Method for manufacturing electroplated members, electro-nickel plating method, method for manufacturing nickel-plated members, method for manufacturing tin-plated members, and method for manufacturing zinc-plated members

Abstract

A method for manufacturing an electroplated member according to one aspect of the present disclosure comprises a step of electroplating a substrate using a plating bath containing an additive, wherein the substrate is irradiated with ultrasonic waves during the electroplating process, and the additive comprises either or both a water-soluble aliphatic monohydric alcohol or a water-soluble aliphatic carboxylic acid. An electroplating apparatus according to another aspect of the present disclosure comprises an electroplating tank configured to hold a plating bath containing an additive, and an ultrasonic oscillator configured to emit ultrasonic waves into the plating bath, wherein the additive comprises either or both a water-soluble aliphatic monohydric alcohol or a water-soluble aliphatic carboxylic acid.

Description

[Technical Field]

[0001] This disclosure relates to a method for manufacturing an electroplated member, an electroplating nickel method, a method for manufacturing a plated member, a method for manufacturing a nickel-plated member, and a method for manufacturing a tin-plated member. This application is based on Japanese Patent Application No. 2025-033717, No. 2025-033829, No. 2025-033635, No. 2025-033789, No. 2025-033624, and No. 2025-033624, which were filed in Japan on March 4, 2025. Priority is claimed in accordance with Japanese Patent Application No. 2025-033613 filed in this book, Japanese Patent Application No. 2025-033632 filed in Japan on March 4, 2025, Japanese Patent Application No. 2025-033745 filed in Japan on March 4, 2025, Japanese Patent Application No. 2025-033737 filed in Japan on March 4, 2025, and Japanese Patent Application No. 2025-033780 filed in Japan on March 4, 2025, and the contents thereof are incorporated herein by reference. [Background technology]

[0002] (Background technology for manufacturing method A) Electroplating is a surface treatment method that electrochemically deposits metal onto the surface of a substrate made of metal or nonmetal. Electroplating allows for the formation of plating films on a wide variety of substrates. Furthermore, various metals can be used as the plating film. Therefore, electroplating is widely used.

[0003] In electroplating, metal ions in the plating bath are reduced on the surface of the substrate to form a plating film. The amount of plating deposited when all the current passing through the substrate is used for the electrodeposition reaction is called the theoretical deposition amount. However, in reality, some of the current is consumed in chemical reactions other than electrodeposition. The ratio of the actual deposition amount to the theoretical deposition amount is referred to in this disclosure as the reduction efficiency or plating efficiency. Increasing the reduction efficiency is important for improving the efficiency of the electroplating process.

[0004] Prior art has attempted to increase reduction efficiency by, for example, incorporating various additives into the plating bath. Patent documents 1 to 3 disclose various additives used in plating baths. (Background technology for manufacturing method A)

[0005] (Background technology for manufacturing method B) Electroplating allows for the formation of various metal films, such as tin, zinc, chromium, and nickel, on the surface of a substrate. This improves the aesthetics and corrosion resistance of the substrate. Therefore, electroplating is used to enhance the functionality of various materials, including steel.

[0006] However, during the electroplating process, a diffusion layer is formed near the surface of the substrate material being plated. The diffusion layer is a thin layer of solution that comes into contact with the substrate during the electroplating process, creating a concentration gradient with the main solution due to mass transfer by diffusion. The diffusion layer imposes constraints on the plating rate and film characteristics.

[0007] As a means of overcoming the constraints imposed by the diffusion layer, stirring using ultrasonically induced cavitation has been investigated.

[0008] For example, Patent Document 4 describes a method for manufacturing a surface-treated steel sheet, which includes a step of using a tin electroplating solution and electroplating a steel sheet as it moves through the tin electroplating solution to form a tin plating layer on at least one surface of the steel sheet, wherein the moving speed of the steel sheet is 1 m / min or more, and during electroplating, the ultrasonic oscillation intensity at a position 20 mm away from the surface of the steel sheet is converted to 0.001 WATT / cm 2 From 100 watts / cm 2 A method for manufacturing a surface-treated steel sheet is disclosed, characterized by applying ultrasonic vibrations to the steel sheet that have an intensity within a certain range and a frequency within the range of 10 Hz to 10 MHz.

[0009] Furthermore, Patent Document 5 discloses a drainage device with an ultrasonic cleaning function, characterized by comprising: a drainage section provided downstream of a water receiving section and forming a reservoir; an ultrasonic oscillator that emits ultrasonic waves into the reservoir in the drainage section; a control device that controls the oscillation of the ultrasonic oscillator; and a suppression section that suppresses the intrusion of bubbles containing surfactants into the reservoir. (Background technology for manufacturing method B)

[0010] (Background technology for manufacturing method C) Electroplating of nickel is used as a surface treatment coating for various components such as battery cans and fuel tanks. In conventional technology, when forming a nickel film on a base material by electroplating, weakly acidic electroplating baths such as sulfamic acid baths and watt baths are used.

[0011] When performing electroplating with nickel using such an electroplating bath, it is considered essential to add a pH buffer to the electroplating bath.

[0012] When the base material is immersed in an electroplating nickel bath and a voltage is applied between the base material and the electroplating nickel bath, a chemical reaction occurs that forms Ni plating around the base material. 2+ This is consumed. Additionally, as a side reaction, hydrogen gas is generated around the base material, causing the pH to rise. As a result, a concentration gradient is created toward the plated surface.

[0013] When a voltage is applied between the base material and the electroplated nickel bath at a high pH, ​​Ni 2+ A reaction occurs in which nickel hydroxide precipitates, hindering the formation of nickel plating. To form a stable nickel film, it is important to suppress fluctuations in the pH of the electroplated nickel bath. For this reason, boric acid has conventionally been used as a pH buffer to suppress pH fluctuations in sulfamic acid baths, watt baths, etc., during electrodeposition.

[0014] However, boric acid is designated as a regulated substance under the Water Pollution Control Law. Using boric acid as a pH buffer increases the cost of wastewater treatment. Therefore, there is a need for electro-nickel plating methods that do not use boric acid. Organic carboxylic acids and other substances have been proposed as alternative pH buffers to boric acid.

[0015] For example, Patent Document 6 discloses an electro-nickel plating bath used when forming a nickel film on an object to be plated by electroplating, characterized in that the pH of the electro-nickel plating bath is 1.0 to 6.0 and it contains a monocarboxylic acid as a pH buffer.

[0016] Patent Document 7 discloses a scanning electroplating method in which, in electroplating, the anode is scanned relative to the cathode substrate on which the plating film is to be formed, the high current density region where the cathode and anode are closest and the most current flows is moved, and the plating film is formed while removing the oxide film on the cathode surface using the reducing action of hydrogen gas generated in the high current density region, wherein the high current density region is point-shaped or linear on the cathode substrate, the average current density obtained by dividing the current by the area of ​​the anode surface that is in contact with the plating solution and faces the cathode substrate at an angle of less than 90 degrees is 20 A / dm2 or more, and a nickel electro-nickel plating bath with added citric acid is used.

[0017] Organic carboxylic acids are superior to boric acid in terms of environmental impact. However, when using organic carboxylic acids as a pH buffer for electroplating nickel, carbon from the pH buffer is incorporated into the plating film, altering the film's properties. Therefore, from the perspective of improving the properties of the plating film, it is necessary to suppress pH fluctuations by means other than organic carboxylic acid-based pH buffers. However, no effective pH buffers other than boric acid and organic carboxylic acids currently exist.

[0018] Another way to suppress pH fluctuations is to disrupt the diffusion layer on the cathode (base material) surface where a hydrogen ion concentration gradient occurs. If the concentration gradient is eliminated, the pH fluctuations during electroplating should become very gradual. However, it has been considered impossible to eliminate the concentration gradient that occurs in electroplated nickel baths by stirring the plating solution. Therefore, under known electroplated nickel conditions, it has been essential to add some kind of pH buffer to the electroplated nickel bath. (Background technology for manufacturing method C)

[0019] (Background technology for manufacturing method D) Electroplating of nickel is used as a surface treatment coating for various components such as battery canisters and fuel tanks. Typically, when forming a nickel plating film on a substrate by electroplating, acidic electroplating baths such as watt baths, sulfuric acid baths, and sulfamic acid baths are used.

[0020] When performing electro-nickel plating using such an electro-nickel plating bath, in order to ensure productivity, the Ni in the electro-nickel plating bath 2+ It is common to set the concentration to 1 mol / L or higher. However, this increases the cost of supplying the plating solution due to the removal of the plating solution, and the Ni content in the waste solution. 2+ The increasing cost of wastewater treatment due to the growing volume of plating is becoming a problem. Plating solution removal refers to the phenomenon where the plating solution adheres to the substrate and is removed from the plating tank.

[0021] Therefore, low Nu 2+ There is a need for an electroplating method for nickel using an electroplating bath of a specific concentration.

[0022] For example, Patent Document 8 describes a surface-treated steel sheet with nickel plating on at least one side of its surface, wherein the nickel plating has a particle density of 2 to 500 particles / μm 2Disclosed is a surface-treated steel sheet for containers having fine particles with an average particle diameter of 0.05 to 0.07 µm and exhibiting excellent processing adhesion to a coating organic resin. Further, in the invention of Patent Document 8, it is described that it is necessary to use a plating bath having a lower ion concentration than conventionally used Watt baths, control the quantity of electricity at a high current density, and perform electroplating at a low deposition efficiency. Note that the plating bath with a low ion concentration contains 5 to 35 g / L of nickel sulfate (in terms of Ni 2+ 0.019 to 0.133 mol / L).

[0023] Patent Document 9 discloses a cold-rolled steel sheet having a Ni flash plating layer of 2 to 20 mg / m 2 on the surface of a base steel sheet, wherein the immersion potential difference Vo defined by the following formula (1) is 5 to 30 mV, the cold-rolled steel sheet being excellent in phosphating treatability and salt warm water resistance after coating. Further, in the invention of Patent Document 9, as Ni flash plating conditions, a bath containing 15 g / L of nickel sulfate (in terms of Ni 2+ 0.057 mol / L), a bath containing 20 g / L of nickel chloride (in terms of Ni 2+ 0.154 mol / L), and a bath containing 100 g / L of nickel sulfate (in terms of Ni 2+ 0.380 mol / L) are described. Vo=E-Eo ...(1) where, E: potential measured when a cold-rolled steel sheet having a Ni flash plating layer is immersed in a nitrogen-deoxidized buffer solution adjusted to 0.05 M sodium borate + 0.1 M hydrochloric acid, pH 6.4, and 43°C, using a saturated calomel electrode as a reference electrode Eo: potential measured when the cold-rolled steel sheet from which the Ni flash plating layer has been removed by dissolution and immersion in a 5% nitric acid solution is immersed in the above buffer solution, using a saturated calomel electrode as a reference electrode

[0024] Patent Document 7 describes a scanning electroplating method in which, in electroplating, the anode is scanned relative to the cathode substrate on which the plating film is to be formed, and the high current density region where the cathode and anode are closest and the highest current flows is moved, and the plating film is formed while removing the oxide film on the cathode surface using the reducing action of hydrogen gas generated in the high current density region, wherein the high current density region is point-shaped or linear on the cathode substrate, and the average current density obtained by dividing the current by the area of ​​the anode surface that is in contact with the plating solution and faces the cathode substrate within a range of less than 90 degrees is 20 A / dm². 2 The above describes a scanning electroplating method characterized by using a nickel plating bath to which citric acid has been added, and a scanning electroplating method characterized by using a plating bath to which fine particles have been added, and forming a composite plating film containing fine particles while collecting the fine particles in the high current density area by the acoustic radiation force acting from the antinode to the nodal part of the sound pressure. (Background technology for manufacturing method D)

[0025] (Background technology for manufacturing method E)

[0026] Electroplating of nickel is used as a surface treatment coating for various components such as battery canisters and fuel tanks. Typically, when forming a nickel plating film on a substrate by electroplating, acidic electroplating baths such as Watt baths, sulfuric acid baths, and sulfamic acid baths are used. Among these, Watt baths are particularly used in processes employing large-scale equipment. Electroplating using a Watt bath allows for the use of soluble anodes. Using soluble anodes makes it easy to control the nickel ion concentration in the plating bath.

[0027] Chloride ions are added to Watt baths to promote the dissolution reaction of the soluble anode. However, chloride ions are corrosive. In electroplating nickel using a Watt bath, there are concerns about the effects of chloride ions on the plating tank and piping.

[0028] Therefore, when using a Watt bath, it is necessary to apply a lining to the inside of the plating tank and the piping to protect them from corrosion by chloride ions. However, the lining itself also deteriorates. Thus, a problem exists with electroplating nickel using a Watt bath: the maintenance of the lining becomes a cost burden.

[0029] To solve these problems, methods for manufacturing nickel-plated components using insoluble anodes have been developed.

[0030] For example, Patent Document 10 describes a method for supplying nickel ions to a plating solution in a nickel-based electroplating facility for metal strips using an insoluble anode, wherein the supply material has a specific surface area of ​​0.01 to 1.0 m². 2 A method for supplying nickel ions to a plating solution is disclosed, characterized by using granular and / or flaky metallic nickel in a metallic nickel dissolution tank, adding 2 to 20 times the saturation dissolution amount of the metallic nickel to an acidic plating solution in which the liquid temperature in the metallic nickel dissolution tank is maintained at 70 to 100°C and the pH at 1 to 2, and stirring the acidic plating solution. (Background technology for manufacturing method E)

[0031] (Background technology for manufacturing method F) Electroplating is used as a surface treatment coating for various canned product components, such as canned goods and beverage cans. Typically, when forming a tin plating film on a substrate by electroplating, acidic electroplating baths such as phenol sulfonic acid baths and alkanol sulfonic acid baths are used.

[0032] When performing electrotin plating using such an electrotin plating bath, it is necessary to reduce the amount of expensive tin used and to reduce costs by suppressing sludge generation. Therefore, low-Sn 2+ There is a need for technology that allows for plating at specific concentrations.

[0033] For example, Patent Document 11 discloses a method for producing a material for welded cans using a plating bath containing 15 to 60 g / L of divalent tin ions, 15 to 40 g / L of phenolsulfonic acid in sulfuric acid equivalent, and 0.5 to 30 g / L of polyethylene glycol with a molecular weight of 400 to 70000 as an additive. Furthermore, the invention in Patent Document 1 states that if the concentration of divalent tin ions in the plating bath used is less than 15 g / L, the electrolysis efficiency is significantly inferior (below 50%).

[0034] Patent Document 12 describes a bright tin plating bath consisting of a tin ion concentration of 1 to 200 g / L, an alkanesulfonic acid or alkanolsulfonic acid of 1 to 300 g / L, and a brightener of 0.01 to 10.0 g / L, wherein the sulfuric acid impurity concentration in the bath is SO4 2- A tin plating bath excellent in suppressing tin sludge is disclosed, characterized by having an ion concentration of less than 0.1 g / L and a total Fe ion concentration of less than 20.0 g / L. (Background technology for manufacturing method F)

[0035] (Background technology for manufacturing method G) Electrogalvanized coatings are used as surface treatment coatings for various components such as electrical equipment, office equipment, and steel furniture. Typically, when forming a zinc plating film on a substrate by electrogalvanizing, a sulfuric acid bath using zinc sulfate and sulfuric acid is often used as the electrogalvanizing bath.

