WO2019176049A1 - 電解ロジウムめっき液 - Google Patents

電解ロジウムめっき液 Download PDF

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WO2019176049A1
WO2019176049A1 PCT/JP2018/010208 JP2018010208W WO2019176049A1 WO 2019176049 A1 WO2019176049 A1 WO 2019176049A1 JP 2018010208 W JP2018010208 W JP 2018010208W WO 2019176049 A1 WO2019176049 A1 WO 2019176049A1
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rhodium
plating
phosphite
plating solution
electrolytic
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PCT/JP2018/010208
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English (en)
French (fr)
Japanese (ja)
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宏治 片倉
理恵 菊池
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日本エレクトロプレイテイング・エンジニヤース株式会社
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Priority to KR1020197017863A priority Critical patent/KR102549660B1/ko
Priority to CN201880005951.4A priority patent/CN110494596B/zh
Priority to JP2018536208A priority patent/JP6474536B1/ja
Priority to PCT/JP2018/010208 priority patent/WO2019176049A1/ja
Priority to TW108107690A priority patent/TWI794440B/zh
Publication of WO2019176049A1 publication Critical patent/WO2019176049A1/ja

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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
    • C25D3/56—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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys

Definitions

  • the present invention relates to an electrolytic rhodium plating solution, and more particularly to an electrolytic rhodium plating solution that forms an amorphous structure of rhodium phosphorus.
  • Rhodium metal is widely used for optical components such as reflectors because of its excellent reflectance. Furthermore, excellent properties such as high hardness, high wear resistance, low contact resistance, oxidation resistance in air, and stability against sparks due to a high melting point, which are characteristics of rhodium metal, are used in the industrial field. Rhodium metal is extremely chemically stable among platinum group metals and does not dissolve in aqua regia. In addition, rhodium metal has the highest reflectance among platinum group metals, and the color tone has a beautiful white gloss, the Vickers hardness of the precipitate is as high as 800 to 1,000 Hv, and has excellent corrosion resistance. In order to show the characteristics, it has gained popularity as a plating material for decorative articles and has been widely used.
  • Rhodium metal Since rhodium metal is expensive, its use as a bare metal is rare. Rhodium metal is used as a contained alloy, or as a deposit for electrolytic plating of parts for electrical, electronic and communication industries, electrolytic plating of optical equipment parts, electrolytic plating for electrodes, electrolytic plating of precision equipment parts, etc. Diluted rhodium metal is widely used in various industrial fields, and is used extensively in platinum ring ornaments.
  • the rhodium electrolytic plating solution is roughly classified into a sulfuric acid plating solution and a phosphoric acid plating solution.
  • Table 4.86 of “4.11.2 Rhodium plating” of “Plating Technology Handbook” includes “metal rhodium (as sulfate or phosphate) 1 to 4 g / L and Electroplating baths of “phosphoric acid 40-80 mL / L” and “metal rhodium (as sulfate or phosphate) 4 g / L and sulfuric acid 20-40 mL / L” are shown.
  • various compounds have been studied in “Development research of rhodium plating bath for thickening” (Non-patent Documents 2 and 3 described later).
  • Japanese Patent Laid-Open No. 52-014538 discloses that a rhodium phosphate plating bath composed of 0.1 to 10 g / L of rhodium as metal rhodium and 30 to 1000 g / L of phosphoric acid has an alkaline phosphate, that is, ammonium. Further, a phosphate rhodium plating bath characterized by adding 0.1 to 10 g / L of any one of potassium, sodium, calcium and magnesium phosphates is disclosed. Japanese Patent Application Laid-Open No.
  • 54-158340 discloses “rhodium ion 0.1 g / L to 30 g / L, polycarboxy organic carboxylic acid 0.1 g / L to 20 g / L containing at least one amino group, and ortholine.
  • An acidic rhodium plating bath comprising acid groups 10 g / L to 100 g / L and having a bath pH of 0 to 2.0 is disclosed.
