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WO2009110598A1 - Produit à placage d'alliage ruthénium-palladium et son procédé de fabrication - Google Patents

Produit à placage d'alliage ruthénium-palladium et son procédé de fabrication Download PDF

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Publication number
WO2009110598A1
WO2009110598A1 PCT/JP2009/054306 JP2009054306W WO2009110598A1 WO 2009110598 A1 WO2009110598 A1 WO 2009110598A1 JP 2009054306 W JP2009054306 W JP 2009054306W WO 2009110598 A1 WO2009110598 A1 WO 2009110598A1
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WO
WIPO (PCT)
Prior art keywords
ruthenium
palladium
palladium alloy
plating film
plating
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.)
Ceased
Application number
PCT/JP2009/054306
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English (en)
Japanese (ja)
Inventor
隆 木名瀬
和義 蔵根
善久 藤平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Metals Trading Co Ltd
Original Assignee
Nikko Shoji Co Ltd
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 Shoji Co Ltd filed Critical Nikko Shoji Co Ltd
Publication of WO2009110598A1 publication Critical patent/WO2009110598A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins

Definitions

  • the present invention relates to a ruthenium-palladium alloy plated product.
  • An object of the present invention is to provide a plated product having characteristics such as hardness, contact resistance, and color tone equivalent to those of the rhodium plated product more economically than the rhodium plated product.
  • the inventors of the present invention made an alloy plating product of ruthenium and palladium, and in a specific range of the composition, hardness, contact resistance, color tone, etc. equivalent to the rhodium plating product
  • the present inventors have found that a plated product having the following characteristics can be obtained, and have reached the present invention.
  • the present invention is as follows.
  • a ruthenium-palladium alloy plated product wherein the balance is made of palladium.
  • the ruthenium-palladium alloy plating film is characterized in that, in Lab color system solid coordinates, L is 70 or more, a is 0.1 to 1.0, and b is 2 to 4.
  • a plated product in which a plating film of an alloy of ruthenium and palladium is formed on a base material by electroplating, and the alloy plating film has a ruthenium content of 35 wt% or more and 65 wt% or less, and the balance
  • a ruthenium-palladium alloy plating film made of palladium a plated product having the same color tone, wear resistance, and contact resistance as a rhodium plated product can be obtained. Therefore, the ruthenium-palladium alloy plated product of the present invention is more economical than the rhodium plated product whose price is rising, and can be effectively used for industrial and decorative purposes as a substitute for the rhodium plated product.
  • FIG. 3 is a surface photograph of the plating film obtained in Example 2 by FE-SEM. It is the result of having analyzed by ESCA (X-ray photoelectron spectroscopy) of the plating film obtained in Example 2.
  • FIG. It is a contact resistance measurement result of the plating film obtained in Example 2 and a rhodium plating film.
  • ruthenium-palladium alloy plating film is 35 wt% or more and 65 wt% or less and the balance is palladium. It can be set as the plated object which has the following color tone characteristics. When the ruthenium concentration exceeds 65% by weight, the color tone becomes more bluish. Further, when the ruthenium concentration is less than 35% by weight, a yellowish color tone is obtained.
  • the ruthenium concentration in the plating film is 35% by weight or more and 65% by weight or less, and the balance is palladium.
  • L is 70 or more
  • a is 0.1 to 1.0
  • b is It is preferably 2 to 4
  • the white noble metal color tone for decoration is more preferably 72 to 75 for L, 0.4 to 0.8 for a, and 2 to 4 for b.
  • L, a, and b in the Lab color system three-dimensional coordinates are coordinate axes indicating a uniform color space proposed by Hunter (RS Hunter), and can be obtained by measuring with a photoelectric colorimeter.
  • the ruthenium concentration and palladium concentration in the plating film can be measured by inductively coupled plasma mass spectrometry (ICP) or atomic absorption spectrometry.
  • the ruthenium-palladium alloy plating film of the present invention is a film comprising ruthenium in an amount of 35 wt% to 65 wt% and the balance being palladium, so that in addition to the color tone, the hardness, corrosion resistance, contact resistance value, etc. are also rhodium. It can be equivalent to a membrane. Even if the concentration of ruthenium is less than 35% by weight or exceeds 65% by weight, hardness and corrosion resistance are lowered. Therefore, the ruthenium-palladium plated product of the present invention can be applied not only to decoration but also to industrial contacts as a response to market needs due to the soaring rhodium metal.
  • the surface of the ruthenium-palladium plating film of the present invention was drawn in three circles on the surface of the plating film at an angle of 45 degrees with a pencil core of hardness 6H in a pencil scratch test of JIS K5400, and the trace was observed with a microscope. There are few traces.
  • this invention when it is hard to leave a trace, when the circle (3 mm in diameter) drawn 3 times is made into an observation photograph with a metal microscope 25 times, a trace is not seen, or a thin trace is only in a part. The case where it is seen.
  • the hardness can be 700 Hv or more, which is higher than that of the ruthenium plating film and the palladium plating film, and approximates the hardness of the rhodium film of 800 Hv.
  • the hardness can be measured using a micro hardness tester. Specifically, the hardness is measured using an ultra micro indentation hardness tester ENT-2100 manufactured by Elionix Co., Ltd. The hardness of the 5 ⁇ m plated film was measured. As a result of the measurement of the contact resistance of the ruthenium-palladium alloy plating film of the present invention, data equivalent to that of the rhodium film is obtained.
  • Examples of industrial uses of the ruthenium-palladium plated product of the present invention include connector reed switches and probe pins.
  • Examples of the decorative use include glasses, necklaces, brooches, tie pins, cuffs, watches, cameras, and compacts.
  • the ruthenium-palladium alloy plating film of the present invention is formed by electroplating.
  • the plating solution preferably contains at least a ruthenium salt and a palladium salt, and further contains a conductive salt, a pH buffer, a stabilizer, a stress reducing agent, and the like.
  • a plating film formed by electroplating using a plating solution containing a ruthenium salt and a palladium salt has ruthenium and palladium precipitated by metal by ESCA (X-ray photoelectron spectroscopy). It can be confirmed that there is.
  • the concentration of ruthenium and palladium in the plating film is most markedly affected by the ruthenium concentration in the plating solution and the ruthenium concentration and palladium concentration ratio. By adjusting these, the concentration of ruthenium and palladium in the resulting plating film can be adjusted, and desired characteristics such as corrosion resistance, color tone, and hardness can be obtained. Further, pH, stress reducing agent concentration, current density, and the like when plating using the ruthenium-palladium plating solution also affect the ruthenium and palladium concentrations of the plating film.
