Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
  • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
  • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
  • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
• • 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
  • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt

Definitions

• the present invention relates to a nickel plating solution containing a nickel component and SiC particles, and a method for producing a nickel or nickel alloy plating film.
• Nickel or nickel alloy plating is used in the field of surface treatment technology for the purpose of improving circuit formation, decoration, and wear resistance and corrosion resistance of mechanical parts.
• plating films in which fine particles of SiC (silicon carbide) are dispersed in nickel or nickel alloy plating films are applied to parts that require high wear resistance, such as sliding parts such as shafts, cylinders, and bearings.
• An example of the method of forming the above plating film is to perform electrolytic plating or electroless plating using a plating solution containing a water-soluble nickel compound and SiC fine particles, thereby forming a plating film in which SiC is dispersed in a nickel matrix. (See Patent Literature 1, for example).
• the SiC fine particles contained in the plating film are dispersed uniformly in the plating film at a high concentration.
• concentration of the SiC fine particles contained in the plating film can be increased.
• the concentration of the SiC fine particles in the plating solution increases, the excessively added SiC fine particles settle to the bottom of the container containing the plating solution. Therefore, even if the concentration of the SiC fine particles in the plating solution is excessively increased, the substantial concentration of the SiC fine particles in the plating solution near the object to be plated reaches a ceiling. As a result, the deposition efficiency of the SiC fine particles onto the nickel plating film is lowered.
• a nickel plating solution for solving the above problems contains a water-soluble nickel compound, SiC fine particles, and a dispersant consisting of at least one selected from deoxycholic acid and deoxycholic acid derivatives.
• the dispersant comprising at least one selected from deoxycholic acid and deoxycholic acid derivatives can enhance the dispersibility of the SiC fine particles contained in the nickel plating solution.
• the SiC fine particles can be uniformly deposited in the nickel matrix of the plating film.
• it is possible to suppress sedimentation of the SiC fine particles in the nickel plating solution it is possible to increase the deposition efficiency of the SiC fine particles onto the plating film.
• the dispersant can enhance the dispersibility of the SiC fine particles contained in the nickel plating solution.
• the SiC fine particles can be uniformly deposited in the nickel matrix of the plating film, and the deposition efficiency of the SiC fine particles onto the plating film can be enhanced.
• the electroless plating solution used for electroless plating contains a nickel component, a reducing agent, a complexing agent, a pH adjuster, SiC fine particles, and a dispersing agent.
• Nickel component As the nickel component, a water-soluble nickel compound that is soluble in the plating solution is used.
• the water-soluble nickel compound is, for example, at least one selected from the group consisting of nickel sulfate, nickel chloride, nickel sulfamate, and nickel hypophosphite.
• nickel sulfate is preferable because it has good solubility in the plating solution.
• concentration of the nickel component is, for example, 0.5 g/L or more and 50 g/L or less.
• the reducing agent is, for example, at least one selected from the group consisting of hypophosphorous acid, hypophosphite (sodium salt, potassium salt, ammonium salt), borohydride compounds such as dimethylamine borane, and hydrazine. .
• the concentration of the reducing agent is, for example, 0.01 g/L or more and 100 g/L or less.
• Complexing agents include, for example, monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, aminopolycarboxylic acids, ethylenediaminediacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and their ammonium, potassium and sodium salts. At least one selected from the group consisting of Monocarboxylic acids are, for example, acetic acid or formic acid. Dicarboxylic acids are, for example, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid. Hydroxycarboxylic acids are, for example, malic acid, lactic acid, glycolic acid, gluconic acid, citric acid.
• Aminopolycarboxylic acids are, for example, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid. Phosphonic acids, amino acids and the like may also be used as complexing agents.
• concentration of the complexing agent is, for example, 5 g/L or more and 180 g/L or less.
• the pH adjuster is, for example, at least one selected from the group consisting of inorganic acids such as sulfuric acid and phosphoric acid, sodium hydroxide, and aqueous ammonia.
• the pH range of the electroless plating solution is usually 2 or more and 9 or less.
• the pH range of the electroless plating solution of this embodiment is 4.0 or more and 6.0 or less.