  • Patent Document 1 Japanese Patent Laid-Open No. 58-048688 (Patent Document 1 to be described later) describes “a black rhodium plating bath characterized by containing hypophosphite as an additive in an acidic rhodium plating bath. Is disclosed.
  • a titanium plate plated with platinum in a plating bath obtained by mixing rhodium sulfate (rhodium: 8 g / L), sodium hypophosphite (1 g / L) and sulfuric acid (free 10 g / L) was used as an anode.
  • the brass plate was placed as a cathode, and electroplated on the brass plate for 10 minutes under the conditions of a bath temperature of 25 ° C. and a current density of 3 A / dm 2.
  • the obtained deposit was specularly glossy and black.
  • the thickness was 0.3 ⁇ m and the adhesion was good.
  • This electroplated rhodium deposit has a black color that includes rhodium black and therefore cannot be used for industrial purposes.
  • an industrial product in which a gold plating film is formed on the rhodium plating film has a poor color tone as viewed from the surface and is considered to be defective in plating.
  • this rhodium plating film had a high porosity, and in the corrosion test with the potential applied, the corrosion was severe.
  • the rhodium electroplating solution containing a rhodium salt and a free acid further contains sulfur or a sulfur-containing substance.
  • the low stress rhodium electroplating solution is disclosed in Example 1.
  • Example 1 “Rh concentration 5 g / L, T—H 2 SO 4 80 g / L, current density 1 A / dm 2 , bath temperature 60 ° C., plating
  • the plating film obtained for 90 minutes was excellent without any cracks even in a corrosive atmosphere.
  • Example 35 in paragraph 0114 of Japanese Patent Laid-Open No. 11-050295 includes “adding 0.3 g / L of surfactant polystar OM to the plating solution of Comparative Example 35”.
  • Comparative Example 35 of paragraph 0113 “Rhodium Phosphate 2 g / L, Sulfuric Acid 30 mL / L, Bath Temperature 45 ° C., Electric Density 4 A / dm” is described. 2 "plating conditions are described.
  • the plating solution of Comparative Example 35 of JP-A No. 11-050295 can be obtained by referring to the plating bath composition described in “Handbook of Plating Technology” (Non-Patent Document 1 described later). Pure rhodium precipitates are obtained rather than alloys. If an electroplating solution bathed with phosphoric acid is used, cracks are more likely to occur than an electroplating bath bathed with sulfuric acid. It seems that rhodium precipitation efficiency in phosphoric acid is worse than the precipitation efficiency in sulfuric acid.
  • the rhodium precipitate plated from the rhodium sulfate plating solution forms an interface structure of the rhodium precipitate according to the form of the underlying surface.
  • the crystal grains of the rhodium plating film have a characteristic characteristic of rhodium plating that internal stress is high. For this reason, as the rhodium plating film increases in thickness, there is a problem that peeling from the base material and generation of cracks are recognized due to internal stress.
  • Satoshi Aoya “Development of rhodium plating bath for thickening (“ Report 1 ”, Plating and Coating, Vol. 8, No. 3, pp.143-152, 1988) Satoshi Aoya, “Development and research of rhodium plating bath for thickening”, Plating and coating, Vol. 9, No. 2, pp. 88-96, 1989
  • the corrosion resistance of the connection terminals is also tested for the corroded cord test in which a voltage is applied from the porosity test in the atmosphere and the salt spray test (NaCl 5%, 20% ⁇ 35 ° C). Strict corrosion testing standards such as accelerated sulfur dioxide testing have begun to be applied.
  • base materials used for rhodium plating have begun to be incorporated into products under conditions that are thin and easily deformed. In such a recent inexpensive electric / electronic component, the application range of the conventional robust rhodium film is narrowed, and it has become difficult to adopt the conventional rhodium plating film.
  • the present invention has been made in order to address the above-described problems, and provides a rhodium plating solution capable of obtaining a plating film having a dense amorphous structure of rhodium phosphorus. That is, the present invention provides various rhodium in the plating solution by at least one compound selected from the group consisting of phosphorous acid, alkali metal phosphite, alkaline earth metal phosphite or ammonium phosphite. The main point is to keep the ionic species in a state of being easily reduced as a rhodium phosphorus amorphous plating film.
