CN1319148A - Black ruthenium plating soluton - Google Patents
Black ruthenium plating soluton Download PDFInfo
- Publication number
- CN1319148A CN1319148A CN00801594A CN00801594A CN1319148A CN 1319148 A CN1319148 A CN 1319148A CN 00801594 A CN00801594 A CN 00801594A CN 00801594 A CN00801594 A CN 00801594A CN 1319148 A CN1319148 A CN 1319148A
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- China
- Prior art keywords
- black
- ruthenium
- soluton
- sulfocompound
- plating
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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
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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)
Abstract
A black ruthenium plating solution, characterized as containing, as effective components in the solution, ruthenium sulfate, sulfamic acid, a thio compound and a sacrificial oxidizing agent being added for preventing the decomposition of the thio compound due to anodic oxidation. The plating solution can be used for inhibiting the decomposition of a thio compound being added as a color former due to anodic oxidation, to thereby maintain dense blackness during electrolysis and thus provide a stable black plating, while keeping the desirable characteristics of a conventional black ruthenium plating solution that it can be controlled with ease, has good gloss, exhibits good adhesion to a substrate, and is excellent in the resistance to corrosion and abrasion.
Description
Technical field
The present invention relates to black ruthenium plating soluton, this electroplate liquid since make in the electrolysis on the anode as sulphur compound stabilization in solution of chromogenic reagent, and can keep the dense blackness of ruthenium electroplating film.
Technical background
As everyone knows, as the electroplate liquid of ruthenium, used complex salt, ruthenium chloride, the ruthenium sulfate of ruthenium.
These mainly are to utilize platinum to electroplate the titanium plate to make anode, are made negative electrode by electronplate, switched on by anode and negative electrode are immersed in the above-mentioned electroplate liquid, thereby separate out electroplating film on negative electrode.
Because the effect of the chromogenic reagent that contains in the solution is so the ruthenium electroplating film can send black, as this chromogenic reagent, preferred especially with sulphur compound.
The black electroplating film is as industrial cut stocks such as decorative platings such as watchcase, spectacle frame, literal dish, lighter shell, lipstick cap or electrical contact, speculum, heat-absorbing bodys, and its value is high especially.As the effective technology example of this black ruthenium plating soluton, special public clear 63-9027 and the clear 63-259095 of Te Kai disclose.
The feature of above-mentioned black ruthenium plating soluton in the past is: management easily; And it is good with tackiness with glossy base material; Erosion resistance and high abrasion resistance.
, a very big problem is arranged, that is exactly characteristic or the function that is difficult to keep as the sulphur compound chromogenic reagent that is added, because the anodic oxidation in the electrolysis, sulphur compound decomposes, and carries out along with electrolytic, and blackness has the tendency that shoals.
Because this situation, when electroplating with black ruthenium plating soluton, the blackness instability if want in the past to keep the blackness that black ruthenium is electroplated the initial stage, just must be added sulfocompound continually.
Here it is the significantly reduced problem of production efficiency, in fact owing to organizing such production system very difficult, so even in the field that requires dense blackness, also often have to compromise with the somber degree that reduces colourity.
According to above-mentioned situation, as problem be: keep the characteristic of ruthenium plating soluton always, promptly electroplate liquid is easy to management; And it is good with the tackiness of glossiness base material; The feature that erosion resistance and high abrasion resistance are such, meanwhile, the decomposition that the sulfocompound that suppresses to add as chromogenic reagent takes place owing to anodic oxidation in electrolysis maintains blackness dense in the electrolytic process, electroplates thereby obtain stable black.
Disclosure of an invention
The present inventor finds, the reason that blackness descends in such black ruthenium is electroplated be owing in electrolysis as the sulfocompound of chromogenic reagent due to oxidized decomposition was lost efficacy on anode, know by making sulfocompound stabilization in electroplate liquid, can keep the dense blackness of ruthenium electroplating film.
