method for preparing a Cu/Cu-Mn alloy plating layer on a surface of a metal connector, using a metal connector as a cathode and graphite as an anode, sequentially performing pulse electrodeposition in the first electrolyte and the second electrolyte, includes:
performing pulse electrodeposition for 10-30 min in the first electrolyte according to the deposition temperature of 25-45 ℃ to obtain a Cu plating layer with a first thickness on the surface of the metal connector;
and performing pulse electrodeposition for 10-40 min in the second electrolyte according to the deposition temperature of 25-55 ℃ to obtain a Cu-Mn coating with a second thickness on the surface of the Cu coating with the first thickness so as to obtain a Cu/Cu-Mn alloy coating on the surface of the metal connector.
The application firstly carries out pulse electrodeposition in the electrolyte for depositing the Cu plating layer, forms the Cu plating layer on the surface of the metal connector, can improve the high-temperature oxidation resistance of the metal connector, carries out pulse electrodeposition in the electrolyte for depositing the Cu-Mn plating layer after forming the Cu plating layer on the surface of the metal connector, and forms a layer of Cu-Mn plating layer on the Cu plating layer, thereby forming a double-layer oxidation resistant coating and further improving the high-temperature conductivity and oxidation resistance of the metal connector.
As one embodiment of the present application, the Cu/Cu-Mn alloy plating layer has a thickness of 20. Mu.m. The thickness of the Cu/Cu-Mn alloy plating layer finally obtained by pulse electrodeposition is 20 mu m, and the compact bonding strength with a metal connector is high.
As an embodiment of the present application, the first thickness is 7 μm and the second thickness is 13 μm.
As an embodiment of the present application, the Cu/Cu-Mn alloy plating layer is cleaned to remove the acidic electrolyte on the surface of the Cu/Cu-Mn alloy plating layer before the drying step.
In order to obtain the Cu/Cu-Mn double-layer coating with excellent performance, the Cu/Cu-Mn alloy coating is cleaned before being dried, so that the residual acid electrolyte on the surface of the Cu/Cu-Mn alloy coating is removed.
In one embodiment of the present application, in the step of drying the Cu/cu—mn alloy plating layer, the drying temperature is 60 ℃ to 80 ℃ and the drying time is 8h to 12h. Drying the Cu/Cu-Mn alloy coating, and removing residual liquid on the surface of the Cu/Cu-Mn alloy coating, so as to prepare for subsequent high-temperature sintering.
In one embodiment of the present application, in the step of sintering, the sintering temperature is 700 ℃ to 900 ℃ and the sintering time is 2h to 4h.
In order to obtain a Cu/Cu-Mn double-layer coating with higher compactness, the Cu/Cu-Mn alloy coating is sintered at high temperature, so that the compactness of the Cu/Cu-Mn double-layer coating can be improved, and the mechanical property and the chemical property of the Cu/Cu-Mn double-layer coating are more stable.
The above technical scheme of the present application will be described in detail with reference to specific embodiments.
Example 1
The preparation method of the Cu-based double-layer coating on the surface of the SOFC metal connector comprises the following steps:
adding 15g/L of copper sulfate pentahydrate, 9g/L of ammonium sulfate, 1.8 of boric acid and 0.0075g/L of sodium dodecyl sulfate into deionized water for dissolution, and adding 20% of sulfuric acid to adjust the pH to be acidic to obtain a first electrolyte for depositing a Cu coating;
dissolving 2.5g/L of copper sulfate pentahydrate and 7.5g/L of disodium ethylenediamine tetraacetate in deionized water, standing for 60min, adding 16.9g/L of manganese sulfate monohydrate, dissolving, adding 13g/L of ammonium sulfate, 6g/L of boric acid and 0.01g/L of sodium dodecyl sulfate, and adding 20% sulfuric acid to adjust the pH to be acidic to obtain a second electrolyte for depositing a Cu-Mn coating;
taking an SUS 430 stainless steel substrate as a cathode and a graphite plate as an anode, firstly performing pulse electrodeposition in the first electrolyte for 15min at a deposition temperature of 25 ℃ to obtain a Cu plating layer with a thickness of 7 mu m, then performing pulse electrodeposition in the second electrolyte for 25min at a deposition temperature of 35 ℃ to obtain a Cu-Mn plating layer with a thickness of 13 mu m, wherein in the two pulse electrodeposition processes, the deposition voltage is 120V, the deposition duty ratio is 20% -80%, and a Cu/Cu-Mn alloy plating layer is obtained on the surface of a metal connector, and the thickness of the Cu/Cu-Mn alloy plating layer is 20 mu m;
and cleaning the Cu/Cu-Mn alloy plating layer, removing the acidic electrolyte on the surface of the Cu/Cu-Mn alloy plating layer, drying the Cu/Cu-Mn alloy plating layer at the drying temperature of 70 ℃ for 10 hours, sintering at the sintering temperature of 800 ℃ for 4 hours, and obtaining the finished Cu/Cu-Mn double-layer coating.