  • Phosphorous acid, alkali metal phosphite, alkaline earth metal phosphite or ammonium phosphite is used in the rhodium plating solution rather than the rhodium atom-rhodium atom metal bond. This is to give priority to the metal bond.
  • rhodium plating solution if rhodium atom-phosphorus atom bonds are formed before plating deposits are formed, rhodium phosphorus atomic groups in which phosphorus atoms are incorporated during electroplating will accumulate. . Therefore, a rhodium phosphorus precipitate formed with a dense amorphous structure of rhodium phosphorus atomic groups having low internal stress can be obtained.
  • the present inventors examined the ionic state of various rhodium complexes present in the sulfuric acid solution.
  • the following large rhodium complex ions are known in the sulfuric acid solution.
  • [Rh (H 2 O) 2 (SO 4 ) 2 ] ⁇ species and [Rh (H 2 O) 4 SO 4 ] + species exist, and [Rh n ( ⁇ -OH) 2 (SO 4 ) 2 (H 2 O) 4 ] 0 species and [Rh n ( ⁇ -SO 4 ) ( ⁇ -OH) (SO 4 ) 2 (H 2 O) 4 ] — species.
  • the present inventors have added alkali metal phosphites, alkaline earth metal phosphites or ammonium phosphites such as phosphorous acid and disodium hydrogen phosphite (Na 2 HPO 3 ) salt in sulfuric acid solution. It has been found that when it coexists with the above, it becomes a deposit of an amorphous structure of rhodium phosphorus by electroplating. The large ion population is decomposed, and low-melting phosphorus atoms and rhodium atoms seem to be combined in the plating solution.
  • sodium dihydrogen phosphate (NaH 2 PO 4 ) salt or sodium hypophosphite (NaH 2 PO 2 ) salt may coexist,
  • the plating solution could be discolored and the rhodium phosphorous amorphous structure as in the present invention could not be obtained.
  • the present inventors diligently studied the rhodium phosphorous plating film having an amorphous structure, and the present invention compared with the cross section of the rhodium plating film obtained by the prior art (see FIG. 3 described later). It turned out that the crystal grain of the cross section (refer FIG. 2 mentioned later) of this rhodium phosphorus plating film becomes fine. As a result of further research on this film, it was found that the interface of the rhodium-phosphorus plating film of the present invention is not influenced by the form of the base surface of the base material or the intermediate layer, and an unprecedented dense amorphous structure can be obtained. The present invention has been completed.
  • One of the electrolytic rhodium plating solutions of the present invention is 1-20 g / L of metal rhodium (as sulfate or phosphate), 10-100 mL / L of sulfuric acid and phosphorous acid, alkali metal phosphite, phosphorous acid It contains 0.001 to 10 g / L of at least one compound selected from the group consisting of alkaline earth metal salts or ammonium phosphite salts.
  • electrolytic rhodium plating solutions of the present invention include metal rhodium (as sulfate or phosphate) 1 to 20 g / L, sulfuric acid 10 to 100 mL / L, phosphorous acid, alkali metal phosphite, phosphorous acid 0.001 to 10 g / L of at least one compound selected from the group consisting of acid alkaline earth metal salts or ammonium phosphite salts, and alkali metal sulfates, alkaline earth metal sulfates or ammonium sulfate salts It contains 0.001 to 30 g / L of at least one compound selected from the group consisting of:
  • electrolytic rhodium plating solutions of the present invention include 1 to 20 g / L of metal rhodium (as sulfate or phosphate), 10 to 100 mL / L of phosphoric acid, phosphorous acid, alkali metal phosphite, It contains 0.001 to 10 g / L of at least one compound selected from the group consisting of alkaline earth metal phosphates or ammonium phosphite salts.
  • electrolytic rhodium plating solutions of the present invention include 1 to 20 g / L of metal rhodium (as sulfate or phosphate), 10 to 100 mL / L of phosphoric acid, phosphorous acid, alkali metal phosphite, 0.001 to 10 g / L of at least one compound selected from the group consisting of alkaline earth metal phosphates or ammonium phosphite salts, and alkali metal phosphates, alkaline earth metal phosphates or It contains 0.001 to 30 g / L of at least one compound selected from the group consisting of ammonium phosphates.