According to these experiences, the invention provides:
1, black ruthenium plating soluton is characterized in that: contain ruthenium sulfate, thionamic acid, sulfocompound and for preventing owing to sulfocompound due to the anodic oxidation in the electrolysis decomposes the sacrificial oxidation agent of adding as electroplating bath components;
2, the black ruthenium plating soluton of being put down in writing in above-mentioned 1 is characterized in that: the sacrificial oxidation agent is selected from the sulfuric acid oxyamine, more than one in formalin and the xitix;
3, the black ruthenium plating soluton of being put down in writing in above-mentioned 1 or 2 is characterized in that: sulfocompound is selected from sulphur, thiourea derivative, contain in the compound of sulfydryl, mercaptosuccinic acid, the ammonium thiocyanate etc. more than one.
The working of an invention scheme
The sacrificial oxidation agent has been added in the decomposition of the sulfocompound that anodic oxidation causes when preventing electrolysis in the ruthenium plating soluton in black ruthenium plating soluton of the present invention.
Thus, the oxidizing reaction of sacrificial oxidation agent is carried out as main reaction on anode, and the oxidizing reaction of sulfocompound can take place hardly.
Therefore, always for making since due to the sulfocompound black of electroplating film turn into and the unlikely deterioration of effect, resembles and must add sulfocompound continually above-mentioned, and the present invention is opposite with it, even do not carry out the supply of sulfocompound, also can keep dense blackness.
Black ruthenium plating soluton of the present invention contains ruthenium sulfate, thionamic acid, sulfocompound and the sacrificial oxidation agent for preventing to add owing to the decomposition of the caused sulfocompound of anodizing in electrolysis.
Ruthenium sulfate has constituted the source metal of the ruthenium of separating out as electroplating film, as the concentration of ruthenium, the viewpoint of the clean caused ruthenium loss (so-called " draining out ") of electrodeposit it seems that the concentration of 1～10 grams per liter suits the requirements from current efficiency, electroplating time and processing.But, be not defined in this concentration especially.
Thionamic acid can suppress can carry out stable ruthenium electroplating operations because the instability of anodic oxidation and the caused ruthenium ion valence of cathodic reduction can prevent the generation of non-metallic low valence ruthenium when using ruthenium sulfate.As this concentration, 50～150 grams per liters are suitable, but there is no need to be limited to especially these concentration.
Sulfocompound is the material that adds for the tone blackization of the electroplating film that makes ruthenium, with regard to sulfocompound, can use in the compound that is selected from thiocarbamide, thiourea derivative, has sulfydryl, mercaptosuccinic acid, ammonium thiocyanate etc. more than one, can be in acidic solution dissolved substances.Particularly from the stability and the price angle of this compound, thiocarbamide is only.
The concentration of sulfocompound is high more, just can obtain dense blackness more; Otherwise, excessive concentration, then electroplate liquid can become unstable.With regard to concentration, 0.1～10.0 grams per liter, particularly 1.0～5.0 grams per liters are suitable.
Use is more vulnerable to anodised material as decomposing the sacrificial oxidation agent of adding for the sulfocompound that prevents to cause because of anodic oxidation in the electrolysis than sulfocompound.
This is subjected to anodic oxidation this compound in electrolysis, change and be consumed, and the compound of compound itself and oxidation must not have influence to the evolution reaction of ruthenium.
With regard to this sacrificial oxidation agent, can list sulfuric acid oxyamine, formalin, xitix or the like.Particularly even the sulfuric acid oxyamine oxidized, remains in the electroplate liquid, also can not exert an influence to electroplating film, so be the most effective.
This sacrificial oxidation agent if be present in fact in the electroplate liquid, then has the effect of the oxygenolysis that prevents sulfocompound, so concentration is not made special regulation, common 0.1～100 grams per liter is suitable.
In black ruthenium plating soluton of the present invention, can adjust use aptly to pH, current density, temperature.Specifically, pH less than 2, current density 5～15 peace/decimetres
2, solution temperature be suitable more than 40 ℃.
Again, carrying out the galvanized base material of black ruthenium of the present invention (starting material) is suitable to implement flash plate gold person again on electroless nickel layer.
Generally use the titanium of platinum or lily gilding as anode again.
But these conditions are selected unnecessary these conditions that are confined to especially aptly by the technician of this technology on top of according to the shape of equipment and plated body product.
Embodiment and comparative example
To describe according to embodiment and comparative example below.And these examples only are an example on earth, there is no need to be confined to this example.That is to say, present invention resides in the whole of other form, distortion or the example that are comprised in the technology of the present invention thought.