Example 2
The preparation method of the Cu-based double-layer coating on the surface of the SOFC metal connector comprises the following steps:
adding 10g/L of copper sulfate pentahydrate, 6g/L of ammonium sulfate, 1.2g/L of boric acid and 0.005g/L of sodium dodecyl sulfate into deionized water for dissolution, and adding 20% of sulfuric acid to adjust the pH to be acidic to obtain a first electrolyte for depositing a Cu coating;
dissolving 2.5g/L of copper sulfate pentahydrate and 2.5g/L of disodium ethylenediamine tetraacetate in deionized water, standing for 50min, adding 16.9g/L of manganese sulfate monohydrate, dissolving, adding 9g/L of ammonium sulfate, 3g/L of boric acid and 0.005g/L of sodium dodecyl sulfate, and adding 20% sulfuric acid to adjust the pH to be acidic to obtain a second electrolyte for depositing a Cu-Mn coating;
taking an SUS 430 stainless steel substrate as a cathode and graphite as an anode, firstly performing pulse electrodeposition in the first electrolyte for 10min at a deposition temperature of 25 ℃ to obtain a Cu plating layer with a thickness of 7 mu m, then performing pulse electrodeposition in the second electrolyte for 10min at a deposition temperature of 25 ℃ to obtain a Cu-Mn plating layer with a thickness of 13 mu m, and obtaining a Cu/Cu-Mn alloy plating layer with a deposition voltage of 120V and a deposition duty ratio of 20% -80% on the surface of a metal connector in the two pulse electrodeposition processes, wherein the thickness of the Cu/Cu-Mn alloy plating layer is 20 mu m;
and cleaning the Cu/Cu-Mn alloy plating layer, removing the acidic electrolyte on the surface of the Cu/Cu-Mn alloy plating layer, drying the Cu/Cu-Mn alloy plating layer at the drying temperature of 60 ℃ for 8 hours, sintering at the sintering temperature of 700 ℃ for 2 hours, and obtaining the finished Cu/Cu-Mn double-layer coating.
Example 3
The preparation method of the Cu-based double-layer coating on the surface of the SOFC metal connector comprises the following steps:
adding 20g/L of copper sulfate pentahydrate, 12g/L of ammonium sulfate, 2.4g/L of boric acid and 0.01g/L of sodium dodecyl sulfate into deionized water for dissolution, and adding 20% of sulfuric acid to adjust the pH to be acidic to obtain a first electrolyte for depositing a Cu coating;
dissolving 5g/L of copper sulfate pentahydrate and 12.5g/L of disodium ethylenediamine tetraacetate in deionized water, standing for 70min, adding 33.8g/L of manganese sulfate monohydrate, dissolving, adding 17g/L of ammonium sulfate, 3g/L-9g/L of boric acid and 0.015g/L of sodium dodecyl sulfate, and adding 20% sulfuric acid to adjust the pH to be acidic to obtain a second electrolyte for depositing a Cu-Mn coating;
taking an SUS 430 stainless steel substrate as a cathode and graphite as an anode, firstly performing pulse electrodeposition in the first electrolyte for 30min at a deposition temperature of 45 ℃ to obtain a Cu plating layer with a thickness of 7 mu m, then performing pulse electrodeposition in the second electrolyte for 40min at a deposition temperature of 55 ℃ to obtain a Cu-Mn plating layer with a thickness of 13 mu m, wherein in the two pulse electrodeposition processes, the deposition voltage is 120V, the deposition duty ratio is 20% -80%, and a Cu/Cu-Mn alloy plating layer is obtained on the surface of a metal connector, and the thickness of the Cu/Cu-Mn alloy plating layer is 20 mu m;
and cleaning the Cu/Cu-Mn alloy plating layer, removing the acidic electrolyte on the surface of the Cu/Cu-Mn alloy plating layer, drying the Cu/Cu-Mn alloy plating layer at 80 ℃ for 12 hours, sintering at 900 ℃ for 4 hours, and obtaining the finished Cu/Cu-Mn double-layer coating.