  • the alkaline earth metal salt means beryllium salt, magnesium salt, calcium salt and barium salt. Practically, magnesium salt and calcium salt are preferable. This is because magnesium phosphite salt or the like becomes phosphite ion in sulfuric acid or phosphoric acid solution. From the above, practically preferred phosphites are lithium phosphite, sodium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite and ammonium phosphite. .
  • rhodium phosphate lowers the cathode deposition efficiency of the electrolytic rhodium plating solution, so the rhodium sulfate salt is preferred in the industrial field from the viewpoint of productivity.
  • a silver-white plating film having a brighter color tone than rhodium sulfate salt can be obtained by using phosphate, rhodium phosphate salt is preferred in the decorative field from the viewpoint of decoration.
  • the rhodium-phosphorous plating film of the present invention has an average rhodium crystal grain size of less than 0.01 ⁇ m when a cross section by a focused ion beam is observed with a scanning electron microscope. Say. That is, it refers to a state of compartments that are too finely divided and cannot be observed with a normal scanning electron microscope.
  • Various effects of the present invention are brought about by such a dense amorphous structure.
  • the metal rhodium concentration is set to 1 to 20 g / L for the following reason. That is, when the metal rhodium concentration is less than 1 g / L, the deposition efficiency of the electrolytic rhodium plating solution is lowered. Further, when the concentration of metal rhodium exceeds 20 g / L, the amount of unused rhodium is excessively increased and the maintenance cost of the plating solution is increased. In addition, the management aspects such as recovery of metal rhodium from an aged rhodium plating bath and treatment of waste liquid are considered.
  • the concentration of metal rhodium is preferably in the range of 2 to 10 g / L, particularly preferably in the range of 2 to 6 g / L. This is because a desired thick plating film can be obtained in a short time.
  • the maximum thickness of the dense amorphous structure is 20 ⁇ m.
  • the concentration of metal rhodium is preferably in the range of 2 to 10 g / L, particularly preferably in the range of 2 to 4 g / L. This is because if a dense amorphous film is obtained, a corrosion-resistant gold plating film, rhodium plating film, or platinum plating film can be formed on the dense surface layer.
  • the concentration of metal rhodium is preferably in the range of 1 to 5 g / L, particularly preferably in the range of 2 to 4 g / L. This is because the ultra-thin and dense amorphous structure prevents the surface form of the base material from reaching the deposited shape of the coating layer and avoids alloying of the base material and the surface layer.
  • the concentration of sulfuric acid is 10 to 100 mL / L for the following reason. That is, when the concentration of sulfuric acid is less than 10 mL / L, the rhodium compound may be hydrolyzed. Further, when the concentration of sulfuric acid exceeds 100 mL / L, the rhodium compound is difficult to move, and the deposit of rhodium phosphorus may cause burn plating.
  • the concentration of sulfuric acid is preferably 10 to 50 mL / L, more preferably 10 to 20 mL / L.
  • the phosphoric acid concentration is set to 10 to 100 mL / L for the following reason. That is, if the concentration of phosphoric acid is less than 10 mL / L, the rhodium compound may be hydrolyzed. Further, when the concentration of phosphoric acid exceeds 100 mL / L, the rhodium compound is difficult to move, and the deposit of rhodium phosphorus may cause burn plating.
  • the concentration of phosphoric acid is preferably 10 to 50 mL / L, more preferably 10 to 20 mL / L.
  • 0.001 to 0.001 to at least one compound selected from the group consisting of phosphorous acid, alkali metal phosphite, alkaline earth metal phosphite or ammonium phosphite The reason for containing 10 g / L is that these compounds form an amorphous structure with rhodium in the precipitate. If the concentration of the compound is less than 0.001 g / L, the rhodium precipitate cannot be formed amorphous. On the other hand, if the concentration of the compound exceeds 10 g / L, a rhodium precipitate may be formed in the electroplating solution.