• SiC fine particles improve the wear resistance and corrosion resistance of the plating film by dispersing in the nickel matrix of the nickel or nickel alloy plating film.
• SiC fine particles for example, particles of arbitrary shapes including plate-like, spherical, and amorphous shapes can be applied.
• the particle diameter of the SiC fine particles is preferably 0.1 ⁇ m or more and 3.0 ⁇ m or less, more preferably 0.2 ⁇ m or more and 2.0 ⁇ m or less, as a 50% particle diameter (median diameter D50).
• the concentration of SiC fine particles in the electroless plating solution is preferably 100 mg/L or more and 5000 mg/L or less, more preferably 300 mg/L or more and 3000 mg/L or less, and further preferably 400 mg/L or more and 2800 mg/L or less. preferable.
• the dispersant enhances the dispersibility of the SiC fine particles contained in the electroless plating solution, thereby uniformly depositing the SiC fine particles in the nickel matrix of the plating film. In addition, the dispersant suppresses sedimentation of the SiC fine particles in the nickel plating solution, thereby increasing the deposition efficiency of the SiC fine particles onto the plating film.
• the dispersant suppresses the sedimentation of the SiC fine particles in the nickel plating solution, thereby suppressing the consumption of the nickel component in the nickel plating solution due to the plating reaction occurring on the surface of the precipitated SiC fine particles.
• At least one selected from deoxycholic acid and deoxycholic acid derivatives is used as the dispersant.
• Deoxycholic acid derivatives are, for example, bile acids such as hyodeoxycholic acid, chenodeoxycholic acid, and cholic acid. These bile acids are added alone or in the form of salts such as sodium.
• the total concentration of the dispersant composed of at least one selected from deoxycholic acid and deoxycholic acid derivatives is preferably 10 ⁇ g/L or more and 10000 ⁇ g/L or less, more preferably 20 ⁇ g/L or more and 5000 ⁇ g/L or less. and more preferably 40 ⁇ g/L or more and 4800 ⁇ g/L or less.
• an example of the concentration of deoxycholic acid in the electroless plating solution is 40 ⁇ g/L or more and 280 ⁇ g/L or less.
• an example of the concentration of hyodeoxycholic acid in the electroless plating solution is 600 ⁇ g/L or more and 4800 ⁇ g/L or less.
• the concentration of the dispersant is below the above lower limit, the effect of improving the uniformity of precipitation of the SiC fine particles and the efficiency of precipitation is reduced. Further, when the concentration of the dispersant exceeds the above upper limit, it is difficult to improve the uniform deposition property and the deposition efficiency of the SiC fine particles with respect to the amount of the dispersant added, and rather they tend to gradually decrease. Therefore, by setting the concentration of the dispersing agent within the above range from the lower limit to the upper limit, the SiC fine particles are deposited more uniformly in the nickel matrix of the plating film, and the deposition efficiency of the SiC fine particles onto the plating film is increased. can be enhanced.
• the concentration of the dispersing agent when the concentration of the dispersing agent is excessively high, the plating solution tends to foam, which may adversely affect the workability of the plating process.
• the concentration of the dispersing agent by setting the concentration of the dispersing agent to be equal to or less than the above upper limit value, it is possible to suppress deterioration of workability in the plating process.
• deoxycholic acid and deoxycholic acid derivatives have dispersibility not only in SiC fine particles but also in graphite. Therefore, even if graphite diffuses into the nickel plating solution, deoxycholic acid and deoxycholic acid derivatives stabilize and disperse graphite, thereby avoiding the above-described poor appearance and poor plating adhesion.
• additives may be added to the electroless plating solution.
• Stabilizers which are examples of additives, are selected from the group consisting of, for example, lead salts such as lead nitrate and lead acetate, bismuth salts such as bismuth nitrate and bismuth acetate, and sulfur compounds such as thiodiglycolic acid and sodium thiosulfate. is at least one
• the amount of stabilizer added is, for example, 0.01 mg/L or more and 100 mg/L or less.
• a pH buffer which is an example of an additive, is, for example, at least one selected from the group consisting of boric acid, phosphoric acid, phosphorous acid, carbonic acid, sodium salts, potassium salts, and ammonium salts thereof.