[0036] When performing electrogalvanizing using such an electrogalvanizing bath, the Zn in the electrogalvanizing bath is used to ensure productivity. 2+ It is common to set the concentration to over 0.80 mol / L. However, this increases costs associated with transporting the liquid and the Zn in the waste liquid. 2+ The increasing environmental burden is becoming a problem. Plating solution removal refers to the phenomenon where the plating solution adheres to the substrate and is removed from the plating tank. Therefore, low Zn 2+ A method for manufacturing plated components at specific concentrations is required.

[0037] For example, Patent Document 13 describes a method for electro-galvanizing steel plates, where a plating solution containing 0.2 to 0.6 mol / l of zinc ions is used in the initial stages of plating, with a current density of 40 to 150 A / dm². 2 At a relative flow velocity of 0.5 m / s or more, 1 g / m³ of material is applied to the steel plate. 2 A method for manufacturing electro-galvanized steel sheets is disclosed, characterized by forming the above-mentioned lower plating layer, and then forming an upper plating layer of a desired basis weight on the lower plating layer. Furthermore, in the invention of Patent Document 13, the zinc deposition amount of the lower plating layer is 10 g / m². 2 It is stated that exceeding this limit will result in a significant decrease in overall current efficiency.

[0038] Patent Document 14 discloses a zinc plating solution for use in zinc plating applied to the surface of steel materials to evaluate hydrogen embrittlement susceptibility, characterized in that the zinc plating solution contains: zinc chloride: 20-70 g / l, ammonium chloride: 140-230 g / l, boric acid: 1-100 g / l, one or more depolarizing agents selected from aromatic carboxylic acids and salts of aromatic carboxylic acids: 0.1-20 g / l, one or more brightening agents selected from aromatic aldehydes, aromatic ketones, sodium naphthalene sulfonate, sodium 2-ethylhexyl sulfate, and phenylthiourea: 0.001-20 g / l, and one or more smoothing agents selected from polyethylene glycol, dicarboxylic acids, and diamines: 0.01-50 g / l. (Background technology for manufacturing method G)

[0039] (Background technology for manufacturing method H) Electroplating of precious metals is used as a surface treatment coating for various components such as semiconductor wiring and terminals, and decorative items. Precious metals are very expensive. Therefore, reducing the concentration of the plating bath and minimizing losses due to solution removal is important for reducing production costs. Plating solution removal is the phenomenon in which the plating solution adheres to the substrate and is removed from the plating bath.

[0040] For example, Patent Document 15 discloses an electrolytic gold plating solution characterized by containing a gold cyanide salt as a gold source, and a specific pyridinium compound in which an alkyl group is bonded to the nitrogen atom at position 1, and one to five of the atoms at positions 2 to 6 are substituted with one or more specific substituents selected from the group consisting of alkyl groups, aryl groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, alkoxysulfonyl groups, amino groups, alkylamino groups, dialkylamino groups, and cyano groups. (Background technology for manufacturing method H)

[0041] (Background technology for manufacturing method I) Electroplating allows for the formation of various metal films, such as tin, zinc, chromium, and nickel, on the surface of a substrate. This improves the aesthetics and corrosion resistance of the substrate. Therefore, electroplating is used to enhance the functionality of various materials, including steel.

[0042] However, during the electroplating process, a diffusion layer is formed on the surface of the substrate material to be plated. The diffusion layer is a thin layer of solution that comes into contact with the substrate during the electroplating process, creating a concentration gradient with the main solution due to mass transfer by diffusion. The diffusion layer imposes constraints on the plating rate and film characteristics.

[0043] As a means to overcome the constraints imposed by the diffusion layer, stirring using ultrasound has been considered. For example, Patent Document 4 describes a method for manufacturing a surface-treated steel sheet, which includes a step of using a tin electroplating bath and electroplating a steel sheet as it moves through the tin electroplating bath to form a tin plating layer on at least one surface of the steel sheet, wherein the moving speed of the steel sheet is 1 m / min or more, and during electroplating, the ultrasonic oscillation intensity at a position 20 mm away from the surface of the steel sheet is converted to 0.001 WATT / cm 2 From 100 watts / cm 2 A method for manufacturing a surface-treated steel sheet is disclosed, characterized by applying ultrasonic vibrations to the steel sheet that have an intensity within a certain range and a frequency within the range of 10 Hz to 10 MHz.

[0044] Patent Document 16 discloses a metal film forming apparatus comprising: an immersion cell containing a metal salt electrolyte; at least one electrode connected to at least one power supply; an electrically conductive substrate holder that holds at least one substrate so as to expose the conductive side of the substrate opposite at least one of the electrodes; a vibration actuator that vibrates the substrate holder according to amplitude and frequency; at least one ultrasonic device having an operating frequency and intensity provided in the metal film forming apparatus; at least one ultrasonic generator connected to the ultrasonic device; at least one inlet for injecting the metal salt electrolyte; and at least one outlet for discharging the metal salt electrolyte.

[0045] Furthermore, in the field of cleaning technology, technologies combining ultrasound and fine bubbles have been explored. The term "fine bubble" is defined in JIS B 8741-1:2019 as a bubble with a diameter of less than 100 μm in volume. (Background technology for manufacturing method I - end)

[0046] (Background technology for manufacturing method J) Electroplating allows for the formation of various metal films, such as tin, zinc, chromium, and nickel, on the surface of a substrate. This improves the aesthetics and corrosion resistance of the substrate. Therefore, electroplating is used to enhance the functionality of various materials, including steel.

[0047] However, since electroplating is generally carried out in an acidic solution, hydrogen generation occurs as a side reaction, and hydrogen is incorporated into the substrate. Therefore, hydrogen embrittlement of the substrate is a problem.

[0048] As a means of suppressing hydrogen incorporation into the substrate, Patent Document 17 discloses a method for manufacturing a highly corrosion-resistant rare earth magnet, characterized by vacuum heating an electrolytically or electrolessly plated RE-B-Fe sintered rare earth magnet or an RE-TM-B hot-worked rare earth magnet (RE represents one or more rare earth elements, and TM represents one or more transition elements) at a temperature of 600°C or higher and less than 800°C. (Background technology for manufacturing method J) [Prior art documents] [Patent Documents]

[0049] [Patent Document 1] International Publication No. 2021 / 117882 [Patent Document 2] Japanese Patent Publication No. 2021-14640 [Patent Document 3] Japanese Patent Publication No. 2020-143308 [Patent Document 4] Patent No. 3206101 [Patent Document 5] Japanese Patent Publication No. 2020-51042 [Patent Document 6] Japanese Patent Publication No. 2012-162786 [Patent Document 7] Patent No. 6303236 [Patent Document 8] Patent No. 5885345 [Patent Document 9] Patent No. 4393349 [Patent Document 10] Patent No. 3017067 [Patent Document 11] Patent No. 3511957 [Patent Document 12] Patent No. 3288584 [Patent Document 13] Patent No. 3267797 [Patent Document 14] Patent No. 4872407 [Patent Document 15] International Publication No. 2015 / 076017 [Patent Document 16] International Publication No. 2012 / 174732 [Patent Document 17] Japanese Patent Application Publication No. 5-226125 [Overview of the project] [Problems that the invention aims to solve]

[0050] (Challenges of manufacturing method A) The additives disclosed in Patent Documents 1 to 3 are only applicable to a limited number of plating types. Therefore, there is a need for a means to improve reduction efficiency that can be applied to a wide range of plating types.

[0051] The purpose of this disclosure is to provide a method for manufacturing an electroplated component and an electroplating apparatus that can improve plating efficiency across a wide range of plating types. (Challenges of manufacturing method A)

[0052] (Challenges of manufacturing method B) According to the technology described in Patent Document 4, it is possible to significantly widen the gloss current density range and increase the amount of tin plating per pass without increasing the number of plating tanks. However, ultrasound is easily attenuated in liquids. For example, in large plating tanks used in steelmaking processes, it is difficult to propagate ultrasound with sufficient intensity to the surface of the substrate.

[0053] The object of this disclosure is to provide a method for manufacturing an electroplated component and an electroplating apparatus that enables electroplating at a high current density in a large-scale plating tank. (Challenges of manufacturing method B - End)

[0054] (Challenges of manufacturing method C) The object of this disclosure is to provide an electroplating method for nickel plating, a method for manufacturing a nickel-plated member, and an electroplating apparatus that can form good electroplated nickel without substantially using a pH buffer. (Challenges of manufacturing method C)

[0055] (Challenges of manufacturing method D) Low Ni 2+High-concentration electroplating nickel baths have the problem of easily causing plating discoloration and granular precipitates. Plating discoloration is a change in the surface of the plating, caused, for example, by excessive current density. In the case of nickel plating, plating discoloration results in a black, brittle film. Granular precipitates do not change the strength of the film, but they cause unevenness in the appearance of the plating film, which is called unevenness, appearing as a whitish haze in some parts.

[0056] Low Ni 2+ In electroplating using a high concentration of nickel, the nickel deposition efficiency is low. Therefore, low Ni 2+ High-concentration electroplating nickel baths are used to obtain fine-grained precipitates or to perform Ni flash plating. In Ni flash plating, the amount of nickel deposited is small, for example, 2-20 mg / m². 2 In conventional technology, battery cans, fuel tanks, etc., use 5g / m³ 2 For products requiring a good coating with the above adhesion amount, low Ni 2+ It is not possible to use an electroplating nickel bath of a high concentration.

[0057] When a substrate is immersed in an electroplating bath and a voltage is applied between the substrate and the electroplating bath, a chemical reaction occurs that forms nickel plating. Then, Ni around the substrate 2+ This is consumed. As a result, Ni is released toward the plated surface. 2+ This results in a concentration gradient.

[0058] Low Ni 2+ In a nickel plating bath with a concentration of 5 g / m², 2 The reason why a good coating cannot be obtained with the above deposition amounts is this concentration gradient. It is necessary to eliminate the concentration gradient. However, it has been thought that it is impossible to eliminate the concentration gradient that occurs in an electro-nickel plating bath by stirring the plating solution. For this reason, under known electro-nickel plating conditions, 5 g / m 2 To obtain a good coating with the above adhesion amount, a Ni concentration of 1 mol / L or higher is required. 2+It is essential to use an electroplated nickel bath with a specific concentration.

[0059] This disclosure is a low-nitrate disclosure. 2+ Using an electroplated nickel bath of a certain concentration, 5 g / m 2 The objective is to provide a method for manufacturing a nickel-plated member and an electro-nickel plating apparatus that can form a good coating with the above-mentioned adhesion amount and without plating discoloration. (Challenges of manufacturing method D)

[0060] (Challenges of manufacturing method E) Using an insoluble anode eliminates the need to add chloride ions to the electroplated nickel bath. Therefore, unlike when using a soluble anode, lining is not required in the manufacturing method of nickel-plated components using an insoluble anode. However, this method requires a nickel dissolution tank in addition to the plating tank. As a result, equipment using insoluble anodes is more expensive than equipment using soluble anodes.

[0061] On the other hand, one way to reduce the effects of corrosion caused by chloride ions while using a soluble anode is to reduce the chloride ion concentration in the electroplated nickel bath. However, if the chloride ion concentration in the electroplated nickel bath is too low, the dissolution reaction of the soluble anode will not proceed. Therefore, the plating equipment is operated with a chloride ion concentration of more than 0.3 mol / L in the electroplated nickel bath.

[0062] The object of this disclosure is to provide a method for manufacturing a nickel-plated member and an electroplating apparatus that can maintain the dissolution reaction of a soluble anode even when using an electroplated nickel plating bath with a low chloride ion concentration. (Challenges of manufacturing method E)

[0063] (Challenges of manufacturing method F) Phenolsulfonic acid baths are the most commonly used plating baths in electroplating of tin. Conventional phenolsulfonic acid baths can produce tin plating films with a high current efficiency of over 90%. However, as described in Patent Document 11, the Sn of phenolsulfonic acid baths... 2+ When the concentration falls below 15 g / L (0.126 mol / L), the current efficiency decreases significantly, falling to 50% or less.

[0064] On the other hand, alkanol sulfonic acid baths are excellent at suppressing tin sludge. Alkanol sulfonic acid baths are effective at suppressing tin sludge. 2+ Plating is possible up to a concentration of 1 g / L (0.008 mol / L). However, the corrosion resistance of the tin plating film obtained from the alkanol sulfonic acid bath is inferior to that of the phenol sulfonic acid bath.

[0065] Therefore, Sn 2+ There is a need to develop a method for manufacturing tin-plated components that allows plating even when using a phenol sulfonic acid bath with a concentration of less than 15 g / L (0.126 mol / L).

[0066] This disclosure is low Sn 2+ The objective is to provide a method for manufacturing a tin-plated component and an electroplating apparatus that can form a good coating even from an electroplating bath of high concentration without a significant decrease in current efficiency. (Challenges of manufacturing method F)

[0067] (Challenges of manufacturing method G) Zn 2+ Using an electro-zinc plating bath with a concentration of 0.2 to 0.6 mol / L, it is used as a surface treatment coating for various components such as electrical equipment, office equipment, and steel furniture, at a density of 10 g / m². 2 If zinc plating is applied with an amount exceeding a certain limit, the current efficiency will decrease significantly.

[0068] Therefore, Zn 2+ Even when using an electroplating bath with a concentration of 0.80 mol / L or less, 10 g / m 2There is a need to develop a method for manufacturing plated components that can obtain a good coating with the above amount of adhesion.

[0069] This disclosure concerns low Zn 2+ Even from a high-concentration electrogalvanizing bath, 10 g / m 2 The objective is to provide a method for manufacturing a zinc-plated member and an electro-zinc plating apparatus capable of forming a good coating with the above amount of adhesion. (Challenges of manufacturing method G)

[0070] (Challenges of manufacturing method H) According to the technology described in Patent Document 15, adding a specific pyridinium compound to a gold plating bath can increase the gold deposition efficiency and enable a lower concentration of gold in the gold plating bath. However, adding a compound to the plating bath may increase the complexity of bath management and cause changes in properties due to the incorporation of compound components into the coating. Furthermore, the effect of the compound in the plating bath varies greatly depending on the plating bath used. Therefore, it is difficult to apply compounds for gold plating baths to other types of plating. For this reason, there is a need for the development of an electroplating method using a low-concentration electroplated precious metal plating bath that can be widely applied to plating baths of various types of plating.

[0071] The object of this disclosure is to provide an electroplating apparatus capable of plating using a low-concentration electroplated precious metal plating bath, and a method for manufacturing an electroplated component. (Challenges of manufacturing method H)

[0072] (Challenges of Manufacturing Method I) According to the technology described in Patent Document 4, it is possible to significantly widen the gloss current density range and increase the amount of tin plating per pass without increasing the number of plating tanks. However, ultrasound is easily attenuated in liquids. For example, in large plating tanks used in steelmaking processes, it is difficult to propagate ultrasound with sufficient intensity to the surface of the substrate.