  • the palladium salt a conventionally known compound used for a palladium plating solution can be used.
  • examples thereof include palladium chloride, palladium nitrate, dichlorodiammine palladium chloride, diammine palladium nitrite, tetraammine palladium nitrate, diammine palladium sulfate, dichlorotetraammine palladium chloride, diammine palladium oxalate, and tetraammine oxalate palladium.
  • ruthenium salt conventionally known compounds used for ruthenium plating solutions can be used. Examples include ruthenium sulfate, ruthenium chloride, ruthenium acochlor complex, ruthenium nitrogen / sulfur acid complex, ruthenium nitrogen / sulfamate complex, ruthenium nitrogen / sulfuric acid complex, nitroso ruthenium chloride and the like.
  • the ruthenium concentration in the plating solution is preferably 0.5 to 6.0 g / L, and the palladium concentration is preferably 0.4 to 1.7 g / L.
  • the ratio of the ruthenium and palladium concentrations in the plating solution is preferably 1: 0.13 to 1: 1.70.
  • Conductive salts, pH buffering agents, stabilizers include these conductive salts, pH buffering agents, sulfuric acid or ammonium sulfate, alkaline sulfates, ammonium chlorides, alkaline chlorides, sulfamic acids or ammonium sulfamates or sulfamines that act as stabilizers. Examples include acid alkali salts. Ammonium sulfamate is preferred, and the concentration is preferably in the range of 10 to 100 g / L, more preferably 20 to 70 g / L. If it is less than 10 g / L, liquid decomposition tends to occur. Further, the ruthenium concentration in the plating film is increased.
  • the stress reducing agent examples include benzenesulfonic acid, saccharin, organic carboxylic acid, pyridine, and polyethylene glycol.
  • the stress reducing agent concentration is preferably in the range of 0.5 to 3 g / L, and a closely plated product without cracks can be obtained.
  • the ruthenium-palladium plating solution in the present invention can be easily prepared by adding and dissolving a predetermined amount of other additives in the ruthenium compound and palladium compound aqueous solution.
  • the pH of the plating solution is too low, the stability is lowered, and when the pH is too high, the ruthenium concentration of the plating film is lowered.
  • the concentration of ruthenium and palladium contained in the plating film is preferably in the range of 5 to 7 within the scope of the present invention, and desired characteristics such as hardness can be obtained.
  • the pH can be adjusted with an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or sulfamic acid, and an inorganic alkali such as an alkali or alkaline earth metal hydroxide or ammonia.
  • the temperature of the solution at the time of plating is not particularly limited, and the ruthenium concentration in the plating film is stable without being influenced by the temperature of the plating solution.
  • the electrodeposition rate increases as the liquid temperature increases. However, if the temperature is too high, the composition of the solution is concentrated by evaporation of the plating solution, so 40 to 70 ° C. is preferable.
  • the current density is not particularly limited, and the plating film ruthenium-containing weight% is stable in a wide range. If the density is too high, burning of the plating may occur. If the density is too low, the electrodeposition rate becomes slow, so 1 to 4 A / dm 2 is preferable. In this range, a desired alloy concentration can be obtained, and characteristics such as hardness, corrosion resistance, and color tone can be obtained.
  • a base material for forming the plating film conductive base materials such as copper and copper alloys such as brass plates, silver and silver alloys, gold and gold alloys, tin and tin alloys can be used. The base material which performed base plating, such as copper and nickel, is preferable.
  • a substrate that is an object to be plated is used for the cathode, an insoluble material such as platinum is used for the anode, and platinum is plated on titanium.
  • Example 1 After adding 67 g of ammonium sulfamate to 600 mL (Ru: 6.7 g) of an aqueous solution of ruthenium chloride and carrying out boiling reflux reaction for 7 hours, 110 g of ammonium sulfamate was further added, dissolved by stirring, and adjusted to pH 6 with aqueous ammonia. .
  • a vinyl chloride container was used as a plating tank having corrosion resistance and heat resistance, and was heated to a predetermined temperature with an electric heater made of quartz, and a platinum-plated titanium mesh was disposed on the anode. The plating solution was stirred with a magnetic stirrer.
  • Example 1 In Example 1, except that the amount of ruthenium was changed and the ruthenium concentration and palladium concentration in the plating solution were changed to the amounts shown in Table 1, the plating solution was adjusted in the same manner as in Example 1, plating was performed, and the plating film was formed. evaluated. The results are shown in Table 1. Further, FIG. 1 shows the results of surface observation (20,000 times) of the plating film obtained in Example 2 by FE-SEM. It can be seen that dense crystals are uniformly deposited, and a plated film without cracks is obtained with a glossy smooth surface. Furthermore, the result of having analyzed the said plating film by ESCA (X-ray photoelectron spectroscopy) is shown in FIG.
  • ESCA X-ray photoelectron spectroscopy
  • the state of the metal can be analyzed from the peak indicated by the binding energy. Analysis from the binding energy confirmed that ruthenium and palladium were deposited as metal. Further, the contact resistance of the plated film obtained in Example 2 was measured. As a result of measuring with a measurement probe: Au, a measurement current: 10 mA, a measurement load: 60 g using MS880-II, manufactured by KS Parts Laboratory, the ruthenium-palladium alloy plating film obtained in Example 2 was measured. The contact resistance was 14.9 m ⁇ . Similarly, the contact resistance of the rhodium plating film was measured and found to be 16.7 m ⁇ . Further, FIG.
  • Example 3 shows the result of comparison of the contact resistance between the rhodium plating film and the ruthenium-palladium plating film obtained in Example 2.
  • the transition of the resistance under constant current load was obtained by bringing the tip of the Au probe pin into contact with the plated surface and applying or decreasing the load sequentially.
  • the weighting line is used, and when the load is reduced from 60 g to 0 g, the resistance transition is the deweighting line.
  • the graph appears as two lines, but each overlaps two.
  • the lower line (the line with the lower resistance) is the weighted line and the deweighted line of the ruthenium-palladium alloy plating film.
  • the upper line is the one where the weighting line and dewetting line of the rhodium plating film overlap.
  • Example 1 Except that the amount of ruthenium was changed and the ruthenium concentration and palladium concentration in the plating solution were changed to the amounts shown in Table 1, the plating solution was adjusted in the same manner as in Example 1, plating was performed, and the plating film was formed. evaluated. The results are shown in Table 1.