Prepared the ruthenium plating soluton of following composition.
Ruthenium sulfate (with regard to ruthenium) 3 grams per liters
Thionamic acid 100 grams per liters
Thiocarbamide 1.5 grams per liters
Then, this electroplate liquid is divided into three parts, two portions add sulfuric acid oxyamine 10 grams per liters, 50 grams per liters respectively as embodiment 1 and example 2, and as the sacrificial oxidation agent, a remaining part is not added the sulfuric acid oxyamine, is used as comparative example.
Use this three kinds of electroplate liquids, repeat to implement to electroplate.Galvanized condition is as follows.
(plating condition)
PH: about 0.1
Cathode current density: 5 peace/decimetres
2
Solution temperature: 50 ℃
Anode: platinum plate
Electroplating time: 30 minutes/time
Base material has used on the sheet brass of electronickelling in common watt is bathed and has carried out flash plate gold person.
Measure 5 ampere-hours/when rising, observe resulting electroplating film state etc. in each energising, it the results are shown in table 1.
Moreover, embodiment 1 since heavy addition as the sulfuric acid oxyamine of sacrificial oxidation agent, so in the galvanized process of black ruthenium, do not need to replenish the sacrificial oxidation agent, but, among the embodiment 2, few at the addition at the initial stage of plating as the oxammonium sulfate of sacrificial oxidation agent, again because the sacrificial oxidation agent is consumed along with plating, institute thinks and keeps concentration and replenish.
Embodiment 1 and example 2 can stably obtain the black ruthenium electroplating film in succession.
In contrast, if in comparative example, seldom replenish thiocarbamide, then can not get black film, its blackness also is the film of light/dark balance at the plating initial stage, formed subfuscous silver color film along with galvanized, 25 ampere-hours/liter and 30 ampere-hours/liter stage, if add the thiocarbamide of 3 grams per liters more respectively, then form the dark brown film of lacklustre ash, make electroplate liquid take place to mix dense.
Therefore, if thiocarbamide replenishes excessively, then electroplate liquid is mixed dense, becomes unstable, does not form dense black plated film, can not get good electroplating film.
Therefore, rely on the sulfuric acid oxyamine that adds as sacrificial oxidation agent of the present invention, black ruthenium is electroplated the electroplating film that can stably obtain dense blackness.Again, sacrificial oxidation agent such as sulfuric acid oxyamine can not constitute obstacle fully for the formation of black ruthenium electroplating film.
The sulfuric acid oxyamine is very resultful as the sacrificial oxidation agent, and other sacrificial oxidation agent of the present invention also roughly obtains same effect.Again, the sulfocompound except that thiocarbamide also obtains same result.
Table 1
| 5 ampere-hours/liter | 10 ampere-hours/liter | 15 ampere-hours/liter | 20 ampere-hours/liter | 25 ampere-hours/liter | 30 ampere-hours/liter | |
| Embodiment 1 | Black film | Black film | Black film | Black film | Black film | Black film |
| Embodiment 2 | Black film | Black film replenishes sulfuric acid oxyamine 5 and exempts from/liter | Black film replenishes sulfuric acid oxyamine 5 and exempts from/liter | Black film replenishes sulfuric acid oxyamine 5 and competes/liter | Black film replenishes sulfuric acid oxyamine 5 grams per liters | Black film replenishes sulfuric acid oxyamine 5 grams per liters |
| Comparative example | Shallow black film | Add the subfuscous silver color film of urea 1.5 grams per liters | Add the subfuscous silver color film of urea 1.5 grams per liters | Add the subfuscous silver color film of urea 1.5 grams per liters | Add the dark brown membrane electroplating liquid of the lacklustre ash of urea 3 grams per liters muddiness | Add the dark brown membrane electroplating liquid of the lacklustre ash of urea 3 grams per liters muddiness |
The invention effect
The reason that blackness descended when black ruthenium was electroplated is because in electrolysis, loses efficacy in the oxidized decomposition of anode as the sulfur-containing compound of colour former, utilizes the stabilisation of sulfur-containing compound in electroplate liquid, can make the ruthenium electroplating film keep dense blackness. Therefore, for preventing in black ruthenium plating soluton because the decomposition of the sulfur-containing compound that the anodic oxidation in the electrolysis causes is sacrificed oxidant and add. Thus, sacrifice the oxidation reaction of oxidant at anode and carry out as main reaction, have the remarkable result that causes hardly the selective oxidation of sulfur containing compounds in particular reaction.
Keeping characteristic as the always black ruthenium plating soluton of the original feature of black ruthenium plating soluton, be that electroplate liquid is easy to management; And good to the adherence of glossiness base material; Also has following excellent results in the time of corrosion resistance and high abrasion resistance: the decomposition that above-mentioned sacrifice oxidant inhibition causes owing to the anodic oxidation of sulfur-containing compound in electrolysis of adding as colour former, keep the dense blackness in the electrolytic process, electroplate thereby can obtain stable black.
Claims (3)
1. black ruthenium plating soluton is characterized in that: as the composition in the electroplate liquid, contain ruthenium sulfate, thionamic acid, sulfocompound and the sacrificial oxidation agent for preventing to add owing to the caused sulfocompound decomposition of anodic oxidation in the electrolysis.
2. the black ruthenium plating soluton of putting down in writing according to claim 1, it is characterized in that: the sacrificial oxidation agent is selected from more than one in sulfuric acid oxyamine, formalin, the xitix.
3. according to claim 1 or 2 black ruthenium plating solutons of being put down in writing, it is characterized in that: sulfocompound is selected from thiocarbamide, thiourea derivative, have in the compound of sulfydryl, mercaptosuccinic acid, the ammonium thiocyanate more than one.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP219684/1999 | 1999-08-03 | ||
| JP21968499A JP3302949B2 (en) | 1999-08-03 | 1999-08-03 | Black ruthenium plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1319148A true CN1319148A (en) | 2001-10-24 |
| CN1193116C CN1193116C (en) | 2005-03-16 |
Family
ID=16739360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008015945A Expired - Fee Related CN1193116C (en) | 1999-08-03 | 2000-05-26 | Black ruthenium plating soluton |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3302949B2 (en) |
| KR (1) | KR100392694B1 (en) |
| CN (1) | CN1193116C (en) |
| WO (1) | WO2001011113A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101675185B (en) * | 2007-03-28 | 2011-04-13 | 尤米科尔电镀技术有限公司 | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
| CN101684565B (en) * | 2009-08-10 | 2012-03-21 | 成都宏明双新科技股份有限公司 | Black ruthenium plating process |
| CN104342731A (en) * | 2013-07-23 | 2015-02-11 | 深圳中宇昭日科技有限公司 | Ruthenium plating method for semiconductor molybdenum material |
| CN106148896A (en) * | 2016-07-29 | 2016-11-23 | 成都立威讯科技有限公司 | A kind of method of the thick ruthenium of molybdenum substrate plating |
| CN107021464A (en) * | 2017-06-07 | 2017-08-08 | 王晓波 | The method that ruthenium is plated on the synthetic method of a kind of [μ nitrogen is double (tetrachloro one is hydrated ruthenium)] sour potassium and electronic component surface |
| CN109234757A (en) * | 2018-10-18 | 2019-01-18 | 任杰 | A kind of preparation method and application of uniform and stable ruthenium iridium bimetal-doped Ti electrode |
| CN110965088A (en) * | 2019-08-27 | 2020-04-07 | 周大福珠宝金行（深圳）有限公司 | Ancient restoring process of gold and ancient restoring gold |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6911068B2 (en) * | 2001-10-02 | 2005-06-28 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
| US6773573B2 (en) * | 2001-10-02 | 2004-08-10 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
| US6736954B2 (en) * | 2001-10-02 | 2004-05-18 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
| EP1308541A1 (en) * | 2001-10-04 | 2003-05-07 | Shipley Company LLC | Plating bath and method for depositing a metal layer on a substrate |
| US6699385B2 (en) | 2001-10-17 | 2004-03-02 | Chevron U.S.A. Inc. | Process for converting waxy feeds into low haze heavy base oil |
| CN101575694B (en) * | 2009-03-13 | 2011-04-20 | 宜兴市科兴合金材料有限公司 | Process for diffusing ruthenium on surface of molybdenum wafer with ultra-large diameter |
| DE102011105207B4 (en) * | 2011-06-17 | 2015-09-10 | Umicore Galvanotechnik Gmbh | Electrolyte and its use for the deposition of black ruthenium coatings and coatings and articles obtained therefrom |
| US10329683B2 (en) | 2016-11-03 | 2019-06-25 | Lam Research Corporation | Process for optimizing cobalt electrofill using sacrificial oxidants |
| KR102313739B1 (en) * | 2019-08-23 | 2021-10-18 | 정광미 | Plating Solution Composition having Ruthenium and Method of plating using the same |
| JP2023056187A (en) | 2021-10-07 | 2023-04-19 | Ｅｅｊａ株式会社 | PtRu ALLOY PLATING SOLUTION, AND PLATING METHOD OF PtRu ALLOY FILM |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06146055A (en) * | 1992-11-06 | 1994-05-27 | Japan Energy Corp | Ruthenium plating liquid |
| JPH06146056A (en) * | 1992-11-06 | 1994-05-27 | Japan Energy Corp | Ruthenium plating liquid |
| JPH06146054A (en) * | 1992-11-06 | 1994-05-27 | Japan Energy Corp | Ruthenium plating liquid |
| JPH1150295A (en) * | 1997-07-28 | 1999-02-23 | Daiwa Kasei Kenkyusho:Kk | Plating bath |
| DE19741990C1 (en) * | 1997-09-24 | 1999-04-29 | Degussa | Electrolyte for low-stress, crack-free ruthenium coatings |
-
1999
- 1999-08-03 JP JP21968499A patent/JP3302949B2/en not_active Expired - Lifetime
-
2000
- 2000-05-26 CN CNB008015945A patent/CN1193116C/en not_active Expired - Fee Related
- 2000-05-26 WO PCT/JP2000/003395 patent/WO2001011113A1/en active Application Filing
- 2000-05-26 KR KR10-2001-7004063A patent/KR100392694B1/en not_active IP Right Cessation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101675185B (en) * | 2007-03-28 | 2011-04-13 | 尤米科尔电镀技术有限公司 | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
| CN101684565B (en) * | 2009-08-10 | 2012-03-21 | 成都宏明双新科技股份有限公司 | Black ruthenium plating process |
| CN104342731A (en) * | 2013-07-23 | 2015-02-11 | 深圳中宇昭日科技有限公司 | Ruthenium plating method for semiconductor molybdenum material |
| CN106148896A (en) * | 2016-07-29 | 2016-11-23 | 成都立威讯科技有限公司 | A kind of method of the thick ruthenium of molybdenum substrate plating |
| CN106148896B (en) * | 2016-07-29 | 2019-10-15 | 泉州市宕存工业设计有限公司 | A kind of method that molybdenum base piece plates thick ruthenium |
| CN107021464A (en) * | 2017-06-07 | 2017-08-08 | 王晓波 | The method that ruthenium is plated on the synthetic method of a kind of [μ nitrogen is double (tetrachloro one is hydrated ruthenium)] sour potassium and electronic component surface |
| CN107021464B (en) * | 2017-06-07 | 2019-10-15 | 王晓波 | A kind of method of the synthetic method and electronic component surface plating ruthenium of [μ-nitrogen-is bis- (hydration of tetrachloro one ruthenium)] acid potassium |
| CN109234757A (en) * | 2018-10-18 | 2019-01-18 | 任杰 | A kind of preparation method and application of uniform and stable ruthenium iridium bimetal-doped Ti electrode |
| CN110965088A (en) * | 2019-08-27 | 2020-04-07 | 周大福珠宝金行（深圳）有限公司 | Ancient restoring process of gold and ancient restoring gold |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100392694B1 (en) | 2003-07-28 |
| JP2001049485A (en) | 2001-02-20 |
| WO2001011113A1 (en) | 2001-02-15 |
| JP3302949B2 (en) | 2002-07-15 |
| CN1193116C (en) | 2005-03-16 |
| KR20010073198A (en) | 2001-07-31 |
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Granted publication date: 20050316 Termination date: 20160526 |