[0073] The attenuation of ultrasound in large plating tanks is thought to be due to energy loss associated with the generation of cavitation of various sizes. Ultrasonic-induced cavitation is thought to be generated and grow due to the negative pressure associated with the propagation of ultrasound. The term "cavitation" is defined in JIS B 0131:2017 "Turbopump Terminology" as a phenomenon in which the pressure of a flowing liquid decreases locally, causing a phase change and generating vapor bubbles. In this disclosure, the term "cavitation" is also used to refer to the bubbles generated by the cavitation phenomenon. Since the cavitation phenomenon is instantaneous, the lifespan of the cavitation is less than one second.

[0074] The diffusion layer reduces the critical current density and the limiting current density. The critical current density is the upper limit of the current density required to produce a normal film. The limiting current density is the maximum current density at which ion replenishment by diffusion reaches its limit, and the current density no longer increases even if the voltage is increased. To improve the plating speed and ensure film characteristics, technology that enables plating at high current densities is necessary.

[0075] Patent Document 16 explains that a high deposition rate can be achieved by cavitation near the substrate surface and by sound wave flow due to the bursting of bubbles. However, Patent Document 16 does not consider the energy loss associated with the generation of cavitation of various sizes. Therefore, the technology described in Patent Document 16 cannot efficiently destroy the diffusion layer and sufficiently increase the current density.

[0076] The object of this disclosure is to provide an electroplating apparatus and a method for manufacturing an electroplated component that enables plating at high current densities. (Challenges of Manufacturing Method I)

[0077] (Challenges of manufacturing method J) According to the technology described in Patent Document 17, it is possible to prevent the incorporation of hydrogen into the magnet and the plating layer, as well as hydrogen embrittlement of the magnet, thereby maintaining high corrosion resistance and high levels of magnetic properties over a long period of time. However, since electroplating lines are usually continuous lines, it is not possible to create a vacuum section in the line as in Patent Document 17, and it is difficult to apply the method of desorbing hydrogen incorporated into the substrate by heating during electroplating. Therefore, there is a need for the development of an electroplating method that suppresses hydrogen incorporation into the substrate in the first place.

[0078] The object of this disclosure is to provide an electroplating apparatus capable of suppressing hydrogen incorporation into a substrate, and a method for manufacturing an electroplated member. (Challenges of manufacturing method J) [Means for solving the problem]

[0079] The gist of this disclosure is as follows:

[0080] (1) A method for manufacturing an electroplated member according to one aspect A of the present disclosure comprises the step of electroplating a substrate using a plating bath containing an additive, wherein in the electroplating process, the substrate is irradiated with ultrasonic waves, and the additive contains either or both of a water-soluble aliphatic monohydric alcohol or a water-soluble aliphatic carboxylic acid. (2) A method for manufacturing an electroplated member according to another embodiment B of the present disclosure comprises a step of electroplating a substrate by passing an electric current through a substrate immersed in a plating bath and a counter electrode, wherein the plating bath contains an ionic surfactant of 0.10 mmol / L or more and 10 mmol / L or less, the HLB value of the ionic surfactant in the Griffin method is 3.0 or more and 8.0 or less, and during the electroplating, ultrasonic waves are irradiated onto the substrate, the frequency of the ultrasonic waves is 15 kHz or more and 80 kHz or less, and the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the center in the width direction of the substrate, and at a location between the center of the substrate in the width direction and the counter electrode, where the distance from the substrate is even closer. (3) An electroplating method according to another embodiment C of the present disclosure comprises a step of electroplating a base material using an electroplating bath containing a nickel salt, wherein the concentration of the pH buffer in the electroplating bath is 0.10 mol / L or less, and in the electroplating treatment, ultrasonic waves are irradiated onto the base material, the frequency of the ultrasonic waves is 15 kHz or more and 180 kHz or less, and the intensity of the ultrasonic waves is 0.20 kPa / kHz or more and 80 kPa / kHz or less at a location 5 cm away from the plating surface in the center of the width direction of the base material, or at a location midway between the center of the width direction of the base material and the counter electrode, which is closer to the center of the width direction of the base material. (4) A method for manufacturing a nickel-plated member according to another embodiment D of the present disclosure comprises a step of electroplating a substrate using an electro-nickel plating bath containing a nickel salt, wherein the Ni in the electro-nickel plating bath 2+ The concentration C (mol / L) is set to 0.10 mol / L or more and 0.80 mol / L or less. In the electroplating process, ultrasonic waves are irradiated onto the substrate, the frequency of the ultrasonic waves is set to 15 kHz or more and 180 kHz or less. The intensity of the ultrasonic waves is set to 0.20 kPa / kHz or more and 80 kPa / kHz or less at a point 5 cm away from the center of the substrate in the width direction, or at a point midway between the center of the substrate in the width direction and the counter electrode, which is closer to the center of the substrate in the width direction. (5) A method for manufacturing a nickel-plated member according to another embodiment E of the present disclosure comprises a step of electroplating a substrate using an electroplated nickel plating bath containing a nickel salt and chloride ions and a soluble anode, wherein the chloride ion concentration C (mol / L) in the electroplated nickel plating bath is 0.05 mol / L or more and 0.30 mol / L or less, and in the electroplating process, ultrasonic waves are irradiated onto the soluble anode, the frequency of the ultrasonic waves is 15 kHz or more and 180 kHz or less, and the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the center in the width direction of the soluble anode, or at a location midway between the center in the width direction of the soluble anode and the substrate, which is closer to the soluble anode. (6) A method for manufacturing a tin-plated member according to another aspect F of the present disclosure comprises a step of electroplating a substrate using an electroplating bath containing a tin salt, wherein the electroplating bath contains Sn 2+ The concentration C (mol / L) is set to 0.020 mol / L or more and 0.120 mol / L or less, and the phenolsulfonic acid concentration of the electroplated tin bath is set to the Sn 2+ The concentration C (mol / L) is set to 1 to 5 times the original value. In the electroplating process, ultrasonic waves are irradiated onto the substrate, with a frequency of 15 kHz to 180 kHz. The intensity of the ultrasonic waves is set to 0.20 kPa / kHz to 80 kPa / kHz at a location 5 cm away from the center of the substrate in the width direction, or at a location midway between the center of the substrate in the width direction and the counter electrode, which is closer to the center of the substrate in the width direction. (7) A method for manufacturing a zinc-plated member according to another aspect G of the present disclosure comprises a step of electroplating a substrate using an electro-zinc plating bath containing a zinc salt, wherein the electro-zinc plating bath contains Zn 2+ The concentration C (mol / L) is set to 0.10 mol / L or more and 0.80 mol / L or less. In the electroplating process, ultrasonic waves are irradiated onto the substrate, the frequency of the ultrasonic waves is set to 15 kHz or more and 180 kHz or less. The intensity of the ultrasonic waves is set to 0.20 kPa / kHz or more and 80 kPa / kHz or less at a point 5 cm away from the center of the substrate in the width direction, or at a point midway between the center of the substrate in the width direction and the counter electrode, which is closer to the center of the substrate in the width direction. (8) A method for manufacturing an electroplated member according to another embodiment H of the present disclosure comprises the step of electroplating a substrate by passing an electric current through a substrate immersed in a plating bath and a counter electrode, wherein during the electroplating, ultrasonic waves having a frequency of 15 kHz or more and 180 kHz or less are applied to the substrate, the intensity of the ultrasonic waves is set to 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the center in the width direction of the substrate, and at a location between the center in the width direction of the substrate and the counter electrode, whichever is closer to the substrate, and the plating bath contains noble metal ions. (9) A method for manufacturing an electroplated member according to another embodiment I of the present disclosure comprises the step of electroplating a substrate by applying an electric current to a substrate immersed in a plating bath and a counter electrode, wherein microbubbles are supplied to the plating bath, ultrasonic waves are applied to the substrate during the electroplating, the frequency of the ultrasonic waves is 15 kHz or more and 80 kHz or less, the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the center in the width direction of the substrate, and at a location between the center of the substrate in the width direction and the counter electrode, where the distance from the substrate is even closer, the lifespan of the microbubbles is 1 minute or more, the average diameter of the microbubbles is 0.01 μm or more and 100 μm or less, and the diameter of the microbubbles decreases over time. (10) A method for manufacturing an electroplated member according to another embodiment J of the present disclosure comprises the steps of: degreasing the substrate by immersing it in a degreasing bath while suppressing hydrogen uptake into the substrate; pickling the substrate by immersing it in a pickling bath while suppressing hydrogen uptake into the substrate; and electroplating the substrate by applying current to the substrate and a counter electrode immersed in a plating bath, wherein, during the electroplating, a first ultrasonic wave is applied to the substrate, the frequency of the first ultrasonic wave is 15 kHz or more and 180 kHz or less, and the intensity of the first ultrasonic wave at a location 5 cm away from the surface of the center in the width direction of the substrate, and at the center location between the center of the substrate in the width direction and the counter electrode, whichever is closer to the substrate, is 0.20 to 80 kPa / kHz.

[0081] <Note A> (A1) A method for manufacturing an electroplated member according to one aspect of the present disclosure comprises the step of electroplating a substrate using a plating bath containing an additive, wherein in the electroplating process, the substrate is irradiated with ultrasonic waves, and the additive contains either or both of a water-soluble aliphatic monohydric alcohol or a water-soluble aliphatic carboxylic acid. (A2) Preferably, in the method for manufacturing the electroplated member described in (A1) above, the water-soluble and aliphatic monohydric alcohol is one or both of a secondary alcohol and a tertiary alcohol. (A3) Preferably, in the method for manufacturing the electroplated member described in (A1) or (A2) above, the number of carbon atoms in the water-soluble and aliphatic monohydric alcohol is 3 or more and 6 or less. (A4) Preferably, in the method for manufacturing an electroplated member described in any one of the above items (A1) to (A3), the water-soluble and aliphatic monohydric alcohol is an alcohol that does not contain a benzene ring. (A5) Preferably, in the method for manufacturing an electroplated member described in any one of (A1) to (A4) above, the water-soluble and aliphatic monohydric alcohol is isopropyl alcohol and tert-butanol, or both. (A6) Preferably, in the method for manufacturing an electroplated member described in any one of the above items (A1) to (A5), the water-soluble and aliphatic carboxylic acid is one or more selected from the group consisting of propionic acid, butyric acid, valeric acid, and caproic acid. (A7) Preferably, in the method for manufacturing an electroplated member described in any one of (A1) to (A6) above, the total concentration of the water-soluble and aliphatic monohydric alcohol and the water-soluble and aliphatic carboxylic acid is in the range of 0.001 mol / L to 5 mol / L. (A8) Preferably, in the method for manufacturing an electroplated member described in any one of the above items (A1) to (A7), the plating bath is a Ni plating bath, a Sn plating bath, or a Zn plating bath. (A9) Preferably, in the method for manufacturing an electroplated member described in any one of (A1) to (A8) above, the frequency of the ultrasonic wave is 15 kHz or more and 1000 kHz or less. (A10) Preferably, in the method for manufacturing an electroplated member described in any one of (A1) to (A9) above, the intensity of the ultrasonic waves at a location 5 cm away from the surface of the center in the width direction of the substrate, and at a location midway between the center in the width direction of the substrate and the counter electrode, whichever is closer to the substrate, is set to 0.20 to 80 kPa / kHz.

[0082] (A11) An electroplating apparatus according to another aspect of the present disclosure comprises an electroplating tank configured to hold a plating bath containing an additive, and an ultrasonic oscillator configured to emit ultrasonic waves into the plating bath, wherein the additive contains either or both of a water-soluble aliphatic monohydric alcohol or a water-soluble aliphatic carboxylic acid.

[0083] <Note B> (B1) A method for manufacturing an electroplated member according to one aspect of the present disclosure comprises a step of electroplating a substrate by applying an electric current to a substrate immersed in a plating bath and a counter electrode, wherein the plating bath contains an ionic surfactant of 0.10 mmol / L or more and 10 mmol / L or less, the HLB value of the ionic surfactant in the Griffin method is 3.0 or more and 8.0 or less, and during the electroplating, ultrasonic waves are irradiated onto the substrate, the frequency of the ultrasonic waves is 15 kHz or more and 80 kHz or less, and the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the center in the width direction of the substrate, and at a location midway between the center in the width direction of the substrate and the counter electrode, where the distance from the substrate is even closer. (B2) Preferably, in the method for manufacturing the electroplated member described in (B1) above, the ionic surfactant is an anionic surfactant. (B3) Preferably, in the method for manufacturing an electroplated member described in (B1) or (B2) above, the capacity of the electroplating tank containing the plating bath is 500 L or more. (B4) Preferably, in the method for manufacturing an electroplated member described in any one of the above items (B1) to (B3), the ultrasonic emitting means for emitting ultrasonic waves are arranged on both sides in the width direction of the substrate, and the distance between the pair of ultrasonic emitting means facing each other across the substrate is 500 mm or more.

[0084] (B5) An electroplating apparatus according to another aspect of the present disclosure comprises an electroplating tank configured to accommodate a plating bath, an ultrasonic oscillating means configured to emit ultrasonic waves inside the electroplating tank, a substrate support means configured to support a substrate in a substrate placement area, and a counter electrode, wherein the plating bath contains an ionic surfactant of 0.10 mmol / L or more and 10 mmol / L or less, the HLB value of the ionic surfactant in the Griffin method is 3.0 or more and 8.0 or less, the frequency of the ultrasonic waves emitted by the ultrasonic oscillating means is 15 kHz or more and 80 kHz or less, and the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the center in the width direction of the substrate placement area, and at a location midway between the center in the width direction of the substrate placement area and the counter electrode, where the distance from the substrate placement area is even closer. (B6) Preferably, in the electroplating apparatus described in (B5) above, the ionic surfactant is an anionic surfactant. (B7) Preferably, in the electroplating apparatus described in (B5) or (B6) above, the capacity of the electroplating tank is 500 L or more. (B8) Preferably, in the electroplating apparatus described in any one of the above items (B5) to (B7), the ultrasonic oscillating means are arranged on both sides in the width direction of the planned substrate placement area, and the distance between a pair of ultrasonic oscillating means facing each other across the planned substrate placement area is 500 mm or more.

[0085] <Note C> (C1) An electroplating method according to one aspect of the present disclosure comprises a step of electroplating a base material using an electroplating nickel bath containing a nickel salt, wherein the concentration of the pH buffer in the electroplating nickel bath is 0.10 mol / L or less, and in the electroplating process, ultrasonic waves are irradiated onto the base material, the frequency of the ultrasonic waves is 15 kHz or more and 180 kHz or less, and the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the plating surface in the center of the width direction of the base material, or at a location midway between the center of the width direction of the base material and the counter electrode, which is closer to the center of the width direction of the base material. (C2) In the electroplating nickel method described in (C1) above, the nickel salt may include a salt of one or more substances selected from the group consisting of nickel sulfate, nickel sulfamate, nickel chloride, and nickel bromide. (C3) In the electroplating nickel method described in (C1) above, the nickel salt may include a salt of one or more substances selected from the group consisting of nickel sulfate and nickel sulfamate. (C4) In the electroplating nickel method described in any one of the above items (C1) to (C3), the temperature of the electroplating nickel bath may be set to 30°C or higher and 70°C or lower. (C5) In the electroplating nickel method described in any one of the above items (C1) to (C4), the cathode current density in the electroplating process is set to 1 A / dm 2 More than 100A / dm 2 The following is also acceptable. (C6) In the electroplating nickel method described in any one of the above items (C1) to (C5), the amount of current supplied in the electroplating treatment is 2C / dm 2 More than 1200C / dm 2 The following is also acceptable. (C7) In the electroplating nickel method described in any one of the above items (C1) to (C6), the concentration of the pH buffer in the electroplating nickel bath may be 0.08 mol / L or less. (C8) In the electro-nickel plating method described in any one of the above items (C1) to (C7), the frequency of the ultrasonic wave may be set to 15 kHz or more and 180 kHz or less. (C9) In the electro-nickel plating method described in any one of the above items (C1) to (C8), the intensity of the ultrasonic wave may be set to 0.40 to 40 kPa / kHz.

[0086] (C10) A method for manufacturing a nickel-plated member according to another aspect of the present disclosure comprises the electro-nickel plating method described in any one of (C1) to (C9) above.

[0087] (C11) An electroplating apparatus according to another aspect of the present disclosure comprises an electroplating tank configured to accommodate an electroplating nickel bath containing a nickel salt, an ultrasonic oscillating means configured to emit ultrasonic waves inside the electroplating tank, a base material support means configured to support a base material in a base material placement area, and a counter electrode, wherein in the electroplating nickel bath, the concentration of the pH buffer is 0.10 mol / L or less, the frequency of the ultrasonic waves emitted by the ultrasonic oscillating means is 15 kHz or more and 80 kHz or less, and the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the center in the width direction of the base material placement area, and at a location midway between the center in the width direction of the base material placement area and the counter electrode, where the distance from the base material placement area is even closer.

[0088] <Note D> (D1) A method for manufacturing a plated member according to one aspect of the present disclosure comprises a step of electroplating a substrate using an electroplated nickel plating bath containing a nickel salt, wherein the Ni in the electroplated nickel plating bath 2+ The concentration C (mol / L) is set to 0.1 mol / L or more and 0.8 mol / L or less. In the electroplating process, the substrate is irradiated with ultrasound, the frequency of the ultrasound is set to 15 kHz or more and 180 kHz or less. The intensity of the ultrasound is set to 0.20 kPa / kHz or more and 80 kPa / kHz or less at a point 5 cm away from the center of the substrate in the width direction, or at a point midway between the center of the substrate in the width direction and the counter electrode, which is closer to the center of the substrate in the width direction. (D2) In the method for manufacturing the plated member described in (D1) above, Ni in the electroplated nickel plating bath 2+ The concentration C (mol / L) and the cathode current density i (A / dm²) of the electroplating process. 2 ) and may also be values ​​that satisfy equation D1. Formula D1 20C≦i≦20C+80 (D3) In the method for manufacturing the plated member described in (D1) or (D2) above, the amount of nickel deposited in the electroplating treatment is 5 g / m 2 That's fine too.

[0089] (D4) An electroplating apparatus according to another aspect of the present disclosure is an electroplating apparatus comprising: an electroplating tank configured to accommodate an electro-nickel plating bath containing a nickel salt; an ultrasonic oscillating means configured to emit ultrasonic waves inside the electroplating tank; a substrate support means configured to support a substrate in a substrate placement area; and a counter electrode, wherein the electro-nickel plating bath contains Ni 2+ The concentration C (mol / L) is 0.1 mol / L or more and 0.8 mol / L or less, the frequency of the ultrasonic waves emitted by the ultrasonic oscillating means is 15 kHz or more and 180 kHz or less, and the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the center of the widthwise surface of the area to be placed on the substrate, and at a location midway between the center of the widthwise surface of the area to be placed on the substrate and the counter electrode, whichever is closer to the area to be placed on the substrate. (D5) Preferably, in the electroplating apparatus described in (D4) above, Ni in the electroplating nickel bath 2+ Concentration C (mol / L) and the cathode current density i (A / dm²) of the electroplating process. 2 ) and are values ​​that satisfy equation D1. Formula D1 20C≦i≦20C+80

[0090] <Note E> (E1) A method for manufacturing a nickel-plated member according to one aspect of the present disclosure comprises a step of electroplating a substrate using an electroplated nickel plating bath containing a nickel salt and chloride ions and a soluble anode, wherein the chloride ion concentration C (mol / L) in the electroplated nickel plating bath is 0.05 mol / L or more and 0.30 mol / L or less, and in the electroplating process, ultrasonic waves are irradiated onto the soluble anode, the frequency of the ultrasonic waves is 15 kHz or more and 180 kHz or less, and the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the center in the width direction of the soluble anode, or at a location midway between the center in the width direction of the soluble anode and the substrate, which is closer to the soluble anode. (E2) Preferably, in the method for manufacturing the nickel-plated member described in (E1) above, the Ni in the electro-nickel plating bath 2+The concentration c (mol / L) is between 0.1 mol / L and 2.0 mol / L. (E3) Preferably, in the method for manufacturing a nickel-plated member described in (E1) or (E2) above, the chloride ion concentration C (mol / L) in the electroplated nickel bath is 0.05 mol / L or more and 0.25 mol / L or less. (E4) Preferably, in the method for manufacturing a nickel-plated member described in any one of (E1) to (E3) above, in the electroplating process, the electro-nickel plating bath is degassed, and in the electroplating process, the output of the ultrasonic emitting means that emits ultrasonic waves is set to 800 W / m 3 The ultrasonic oscillating means are arranged on both sides of the width direction of the soluble anode, and the distance between the ultrasonic oscillating means and the closest ultrasonic oscillating means facing it across the soluble anode is 500 mm or more and 2000 mm or less. (E5) Preferably, in the method for manufacturing a nickel-plated member described in any one of the above items (E1) to (E4), the nickel salt contains nickel sulfate, and in the electroplating treatment, the following formula is satisfied, 0.80 ≤ SO4 2- Concentration / Ni 2+ concentration SO4 2- The concentration is the sulfate ion concentration in the electroplated nickel bath in units of mol / L, and Ni 2+ The concentration refers to the nickel ion concentration in the electroplated nickel bath in units of mol / L.

[0091] (E6) An electroplating apparatus according to another aspect of the present disclosure comprises an electroplating tank configured to accommodate an electroplating nickel bath containing a nickel salt and chloride ions, an ultrasonic oscillating means configured to emit ultrasonic waves inside the electroplating tank, a substrate support means configured to support a substrate in a substrate placement area, and a soluble anode, wherein the chloride ion concentration C (mol / L) in the electroplating nickel bath is 0.05 mol / L or more and 0.30 mol / L or less, the frequency of the ultrasonic waves emitted by the ultrasonic oscillating means is 15 kHz or more and 80 kHz or less, and the intensity of the ultrasonic waves at a location 5 cm away from the center of the soluble anode in the width direction, or at a location midway between the center of the soluble anode in the width direction and the substrate placement area, which is closer to the soluble anode, is 0.20 to 80 kPa / kHz. (E7) Preferably, in the electroplating apparatus described in (E6) above, Ni in the electroplating nickel bath 2+ The concentration c (mol / L) is between 0.1 mol / L and 2.0 mol / L. (E8) Preferably, in the electroplating apparatus described in (E6) or (E7) above, the chloride ion concentration C (mol / L) in the electroplated nickel bath is 0.05 mol / L or more and 0.25 mol / L or less. (E9) Preferably, in the electroplating apparatus described in any one of the above items (E6) to (E8), the electroplating apparatus further comprises a degassing means and the output of the ultrasonic oscillation means is 800 W / m 3 The ultrasonic oscillating means are arranged on both sides of the width direction of the soluble anode, and the distance between the ultrasonic oscillating means and the closest ultrasonic oscillating means facing it across the soluble anode is 500 mm or more and 2000 mm or less. (E10) Preferably, in the electroplating apparatus described in any one of the above items (E6) to (E9), the nickel salt contains nickel sulfate and satisfies the following formula: 0.80 ≤ SO4 2- Concentration / Ni 2+ concentration SO4 2-The concentration is the sulfate ion concentration in the electroplated nickel bath in units of mol / L, and Ni 2+ The concentration refers to the nickel ion concentration in the electroplated nickel bath in units of mol / L.

[0092] <Note F>

[0093] (F1) A method for manufacturing a tin-plated member according to one aspect of the present disclosure comprises a step of electroplating a substrate using an electroplating bath containing a tin salt, wherein the electroplating bath contains Sn 2+ The concentration C (mol / L) is set to 0.02 mol / L or more and 0.12 mol / L or less, and the phenolsulfonic acid concentration of the electroplated tin bath is set to the Sn 2+ The concentration C (mol / L) is set to 1 to 5 times the original value. In the electroplating process, ultrasonic waves are irradiated onto the substrate, with a frequency of 15 kHz to 180 kHz. The intensity of the ultrasonic waves is set to 0.20 kPa / kHz to 80 kPa / kHz at a location 5 cm away from the center of the substrate in the width direction, or at a location midway between the center of the substrate in the width direction and the counter electrode, which is closer to the center of the substrate in the width direction. (F2) Preferably, in the method for manufacturing the tin-plated member described in (F1) above, the Sn of the electro-tin plating bath 2+ Concentration C (mol / L) and cathode current density i (A / dm²) 2 ) and satisfy equation F1. Formula F1 30C+6.0 <i≦30C+35.0 (F3) Preferably, in the method for manufacturing the tin-plated member described in (F1) or (F2) above, the Sn of the electro-tin plating bath 2+ Concentration C (mol / L) and cathode current density i (A / dm²) 2 ) satisfies equation F2. Formula F2 30C+17.5≦i≦30C+35.0

[0094] (F4) An electroplating apparatus according to another aspect of the present disclosure comprises an electroplating tank configured to accommodate an electroplating bath containing a tin salt, an ultrasonic oscillating means configured to emit ultrasonic waves inside the electroplating tank, a substrate support means configured to support a substrate in a substrate placement area, and a counter electrode, wherein the electroplating bath contains Sn 2+ The concentration C (mol / L) is 0.02 mol / L or more and 0.12 mol / L or less, and the phenolsulfonic acid concentration of the electroplated tin bath is the same as that of Sn 2+ The concentration C (mol / L) is 1 to 5 times the normal level, the frequency of the ultrasonic waves emitted by the ultrasonic oscillating means is 15 kHz to 80 kHz, and the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the center in the width direction of the planned substrate placement area, and at a location midway between the center in the width direction of the planned substrate placement area and the counter electrode, where the distance from the planned substrate placement area is even closer. (F5) Preferably, in the electroplating apparatus described in (F4) above, the Sn of the electroplating bath 2+ Concentration C (mol / L) and cathode current density i (A / dm²) 2 ) and satisfy equation D1. Formula D1 30C+6.0 <i≦30C+35.0 (F6) Preferably, in the electroplating apparatus described in (F4) or (F5) above, the Sn of the electroplating bath 2+ Concentration C (mol / L) and cathode current density i (A / dm²) 2 ) and satisfy equation D2. Formula D2 30C+17.5≦i≦30C+35.0

[0095] <Note G> (G1) A method for manufacturing a plated member according to one aspect of the present disclosure comprises a step of electroplating a substrate using an electrogalvanizing bath containing a zinc salt, wherein the electrogalvanizing bath contains Zn 2+The concentration C (mol / L) is 0.10 mol / L or more and 0.80 mol / L or less. In the electroplating process, ultrasonic waves are irradiated onto the base material, the frequency of the ultrasonic waves is 15 kHz or more and 180 kHz or less, and the intensity of the ultrasonic waves at a position that is 5 cm away from the surface at the center in the width direction of the base material, or an intermediate position between the center in the width direction of the base material and a counter electrode, which is closer to the center in the width direction of the base material, is 0.20 kPa / kHz or more and 80 kPa / kHz or less. (G2) Preferably, in the method for producing a plated member according to (G1) above, Zn in the electrogalvanizing bath 2+ concentration C (mol / L) and the cathode current density i (A / dm 2 ) are values that satisfy Formula G1. Formula G1 100C≦i≦300C+60

[0096] (G3) An electroplating apparatus according to another aspect of the present disclosure includes: an electroplating tank configured to be capable of accommodating an electrogalvanizing bath containing a zinc salt; an ultrasonic oscillation means configured to be capable of oscillating ultrasonic waves inside the electroplating tank; a base material support means configured to be capable of supporting a base material at a planned base material arrangement portion; and a counter electrode, wherein Zn in the electrogalvanizing bath 2+ concentration C (mol / L) is 0.10 mol / L or more and 0.80 mol / L or less, the frequency of the ultrasonic waves oscillated by the ultrasonic oscillation means is 15 kHz or more and 180 kHz or less, and the intensity of the ultrasonic waves at a position 5 cm away from the center in the width direction of the planned base material arrangement portion, or an intermediate position between the center in the width direction of the planned base material arrangement portion and the counter electrode, which is closer to the planned base material arrangement portion, is 0.20 to 80 kPa / kHz. (G4) Preferably, in the electroplating apparatus according to (G3) above, Zn in the electrogalvanizing bath 2+ concentration C (mol / L) and the cathode current density i (A / dm 2 ) are values that satisfy Formula G1. Formula G1 100C≦i≦300C+60

[0097] <Supplemental Note H> (H1) An electroplating apparatus according to one aspect of the present disclosure comprises: an electroplating tank configured to accommodate a plating bath; an ultrasonic oscillating means configured to emit ultrasonic waves inside the electroplating tank; a substrate support means configured to support a substrate in a substrate placement area; and a counter electrode, wherein the frequency of the ultrasonic waves emitted by the ultrasonic oscillating means is 15 kHz or more and 180 kHz or less; the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the center of the substrate placement area in the width direction, and at a location between the center of the substrate placement area in the width direction and the counter electrode, whichever is closer to the substrate placement area; and the plating bath contains noble metal ions. (H2) Preferably, in the electroplating apparatus described in (H1) above, the electroplating apparatus is equipped with a plating bath degassing means. (H3) Preferably, in the electroplating apparatus described in (H1) or (H2) above, the noble metal ion is one or more metals selected from the group consisting of gold, silver, palladium, and platinum. (H4) Preferably, in the electroplating apparatus described in any one of the above items (H1) to (H3), the concentration of the noble metal ions in the plating bath is 1 mmol / L or less.

[0098] (H5) A method for manufacturing an electroplated member according to another aspect of the present disclosure comprises the step of electroplating a substrate by passing an electric current through a substrate immersed in a plating bath and a counter electrode, wherein during the electroplating, ultrasonic waves having a frequency of 15 kHz or more and 180 kHz or less are applied to the substrate, the intensity of the ultrasonic waves is set to 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the center in the width direction of the substrate, and at a location between the center in the width direction of the substrate and the counter electrode, whichever is closer to the substrate, and the plating bath contains noble metal ions. (H6) Preferably, in the method for manufacturing an electroplated member described in (H5) above, the plating bath is degassed to remove dissolved gases in the plating bath. (H7) Preferably, in the method for manufacturing an electroplated member described in (H5) or (H6) above, the noble metal ion is one or more metals selected from the group consisting of gold, silver, palladium, and platinum. (H8) Preferably, in the method for manufacturing an electroplated member described in any one of (H5) to (H7) above, the concentration of the noble metal ions in the plating bath is 1 mmol / L or less.