Comparative example 1
Compared with example 1, pulse electrodeposition of Cu plating was performed only on SUS 430 stainless steel substrate, and the remaining steps were unchanged, resulting in Cu coating.
Comparative example 2
Compared with example 1, pulse electrodeposition of Cu-Mn plating was performed only on SUS 430 stainless steel substrate, and the remaining steps were unchanged, resulting in Cu-Mn coating.
Comparative example 3
Cutting SUS 430 stainless steel substrate into sheet samples of 20mm multiplied by 2mm, sequentially polishing the surfaces of the sheet samples by using 400-mesh, 600-mesh, 800-mesh, 1000-mesh, 1200-mesh and 1500-mesh sand paper, polishing by using a diamond polishing agent, and then ultrasonically cleaning and drying;
the dried sheet sample was placed in 10% H 2 SO 4 Removing surface oxide layer in the solution, and adding 5% HCl+25% HNO 3 Performing activation treatment in the mixed solution of (2) for 30s;
and (3) placing the activated sheet sample into a muffle furnace for high-temperature sintering at 800 ℃ for 4 hours to obtain a non-coating comparative sample.
Experimental example
Because the metal connector reacts with oxygen in the air at high temperature to generate non-conductive oxides, such as nickel oxide, iron oxide and other metal oxides, the oxides can adhere to the surface of the metal connector, the quality of the metal connector is increased, and the conductivity of the metal connector is reduced. In this experiment, the coating in example 1 and comparative examples 1-2 and the uncoated comparative sample in comparative example 3 were subjected to cyclic oxidation in a muffle furnace, and the oxidation weight gain conditions before and after the oxidation were observed with air as an atmosphere, the oxidation temperature was 800 ℃, the oxidation time was 168 hours, and the cycle interval time was 24 hours. The oxidation weight gain curves of the uncoated comparative sample, the Cu coating sample, the Cu-Mn coating sample and the Cu/Cu-Mn coating sample shown in the figure 1 after the high-temperature cyclic oxidation at 800 ℃ for 168 hours are obtained.
As can be seen from FIG. 1, the oxidation weight gain rate and weight gain amount of the coated sample were significantly lower than those of the uncoated comparative sample, and the oxidation weight gain of the uncoated comparative sample was 0.2614mg/cm after being oxidized for 168 hours at 800 ℃ in a high-temperature cycle 2 The oxidation weight gain of the Cu coated sample was 0.1716mg/cm 2 The oxidation weight gain of the Cu-Mn coating sample was 0.1423mg/cm 2 The oxidation weight gain of the Cu/Cu-Mn coating sample was 0.1192mg/cm 2 Compared with a non-coated comparative sample, the oxidation weight of the Cu/Cu-Mn coated sample is reduced by about 54%, and the Cu/Cu-Mn coated sample has the least oxidation weight, so that the continuous oxidation of the substrate can be effectively delayed by preparing the coating on the surface of the substrate after high-temperature oxidation, and the high-temperature oxidation resistance of the Cu/Cu-Mn double-layer coating is optimal.
The foregoing description is only of the optional embodiments of the present application, and is not intended to limit the scope of the application, and all the equivalent structural changes made by the description of the present application and the accompanying drawings or the direct/indirect application in other related technical fields are included in the scope of the application.
Claims (10)
1. The preparation method of the Cu-based double-layer coating on the surface of the SOFC metal connector is characterized by comprising the following steps of:
adding copper sulfate pentahydrate, ammonium sulfate, boric acid and sodium dodecyl sulfate into water for dissolution, and adjusting pH to be acidic to obtain a first electrolyte for depositing a Cu coating;
dissolving copper sulfate pentahydrate and disodium ethylenediamine tetraacetate in water, standing, adding manganese sulfate monohydrate to dissolve, adding ammonium sulfate, boric acid and sodium dodecyl sulfate, and regulating pH to be acidic to obtain a second electrolyte for depositing a Cu-Mn coating;
sequentially performing pulse electrodeposition in the first electrolyte and the second electrolyte by taking a metal connector as a cathode and graphite as an anode to obtain a Cu/Cu-Mn alloy coating on the surface of the metal connector;
and drying the Cu/Cu-Mn alloy coating, and sintering to obtain the finished Cu/Cu-Mn double-layer coating.