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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)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention porte sur un produit plaqué caractérisé par le fait qu'il présente une dureté, une résistance au contact, une teinte de couleur et autres, qui sont équivalentes à un produit à placage de rhodium, et par le fait qu'il est plus économique qu'un produit à placage de rhodium. Le produit à placage d'alliage ruthénium-palladium a un film de placage d'alliage ruthénium et palladium formé sur un substrat par dépôt électrolytique, le film plaqué étant caractérisé par le fait qu'il contient de 35 % à 65 % en poids de ruthénium, le reste étant constitué de palladium.
PCT/JP2009/054306 2008-03-06 2009-03-06 Produit à placage d'alliage ruthénium-palladium et son procédé de fabrication Ceased WO2009110598A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008055993A JP2009209436A (ja) 2008-03-06 2008-03-06 ルテニウム−パラジウム合金めっき物およびその製造方法
JP2008-055993 2008-03-06

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WO2009110598A1 true WO2009110598A1 (fr) 2009-09-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111678870A (zh) * 2020-06-01 2020-09-18 肇庆宏旺金属实业有限公司 一种不锈钢卷连续真空镀膜的在线检测方法及系统
EP3964610A1 (fr) * 2020-09-08 2022-03-09 IWG Ing. W. Garhöfer Gesellschaft m. b. H. Bain d'électrodéposition pour revêtements palladium-ruthénium

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7766290B2 (ja) * 2021-03-26 2025-11-10 石福金属興業株式会社 プローブピン用合金材料

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1046384A (ja) * 1996-05-10 1998-02-17 Lucent Technol Inc パラジウム合金メッキ浴

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1046384A (ja) * 1996-05-10 1998-02-17 Lucent Technol Inc パラジウム合金メッキ浴

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111678870A (zh) * 2020-06-01 2020-09-18 肇庆宏旺金属实业有限公司 一种不锈钢卷连续真空镀膜的在线检测方法及系统
EP3964610A1 (fr) * 2020-09-08 2022-03-09 IWG Ing. W. Garhöfer Gesellschaft m. b. H. Bain d'électrodéposition pour revêtements palladium-ruthénium

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