  • rhodium phosphorus The formation of an amorphous structure of rhodium phosphorus can be understood as follows. Generally, if a phosphorus compound can enter the rhodium plating film, the rhodium precipitate becomes finer. However, rhodium deposited from various rhodium species during electroplating has very strong internal stress. This means that even if the amount of the phosphorus compound increases in the liquid, the phosphorus compound cannot enter the precipitated rhodium, and the rhodium precipitate is not refined. When rhodium is deposited by electroplating, it seems that a huge network of various rhodium complexes is formed in the plating solution. When there is no phosphorus compound inside the rhodium crystal grains and phosphorus is co-deposited at the grain boundaries of the crystal grains, the rhodium crystal grains become strong and peel off.
  • phosphorus compounds such as sodium phosphite described above lead to various rhodium species in the plating solution to be easily decomposed in advance before rhodium crystal grains are deposited by electroplating. It is thought that an atomic group in which phosphorus is bonded is formed. For this reason, when electrolytic rhodium plating is performed, the rhodium phosphorus deposit has a dense structure in which the following rhodium phosphorus atomic groups are stacked like snow on a small rhodium phosphorus atomic group. Each rhodium phosphorus atomic group having such a dense amorphous structure is an aggregate of rhodium metal atoms and phosphorus metal atoms. This rhodium phosphorus plating deposit has no crystal orientation, and the rhodium phosphorus plating film has no orientation.
  • the compound containing 0.001 to 10 g / L of a compound such as sodium phosphite cannot be made amorphous at less than 0.001 g / L, This is because if it exceeds 10 g / L, the melting point of the rhodium phosphorus plating film becomes too low.
  • the compound such as sodium phosphite is preferably contained in an amount of 0.05 to 5.0 g / L, more preferably 1.0 to 3.0 g / L. In particular, an amount of less than 1/10 is preferable and an amount of less than 1/20 is particularly preferable with respect to the metal rhodium concentration.
  • the electrolytic rhodium plating solution of the present invention does not contain hypophosphite such as sodium hypophosphite (NaH 2 PO 2 .H 2 O) salt. This is because the deposited rhodium film turns black, is not stable, or cannot be made amorphous.
  • hypophosphite such as sodium hypophosphite (NaH 2 PO 2 .H 2 O) salt.
  • NaH 2 PO 2 .H 2 O sodium hypophosphite
  • various rhodium species in the electrolytic rhodium plating solution may be decomposed and deposited on the anode.
  • electrolytic rhodium plating solution of the present invention additives such as organic sulfur compounds and surfactants used in general electrolytic rhodium plating solutions can also be used. This is because the effect of the electrolytic rhodium plating solution of the present invention is exhibited as long as the amorphous structure of the present invention is not broken.
  • the present inventors have found that the above phosphorus compounds such as sodium phosphite tend to have a certain precipitation ratio with rhodium precipitates. That is, when the concentration of rhodium metal is fixed and the concentration of the compound such as sodium phosphite is appropriately changed every 1/10 unit, the concentration of the compound such as sodium phosphite is rhodium in weight ratio. : Phosphorus ⁇ 4: 1, 9: 1, 20: 1, etc. This makes it speculated that a predetermined rhodium phosphorus atomic group is formed in the electroplating solution.
  • the concentration of metal rhodium and phosphorous acid, alkali metal phosphite such as sodium phosphite, alkaline earth metal phosphite or ammonium phosphite is reduced.
  • alkali metal phosphite such as sodium phosphite, alkaline earth metal phosphite or ammonium phosphite
  • the deteriorated electrolytic rhodium plating solution can be recovered, and the number of turnovers of the electrolytic rhodium plating solution can be dramatically improved as compared with the conventional case.
  • “sodium phosphite salt” means sodium phosphite pentahydrate, which has a composition formula of HNa 2 O 3 P ⁇ 5H 2 O or Na 2 HPO 3 ⁇ 5H 2 O. .
  • the electrolytic rhodium plating solution of the present invention contains 0.001 to 30 g / L of at least one compound selected from the group consisting of alkali metal sulfates, alkaline earth metal sulfates or ammonium sulfates. This is because these inorganic compounds are conductive salts.