2. The method for preparing a Cu-based bilayer coating on a surface of a metal connector as recited in claim 1, wherein the step of adding copper sulfate pentahydrate, ammonium sulfate, boric acid and sodium dodecyl sulfate to water for dissolution and adjusting pH to acidity to obtain a first electrolyte for depositing a Cu plating layer comprises:
10g/L-20g/L of copper sulfate pentahydrate, 6g/L-12g/L of ammonium sulfate, 1.2g/L-2.4g/L of boric acid and 0.005g/L-0.01g/L of sodium dodecyl sulfate are added into deionized water for dissolution, and 20% sulfuric acid is added for regulating the pH to be acidic, so that a first electrolyte for depositing a Cu coating is obtained.
3. The method for preparing a Cu-based bilayer coating on a surface of a metal connector of an SOFC according to claim 1, wherein the step of dissolving copper sulfate pentahydrate and disodium ethylenediamine tetraacetate in water, standing, adding manganese sulfate monohydrate, dissolving, adding ammonium sulfate, boric acid and sodium dodecyl sulfate, and adjusting pH to acidity to obtain a second electrolyte for depositing a Cu-Mn plating layer comprises:
dissolving 2.5g/L-5g/L of copper sulfate pentahydrate and 2.5g/L-12.5g/L of disodium ethylenediamine tetraacetate in deionized water, standing for 50min-70min, adding 16.9g/L-33.8g/L of manganese sulfate monohydrate, dissolving, adding 9g/L-17g/L of ammonium sulfate, 3g/L-9g/L of boric acid and 0.005g/L-0.015g/L of sodium dodecyl sulfate, and adding 20% sulfuric acid to adjust pH to be acidic to obtain a second electrolyte for depositing Cu-Mn plating layers.
4. The method for preparing a Cu-based bilayer coating on a surface of a metal connector as recited in claim 1, wherein in the step of performing pulsed electrodeposition, the deposition voltage is 120V and the deposition duty cycle is 20% -80%.
5. The method for preparing the Cu-based bilayer coating on the surface of the SOFC metal connector according to claim 1, wherein the step of sequentially performing pulse electrodeposition in the first electrolyte and the second electrolyte with the metal connector as a cathode and graphite as an anode to obtain a Cu/Cu-Mn alloy coating on the surface of the metal connector comprises the steps of:
performing pulse electrodeposition for 10-30 min in the first electrolyte according to the deposition temperature of 25-45 ℃ to obtain a Cu plating layer with a first thickness on the surface of the metal connector;
and performing pulse electrodeposition for 10-40 min in the second electrolyte according to the deposition temperature of 25-55 ℃ to obtain a Cu-Mn coating with a second thickness on the surface of the Cu coating with the first thickness so as to obtain a Cu/Cu-Mn alloy coating on the surface of the metal connector.
6. The method for preparing a Cu-based bilayer coating for a SOFC metal connector surface of claim 5, wherein the Cu/Cu-Mn alloy plating has a thickness of 20 μm.
7. The method of claim 6, wherein the first thickness is 7 μm and the second thickness is 13 μm.
8. The method for preparing a Cu-based bilayer coating on a surface of a SOFC metal interconnect according to claim 1, wherein the Cu/Cu-Mn alloy coating is cleaned to remove the acidic electrolyte from the surface of the Cu/Cu-Mn alloy coating prior to the step of drying the Cu/Cu-Mn alloy coating.
9. The method for preparing a Cu-based bilayer coating on a surface of a SOFC metal connector according to claim 1, wherein in the step of drying the Cu/Cu-Mn alloy plating layer, the drying temperature is 60-80 ℃ and the drying time is 8-12 h.
