WO2001011113A1 - Bain de depot galvanoplastique de ruthenium noir - Google Patents

Bain de depot galvanoplastique de ruthenium noir Download PDF

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Publication number
WO2001011113A1
WO2001011113A1 PCT/JP2000/003395 JP0003395W WO0111113A1 WO 2001011113 A1 WO2001011113 A1 WO 2001011113A1 JP 0003395 W JP0003395 W JP 0003395W WO 0111113 A1 WO0111113 A1 WO 0111113A1
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WO
WIPO (PCT)
Prior art keywords
black
ruthenium
plating
plating solution
solution
Prior art date
Application number
PCT/JP2000/003395
Other languages
English (en)
Japanese (ja)
Inventor
Akihiro Aiba
Tomoharu Mimura
Toshikazu Okubo
Original Assignee
Nikko Materials Company, Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nikko Materials Company, Limited filed Critical Nikko Materials Company, Limited
Publication of WO2001011113A1 publication Critical patent/WO2001011113A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals

Definitions

  • the present invention relates to a black ruthenium plating solution capable of maintaining a strong blackness with a high ruthenium adhesion by stabilizing a thioic compound as a color former at the anode during electrolysis.
  • a platinum-plated titanium plate is used as an anode
  • an object to be coated is used as a cathode, and these are immersed in the above-mentioned plating solution and energized to deposit a plating film on the cathode.
  • the ruthenium plating film can be colored black by the action of a coloring agent contained in the solution, and as the coloring agent, a thioic compound is particularly excellent.
  • the black coating is particularly valuable as a decorative coating for watches, eyeglass frames, dials, lighter cases, lipstick caps, etc. or as an industrial material such as electrical contacts, reflectors, and heat absorbers.
  • JP-B-63-99027 and JP-A-63-259,095 are known.
  • the conventional black ruthenium plating solution is characterized in that the solution is easy to manage, has a high luster, has good adhesion to the substrate, and is excellent in corrosion resistance and abrasion resistance.
  • the characteristics of the conventional black ruthenium plating solution that is, the features that the solution is easy to manage, and that it is glossy, has good adhesion to the substrate, and is excellent in corrosion resistance and abrasion resistance. It is an object of the present invention to suppress the decomposition of the thio compound to be added as a color former due to anodic oxidation during electrolysis, to maintain a strong blackness during the electrolysis process, and to obtain a stable black plating. . Disclosure of the invention
  • the present inventor has found that the cause of the decrease in blackness in such black ruthenium plating is that the thio compound which is a color former is oxidized at the anode during electrolysis and loses its effect. It has been found that by stabilizing the thio compound in the solution, the ruthenium plating film is maintained at a high level and blackness.
  • Black ruthenium plating solution containing ruthenium sulfate, sulfamic acid, a thio compound and a sacrificial oxidizing agent added to prevent thio compounds from being anodized during electrolysis as components in the solution.
  • a sacrificial oxidizing agent is added to the ruthenium plating solution in order to prevent the formation of a thioic compound due to the positive electrode during electrolysis.
  • the oxidation reaction of the sacrificial oxidant proceeds as the main reaction at the anode, and the oxidation reaction of the thio compound hardly occurs.
  • the action and effect of the thio compound for blackening the plating film do not deteriorate.
  • the thioic compound had to be added frequently as described above. A strong blackness can be maintained without replenishing the compound.
  • the black ruthenium plating solution of the present invention contains norethenium sulfate, sulfamic acid, a thio compound, and a sacrificial oxidizing agent added to prevent decomposition of the thio compound due to anodic oxidation during electrolysis.
  • Ruthenium sulfate becomes a source of ruthenium metal that precipitates as plating, and the ruthenium concentration is from 1 to 10 g ZL.
  • Current efficiency, plating time and loss of ruthenium due to washing of electrodeposits during handling (so-called “pumping”) ) Is desirable. However, it is not particularly limited to this concentration.
  • Sulfamic acid suppresses the instability of ruthenium ion valence due to anodic oxidation and cathodic reduction when ruthenium sulfate is used, prevents the formation of non-metallized, low-valent ruthenium, and provides stable ruthenium. It enables plating work.
  • An appropriate concentration is 50 to 150 g / L, but it is not particularly necessary to limit the concentration.
  • the thioic compound is added to blacken the color tone of the ruthenium plating 3 ⁇ 4.
  • the thio compound is selected from thiourea, a thiourea derivative, a compound having a mercapto group, thiomalic acid, ammonium thiocyanate, and the like.
  • thiourea is most suitable in view of the stability and price of the compound.
  • concentration of the thio compound the stronger the blackness is obtained, but if the concentration is too high, the solution becomes unstable.
  • a suitable concentration is 0.1 to 10 Og / L, particularly 1.0 to 5.0 g / L.
  • a sacrificial oxidizing agent added to prevent the decomposition of the thio compound due to anodic oxidation during electrolysis, a sacrificial oxidizing agent that is more susceptible to anodic oxidation than the thio compound is used.
  • the compound itself undergoes anodization during electrolysis and changes and is consumed, but it is necessary that the compound itself and the oxidized compound do not affect the ruthenium deposition reaction.
  • the sacrificial oxidizing agent include hydroxylamine sulfate, formalin, and ascorbic acid.
  • hydroxylamine sulphate is the most effective because it remains in the solution even when acidified and does not affect the coating.
  • the sacrificial oxidizing agent has an effect of preventing oxidation of the thio compound if it is substantially present in the solution. Therefore, the concentration of the sacrificial oxidizing agent is not particularly limited, but usually 0.1 to 100 g L. Appropriate.
  • the pH, the current density, and the solution temperature can be appropriately adjusted and used. Specifically, it is appropriate that the pH is less than 2, the current density is 5 to 15 AZdm, and the liquid temperature is 40 ° C or higher.
  • the substrate (material) on which the black ruthenium plating of the present invention is performed is suitably a nickel plating plated with flash plating.
  • platinum or platinum-plated titanium is used as the anode.
  • these conditions should be appropriately selected by the trader according to the equipment and the shape of the covering object, and need not be particularly limited. Examples and comparative examples
  • this solution was divided into 3 parts, and 2 parts each were added with 10 gZL of hydroxylamine sulfate and 50 gZL as a sacrificial oxidizing agent, respectively, to obtain Examples 1 and 2, and the remaining 1 part was not added. This was used as a comparative example.
  • Plating was repeatedly performed using these three solutions.
  • the plating conditions are as follows.
  • the material used was a brass plate plated with Ni in a normal watt bath and flash-flashed.
  • Example 1 since a large amount of sacrificial oxidizing agent, hydroxylamine was added, it was not necessary to supply the same agent during black ruthenium plating, but in Example 2, sacrificed during electrolysis. Since the amount of hydroxylamine sulfate, which is an acidifying agent, was small in the initial stage of plating and was consumed with plating, replenishment was performed to maintain the concentration.
  • hydroxylamine sulfate as the sacrificial oxidizing agent of the present invention, it became possible to stably obtain a plating film having a strong blackness in black ruthenium plating.
  • a sacrificial oxidizing agent such as hydroxynoramine sulfate did not hinder the formation of a black ruthenium plating film.
  • Hydroxylamine sulfate was the most effective as a sacrificial oxidizing agent, but other sacrificial oxidizing agents of the present invention obtained almost the same effect. Similar results were obtained with thio compounds other than thiourea.
  • the reason why the blackness of black ruthenium plating decreases is that the thio compound, which is a color former, is oxidatively decomposed at the anode during electrolysis and loses its effect.By stabilizing the thio compound in the solution, The ruthenium plating film can maintain a strong blackness. Therefore, a sacrificial oxidizing agent is added to the black ruthenium plating solution to prevent decomposition of the thio compound due to anodic oxidation during electrolysis. As a result, at the anode, the oxidation reaction of the sacrificial oxidant proceeds as a main reaction, and the oxidation reaction of the thio compound hardly occurs.
  • the characteristics of the conventional black ruthenium plating solution that is, the easy management of the solution, the glossiness, good adhesion to the substrate, and excellent corrosion resistance and abrasion resistance are the original characteristics of the black ruthenium plating solution.
  • the sacrificial acid suppresses the thiol conjugate added as a coloring agent by anodic oxidation during electrolysis, and maintains a strong blackness during the electrolysis process. It has an excellent effect that a stable black plating can be obtained.

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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

L'invention concerne un bain de dépôt galvanoplastique à base de ruthénium noir caractérisé par la présence dans la solution des constituants efficaces suivants: sulfate de ruthénium, acide sulfamique, un composé thio et un agent oxydant sacrificiel ajouté afin d'empêcher la décomposition du composé thio due à l'oxydation anodique. Le bain de l'invention peut s'utiliser pour inhiber la décomposition d'un composé thio ajouté en tant que substance chromogène en raison de l'oxydation anodique, et ce afin de maintenir une noirceur dense lors de l'électrolyse et d'assurer par là un revêtement noir stable tout en préservant les caractéristiques souhaitées d'un bain de dépôt galvanoplastique classique au ruthénium noir. Il peut également être régulé facilement, présente une bonne brillance, une bonne adhérence à un substrat et s'avère excellent en matière de résistance à la corrosion et à l'abrasion.
PCT/JP2000/003395 1999-08-03 2000-05-26 Bain de depot galvanoplastique de ruthenium noir WO2001011113A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/219684 1999-08-03
JP21968499A JP3302949B2 (ja) 1999-08-03 1999-08-03 黒色ルテニウムめっき液

Publications (1)

Publication Number Publication Date
WO2001011113A1 true WO2001011113A1 (fr) 2001-02-15

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PCT/JP2000/003395 WO2001011113A1 (fr) 1999-08-03 2000-05-26 Bain de depot galvanoplastique de ruthenium noir

Country Status (4)

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JP (1) JP3302949B2 (fr)
KR (1) KR100392694B1 (fr)
CN (1) CN1193116C (fr)
WO (1) WO2001011113A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6699385B2 (en) 2001-10-17 2004-03-02 Chevron U.S.A. Inc. Process for converting waxy feeds into low haze heavy base oil
US8211286B2 (en) 2007-03-28 2012-07-03 Umicore Galvotechnik GmbH Electrolyte and method for depositing decorative and technical layers of black ruthenium
DE102011105207A1 (de) 2011-06-17 2012-12-20 Umicore Galvanotechnik Gmbh Elektrolyt und seine Verwendung zur Abscheidung von Schwarz-Ruthenium-Überzügen und so erhaltene Überzüge
US10329683B2 (en) 2016-11-03 2019-06-25 Lam Research Corporation Process for optimizing cobalt electrofill using sacrificial oxidants

Families Citing this family (13)

* Cited by examiner, † Cited by third party
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 (fr) * 2001-10-04 2003-05-07 Shipley Company LLC Bain et procédé pour le dépôt d'une couche metallique sur un substrat
CN101575694B (zh) * 2009-03-13 2011-04-20 宜兴市科兴合金材料有限公司 一种超大直径钼圆片表面渗钌工艺
CN101684565B (zh) * 2009-08-10 2012-03-21 成都宏明双新科技股份有限公司 一种镀黑钌的工艺
CN104342731A (zh) * 2013-07-23 2015-02-11 深圳中宇昭日科技有限公司 一种半导体钼材电镀钌方法
CN106148896B (zh) * 2016-07-29 2019-10-15 泉州市宕存工业设计有限公司 一种钼基片镀厚钌的方法
CN107021464B (zh) * 2017-06-07 2019-10-15 王晓波 一种[μ-氮-双(四氯一水合钌)]酸钾的合成方法以及电子元器件表面镀钌的方法
CN109234757B (zh) * 2018-10-18 2020-07-28 任杰 一种均匀稳定的钌铱双金属掺杂钛电极的制备方法
KR102313739B1 (ko) * 2019-08-23 2021-10-18 정광미 루테늄을 포함하는 합금 도금액 조성물 및 이를 이용한 루테늄 도금 방법
CN110965088A (zh) * 2019-08-27 2020-04-07 周大福珠宝金行（深圳）有限公司 一种黄金的复古工艺以及复古黄金
JP2023056187A (ja) 2021-10-07 2023-04-19 Ｅｅｊａ株式会社 ＰｔＲｕ合金めっき液及びＰｔＲｕ合金膜のめっき方法

Citations (5)

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Publication number Priority date Publication date Assignee Title
JPH06146056A (ja) * 1992-11-06 1994-05-27 Japan Energy Corp ルテニウムめっき液
JPH06146055A (ja) * 1992-11-06 1994-05-27 Japan Energy Corp ルテニウムめっき液
JPH06146054A (ja) * 1992-11-06 1994-05-27 Japan Energy Corp ルテニウムめっき液
JPH1150295A (ja) * 1997-07-28 1999-02-23 Daiwa Kasei Kenkyusho:Kk めっき浴
DE19741990C1 (de) * 1997-09-24 1999-04-29 Degussa Elektrolyt zur galvanischen Abscheidung von spannungsarmen, rißfesten Rutheniumschichten, Verfahren zur Herstellung und Verwendung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06146056A (ja) * 1992-11-06 1994-05-27 Japan Energy Corp ルテニウムめっき液
JPH06146055A (ja) * 1992-11-06 1994-05-27 Japan Energy Corp ルテニウムめっき液
JPH06146054A (ja) * 1992-11-06 1994-05-27 Japan Energy Corp ルテニウムめっき液
JPH1150295A (ja) * 1997-07-28 1999-02-23 Daiwa Kasei Kenkyusho:Kk めっき浴
DE19741990C1 (de) * 1997-09-24 1999-04-29 Degussa Elektrolyt zur galvanischen Abscheidung von spannungsarmen, rißfesten Rutheniumschichten, Verfahren zur Herstellung und Verwendung

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6699385B2 (en) 2001-10-17 2004-03-02 Chevron U.S.A. Inc. Process for converting waxy feeds into low haze heavy base oil
US8211286B2 (en) 2007-03-28 2012-07-03 Umicore Galvotechnik GmbH Electrolyte and method for depositing decorative and technical layers of black ruthenium
DE102011105207A1 (de) 2011-06-17 2012-12-20 Umicore Galvanotechnik Gmbh Elektrolyt und seine Verwendung zur Abscheidung von Schwarz-Ruthenium-Überzügen und so erhaltene Überzüge
WO2012171856A2 (fr) 2011-06-17 2012-12-20 Umicore Galvanotechnik Gmbh Électrolyte et son utilisation pour le dépôt de revêtements de ruthénium noir et revêtements obtenus en utilisant ledit électrolyte
DE102011105207B4 (de) * 2011-06-17 2015-09-10 Umicore Galvanotechnik Gmbh Elektrolyt und seine Verwendung zur Abscheidung von Schwarz-Ruthenium-Überzügen und so erhaltene Überzüge und Artikel
US10329683B2 (en) 2016-11-03 2019-06-25 Lam Research Corporation Process for optimizing cobalt electrofill using sacrificial oxidants
US11078591B2 (en) 2016-11-03 2021-08-03 Lam Research Corporation Process for optimizing cobalt electrofill using sacrificial oxidants

Also Published As

Publication number Publication date
KR100392694B1 (ko) 2003-07-28
JP2001049485A (ja) 2001-02-20
CN1319148A (zh) 2001-10-24
JP3302949B2 (ja) 2002-07-15
CN1193116C (zh) 2005-03-16
KR20010073198A (ko) 2001-07-31

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