[0099] <Note I> (I1) An electroplating apparatus according to one aspect of the present disclosure comprises: an electroplating tank configured to accommodate a plating bath; an ultrasonic oscillating means configured to emit ultrasonic waves inside the electroplating tank; a substrate support means configured to support a substrate in a substrate placement area; a counter electrode; and a microbubble supply means configured to supply microbubbles to the plating bath, wherein the frequency of the ultrasonic waves is 15 kHz or more and 80 kHz or less; the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the center in the width direction of the substrate placement area, and at a location between the center in the width direction of the substrate placement area and the counter electrode, where the distance from the substrate placement area is even closer; the average diameter of the microbubbles is 0.01 μm or more and 100 μm or less; and the diameter of the microbubbles decreases over time. (I2) Preferably, in the electroplating apparatus described in (I1) above, the microbubble supply means is one of a swirling flow type, an ejector type, a mechanical shear type, or a venturi type. (I3) Preferably, in the electroplating apparatus described in (I1) or (I2) above, the electroplating apparatus further comprises a microbubble supply area provided outside the electroplating tank and a flow path connecting the microbubble supply area and the electroplating tank, wherein the microbubble supply means is arranged in the microbubble supply area. (I4) Preferably, in the electroplating apparatus described in any one of (I1) to (I3) above, the microbubble supply means is arranged in the electroplating tank. (I5) Preferably, in the electroplating apparatus described in any one of the above items (I1) to (I4), the number of ultrasonic oscillating means is two or more.

[0100] (I6) A method for manufacturing an electroplated member according to another aspect of the present disclosure comprises the step of electroplating a substrate by applying an electric current to a substrate immersed in a plating bath and a counter electrode, wherein microbubbles are supplied to the plating bath, ultrasonic waves are applied to the substrate during the electroplating, the frequency of the ultrasonic waves is 15 kHz or more and 80 kHz or less, the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the center in the width direction of the substrate, and at a location between the center in the width direction of the substrate and the counter electrode, where the distance from the substrate is even closer, the lifespan of the microbubbles is 1 minute or more, the average diameter of the microbubbles is 0.01 μm or more and 100 μm or less, and the diameter of the microbubbles decreases over time. (I7) Preferably, in the method for manufacturing the electroplated member described in (I6) above, the bubble diameter ratio, as defined by the following formula, is set to 80% or less. Bubble diameter ratio = 100 × (D1 / D2) D1 is the average diameter of the microbubbles measured immediately after sampling from the plating bath during electroplating, and D2 is the average diameter of the microbubbles measured after sampling from the plating bath during electroplating and allowing it to stand for 1 minute. (I8) Preferably, in the method for manufacturing an electroplated member described in (I6) or (I7) above, the method for generating the fine bubbles is one of the swirling flow type, ejector type, mechanical shear type, or Venturi type.

[0101] <Note J> (J1) An electroplating apparatus according to one aspect of the present disclosure comprises: a degreasing tank configured to accommodate a degreasing bath and having a first means for suppressing hydrogen uptake into a substrate; a pickling tank configured to accommodate a pickling bath and having a second means for suppressing hydrogen uptake into the substrate; an electroplating tank configured to accommodate a plating bath; a first ultrasonic emitting means configured to emit a first ultrasonic wave inside the electroplating tank; a substrate support means configured to support the substrate in a substrate placement area; and a counter electrode, wherein the frequency of the first ultrasonic wave is 15 kHz or more and 180 kHz or less, and in the electroplating tank, the intensity of the first ultrasonic wave is 0.20 to 80 kPa / kHz at a location 5 cm away from the center of the width direction of the substrate placement area and at a location midway between the center of the width direction of the substrate placement area and the counter electrode, whichever is closer to the substrate. (J2) Preferably, in the electroplating apparatus described in (J1) above, the first means of the degreasing tank has a cathode for degreasing. (J3) Preferably, in the electroplating apparatus described in (J1) or (J2) above, the first means of the degreasing tank has a second ultrasonic oscillating means configured to emit a second ultrasonic wave inside the degreasing tank. (J4) Preferably, in the electroplating apparatus described in (J3) above, the degreasing tank has a substrate support means configured to support the substrate in the substrate placement area of ​​the degreasing tank, and a degreasing electrode, the frequency of the second ultrasonic wave is 15 kHz or more and 180 kHz or less, and the intensity of the second ultrasonic wave is 0.20 to 80 kPa / kHz in the degreasing tank at a location 5 cm away from the center of the substrate placement area in the width direction, and at an intermediate location between the center of the substrate placement area in the width direction and the degreasing electrode, whichever is closer to the substrate placement area of ​​the degreasing tank. (J5) Preferably, in the electroplating apparatus described in any one of the above items (J1) to (J4), the first means further comprises a degreasing bath degassing means configured to degas the degreasing bath contained in the degreasing tank. (J6) Preferably, in the electroplating apparatus described in any one of the above items (J1) to (J5), the second means of the pickling tank has a cathode for pickling. (J7) Preferably, in the electroplating apparatus described in any one of the above items (J1) to (J6), the second means of the pickling tank has a third ultrasonic oscillating means configured to emit a third ultrasonic wave inside the pickling tank. (J8) Preferably, in the electroplating apparatus described in (J7) above, the pickling tank has a substrate support means configured to support the substrate in the substrate placement area of ​​the pickling tank, and a pickling electrode, the frequency of the third ultrasonic wave is 15 kHz or more and 180 kHz or less, and the intensity of the third ultrasonic wave is 0.20 to 80 kPa / kHz in the pickling tank at a location 5 cm away from the center of the substrate placement area in the width direction, and at an intermediate location between the center of the substrate placement area in the width direction and the pickling electrode, whichever is closer to the substrate placement area. (J9) Preferably, in the electroplating apparatus described in (J7) or (J8) above, the second means further comprises an pickling bath degassing means configured to degas the pickling bath. (J10) Preferably, the electroplating apparatus described in any one of the above items (J1) to (J9) further comprises a plating bath degassing means configured to degas the plating bath.

[0102] (J11) A method for manufacturing an electroplated member according to another aspect of the present disclosure comprises the steps of: degreasing the substrate by immersing it in a degreasing bath while suppressing hydrogen uptake into the substrate; pickling the substrate by immersing it in a pickling bath while suppressing hydrogen uptake into the substrate; and electroplating the substrate by applying current to the substrate and counter electrode immersed in a plating bath, wherein, during the electroplating, a first ultrasonic wave is applied to the substrate, the frequency of the first ultrasonic wave is 15 kHz or more and 180 kHz or less, and the intensity of the first ultrasonic wave at a location 5 cm away from the surface of the center in the width direction of the substrate, and at the center location between the center of the substrate in the width direction and the counter electrode, whichever is closer to the substrate, is 0.20 to 80 kPa / kHz. (J12) Preferably, in the method for manufacturing an electroplated member described in (J11) above, the degreasing step includes anode electrolytic degreasing, and the anode electrolytic degreasing suppresses hydrogen uptake into the substrate. (J13) Preferably, in the method for manufacturing an electroplated member described in (J11) or (J12) above, the degreasing step comprises electrolytic degreasing and a second ultrasonic oscillation step of emitting a second ultrasonic wave into the degreasing bath, wherein the second ultrasonic wave suppresses hydrogen uptake into the substrate, the frequency of the second ultrasonic wave is 15 kHz or more and 180 kHz or less, and the intensity of the second ultrasonic wave is 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the center in the width direction of the substrate, and at a location between the center in the width direction of the substrate and the degreasing electrode, whichever is closer to the substrate. (J14) Preferably, in the method for manufacturing an electroplated member described in any one of the above items (J11) to (J13), the degreasing step includes a step of degassing the degreasing bath. (J15) Preferably, in the method for manufacturing an electroplated member described in any one of the above items (J11) to (J14), the pickling step includes anode electrolytic pickling, and the anode electrolytic pickling suppresses hydrogen uptake into the substrate. (J16) Preferably, in the method for manufacturing an electroplated member described in any one of (J11) to (J15) above, the pickling step comprises electrolytic pickling and a third ultrasonic oscillation step of emitting a third ultrasonic wave in the pickling bath, wherein the third ultrasonic wave suppresses hydrogen uptake into the substrate. (J17) Preferably, in the method for manufacturing an electroplated member described in (J16) above, the frequency of the third ultrasonic wave is set to 15 kHz or more and 180 kHz or less, and the intensity of the third ultrasonic wave is set to 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the center of the substrate in the width direction, and at a location midway between the center of the substrate in the width direction and the pickling electrode, whichever is closer to the substrate. (J18) Preferably, in the method for manufacturing an electroplated member described in any one of the above items (J11) to (J17), the pickling step includes a step of degassing the pickling bath. (J19) Preferably, in the method for manufacturing an electroplated member described in any one of the above items (J11) to (J18), the electroplating step includes a plating bath degassing step of degassing the plating bath. [Effects of the Invention]

[0103] (Effects of manufacturing method A) This disclosure provides a method for manufacturing an electroplated member and an electroplating apparatus that can improve plating efficiency across a wide range of plating types. (Effects of manufacturing method A)

[0104] (Effects of manufacturing method B) According to this disclosure, it is possible to provide a method for manufacturing an electroplated member and an electroplating apparatus that enables electroplating at a high current density in a large-scale plating tank. (Effects of manufacturing method B)

[0105] (Effects of manufacturing method C) According to this disclosure, it is possible to provide an electroplating method for nickel plating that can form good electroplated nickel without using a pH buffer, a method for manufacturing a nickel-plated member, and an electroplating apparatus. (Effects of manufacturing method C)

[0106] (Effects of manufacturing method D) According to this disclosure, low Ni 2+ Using an electroplated nickel bath of a certain concentration, 5 g / m 2 A method for manufacturing a nickel-plated member and an electro-nickel plating apparatus can be provided that can form a coating with the above-mentioned adhesion amount and good appearance. (Effects of manufacturing method D)

[0107] (Effects of manufacturing method E) According to this disclosure, it is possible to provide a method for manufacturing a nickel-plated member and an electroplating apparatus that can maintain the dissolution reaction of a soluble anode even when using an electroplated nickel plating bath with a low chloride ion concentration. (Effect of Production Method E: End)

[0108] (Effect of Production Method F) According to the present disclosure, low Sn 2+ concentration electroplating bath can provide a method for producing a tin-plated member and an electroplating apparatus capable of forming a favorable coating without significant reduction in current efficiency even from an electroplating bath. (Effect of Production Method F: End)

[0109] (Effect of Production Method G) According to the present disclosure, low Zn 2+ concentration electrogalvanizing bath can provide a method for producing a zinc-plated member and an electrogalvanizing apparatus capable of forming a favorable coating with an adhesion amount of 10 g / m 2 or more even from an electrogalvanizing bath. (Effect of Production Method G: End)

[0110] (Effect of Production Method H) According to the present disclosure, an electroplating apparatus capable of plating using a low-concentration electric noble metal plating bath, and a method for producing an electroplated member can be provided. (Effect of Production Method H: End)

[0111] (Effect of Production Method I) According to the present disclosure, an electroplating apparatus and a method for producing an electroplated member that enable plating at a high current density can be provided. (Effect of Production Method I: End)

[0112] (Effect of Production Method J) According to the present disclosure, an electroplating apparatus capable of suppressing hydrogen uptake into a base material, and a method for producing an electroplated member can be provided. (Effect of Production Method J: End) BRIEF DESCRIPTION OF THE DRAWINGS

[0113] [Figure 1] It is a schematic diagram of the electroplating apparatus viewed from the width direction of the base material. [Figure 2]It is a schematic diagram of an electroplating apparatus viewed from a direction perpendicular to the surface of a base material. [Figure 3] It is a plan view in the width direction of a base material, showing ultrasonic intensity measurement positions when the distance between the base material and a counter electrode is 10 cm or more. [Figure 4] It is a plan view in the width direction of a base material, showing ultrasonic intensity measurement positions when the distance between the base material and a counter electrode is less than 10 cm. [Figure 5] It is a plan view in the width direction of a base material, showing ultrasonic intensity measurement positions when the distance between the base material and a counter electrode is 10 cm or more. [Figure 6] It is a plan view in the width direction of a base material, showing ultrasonic intensity measurement positions when the distance between the base material and a counter electrode is less than 10 cm. [Figure 7] It is a schematic diagram of an electroplating apparatus viewed from the width direction of a base material. [Figure 8] It is a schematic diagram of an electroplating apparatus viewed from a direction perpendicular to the surface of a base material. [Figure 9] This shows cavitation generated when ultrasonic waves are applied to a plating bath of a comparative example to which no ionic surfactant has been added. [Figure 10] This shows cavitation generated when ultrasonic waves are applied to the plating bath of the present disclosure to which 1.0 mmol / L of sodium oleate has been added. [Figure 11] It is a plan view in the width direction of a base material, showing ultrasonic intensity measurement positions when the distance between the base material and a counter electrode is 10 cm or more. [Figure 12] It is a plan view in the width direction of a base material, showing ultrasonic intensity measurement positions when the distance between the base material and a counter electrode is less than 10 cm. [Figure 13] It is a plan view in the width direction of a base material, showing ultrasonic intensity measurement positions when the distance between the base material and a counter electrode is 10 cm or more. [Figure 14] It is a plan view in the width direction of a base material, showing ultrasonic intensity measurement positions when the distance between the base material and a counter electrode is less than 10 cm. [Figure 15] It is another schematic diagram of an electroplating apparatus viewed from a direction perpendicular to the surface of a base material. [Figure 16]These are the results of an example obtained by using nickel sulfate as the nickel salt and plating from a bath without pH buffering agent while irradiating with ultrasound. [Figure 17] This is the result of a comparative example obtained by using nickel sulfate as the nickel salt and plating from a bath without the addition of a pH buffer, without irradiation with ultrasound. [Figure 18] This is a schematic diagram of an example of a continuous plating apparatus. [Figure 19] This is a schematic diagram of an example of a means of irradiating with ultrasound. [Figure 20] This is a plan view in the width direction of the base material, showing the ultrasonic intensity measurement position when the distance between the base material and the counter electrode is 10 cm or more. [Figure 21] This is a plan view in the width direction of the base material, showing the ultrasonic intensity measurement position when the distance between the base material and the counter electrode is less than 10 cm. [Figure 22] This is a plan view in the width direction of the base material, showing the ultrasonic intensity measurement position when the distance between the base material and the counter electrode is 10 cm or more. [Figure 23] This is a plan view in the width direction of the base material, showing the ultrasonic intensity measurement position when the distance between the base material and the counter electrode is less than 10 cm. [Figure 24] These are the results of an example obtained by using a Watt bath as the nickel plating bath, plating from a bath with a Ni2+ concentration of 0.3 mol / L under conditions of a cathode current density of 20 A / dm2 while irradiating with ultrasound. [Figure 25] This is the result of a comparative example obtained by using a Watt bath as the nickel plating bath, with a Ni2+ concentration of 0.3 mol / L, under conditions of a cathode current density of 20 A / dm2, and without ultrasonic irradiation. [Figure 26] This is a schematic diagram of an example of a continuous plating apparatus. [Figure 27] This is a schematic diagram of an example of a means of irradiating with ultrasound. [Figure 28] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is 10 cm or more. [Figure 29]This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is less than 10 cm. [Figure 30] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is 10 cm or more. [Figure 31] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is less than 10 cm. [Figure 32] This graph shows the current efficiency of the dissolution reaction of the soluble anode in electroplating of nickel under various conditions. [Figure 33] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the soluble anode and the substrate is 10 cm or more. [Figure 34] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the soluble anode and the substrate is less than 10 cm. [Figure 35] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the soluble anode and the substrate is 10 cm or more. [Figure 36] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the soluble anode and the substrate is less than 10 cm. [Figure 37] This is a schematic diagram showing an example of the arrangement of a soluble anode and an ultrasonic oscillation means. [Figure 38] These are the results of an example obtained by plating using an electroplated tin bath containing phenolsulfonic acid with a Sn2+ concentration of 0.08 mol / L, under conditions of a cathode current density of 5 A / dm2 while irradiating with ultrasound. [Figure 39] This is a schematic diagram of an example of a continuous plating apparatus. [Figure 40] This is a schematic diagram of an example of a means of irradiating with ultrasound. [Figure 41] This is a plan view of the substrate and counter electrode, showing the ultrasonic intensity measurement position when the distance between the central surface of the substrate in the width direction and the counter electrode is 10 cm or more. [Figure 42]It is a plan view of a base material and a counter electrode, showing the ultrasonic intensity measurement position when the distance between the surface at the center in the width direction of the base material and the counter electrode is less than 10 cm. [Figure 43] It is a plan view of a base material and a counter electrode, showing the ultrasonic intensity measurement position when the distance between the surface at the center in the width direction of the base material and the counter electrode is 10 cm or more. [Figure 44] It is a plan view of a base material and a counter electrode, showing the ultrasonic intensity measurement position when the distance between the surface at the center in the width direction of the base material and the counter electrode is less than 10 cm. [Figure 45] These are the results of an example obtained by plating from a bath having a Zn²⁺ concentration of 0.4 mol / L using a sulfuric acid bath under the condition of a cathode current density of 60 A / dm² while irradiating ultrasonic waves. [Figure 46] It is a schematic diagram of an example of a continuous plating apparatus. [Figure 47] It is a schematic diagram of an example of a means for irradiating ultrasonic waves. [Figure 48] It is a plan view in the width direction of a base material, showing the ultrasonic intensity measurement position when the distance between the base material and the counter electrode is 10 cm or more. [Figure 49] It is a plan view in the width direction of a base material, showing the ultrasonic intensity measurement position when the distance between the base material and the counter electrode is less than 10 cm. [Figure 50] It is a plan view in the width direction of a base material, showing the ultrasonic intensity measurement position when the distance between the base material and the counter electrode is 10 cm or more. [Figure 51] It is a plan view in the width direction of a base material, showing the ultrasonic intensity measurement position when the distance between the base material and the counter electrode is less than 10 cm. [Figure 52] It is a schematic diagram of an example of a continuous plating apparatus. [Figure 53] It is a schematic diagram of an example of a means for irradiating ultrasonic waves. [Figure 54] It is a plan view in the width direction of a base material, showing the ultrasonic intensity measurement position when the distance between the base material and the counter electrode is 10 cm or more. [Figure 55] It is a plan view in the width direction of a base material, showing the ultrasonic intensity measurement position when the distance between the base material and the counter electrode is less than 10 cm. [Figure 56]This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is 10 cm or more. [Figure 57] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is less than 10 cm. [Figure 58] This is a schematic diagram of an electroplating apparatus viewed from the width direction of the substrate. [Figure 59] This is a schematic diagram of an electroplating apparatus viewed from a direction perpendicular to the surface of the substrate. [Figure 60] This is cavitation that occurred when ultrasonic waves were irradiated onto a plating bath in a comparative example that was supplied with microbubbles having expansion pressure. [Figure 61] This is cavitation that occurs when ultrasonic waves are irradiated onto the plating bath of the present disclosure, which is supplied with microbubbles having contraction pressure. [Figure 62] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is 10 cm or more. [Figure 63] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is less than 10 cm. [Figure 64] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is 10 cm or more. [Figure 65] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is less than 10 cm. [Figure 66] This shows the results of measuring the amount of hydrogen in the substrate by a temperature-controlled desorption test for two samples: one (Example 1) where the substrate was pretreated by anode electrolytic degreasing and anode electrolytic pickling, and then nickel-plated while irradiating with ultrasound; and another (Comparative Example 1) where the substrate was pretreated by cathode electrolytic degreasing and cathode electrolytic pickling, and then nickel-plated without irradiating with ultrasound. [Figure 67] This is a schematic diagram of an example of a continuous plating apparatus. [Figure 68] This is a schematic diagram of an example of an ultrasonic oscillation means in a continuous plating apparatus. [Figure 69]This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is 10 cm or more. [Figure 70] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is less than 10 cm. [Figure 71] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is 10 cm or more. [Figure 72] This is a plan view in the width direction of the substrate, showing the ultrasonic intensity measurement position when the distance between the substrate and the counter electrode is less than 10 cm. [Modes for carrying out the invention]

[0114] Various embodiments of this disclosure are described below in detail. The manufacturing methods included in this disclosure are classified into 10 types. Hereinafter, the 10 types of manufacturing methods will be distinguished by the symbols A to J. The symbols assigned to the components of a certain manufacturing method are generally used uniformly in the description of that manufacturing method, but may not be consistent in the description of a different manufacturing method. However, the reason for the lack of uniformity in the symbols is solely for the convenience of explanation. Naturally, a preferred embodiment of a certain manufacturing method can be combined with another manufacturing method. For example, the configuration of manufacturing method I and / or manufacturing method J described later can be applied to other manufacturing methods A to H.

[0115] (Embodiment of manufacturing method A) (1. Method for manufacturing electroplated components) A method for manufacturing an electroplated member according to one embodiment of the present disclosure comprises a step of electroplating a substrate using a plating bath containing an additive, wherein the substrate is irradiated with ultrasound during the electroplating process, and the additive contains either or both of a water-soluble aliphatic monohydric alcohol or a water-soluble aliphatic carboxylic acid. The method for manufacturing an electroplated member will be described in detail below.

[0116] The method for manufacturing an electroplated member according to this embodiment includes a step of electroplating a substrate. The substrate is a material on which a plating film is deposited or formed, i.e., a base material. The material and shape of the substrate are not particularly limited.

[0117] (Types of plating baths) The type of metal ions contained in the plating bath is not particularly limited. Preferred examples of metal ions include Ni ions, Sn ions, and Zn ions. However, the plating baths that can be used in the manufacturing method of the electroplated member according to this embodiment are not limited to Ni plating baths, Sn plating baths, or Zn plating baths. Various types of plating baths can be used in the manufacturing method of the electroplated member according to this embodiment.

[0118] (Additives) The plating bath needs to contain additives in addition to metal ions. The additives are: (1) A water-soluble and aliphatic monohydric alcohol, (2) Water-soluble and aliphatic carboxylic acids It contains one or both of the above. "Water-soluble" means that the solubility of the additive in water is 100 mg / L or more. Components that are not water-soluble are difficult to effectively add to the plating bath. These additives are expected to function as radical scavengers in the plating bath. Specific examples of additives will be described later. The types of additives in the plating bath can be analyzed using liquid chromatography-mass spectrometry.

[0119] (Ultrasound) In the plating process, ultrasonic waves are irradiated onto the substrate. The ultrasonic waves are generated, for example, using an ultrasonic oscillator in an electroplating apparatus. The frequency and intensity of the ultrasonic waves are not particularly limited. It is sufficient to generate ultrasonic waves with a frequency and intensity capable of generating radicals on the plated surface of the substrate. Specific examples of ultrasonic waves will be described later.

[0120] (Effects and Benefits) The inventors of this invention believed there was an important relationship between the plating efficiency of electroplating and the state of existence of metal ions in the plating bath. Therefore, the inventors investigated various external energies that could change the state of existence of metal ions. External energy refers to energy other than the electrical energy used in conventional electroplating.

[0121] The inventors have discovered that applying ultrasound to the plated surface of a substrate improves plating efficiency across a wide range of current densities. The application of ultrasound promotes the supply of metal ions to the plated surface of the substrate under high current density conditions, thereby improving plating efficiency. Furthermore, this disclosure reveals that ultrasound-induced radicals improve plating efficiency across a wide range of current densities. The inventors speculate that radicals are generated within the cavitation caused by the application of ultrasound, and that these radicals change the electronic state of metal ions in the plating bath.

[0122] A radical is an atom or molecule that has unpaired electrons. Cavitation is a phenomenon in which the pressure of a flowing liquid decreases locally, causing a phase change and generating vapor bubbles, and a phenomenon in which a cavity is created in a part of the flow due to low pressure or high speed. In this disclosure, the bubbles and cavities produced by this phenomenon are also referred to as cavitation.

[0123] Furthermore, the inventors have found that plating efficiency can be further enhanced by adding a water-soluble, aliphatic monohydric alcohol and / or a water-soluble, aliphatic carboxylic acid to the plating bath. These substances function as radical scavengers. Radical scavengers are compounds that have an unsaturated bond that undergoes an addition reaction with short-lived radicals, causing unpaired electrons to be resonance-stabilized and resulting in relatively long-lived secondary radicals. The discovery that plating efficiency can be enhanced by combining radical scavengers with ultrasound supports the inventors' hypothesis that radicals generated by ultrasound improve plating efficiency.

[0124] The inventors hypothesize that hydrogen radicals and hydroxyl radicals originating from water molecules are generated during cavitation. Hydrogen radicals have reducing properties, while hydroxyl radicals have oxidizing properties. Hydrogen radicals promote the chemical reaction in which metal ions in the plating bath are reduced to form a plating film. On the other hand, hydroxyl radicals inhibit this chemical reaction. The inventors believe that when using radicals to promote plating efficiency, it is preferable to utilize the effects of hydrogen radicals while suppressing the adverse effects of hydroxyl radicals.

[0125] Water-soluble, aliphatic monohydric alcohols and / or water-soluble, aliphatic carboxylic acids absorb hydrogen radicals and hydroxyl radicals as radical scavengers, becoming reducing secondary radicals. Therefore, the inventors hypothesize that by adding these substances to the plating bath, the reducing effect of radicals can be ensured while suppressing the adverse effects of hydroxyl radicals, thereby further promoting plating efficiency.

[0126] Furthermore, it is presumed that alcohols with a valency of two or more are not suitable as radical scavengers in this embodiment. The inventors believe that when an alcohol molecule has two or more hydroxyl groups, multiple hydroxyl groups within the same molecule become radicals simultaneously, and these radicals react within the same molecule, thereby reducing the effectiveness of the radical scavenger.

[0127] Furthermore, non-aliphatic alcohols, such as aromatic alcohols, are presumed to be unsuitable as radical scavengers in this embodiment. The inventors believe that such alcohols excessively stabilize radicals within the molecule, resulting in a weak reducing effect.

[0128] As described above, the method for manufacturing electroplated members according to this embodiment can significantly improve plating efficiency for various types of plating baths by combining ultrasonic irradiation and a radical scavenger.

[0129] The most basic embodiment of the method for manufacturing an electroplated member according to this embodiment has been described above. A more preferred embodiment will be described below.

[0130] (Preferred composition of additives) Suitable examples of monohydric alcohols used as additives are secondary and tertiary alcohols. Therefore, it is preferable that the additive contains either or both of a secondary and a tertiary alcohol. Secondary and tertiary alcohols have a higher ability to extend the lifetime of secondary radicals than primary alcohols.

[0131] Furthermore, the number of carbon atoms in the monohydric alcohol is preferably between 3 and 6. By increasing the number of carbon atoms to between 3 and 6, it is expected that the solubility in water will increase, the diffusivity of the molecule will improve, and the ability as a radical scavenger will be further enhanced.

[0132] Furthermore, it is preferable that the monohydric alcohol is an alcohol that does not contain a benzene ring. The inventors surmise that the benzene ring may worsen the solubility of the monohydric alcohol in water and may also inhibit its ability as a radical scavenger.

[0133] More preferred examples of monohydric alcohols are isopropyl alcohol, isobutyl alcohol, 2-butanol, and tertiary butanol. It is preferable that the plating bath contains one or more alcohols selected from the group consisting of isopropyl alcohol, isobutyl alcohol, 2-butanol, and tertiary butanol.

[0134] More preferred examples of carboxylic acids used as additives are propionic acid, butyric acid, valeric acid, and caproic acid. It is preferable that the plating bath contains one or more selected from the group consisting of propionic acid, butyric acid, valeric acid, and caproic acid.

[0135] (Preferred concentration of radical scavenger) In the plating bath, the total concentration of the water-soluble, aliphatic monohydric alcohol and the water-soluble, aliphatic carboxylic acid is preferably within the range of 0.001 mol / L to 5 mol / L. By setting the total concentration to 0.001 mol / L or higher, the radical scavenging effect can be further enhanced. On the other hand, by setting the total concentration to 5 mol / L or lower, the incorporation of carbon into the plating film can be suppressed. The total concentration of the water-soluble, aliphatic monohydric alcohol and the water-soluble, aliphatic carboxylic acid may be 0.005 mol / L or higher, 0.01 mol / L or higher, 0.05 mol / L or higher, or 0.1 mol / L or higher. The total concentration of the water-soluble, aliphatic monohydric alcohol and the water-soluble, aliphatic carboxylic acid may be 2 mol / L or lower, 1 mol / L or lower, 0.8 mol / L or lower, or 0.5 mol / L or lower.

[0136] Furthermore, water-soluble, aliphatic monohydric alcohols and water-soluble, aliphatic carboxylic acids are consumed as the plating process progresses. Consequently, the concentration of these substances in the plating bath decreases as the plating process progresses. In the method for manufacturing an electroplated member according to this embodiment, it is preferable to add water-soluble, aliphatic monohydric alcohols and water-soluble, aliphatic carboxylic acids to the plating bath during the plating process to maintain their concentration within the above-mentioned range.

[0137] In this case, the concentrations of water-soluble, aliphatic monohydric alcohols and water-soluble, aliphatic carboxylic acids in the plating bath may be monitored to determine their consumption. Alternatively, the consumption of water-soluble, aliphatic monohydric alcohols and water-soluble, aliphatic carboxylic acids may be estimated based on the amount of current applied, etc.

[0138] (Suitable types of plating baths) As described above, examples of plating baths include Ni plating baths, Sn plating baths, or Zn plating baths. Here, an M plating bath (where M represents the metals Ni, Sn, or Zn) means a plating bath containing 0.1 mol / L or more of the metal M, and in which the plating film obtained by electroplating using the plating bath contains 50% or more of the metal. The metal ion concentration in the plating bath can be measured by ICP emission spectrometry. The method for manufacturing electroplated members according to this embodiment can dramatically improve the plating efficiency of plating processes using these plating baths. Furthermore, the method for manufacturing electroplated members according to this embodiment can also be applied to plating baths containing other metal ions.

[0139] Naturally, the plating bath may contain two or more metals. For example, when manufacturing nickel-plated steel sheets for batteries, Co ions and W ions can be added to a plating bath mainly composed of Ni ions. Other options include Ni-Fe plating baths, Sn-Pb plating baths, Sn-Cu plating baths, Sn-Ag plating baths, Sn-Bi plating baths, Sn-Co plating baths, Zn-Ni plating baths, or Zn-Fe plating baths. The manufacturing method for electroplated members according to this embodiment can also be applied to such plating baths.

[0140] (Suitable frequency and intensity of ultrasound) A suitable example of the ultrasonic frequency is between 15 kHz and 1000 kHz. The inventors predict that setting the ultrasonic frequency within this range can further improve plating efficiency. The ultrasonic frequency may also be 50 kHz or higher, 80 kHz or higher, or 100 kHz or higher. The ultrasonic frequency may also be 800 kHz or lower, 600 kHz or lower, or 500 kHz or lower.

[0141] The ultrasonic intensity at the predetermined ultrasonic intensity measurement position A4 is preferably, for example, 0.20 to 80 kPa / kHz. The ultrasonic intensity measurement position A4 is the location that is closest to the substrate A3 or the planned substrate placement area among (a) and (b) below. (a) A location 5 cm away from the center of the width direction of the substrate A3 or the area where the substrate is to be placed. (b) The midpoint between the center in the width direction of the base material A3 or the area where the base material is to be placed and the counter pole 15 Details of the ultrasonic intensity measurement position 4 will be described later.

[0142] Plating efficiency can be further improved by setting the ultrasonic intensity to 0.20 kPa / kHz or higher. While there is no upper limit to the ultrasonic intensity, setting it to 80 kPa / kHz or lower can improve the working environment, extend the lifespan of the plating equipment, and reduce operating energy. The ultrasonic intensity at a distance of 5 cm from the plating surface of the substrate may be 0.40 kPa / kHz or higher, or 1.2 kPa / kHz or higher. Alternatively, the ultrasonic intensity at a distance of 5 cm from the plating surface of the substrate may be 40 kPa / kHz or lower, or 10 kPa / kHz or lower.

[0143] (2. Electroplating equipment) Another embodiment of the present disclosure is an electroplating apparatus A1 for carrying out a method for manufacturing an electroplated member according to the present embodiment, comprising: an electroplating tank A11 for holding a plating bath A2 containing an additive; and an ultrasonic oscillator A12 for emitting ultrasonic waves into the plating bath A2, wherein the frequency of the ultrasonic waves is 15 kHz or more and 1000 kHz or less; and the additive includes either or both of a water-soluble aliphatic monohydric alcohol or a water-soluble aliphatic carboxylic acid.

[0144] The details of the electroplating apparatus A1 will be described below, with the continuous plating apparatus shown in Figures 1 and 2 as an example. However, it should be noted that the configuration described below is merely an exemplary configuration of the electroplating apparatus A1. The method for manufacturing the electroplated member according to this embodiment can be carried out by various electroplating apparatuses A1. Furthermore, the preferred embodiment of the method for manufacturing the electroplated substrate A3 described above can also be applied to the electroplating apparatus A1. Hereinafter, the left-right direction in Figure 1 will be referred to as the X direction, and the up-down direction will be referred to as the Y direction. The direction perpendicular to the X and Y directions will be referred to as the Z direction. The width direction of the substrate A3 is the Z direction.

[0145] (Electroplating tank A11) The electroplating tank A11 is a container configured to hold the plating bath A2. The number of electroplating tanks A11 included in the electroplating apparatus A1 may be one or two or more. For example, the electroplating apparatus A1 illustrated in Figure 1 is provided with two or more electroplating tanks A11. The plate-shaped substrate A3 passes through these electroplating tanks A11 in a continuous manner.

[0146] (Plating bath A2) Plating bath A2 contains additives. The additives include either a water-soluble, aliphatic monohydric alcohol or a water-soluble, aliphatic carboxylic acid, or both. The inventors hypothesize that these components act as radical scavengers and promote the reduction reaction of metal ions on the plated surface of substrate A3. Preferred embodiments of plating bath A2 are as described above.

[0147] (Ultrasonic oscillator A12) The ultrasonic oscillator A12 is configured to emit ultrasonic waves inside the electroplating bath A11. The ultrasonic frequency is, for example, between 15 kHz and 1000 kHz. The ultrasonic intensity is, for example, 0.20 to 80 kPa / kHz at a distance of 5 cm from the plated surface of the substrate A3.

[0148] The arrangement of the ultrasonic oscillator A12 is not particularly limited. The ultrasonic oscillator A12 can be arranged in various ways depending on the arrangement of the substrate A3 and the counter electrode A15. For example, in the continuous electroplating apparatus A1 illustrated in Figures 1 and 2, the ultrasonic oscillator A12 is arranged laterally with respect to the direction of passage of the substrate A3. This is to prevent the counter electrode A15, which is arranged parallel to the surface of the substrate A3, from interfering with the irradiation of the ultrasonic waves.

[0149] (Substrate support device A14, A141) The electroplating apparatus A1 may have substrate support devices A14 and A141. In Figure 1, the substrate support device immersed in the plating bath is denoted as A14, and the substrate support device not immersed is denoted as A141. The substrate support devices A14 and A141 are configured to support the substrate A3 to be electroplated by the electroplating apparatus A1 in the substrate placement area in the plating bath A2. In this disclosure, the position where the substrate A3 is placed is referred to as the substrate placement area. The position and shape of the substrate placement area are not particularly limited. The position and shape of the substrate placement area can be determined according to the shape of the substrate A3 and the position and shape of the counter electrode A15, which will be described later. In Figures 1 to 6, the area where the substrate A3 is placed is the substrate placement area.

[0150] In this embodiment, the term "support" differs from "fixing" in that it means supporting an object so that it is contained within a certain range. For example, in the continuous plating apparatus shown in Figure 1, the substrate support devices A14 and A141 are rollers for feeding the substrate. By rotating the rollers for feeding the substrate, the substrate A3 can be moved within a certain range. This allows the substrate A3 to be immersed in the plating bath A2 inside the plating tank and then lifted out. On the other hand, if the electroplating apparatus A1 is a batch processing apparatus, the substrate support devices may be, for example, hooks and clamps.

[0151] Furthermore, the substrate support device A141, which is not immersed in the plating bath A2, is energized to the substrate A3. Therefore, at least a portion of the substrate support device A141, which is located outside the plating bath A2, is made of a conductive material such as copper. In addition, the substrate support device A141, which is located outside the plating bath A2, is configured to be connectable to a power supply, which is not shown in Figure 1, etc.

[0152] (Opposite pole A15) The electroplating apparatus A1 has a counter electrode A15. The counter electrode A15 is positioned near the substrate support device A14. The counter electrode A15 and the substrate support device A141 are connected to a power supply. By passing current through the counter electrode A15 and the substrate support device A141, an electrolytic reaction occurs on the surface of the substrate A3 supported by the substrate support devices A14 and A141. The position of the counter electrode A15 can be appropriately selected depending on the position where the substrate A3 is placed. For example, in the plating apparatus shown in Figure 1, the counter electrode A15 is positioned parallel to the substrate A3.

[0153] (Plating bath degassing device A16) The electroplating apparatus A1 may have a plating bath degasser A16. The plating bath degasser A16 degasses the dissolved gas contained in the plating bath A2 that is filled inside the electroplating tank A11. An example of the plating bath degasser A16 is, for example, a liquid degassing pump A162, or a buffer tank A161 configured to be connectable to the degassing pump A162, or piping, etc. The plating bath degasser A16 removes dissolved gas from the plating bath.

[0154] Dissolved gases attenuate ultrasound. Removing dissolved gases can further enhance the effectiveness of the ultrasonic oscillator. However, degassing the plating bath A2 may suppress the generation of cavitation by ultrasound. In the manufacturing method of the electroplated member according to this embodiment, a radical scavenger is used to enhance the action of radicals that are presumed to be generated in the cavitation. Therefore, it is considered that removing dissolved gases does not impair the effect of cavitation on improving plating efficiency.

[0155] The electroplating apparatus A1 shown in Figure 1 has a buffer tank A161 connected to the electroplating tank A11 via a means for the flow of the plating bath A2, such as piping. The buffer tank A161 is equipped with a degassing pump A162. The plating bath A2 circulates between the buffer tank A161 and the electroplating tank A11. The plating bath A2 that has moved from the electroplating tank A11 to the buffer tank A161 is degassed in the buffer tank A161 by the degassing pump A162. The plating bath A2 that has moved from the buffer tank A161 to the electroplating tank A11 reduces the amount of dissolved gas in the plating bath A2 in the electroplating tank A11. Alternatively, the amount of dissolved gas in the plating bath A2 can also be reduced by connecting the piping or the electroplating tank A11 to the degassing pump A162.

[0156] The electroplating apparatus A1 shown in Figure 1 employs a so-called overflow cell system. In the electroplating apparatus A1 employing the overflow cell system, the plating bath A2 is supplied from the buffer tank A161 to the bottom of the electroplating tank. Furthermore, the plating bath A2 is allowed to overflow from the top of the electroplating tank. The overflowed plating bath A2 is collected in the buffer tank A161. However, the method of circulating the plating bath A2 can be appropriately changed depending on the type and size of the substrate A3, etc.

[0157] (power supply) The power supply is electrically connected to the counter electrode A15 and the substrate support device A141. The power supply supplies current to the counter electrode A15 and the substrate support device A141, causing an electrolytic reaction on the surface of the substrate A3. The power supply may be incorporated into the electroplating apparatus A1. Alternatively, the electroplating apparatus A1 and the power supply may be provided separately and electrically connected as needed.

[0158] The electroplating apparatus A1 having the above-described configuration can suitably carry out the method for manufacturing an electroplated member according to this embodiment.

[0159] While embodiments of the present disclosure have been described above, the disclosure is not limited thereto and can be modified as appropriate without departing from the technical idea. Further preferred examples of a method for manufacturing an electroplated member and an electroplating apparatus according to the present embodiment will be described below.

[0160] (Temperature of the plating bath) The temperature of the plating bath is preferably between 30°C and 70°C. Maintaining a temperature of 30°C or higher ensures the efficiency of the electroplating process. Furthermore, maintaining a temperature of 70°C or lower suppresses concentration fluctuations due to evaporation of the plating bath.

[0161] (Number of ultrasonic oscillation devices) The number of ultrasonic emitting means is not particularly limited. For example, by attaching ultrasonic emitting means to both sides of the substrate at regular intervals, ultrasonic waves can be applied to the substrate from two or more directions. Therefore, it becomes easier to apply ultrasonic waves to the entire surface of the substrate. For the reasons above, it is preferable to have two or more ultrasonic emitting means. On the other hand, if the substrate is small, it is possible to have only one ultrasonic emitting means. Various numbers can be selected depending on the shape and arrangement of the substrate.

[0162] (Measurement and control of dissolved oxygen in the plating bath) The electroplating apparatus may further include a dissolved oxygen measuring means. Using the dissolved oxygen measuring means, the amount of dissolved oxygen in the plating bath is measured, and the amount of dissolved oxygen is determined to be 6 mg·L. -1 Dissolved gases in the plating bath may be removed as described below. However, a portable dissolved oxygen measuring device may be used to control the amount of dissolved oxygen within the above range. In this case, the electroplating apparatus does not need to be equipped with a means for measuring dissolved oxygen.

[0163] The dissolved gases in the plating bath mainly consist of nitrogen and oxygen, which are present in the atmosphere. Hydrogen generated by the electrolytic reaction is presumed to be almost completely insoluble in the plating bath. Therefore, the amount of dissolved oxygen can be used as an indicator of the total amount of dissolved gases in the plating bath. According to the inventor's findings, the dissolved oxygen content of the plating bath is 6 mg·L. -1 The ultrasonic waves are further amplified by controlling the following: the dissolved oxygen level in the plating bath to 5 mg / L. -1 The following is also acceptable.

[0164] (Ultrasonic intensity and measurement location) The ultrasonic oscillation means is preferably configured to be able to set the ultrasonic intensity at a predetermined ultrasonic intensity measurement position A4 to 0.20 to 80 kPa / kHz. The ultrasonic intensity measurement position A4 is the location that is closest to the base material A3 or the planned base material placement area among (a) and (b) below. (a) A location 5 cm away from the center of the width direction of the substrate A3 or the area where the substrate is to be placed. (b) The midpoint between the center in the width direction of the base material A3 or the area where the base material is to be placed and the counter electrode A15 Examples of ultrasonic intensity measurement position A4 are shown in Figures 3 to 6. Figures 3 to 6 are top views of the substrate A3 and counter electrode A15 in the continuous electroplating apparatus A1 of Figure 1. The vertical direction in Figures 3 to 6 is the Z direction, i.e., the width direction of the substrate A3. The width direction of the substrate A3 is the direction perpendicular to the longitudinal direction of the substrate A3, i.e., the direction of travel, and parallel to the surface of the substrate A3. The horizontal direction in Figures 3 to 6 is the X direction.

[0165] In the continuous electroplating apparatus shown in Figure 3, both the substrate A3 and the counter electrode A15 are flat and are arranged parallel to each other. The distance D between the center surface of the substrate A3 in the width direction and the counter electrode A15 is 10 cm or more. In the continuous electroplating apparatus shown in Figure 3, the ultrasonic intensity measurement position A4 is located 5 cm away from the center surface of the substrate A3 in the width direction.

[0166] In the continuous electroplating apparatus shown in Figure 4, both the substrate A3 and the counter electrode A15 are flat and are arranged parallel to each other. The distance D between the center surface of the substrate A3 in the width direction and the counter electrode A15 is less than 10 cm. In the continuous electroplating apparatus shown in Figure 4, the ultrasonic intensity measurement position A4 is set midway between the center of the substrate A3 in the width direction and the counter electrode A15.

[0167] In the continuous electroplating apparatus shown in Figure 5, the substrate A3 is curved, while the counter electrode A15 is flat. The substrate A3 and the counter electrode A15 are not parallel. The distance D between the center surface of the substrate A3 in the width direction and the counter electrode A15 is 10 cm or more. In the continuous electroplating apparatus shown in Figure 5, the ultrasonic intensity measurement position A4 is set 5 cm away from the center surface of the substrate A3 in the width direction.

[0168] In the continuous electroplating apparatus shown in Figure 6, the substrate A3 is curved, while the counter electrode A15 is flat. The substrate A3 and the counter electrode A15 are not parallel. The distance D between the center surface of the substrate A3 in the width direction and the counter electrode A15 is less than 10 cm. In the continuous electroplating apparatus shown in Figure 6, the ultrasonic intensity measurement position A4 is set midway between the center of the substrate A3 in the width direction and the counter electrode A15.

[0169] (Other embodiments) A larger electroplating tank is preferable because it improves the efficiency of the electroplating process and increases the number of substrates that the electroplating apparatus can electroplat. For example, the capacity of a single electroplating tank may be 10L or more, 100L or more, 500L or more, or 1000L or more.