  • the conductive salt stabilizes the electrolytic rhodium plating solution of the present invention, but if it exceeds 30 g / L, it is necessary to increase the amount of metal rhodium. In particular, when the content is 0.001 to 30 g / L, stable plating deposits can be obtained when a large plating bath is used.
  • Sodium salt, potassium salt, magnesium salt, calcium salt and ammonium salt are preferred, and sodium salt, potassium salt and ammonium salt are particularly preferred.
  • the concentration is preferably 20 to 30 g / L.
  • the sulfuric acid bath and the phosphoric acid bath preferably have a pH of 1 or less. This is because a dense amorphous rhodium-phosphorous plating film can be obtained.
  • the temperature of the solution is preferably 40 to 70 ° C. in both the sulfuric acid bath and the phosphoric acid bath. This is because the hardness of the rhodium phosphorous plating film is lowered and the flexibility of the rhodium phosphorous plating film is increased.
  • the lowermost layer of the dense amorphous structure has an amorphous structure regardless of the form of precipitation on the underlying surface.
  • the intermediate layer having a dense amorphous structure has no crystal grains and low internal stress. For this reason, even if a dense amorphous structure is formed by thick plating, it does not peel off from the surface layer.
  • a dense amorphous structure is used for the intermediate layer, even in an ultrathin intermediate layer such as strike plating, the precipitation structure of the noble metal plating on the surface layer is affected by the intermediate layer and has an effect of becoming dense.
  • the concentration ratio and the film thickness are appropriately selected in accordance with the required characteristics of electrical parts such as electrical contacts, electronic parts such as connectors, and automobile parts such as corrosion resistance.
  • a rhodium phosphorous plating film having a crystalline structure can be provided. For example, since a uniform smooth surface can be obtained, the contact point area becomes large when applied to a contact. Moreover, when the rhodium concentration is high, the hardness of the rhodium phosphorous plating film is high as before, and stable wear characteristics are obtained. In addition, the rhodium precipitates on the rhodium-phosphorous plating film do not have strong internal stress and do not easily generate wear powder as in the past.
  • the appearance of the obtained rhodium phosphorus plating test pieces was in a silver-white amorphous state.
  • the rhodium phosphorus plating test piece was used as an anode, a 40 mm ⁇ 20 mm copper test piece was used as a cathode, a low voltage of 0.74 V was applied, and the porosity was measured for 20 minutes in a 5% sulfuric acid solution. The result was obtained.
  • the porosity when the test piece not subjected to rhodium phosphorus plating was used as an anode was defined as 100%.
  • the rhodium (as rhodium sulfate) was 3 g / L
  • the phosphorus concentration (as sodium hypophosphite) was 0.05 g / L and 1.0 g / L.
  • a 20 mm ⁇ 20 mm copper test piece was electroplated to a thickness of 0.10 ⁇ m at a current density of 4 A / dm 2 .
  • the appearance of the obtained rhodium phosphorus plating test piece was a black precipitate.
  • a 40 mm ⁇ 20 mm copper test piece as a cathode
  • a low voltage of 0.74 V was applied, and the porosity was measured for 20 minutes in a 5% sulfuric acid solution.
  • the results of 12.0% and 8% in the column were obtained.
  • the effectiveness 12.0% of the trial number 07 is compared with the effectiveness 4.1% of the trial number 04. That is, it can be seen that the black rhodium precipitate film has a porosity that is twice or more worse than the rhodium phosphorus amorphous structure film of the present invention.
  • FIG. 1 shows a scanning electron microscope image (30,000 times) obtained by applying gold strike plating to the surface of the nickel coating. It can be seen that a wavy pattern is formed on the surface form of the nickel coating whose contrast is enhanced by gold strike plating.
  • rhodium phosphorus strike plating of 10 V ⁇ 10 seconds was performed on this nickel coating in a rhodium phosphorus strike bath with rhodium (as rhodium sulfate) at 1 g / L and phosphorus concentration (as calcium phosphite) at 1 g / L.