• the amount of the pH buffer added is, for example, 0.1 g/L or more and 200 g/L or less.
• a surfactant which is an example of an additive, is, for example, at least one selected from the group consisting of nonionic, cationic, anionic, and amphoteric.
• the amount of surfactant added is, for example, 0.1 mg/L or more and 100 mg/L or less.
• An example of an electroless plating solution is 25 g/L nickel sulfate hexahydrate, 25 g/L sodium hypophosphite monohydrate, 20 g/L malic acid, and 10 g/L sodium acetate. , 10 g/L of sodium hydroxide, 100 mg/L or more and 5000 mg/L or less of SiC fine particles, and 10 ⁇ g/L or more and 10000 ⁇ g/L or less of a dispersant.
• an optional stabilizer is added to the electroless plating solution so that the bismuth ion in the electroless plating solution is 0.5 mg/L.
• Electroplating solution In the case of the electroplating method, an electroplating solution such as Watt's bath or nickel sulfamate bath is used. All of these electroplating solutions contain a nickel component, SiC fine particles, and a dispersant. A metal component such as tungsten may be added to the plating solution for the purpose of increasing the hardness of the plating film.
• the nickel component is, for example, at least one selected from the group consisting of water-soluble nickel compounds such as nickel sulfate hexahydrate, nickel chloride hexahydrate, and nickel carbonate tetrahydrate.
• water-soluble nickel compounds nickel sulfate hexahydrate or nickel chloride hexahydrate is preferable in terms of excellent deposition on the material to be plated, and nickel sulfate hexahydrate and nickel chloride hexahydrate are preferred. A mixture is more preferred.
• nickel sulfate hexahydrate and nickel chloride hexahydrate are mixed and used as a nickel component
• the amount of nickel sulfate hexahydrate added is 200 g / L or more and 500 g / L or less, and nickel chloride hexahydrate The amount added is preferably 70 g/L or less.
• the nickel component is, for example, a water-soluble nickel compound such as nickel sulfamate, nickel chloride hexahydrate, or a mixture thereof.
• SiC fine particles Regarding the SiC fine particles contained in the electrolytic plating solution, there is no great difference in the shape, proper value of particle size, and proper value of concentration of the SiC fine particles used in the electroless plating solution. That is, the SiC fine particles contained in the electrolytic plating solution can be used in the same form as the SiC fine particles used in the electroless plating solution and at the same concentration as the SiC fine particles used in the electroless plating solution.
• the dispersant contained in the electrolytic plating solution can be of the same type and form as the dispersant used in the electroless plating solution. Also, the proper value of the concentration of the dispersant in the electrolytic plating solution is equivalent to the proper value of the concentration of the dispersant used in the electroless plating solution.
• the primary brightener is, for example, at least one selected from the group consisting of saccharin, benzene such as sodium naphthalenesulfonate, derivatives such as naphthalene, sulfonates, and sulfonamides.
• the secondary brightener is at least one selected from the group consisting of butynediol, propargyl alcohol and coumarin.
• An example of an electroplating solution for a Watt bath is 240 g/L nickel sulfate hexahydrate, 45 g/L nickel chloride hexahydrate, 45 g/L boric acid, and 5 g/L oxalic acid. It contains nickel dihydrate particles, SiC fine particles of 100 mg/L or more and 5000 mg/L or less, and a dispersant of 10 ⁇ g/L or more and 10000 ⁇ g/L or less. Other brighteners may include 2 g/L or less of saccharin and 0.2 g/L or less of butynediol. Further, the pH range of the electroplating solution in the Watt bath is 4.0 or more and 4.5 or less.
• An example plating solution for a nickel sulfamate bath is 450 g/L nickel sulfamate tetrahydrate, 15 g/L nickel chloride hexahydrate, 30 g/L boric acid, and 5 g/L oxalic acid. It contains nickel dihydrate particles, SiC fine particles of 100 mg/L or more and 5000 mg/L or less, and a dispersant of 10 ⁇ g/L or more and 10000 ⁇ g/L or less. Further, the pH range of the electrolytic plating solution in the nickel sulfamate bath is 4.0 or more and 4.5 or less.
• the method for producing the nickel plating solution is not particularly limited to either the electroless plating solution or the electrolytic plating solution.
• Any of the nickel plating solutions can be prepared by diluting one or two or more chemicals in which a plurality of components are mixed with water, or by dissolving a single raw material in water one by one.
• a method for adding the SiC fine particles is not particularly limited. From the viewpoint of maximizing the interaction with the dispersant, for example, SiC fine particles are added to a dispersant diluted with water to prepare a dispersion liquid in which the SiC fine particles are sufficiently dispersed, and then the dispersion is added to the nickel plating solution. Thus, a desired nickel plating solution may be obtained.
• LC-MS/MS is a combination of high-performance liquid chromatograph (HPLC) and triple quadrupole mass spectrometer (MS/MS).
• HPLC high-performance liquid chromatograph
• MS/MS triple quadrupole mass spectrometer
• the dispersant comprising at least one selected from deoxycholic acid and deoxycholic acid derivatives can enhance the dispersibility of the SiC fine particles contained in the nickel plating solution.
• the SiC fine particles can be uniformly deposited in the nickel matrix of the plating film.
• the dispersant can suppress the sedimentation of the SiC fine particles in the nickel plating solution, the deposition efficiency of the SiC fine particles onto the plating film can be enhanced.
• the dispersant suppresses the sedimentation of the SiC fine particles in the nickel plating solution, causing a plating reaction on the surface of the precipitated SiC fine particles to consume the nickel component in the nickel plating solution. can be suppressed.
• the dispersant disperses and stabilizes the graphite, which is the residue of the raw material of the SiC fine particles, in the plating solution. Defects can be suppressed.
• the concentration of SiC fine particles contained in the nickel plating solution is preferably 100 mg/L or more and 5000 mg/L or less, more preferably 300 mg/L or more and 3000 mg/L or less, and still more preferably 400 mg/L or more and 2800 mg. /L or less.
• the concentration of the dispersant contained in the nickel plating solution is preferably 10 ⁇ g/L or more and 10000 ⁇ g/L or less, more preferably 20 ⁇ g/L or more and 5000 ⁇ g/L or less, and still more preferably 40 ⁇ g/L or more and 4800 ⁇ g/L or less. is.
• the concentration of the SiC fine particles contained in the nickel plating solution and the concentration of the dispersing agent within the above ranges, the dispersibility of the SiC fine particles contained in the nickel plating solution can be favorably enhanced.
• the SiC fine particles can be more uniformly deposited in the nickel matrix of the plating film, and the deposition efficiency of the SiC fine particles onto the plating film can be further enhanced.
• the dispersant enhances the dispersibility of the SiC fine particles contained in the nickel plating solution.
• the SiC fine particles can be uniformly deposited in the nickel matrix of the plating film, and the deposition efficiency of the SiC fine particles onto the plating film can be enhanced.
• SiC fine particle additives 1 to 5 were prepared by adding SiC fine particles to pure water.
• the SiC fine particle additives 3 to 5 contain a dispersant in addition to pure water and SiC fine particles.
• Electroless plating was performed using an electroless nickel plating solution obtained by adding 4 mL/L of SiC fine particle additive 3 to medium-high phosphorus type electroless nickel plating solution “SEC-930” (manufactured by Nippon Kanigen Co., Ltd.).
• the base material was immersed in an electroless plating solution stirred with a stirrer, electroless plated at 90° C. until the film thickness reached about 5 ⁇ m, then washed with water and dried.
• Example 2 Using an electroless nickel plating solution obtained by adding 28 mL / L of SiC fine particle additive 3 to a medium-high phosphorous type electroless nickel plating solution “SEC-930” (manufactured by Nippon Kanigen Co., Ltd.), the same procedure as in Example 1 was performed. Electroplating treatment was applied.
• Example 3 Using an electroless nickel plating solution obtained by adding 3 mL / L of SiC fine particle additive 4 to a medium-high phosphorous type electroless nickel plating solution “SEC-930” (manufactured by Nippon Kanigen Co., Ltd.), the same procedure as in Example 1 was performed. Electroplating treatment was applied.