10. The method for preparing a Cu-based bilayer coating on a surface of a metal connector as recited in claim 1, wherein in the step of sintering, the sintering temperature is 700 ℃ to 900 ℃ and the sintering time is 2h to 4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310895895.9A CN116905059A (en) | 2023-07-20 | 2023-07-20 | Preparation method of Cu-based double-layer coating on surface of SOFC (solid oxide fuel cell) metal connector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310895895.9A CN116905059A (en) | 2023-07-20 | 2023-07-20 | Preparation method of Cu-based double-layer coating on surface of SOFC (solid oxide fuel cell) metal connector |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116905059A true CN116905059A (en) | 2023-10-20 |
Family
ID=88366396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310895895.9A Pending CN116905059A (en) | 2023-07-20 | 2023-07-20 | Preparation method of Cu-based double-layer coating on surface of SOFC (solid oxide fuel cell) metal connector |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116905059A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117071014A (en) * | 2023-10-12 | 2023-11-17 | 成都岷山绿氢能源有限公司 | Preparation method of rare earth modified coating on surface of SOFC (solid oxide Fuel cell) metal connector |
-
2023
- 2023-07-20 CN CN202310895895.9A patent/CN116905059A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117071014A (en) * | 2023-10-12 | 2023-11-17 | 成都岷山绿氢能源有限公司 | Preparation method of rare earth modified coating on surface of SOFC (solid oxide Fuel cell) metal connector |
| CN117071014B (en) * | 2023-10-12 | 2024-01-26 | 成都岷山绿氢能源有限公司 | Preparation method of rare earth modified coating on surface of SOFC (solid oxide Fuel cell) metal connector |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101736390B (en) | Lead dioxide electrode plate and preparation method thereof | |
| CN103746128B (en) | High-temperature solid oxide battery metal connector surface duplex coating and preparation method | |
| CN116905059A (en) | Preparation method of Cu-based double-layer coating on surface of SOFC (solid oxide fuel cell) metal connector | |
| CN107142485B (en) | A kind of method of mesohigh anode high-purity aluminum foil surface generalization modification | |
| CN111600036A (en) | Three-dimensional porous copper oxide modified copper foil for lithium metal battery current collector and preparation method and application thereof | |
| CN101694005A (en) | Activated solution of magnesium alloy surface micro-arc oxidation ceramic coating surface and activation method | |
| CN104393315A (en) | Solid oxide fuel cell stainless steel bipolar connector and manufacturing method thereof | |
| CN108270011B (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN111593379B (en) | Electroplating method for preparing (Ni, co, cu) 3 O 4 Method for coating spinel and application thereof | |
| CN103151424B (en) | A kind of improvement chemical plating process prepares the method for metal electrode at porous silicon surface | |
| CN101892502A (en) | Copper-chromium-molybdenum ternary alloy coating and preparation method thereof | |
| CN113328111B (en) | Stainless steel bipolar plate with chromium-based nitride composite coating and preparation method thereof | |
| CN102673040B (en) | Cu-Ni functionally gradient material and preparation method thereof | |
| CN112779574B (en) | Electroplating solution for enhancing conductivity of electronic copper foil, preparation method and electroplating process | |
| CN117071014B (en) | Preparation method of rare earth modified coating on surface of SOFC (solid oxide Fuel cell) metal connector | |
| CN113293411B (en) | Gradient composite lead dioxide anode plate and preparation method and application thereof | |
| CN103474642B (en) | A kind of tin oxide negative material for lithium ion battery and preparation method thereof | |
| CN103280567B (en) | A kind of surface chemical metal plating modifies Li4ti5o12and preparation method thereof | |
| CN102978629B (en) | Preparation method and application of SERS (surface enhanced Raman scattering) substrate of Mo/Ag laminated metal-matrix composite material | |
| CN101425586B (en) | Modification method for thin-film aluminum dual polar plates of proton exchange membrane fuel cell | |
| CN104218245B (en) | A kind of preparation method of titanium/Asia titanium oxide/lead composite base plate | |
| CN106011958A (en) | Copper-manganese alloy plating solution for preparing copper-manganese spinel coating and use thereof | |
| CN103490053A (en) | CNTS-doped tin oxide negative electrode material for lithium-ion battery and preparation method thereof | |
| CN110474058B (en) | Preparation method of cathode oxygen reduction electrocatalytic Pt electrode by template method | |
| CN202326732U (en) | Improved bearing bush |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |