CN1329969A - Method for preparing one-sided platinum plated refractory metal plate and extended metal grid - Google Patents

Method for preparing one-sided platinum plated refractory metal plate and extended metal grid Download PDF

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Publication number
CN1329969A
CN1329969A CN01115982A CN01115982A CN1329969A CN 1329969 A CN1329969 A CN 1329969A CN 01115982 A CN01115982 A CN 01115982A CN 01115982 A CN01115982 A CN 01115982A CN 1329969 A CN1329969 A CN 1329969A
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CN
China
Prior art keywords
platinum
refractory metal
plate
metal plate
sided
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Pending
Application number
CN01115982A
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Chinese (zh)
Inventor
托马斯·恩格特
格哈德·施泰因希尔伯
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Umicore Galvanotechnik GmbH
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Degussa Galvanotechnik GmbH
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Publication of CN1329969A publication Critical patent/CN1329969A/en
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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
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/028—Electroplating of selected surface areas one side electroplating, e.g. substrate conveyed in a bath with inhibited background plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • 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
    • C25D3/66—Electroplating: Baths therefor from melts
    • 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
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/026—Electroplating of selected surface areas using locally applied jets of electrolyte

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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 Methods And Accessories (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

A process for the production of refractory metal plates platinized on one side, in which refractory metal plates of predetermined dimensions are tightly, form-fittingly joined together back to back, are coated with platinum on their exposed surfaces by melt electrolysis and the plates are then separated one from the other. These plates may be processed into expanded metal grids platinized on one side. These refractory metal plates platinized on one side and the expanded metal grids platinized on one side produced therefrom may be used highly advantageously as anodes in electrolytic and electroplating processes.

Description

The preparation method of the one-sided platinum plated refractory metal plate and the metal gates of extension
The present invention relates to the preparation method of the metal gates of one-sided platinum plated refractory metal plate and extension.
Refractory metal plate that platinum applies or sheet and the anode of metal gates in being commonly used for electrolysis or electroplating process of the extension of preparation thus.Its typical application is for example, to be used as inert anode when electro-deposition of metal and alloy-layer, in the preparation especially for noble metal or precious metal alloys decoration and/or functional coating.It is further used as electrode and is applied to processing by bichromate electrolytic preparation chromic acid, chromic acid (with Cr 3+Be oxidized to Cr 6+), in electrolytic recovery, electrodialysis and the cathodic anti-corrosion of the oxidation of cyanide, metal.
The method of the refractory metal plate of traditional preparation platinum plating is based on roll extrusion one bonding (roll-bonding), wherein thin platinum foil is rolled to the one or both sides of refractory metal plate.Can delineate plate by known method then, and stretch, thus the metal gates of preparation extension.Since mechanically with handle, it is about 3 microns at least that said method causes the minimum thickness of platinum foil, can not further reduce the thickness of expensive platinum foil.
In theory, can platinum be deposited on the refractory metal with desirable thickness by electrochemical method.Certainly, the both sides that are suspended in the refractory metal plate in the platinum electroplating bath have all been applied by platinum.But as electrode, it is just enough only to electroplate a side, can further save expensive platinum like this.Yet partly covering refractory metal plate effectively under the aggressive conditions of platinum electroplate liquid is impossible basically, and this needs extra material and processing cost.
From the aqueous electrolyte electrocladding refractory metal is extremely difficult, and this is owing to formed the protectiveness film simultaneously in aqueous solution.The pre-grinding light time in refining dipping process,, can cause the bonding insufficient of coating mainly due to mechanical adhesion.Can in reducing atmosphere, heat-treat so that bonding improving.Codeposition hydrogen can make the platinum coating become fragile owing to having mixed hydrogen in the process of platinum deposition.
To the cohesive deficiency of refractory metal, and the low ductility of the platinum coating of aqueous solution deposition makes it can not be used to relate to big mechanical stress and distortion, particularly in the application of the metal gates that is extended by plate that applies or sheet preparation.
Therefore, the objective of the invention is to develop a kind of method, can prepare the one-sided platinum plated refractory metal plate that is more suitable for being used for preparing the metal gates of extension, for example as the electrode in electrolysis and the electroplating process by this method.
Through finding that above-mentioned purpose can realize by following method: the refractory metal plate of the form fit of two preliminary dimensions is closely linked back-to-back, applies the surface of their exposures with platinum, then they are separated from each other by fusion electrolysis.
The method according to this invention is by fastening or welding can make in advance the refractory metal plate form fit that is applied by platinum easily and be closely linked with screw with the edge of plate.Described plate is cut into needed size.The plate that is of a size of 400 * 600mm is more typical.Provide enough suitable assembly holes at the edge of plate, assembling screw leans against two boards privately by these holes and is fixed together.When being welded to connect, will harden by spot welding or sequential welding at the edge of two blocks of plates that are close together lumps together.
Described refractory metal can be the alloy of titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten or these metals.Titanium is particularly preferred.
At plate combined and apply before, preferably remove the oxide on plate surface and activate the surface on these surfaces, particularly pre-coated platinum.Method is with sand friction (sandblasting) or floods in the acid of for example nitric acid/hydrofluoric acid mixture easily.
By fusion electrolysis platinum being carried out on the surface of the exposure of a pair of plate of assembling applies.Described plate is placed the electroplating unit of a traditional suitable fusion electrolysis, be connected to negative electrode.Plating is carried out in the fused mass of Cymag and potassium cyanide, and temperature is between 500 ℃ to 600 ℃, and the form with the solubility antianode provides pure platinum coating on pre-coated refractory metal plate thus.Molten electrolyte preferably is made up of the Cymag of about 50 weight % and the potassium cyanide of about 50 weight %, and when operation, platinum content is about 0.5-3 weight %.Preferred 1-the 5A/dm that uses 2Current density.The thickness of the platinum coating that will obtain is by the time control of current density and coating operation.The coating of preferred for preparation 0.5-2.5 μ m thickness.Under specific situation, can certainly obtain the coating layer thickness of some greatly, for example can reach 10 μ m.
After a pair of plate is finished by plating, by unscrewing screw and/or pruning away the edge and plate is separated.
Through after the known cleaning and drying process, just obtained required one-sided platinum plated refractory metal plate or sheet, they can be used for required purposes or be further processed.
After coating was finished, the treatment step of next step of separated plate can be to heat-treat under 500-650 ℃ in oxygen containing atmosphere, the surface of a side that is not applied by platinum with oxidation.Heat treatment can continue 1-60 minutes.Heat treatment is passivation one side of not electroplated at first, and this is used as electrode to it in electrolytic process be very important, because a side of only wishing to be electroplated is as functional layer.In addition, not coated side of heat treatment oxidation refractory metal causes this side to have and the visibly different outward appearance of a side of electroplating.When during as basic material, forming the blueness of distinct easy identification in not function one side with titanium.This has guaranteed can easily distinguish functional layer and NOT function ergosphere when practical application.
Another processing procedure is, plate delineated and stretched form the metal gates of one-sided platinum plated extension.The metal gates that preparation is extended is known technology, does not need more detailed description at this.Typical order size (mesh dimensions) is about 10 * 5 * 1 * 1mm.Under with the situation of drawn metal grid, after the metal gates that extends is produced out, easily heat-treats with passivation and distinguish not function one side it as electrode.According to the needs of using, the drawn metal grid can be cut into required form subsequently and/or form suitable electrode size.
Method of the present invention is not only compared with traditional rolling-associated methods, thereby can save platinum by the thickness that reduces the platinum coating, and because method of the present invention has realized one-sided plating, compare with the drawn metal grid that bilateral is electroplated, the present invention can save platinum about 70%, electroplate the refractory metal plate of monoblock with bilateral and compare, the present invention can save about 48% platinum.Give the cohesive of platinum coating excellence by the plating of fusion electrolysis, when particularly planning to carry out one-sided coating.This cohesive shows especially when plate and is subjected to the flexural stress of strong mechanical stress-for example and when carrying out stretched operation, these can take place when operating in preparation drawn metal grid usually.
Fig. 1 is the cross section enlarged drawing of the one-sided platinum plated titanium drawn metal grid of the inventive method preparation.From figure, can be clear that the platinum coating (light color) that does not have crackle that is close to titanium basic material (dark color) surface.
The one-sided platinum plated drawn metal grid of one-sided platinum plated refractory metal plate prepared according to the methods of the invention and thus preparation has a lot of advantages as the anode in electrolysis and the electroplating process.

Claims (9)

1. the preparation method of one-sided platinum plated refractory metal plate is characterized in that being combined closely back-to-back in the refractory metal plate form fit ground with preliminary dimension, applies platinum by fusion electrolysis on the surface of the exposure of described plate, then they is separated from each other.
2. the method for claim 1 is characterized in that the combining closely of form fit of the refractory metal plate of pre-coated platinum is to realize by or welding fastening at the edge of plate usefulness screw.
3. the method for claim 2 is characterized in that making plate separately by the described edge that prunes away.
4. the method for claim 1-3 is characterized in that described refractory metal is the alloy of titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten or these metals.
5. the method for claim 1-4 is characterized in that providing the platinum coating under 500-600 ℃ of temperature in fusion Cymag and potassium cyanide, wherein the form of pure platinum coating with the solubility antianode is provided on the described pre-coated refractory metal plate.
6. the method for claim 1-5 is characterized in that applying in case finish, and the plate that separates is heat-treated a side that is not applied by platinum with oxidation in containing the atmosphere of aerobic at 500-650 ℃.
7. the method for claim 1-6 is characterized in that described plate delineated and stretch forming the metal gates of one-sided platinum plated extension.
The one-sided platinum plated refractory metal plate of claim 1-6 method preparation in electrolysis and electroplating process as the application of anode.
The described one-sided platinum plated refractory metal grid of claim 7 in electrolysis and electroplating process as the application of anode.
CN01115982A 2000-06-16 2001-06-15 Method for preparing one-sided platinum plated refractory metal plate and extended metal grid Pending CN1329969A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10029837.0 2000-06-16
DE10029837A DE10029837B4 (en) 2000-06-16 2000-06-16 Process for the production of unilaterally platinated plates and expanded metal gratings of refractory metals

Related Child Applications (1)

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CN02130365A Division CN1439745A (en) 2000-06-16 2002-08-16 One sided platinizing refractory metal plate and preparation for extended metal grid

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CN02130365A Pending CN1439745A (en) 2000-06-16 2002-08-16 One sided platinizing refractory metal plate and preparation for extended metal grid

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JP (1) JP2002030479A (en)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105324521A (en) * 2013-06-14 2016-02-10 Ｋｙｂ株式会社 Anode and high-speed plating device provided with same
US10006143B2 (en) 2013-06-14 2018-06-26 Kyb Corporation Power supplying member and high-speed plating machine provided with the same
US10006137B2 (en) 2013-06-14 2018-06-26 Kyb Corporation Holding device and high-speed plating machine provided with the same
CN108736017A (en) * 2017-04-20 2018-11-02 徐煜 A kind of electrode plate for hydrogen fuel cell
CN113481505A (en) * 2021-07-07 2021-10-08 南京科技职业学院 Blind plate manufacturing method

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT13521U1 (en) * 2013-01-18 2014-02-15 Plansee Se module
CN110948182B (en) * 2019-11-11 2024-06-11 中国航天空气动力技术研究院 Forming method of refractory metal capillary core

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4923975B1 (en) * 1965-03-18 1974-06-19
DE2450291A1 (en) * 1974-10-23 1976-05-06 Friedrich Von Dipl Stutterheim PROCESS FOR CONTINUOUS ELECTROLYTIC METAL COATING OF WIRES, TAPES, CHAINS AND NETWORK TAPES
JPS53119226A (en) * 1977-03-28 1978-10-18 Sumitomo Metal Ind Ltd Continuous one-siede electroplating method
FR2426095A1 (en) * 1978-05-19 1979-12-14 Anger Roger ANODIC ELECTRODE STABLE IN DIMENSIONS AND MANUFACTURING PROCESS
DE3905082A1 (en) * 1989-02-18 1990-08-23 Bayer Ag STABLE ANODES AND THEIR USE IN THE PRODUCTION OF ALKALIDICHROMATES AND CHROME ACID

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105324521A (en) * 2013-06-14 2016-02-10 Ｋｙｂ株式会社 Anode and high-speed plating device provided with same
US10006143B2 (en) 2013-06-14 2018-06-26 Kyb Corporation Power supplying member and high-speed plating machine provided with the same
US10006137B2 (en) 2013-06-14 2018-06-26 Kyb Corporation Holding device and high-speed plating machine provided with the same
CN108736017A (en) * 2017-04-20 2018-11-02 徐煜 A kind of electrode plate for hydrogen fuel cell
CN113481505A (en) * 2021-07-07 2021-10-08 南京科技职业学院 Blind plate manufacturing method

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Publication number Publication date
EP1170401A2 (en) 2002-01-09
DE10029837B4 (en) 2005-02-17
CN1439745A (en) 2003-09-03
JP2002030479A (en) 2002-01-31
DE10029837A1 (en) 2002-01-03
EP1170401A3 (en) 2004-01-28

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