  • the rhodium (as rhodium sulfate) concentration was 4.0 g / L
  • sulfuric acid was 50 mL / L
  • the pure rhodium coating was electroplated to a thickness of 0.5 ⁇ m at a current density of 4 A / dm 2 .
  • a test piece electroplated with this pure rhodium film was subjected to a defect detection test at a voltage of 5 V ⁇ 10 minutes in a 5% sodium chloride aqueous solution using a 20 mm ⁇ 20 mm stainless steel piece as a cathode. Corrosion defects were detected.
  • Comparative Example 3 A sample of Comparative Example 3 was prepared except for rhodium phosphorus strike plating, and a corrosion resistance test was performed. Corrosion defects were detected at the first time.
  • a 20 mm ⁇ 20 mm copper test piece was plated with nickel of 5 ⁇ m with an electrolytic nickel plating solution of nickel sulfate salt 300 g / L, sodium chloride salt 20 g / L and phosphoric acid 0.30 mL / L.
  • a rhodium phosphorus amorphous film having a rhodium concentration (as rhodium sulfate) of 10 g / L and a phosphorus concentration (as sodium phosphite salt) of 1 g / L was deposited on this nickel film by 4.5 ⁇ m. This scanning ion microscope image is shown in FIG.
  • the white portion at the top of FIG. 2 is a rhodium phosphorous amorphous film with enhanced contrast.
  • this surface morphology is compared with the surface morphology of the nickel coating in FIG. 1, it can be seen that the presence of crystal grains is not confirmed.
  • the black part of the middle stage of FIG. 2 is an amorphous structure of rhodium phosphorus. In the middle black portion of FIG. 2, no crystal structure is found.
  • the crystal grains of the nickel plating shown in FIG. 1 are not formed at the interface between the black portion in the middle stage of FIG. 2 and the nickel plating in the lower stage. That is, it can be seen that the precipitation form of the base does not reach the amorphous structure of rhodium phosphorus just above.
  • rhodium (as rhodium sulfate) concentration was kept constant at 2.0 g / L
  • the sulfuric acid concentration was 30 mL / L
  • the phosphorus concentration (sodium phosphite) was as shown in the left column of Table 3.
  • a 20 mm ⁇ 20 mm copper test piece was electroplated in the same manner as in Test No. 14 except that sodium phosphite was not added. This was designated as trial number 19.
  • the film thicknesses at the four corners and the center of the test piece 19 were measured, the results in the right column of Table 3 were obtained. From this result, it can be seen that the pure rhodium film is an unstable precipitate with large variations.
  • a 20 mm ⁇ 20 mm copper test piece was electroplated in the same manner as in Test No. 17 except that 1 g / L of hypophosphite sodium salt was added. This was designated as trial number 20.
  • the film thicknesses at the four corners and the center of the copper test piece of sample number 20 were measured, the results in the right column of Table 3 were obtained. From this result, it can be seen that the rhodium phosphorous film deposited by sodium hypophosphite is an unstable precipitate with large variations.
  • the ratio of the rhodium phosphorus amorphous coating was determined by an energy dispersive X-ray analyzer (X-max N manufactured by Horiba, Ltd.), it was 92% rhodium and 8% phosphorus. Further, in the intensity analysis using an X-ray diffractometer, no diffraction image specific to Rh metal was observed. The melting point of the rhodium-phosphorus 8.2% eutectic alloy is 1,255 ° C.
  • a pure rhodium electrolytic plating film was deposited on the nickel film in a thickness of 4.5 ⁇ m in the same manner as in Example 4 except that the phosphorus concentration (as sodium hypophosphite salt) was changed to 0 g / L.
  • the crystal structure of this robust rhodium coating is shown in FIG.
  • the electrolytic rhodium plating solution of the present invention can obtain a rhodium phosphorous plating film in a fine amorphous state, so that it can be used as an alternative to conventional thick / thin rhodium plating products, or as a substrate and other noble metal plating surface layers. It can be used as an intermediate layer for connecting, and as a strike-plated product for applications such as electrical parts, electronic parts, automobile parts, catalyst / sensor parts, and decorative products.