• Example 4 Using an electroless nickel plating solution obtained by adding 24 mL / L of SiC fine particle additive 4 to a medium-high phosphorus type electroless nickel plating solution “SEC-930” (manufactured by Nippon Kanigen Co., Ltd.), the same procedure as in Example 1 was performed. Electroplating treatment was applied.
• Example 5 Using an electroless nickel plating solution obtained by adding 10 mL / L of SiC fine particle additive 5 to a medium-high phosphorus type electroless nickel plating solution “SEC-930” (manufactured by Nippon Kanigen Co., Ltd.), the same procedure as in Example 1 was performed. Electroplating treatment was applied.
• Electrolytic plating was performed using an electrolytic nickel plating solution containing 4 mL/L of SiC fine particle additive 3 in a Watts bath.
• the Watt bath contained 280 g/L nickel sulfate, 40 g/L nickel chloride, and 20 g/L boric acid with a pH of 4.5.
• the substrate was immersed while being stirred with a stirrer, electroplated at 50° C. by DC electrolysis with a current density of 2 A/dm 2 until the film thickness reached about 5 ⁇ m, then washed with water and dried.
• Example 1 Using an electroless nickel plating solution obtained by adding 4 mL / L of SiC fine particle additive 1 to a medium-high phosphorus type electroless nickel plating solution “SEC-930” (manufactured by Nippon Kanigen Co., Ltd.), the same procedure as in Example 1 was performed. Electroplating treatment was applied.
• Electroplating was performed in the same procedure as in Example 6 using an electrolytic nickel plating solution in which 4 mL/L of SiC fine particle additive 1 was added to the same Watt bath as in Example 6.
• Tables 1 and 2 show the plating solution preparation conditions, plating solution compositions, and evaluation results of evaluations 1 to 3 in Examples 1 to 6 and Comparative Examples 1 to 3.
• Example 5 which contains 50 mg/L of deoxycholic acid and 2000 mg/L of cholic acid, and the total concentration of the dispersant is 2050 mg/L, uniform deposition of SiC fine particles and an effect of improving the deposition efficiency were confirmed. was done.
• Example 1 when comparing Example 1 and Comparative Example 1 in which conditions other than the presence or absence of a dispersant are the same for the case of electroless plating, the plating solution of Example 1 containing a dispersant was superior to Comparative Example 1 in the stability of the plating solution and the dispersibility of the SiC fine particles in the plating film.
• the content of SiC fine particles in the plating film of Example 1 was significantly higher than that of Comparative Example 1. Therefore, by adding a dispersant to the plating solution, the deposition efficiency of the SiC fine particles on the plating film was improved.
• Example 4 and Comparative Example 2 which were identical in conditions other than the presence or absence of the dispersant, were compared.
• Example 6 containing a dispersant is more SiC in the plating film than Comparative Example 3. Excellent fine particle dispersibility.
• the content of SiC fine particles in the plating film of Example 6 was significantly higher than that of Comparative Example 3. Therefore, it was confirmed that the deposition efficiency of the SiC fine particles onto the plated film was enhanced by adding a dispersant to the plating solution not only in the electroless plating but also in the electroplating.
• the plating film manufactured using the nickel plating solution of the present embodiment is not limited to the nickel plating film, and a nickel alloy plating film is produced by adding a metal component to the components of the nickel plating solution of the present embodiment. may be formed.
• the concentration of hyodeoxycholic acid should be less than 600 ⁇ g/L as long as the dispersibility of the SiC fine particles contained in the nickel plating solution is ensured. may be greater than 4800 ⁇ g/L.
• the concentration of deoxycholic acid may be less than 40 ⁇ g/L as long as the dispersibility of the SiC fine particles contained in the nickel plating solution is ensured. , may be greater than 280 ⁇ g/L.
• the total concentration of the components constituting the dispersant may be less than 10 ⁇ g/L. Further, the total concentration of the components constituting the dispersant may exceed 10000 ⁇ g/L as long as the nickel plating solution and the plating film produced using the nickel plating solution are not adversely affected.

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• 2021
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