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PCT/JP2018/010208 2018-03-15 2018-03-15 電解ロジウムめっき液 WO2019176049A1 (ja)

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KR1020197017863A KR102549660B1 (ko) 2018-03-15 2018-03-15 전해 로듐 도금액
CN201880005951.4A CN110494596B (zh) 2018-03-15 2018-03-15 电解铑电镀液
JP2018536208A JP6474536B1 (ja) 2018-03-15 2018-03-15 電解ロジウムめっき液
PCT/JP2018/010208 WO2019176049A1 (ja) 2018-03-15 2018-03-15 電解ロジウムめっき液
TW108107690A TWI794440B (zh) 2018-03-15 2019-03-07 電解銠電鍍液

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5848688A (ja) * 1981-09-17 1983-03-22 Nippon Mining Co Ltd 電気黒色ロジウムメッキ浴
JPS60131994A (ja) * 1983-12-21 1985-07-13 C Uyemura & Co Ltd 鉄・リン電気めつき浴
JPH01290788A (ja) * 1988-05-16 1989-11-22 Nippon Mining Co Ltd 低応カロジウムめっき液及びその製造方法
JPH06264281A (ja) * 1993-03-11 1994-09-20 Bikutoria:Kk パラジウムメッキ液及び該メッキ液を用いたパラジウムメッキ方法
JPH1060680A (ja) * 1996-08-14 1998-03-03 C Uyemura & Co Ltd ニッケル、コバルト又はニッケル・コバルト合金とリンとの合金めっき浴及びめっき方法
JP2002241985A (ja) * 2001-02-14 2002-08-28 Satosen Co Ltd ニッケル−タングステン−リン合金皮膜及びそのめっき液

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58519B2 (ja) * 1975-07-25 1983-01-06 タナカキキンゾクコウギヨウ カブシキガイシヤ ロジウムメツキヨク
JPS5224131A (en) * 1975-08-14 1977-02-23 Dowa Mining Co Luster* thick rhodium plating method
JPH0752591B2 (ja) 1987-12-07 1995-06-05 日本電気株式会社 半導体光メモリーの駆動方法
JPH0741985A (ja) * 1993-07-29 1995-02-10 Pentel Kk ニッケル−リン合金めっきの製造方法
US6325910B1 (en) * 1994-04-08 2001-12-04 Atotch Deutschland Gmbh Palladium colloid solution and its utilization
JP5337760B2 (ja) * 2010-05-24 2013-11-06 ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． 金属表面処理水溶液および金属表面の変色防止方法
JP5687051B2 (ja) * 2010-12-27 2015-03-18 株式会社ブリヂストン 銅−亜鉛合金めっき方法およびそれに用いる銅−亜鉛合金めっき浴
KR20150020686A (ko) * 2012-10-04 2015-02-26 니혼 엘렉트로플레이팅 엔지니어스 가부시키가이샤 비시안계 전해 금도금액
CN103484905B (zh) * 2013-10-12 2015-11-18 中南大学 一种电镀铑层的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5848688A (ja) * 1981-09-17 1983-03-22 Nippon Mining Co Ltd 電気黒色ロジウムメッキ浴
JPS60131994A (ja) * 1983-12-21 1985-07-13 C Uyemura & Co Ltd 鉄・リン電気めつき浴
JPH01290788A (ja) * 1988-05-16 1989-11-22 Nippon Mining Co Ltd 低応カロジウムめっき液及びその製造方法
JPH06264281A (ja) * 1993-03-11 1994-09-20 Bikutoria:Kk パラジウムメッキ液及び該メッキ液を用いたパラジウムメッキ方法
JPH1060680A (ja) * 1996-08-14 1998-03-03 C Uyemura & Co Ltd ニッケル、コバルト又はニッケル・コバルト合金とリンとの合金めっき浴及びめっき方法
JP2002241985A (ja) * 2001-02-14 2002-08-28 Satosen Co Ltd ニッケル−タングステン−リン合金皮膜及びそのめっき液

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