[0170] The ultrasonic oscillation means may be capable of pulse oscillation, which switches the ultrasonic oscillation on and off at a constant period, or sweep oscillation, which vibrates the frequency in the range of several kHz. By performing pulse oscillation or sweep oscillation, the state of the ultrasonic waves in the plating bath changes, making it less likely for standing waves to form, thereby further enhancing the effect of the ultrasonic waves. (Embodiment of Manufacturing Method A)

[0171] (Embodiment of manufacturing method B) (1. Method for manufacturing electroplated components) Hereinafter, a method for manufacturing an electroplated member according to the embodiment of this disclosure (hereinafter simply referred to as the "manufacturing method") will be described with reference to Figures 7 and 8. The manufacturing method according to this embodiment comprises a step of electroplating a substrate B3 by passing an electric current through a substrate B3 and a counter electrode B14 immersed in a plating bath B2, wherein the plating bath B2 contains an ionic surfactant of 0.10 mmol / L to 10 mmol / L, and during electroplating, ultrasonic waves are irradiated onto the substrate B3, with the frequency of the ultrasonic waves being 15 kHz to 80 kHz, and the intensity of the ultrasonic waves being 0.20 to 80 kPa / kHz at a location 5 cm away from the surface of the substrate B3, and at an intermediate location between the substrate B3 and the counter electrode B14, where the distance from the substrate B3 is even closer.

[0172] The inventors diligently investigated means to alleviate the constraints imposed by the diffusion layer of the plating solution on the plating speed and film characteristics. It is conventionally known that applying ultrasonic vibration to the plating solution can mitigate the adverse effects of the diffusion layer. However, when a large amount of plating bath B2 was filled into a large electroplating tank B11, the ultrasonic vibration was attenuated, and the adverse effects of the diffusion layer were not sufficiently mitigated.

[0173] Our investigations revealed that this is due to energy loss associated with the generation of cavitation of various sizes. Ultrasonic-induced cavitation is thought to be generated and grow due to the negative pressure caused by the propagation of ultrasound. In existing electroplating techniques, the focus has been on ultrasonic irradiation conditions such as the output and frequency of the ultrasound. On the other hand, the fact that cavitation attenuates ultrasound has not been considered in the field of electroplating technology.

[0174] Therefore, the inventors investigated an ultrasonic irradiation method to control the cavitation size. It has been conventionally known that the cavitation size is affected by the frequency and intensity of the ultrasound. Accordingly, the inventors predicted that by selecting appropriate ultrasonic irradiation conditions, it would be possible to reduce the loss of ultrasound and eliminate the adverse effects of the diffusion layer even in a large electroplating tank B11.

[0175] However, the inventors found that controlling the cavitation size and reducing ultrasound loss is difficult by controlling the ultrasound irradiation conditions alone. While the ultrasound irradiation conditions certainly seem to influence cavitation generation, it was not possible to control how the generated cavitation subsequently grows through the ultrasound irradiation conditions.

[0176] The inventors considered that in order to control the cavitation size, it is necessary to appropriately control the interfacial energy of the cavitation itself. As a means of controlling interfacial energy, the use of surfactants is conventionally known, particularly in the field of cleaning. However, according to Patent Document 5, when surfactants contained in dish soap, etc., enter the drainage system, the cleaning performance of ultrasonic cleaning decreases. This is because relatively large bubbles containing surfactants are generated, which hinder the transmission of ultrasonic waves emitted from the ultrasonic oscillator. Therefore, in order to suppress ultrasonic attenuation, it is common to eliminate surfactants. Furthermore, since cavitation is also a high-temperature, high-pressure reaction field, it is difficult to use the same surfactants used in cleaning for plating.

[0177] To solve these problems and control the cavitation size, the inventors conducted further intensive research. They discovered that the cavitation size can be suitably controlled by adding a predetermined amount of an ionic surfactant having a predetermined HLB value to the plating bath B2. Even when a large amount of plating bath B2 was filled into a large electroplating tank B11, the ionic surfactant was able to eliminate the adverse effects of the diffusion layer while reducing ultrasonic loss.

[0178] The configuration of the manufacturing method for electroplated members according to this embodiment, and its effects, will be described in detail below. An example of an electroplating apparatus B1 suitable for carrying out the manufacturing method for electroplated members according to this embodiment will also be described below. However, the configuration of the plating apparatus in the manufacturing method for electroplated members according to this embodiment is not particularly limited.

[0179] (Electroplating tank B11) The electroplating tank B11 is a container for housing the plating bath B2. The electroplating apparatus B1 may contain one or more electroplating tanks B11. For example, the electroplating apparatus B1 illustrated in Figure 7 is provided with two or more electroplating tanks B11. The substrate B3 passes through these electroplating tanks B11 in a continuous manner.

[0180] (Ultrasonic oscillation means B12) The ultrasonic emitting means B12 emits ultrasonic waves inside the electroplating bath B11. The frequency of the ultrasonic waves is between 15 kHz and 80 kHz. The frequency of the ultrasonic waves may also be 18 kHz or higher, 20 kHz or higher, or 30 kHz or higher. Alternatively, the frequency of the ultrasonic waves may be 70 kHz or lower, 60 kHz or lower, or 50 kHz or lower.

[0181] The arrangement of the ultrasonic oscillating means B12 is not particularly limited. The ultrasonic oscillating means B12 can be arranged in various ways depending on the arrangement of the substrate B3 and the counter electrode B14. For example, in the continuous electroplating apparatus B1 illustrated in Figures 7 and 8, the ultrasonic oscillating means B12 is arranged laterally with respect to the direction of passage of the substrate B3. This is to prevent the counter electrode B14, which is arranged parallel to the surface of the substrate B3, from interfering with the irradiation of ultrasonic waves.

[0182] Preferably, the exterior material of the ultrasonic oscillation means B12 is made of a corrosion-resistant material, at least in the portion that is in contact with the plating bath B2. A corrosion-resistant material is, for example, stainless steel.

[0183] (Base material support means B13, B131) The substrate support means B13 and B131 support the substrate B3, which is to be electroplated by the electroplating apparatus B1, in the plating bath B2. In this embodiment, the term "support" differs from "fixing" and means supporting an object so that it is contained within a certain range. For example, in the continuous electroplating apparatus B1 shown in Figure 7, the substrate support means B13 and B131 are feed rollers. By rotating the feed rollers, the substrate B3 can be moved within a certain range. This allows the substrate B3 to be immersed in the plating bath B2 inside the plating tank and then lifted out. On the other hand, if the plating apparatus is a batch processing apparatus, the substrate support means B13 and B131 may be, for example, hooks and clamps.

[0184] Furthermore, the substrate support means B131 that is not immersed in the plating bath B2 is energized to the substrate B3. Therefore, at least a portion of the substrate support means B131 located outside the plating bath B2 is made of a conductive material such as copper. In addition, the substrate support means B131 located outside the plating bath B2 is configured to be connectable to a power supply, which is not shown in Figure 7, etc.

[0185] (Opposite pole B14) The counter electrode B14 is positioned near the substrate support means B13. The counter electrode B14 and the substrate support means B13 are connected to a power source. By passing current through the counter electrode B14 and the substrate support means B131, an electrolytic reaction occurs on the surface of the substrate B3 supported by the substrate support means B13 and B131. The position of the counter electrode B14 can be appropriately selected depending on the position where the substrate B3 is placed. For example, in the plating apparatus shown in Figure 7, the counter electrode B14 is positioned parallel to the substrate B3.

[0186] (Buffer Tank B15) The electroplating apparatus B1 shown in Figure 7 has a buffer tank B15 connected to the electroplating tank B11 via a means for the flow of the plating bath B2, such as piping. The plating bath B2 circulates between the buffer tank B15 and the electroplating tank B11.

[0187] The electroplating apparatus B1 shown in Figure 7 employs a so-called overflow cell system. In the electroplating apparatus B1 employing the overflow cell system, the plating bath B2 is supplied from the buffer tank B15 to the bottom of the electroplating tank. Furthermore, the plating bath B2 is allowed to overflow from the top of the electroplating tank. The overflowed plating bath B2 is collected in the buffer tank B15. However, the method of circulating the plating bath B2 can be appropriately changed depending on the type and size of the substrate B3, etc.

[0188] Buffer tank B15 increases the amount of plating bath B2 in the electrolytic reaction system. By increasing the amount of plating bath B2, fluctuations in the ion concentration in plating bath B2 are suppressed.

[0189] (power supply) The power supply is electrically connected to the counter electrode B14 and the substrate support means B131. The power supply supplies current to the counter electrode B14 and the substrate support means B131, causing an electrolytic reaction on the surface of the substrate B3. The power supply may be incorporated into the electroplating apparatus B1. Alternatively, the electroplating apparatus B1 and the power supply may be provided separately and electrically connected as needed.

[0190] (immersion) A substrate B3, supported by substrate support means B13 and B131, is immersed in a plating bath B2 contained in an electroplating tank B11. The location where the substrate B3 is placed is determined according to the shape and size of the substrate B3. The substrate B3 may be fixed in place within the plating bath B2 or it may be moved. For example, in the continuous electroplating apparatus B1 shown in Figure 7, the substrate B3 moves within the plating bath B2 along a predetermined direction after being immersed in the plating bath B2. The strength of the electrolytic reaction depends on the current density between the substrate B3 and the counter electrode B14. The type of plating bath B2 is not particularly limited. A plating bath B2 can be appropriately adopted according to the desired plating film. Preferred examples of plating bath B2 include Zn plating baths, Ni plating baths, Cu plating baths, Cr plating baths, and Sn plating baths.

[0191] (Electroplating) Next, current is applied to the substrate B3 and the counter electrode B14 immersed in the plating bath B2. This causes an electrolytic reaction on the surface of the substrate B3 supported by the substrate support means B13 and B131, thereby electroplating the substrate B3.

[0192] The energizing conditions are not particularly limited. Appropriate energizing conditions can be adopted depending on the desired plating film. In general electroplating methods, a diffusion layer forms on the surface of the substrate B3, reducing the limiting current density. However, in the electroplating method according to this embodiment, the adverse effects of the diffusion layer are reduced, allowing for the adoption of a higher current density. "High current density" refers to the current density at which plating discoloration occurs under conditions without ultrasonic irradiation. Plating discoloration is, for example, a deterioration of the plating surface caused by excessively high current density.

[0193] High current densities can vary depending on the type of plating bath and plating conditions. In the embodiments of this disclosure, the current density is 60 A / dm in a Ni plating bath. 2 The above results in a high current density. However, the description in the examples is merely an example. By using the manufacturing method for electroplated members according to this embodiment, plating becomes possible even at current densities where conventional techniques would cause plating burn in individual plating baths and plating conditions.

[0194] (Mitigation of adverse effects of the diffusion layer by ultrasound) When an electrolytic reaction progresses due to the application of electricity, plating metal adheres to the surface of substrate B3, while metal ions are consumed in the plating solution near substrate B3. This creates a concentration gradient of metal ions in the region near substrate B3. The region where the concentration gradient occurs is called the diffusion layer. Since the metal ion concentration is low in the diffusion layer, the electrolytic reaction is inhibited. Therefore, the diffusion layer imposes constraints on the plating rate and film characteristics.

[0195] The diffusion layer cannot be adequately removed by means of generating liquid flow, such as agitators, agitator propellers, and pumps. In the continuous electroplating apparatus B1 illustrated in Figure 7, the substrate B3 moves through the plating bath B2, which generates a liquid flow called an accompanying flow around the substrate B3. However, even with the accompanying flow, the diffusion layer cannot be adequately removed.

[0196] Therefore, an ionic surfactant is added to the plating bath B2 at a concentration of 0.10 mmol / L to 10 mmol / L. The HLB (Hydrophile-Lipophile Balance) value of the ionic surfactant in the Griffin method is set to 3.0 to 8.0. In addition, during electroplating, ultrasonic waves with a frequency of 15 kHz to 80 kHz are applied to the substrate B3 using an ultrasonic oscillation means B12. Furthermore, during electroplating, the ultrasonic intensity at a predetermined ultrasonic intensity measurement position is set to 0.20 to 80 kPa / kHz.

[0197] (Ultrasonic intensity at ultrasonic intensity measurement position B4: 0.20~80 kPa / kHz) The ultrasonic intensity measurement position B4 is the location that is closest to the substrate B3 among (a) and (b) below. (a) A point 5 cm away from the surface of base material B3 (b) Intermediate point between base material B3 and counter electrode B14 Examples of measurement positions are shown in Figures 11 to 14. Figures 11 to 14 are top views of the substrate B3 and counter electrode B14 in the continuous electroplating apparatus B1 of Figure 7. The vertical direction in Figures 11 to 14 is the Z direction, i.e., the width direction of the substrate B3. The width direction of the substrate B3 is the direction perpendicular to the longitudinal direction of the substrate B3, i.e., the direction of travel, and parallel to the surface of the substrate B3. The horizontal direction in Figures 11 to 14 is the X direction.

[0198] In the continuous electroplating apparatus shown in Figure 11, both the substrate B3 and the counter electrode B14 are flat and are arranged parallel to each other. The distance D between the center surface of the substrate B3 in the width direction and the counter electrode B14 is 10 cm or more. In the continuous electroplating apparatus shown in Figure 11, the ultrasonic intensity measurement position B4 is located 5 cm away from the center surface of the substrate B3 in the width direction.

[0199] In the continuous electroplating apparatus shown in Figure 12, both the substrate B3 and the counter electrode B14 are flat and are arranged parallel to each other. The distance D between the center surface of the substrate B3 in the width direction and the counter electrode B14 is less than 10 cm. In the continuous electroplating apparatus shown in Figure 12, the ultrasonic intensity measurement position B4 is set midway between the center of the substrate B3 in the width direction and the counter electrode B14.

[0200] In the continuous electroplating apparatus shown in Figure 13, the substrate B3 is curved, while the counter electrode B14 is flat. The substrate B3 and the counter electrode B14 are not parallel. The distance D between the center surface of the substrate B3 in the width direction and the counter electrode B14 is 10 cm or more. In the continuous electroplating apparatus shown in Figure 13, the ultrasonic intensity measurement position B4 is located 5 cm away from the center surface of the substrate B3 in the width direction.

[0201] In the continuous electroplating apparatus shown in Figure 14, the substrate B3 is curved, while the counter electrode B14 is flat. The substrate B3 and the counter electrode B14 are not parallel. The distance D between the center surface of the substrate B3 in the width direction and the counter electrode B14 is less than 10 cm. In the continuous electroplating apparatus shown in Figure 14, the ultrasonic intensity measurement position B4 is set to a point midway between the center of the substrate B3 in the width direction and the counter electrode B14.

[0202] It should be noted that if the ultrasonic intensity is less than 0.20 kPa / kHz, local agitation around the substrate B3 will be difficult to occur, and the desired effect will not be achieved. Therefore, the ultrasonic intensity at ultrasonic intensity measurement position B4 should be 0.20 kPa / kHz or higher.

[0203] From the perspective of mitigating the adverse effects of ultrasound on the diffusion layer, there is no upper limit to the ultrasound intensity. However, if the ultrasound intensity exceeds 80 kPa / kHz, its effect may saturate, potentially leading to unnecessary equipment load and deterioration of the working environment. Therefore, the ultrasound intensity at ultrasound intensity measurement position B4 should be kept below 80 kPa / kHz. On the other hand, ultrasound within the above-mentioned range of frequency and intensity will reduce the adverse effects of the diffusion layer regardless of the type of plating bath B2.

[0204] The ultrasonic intensity at ultrasonic intensity measurement position B4 may be set to 0.40 kPa / kHz or higher, or 1.2 kPa / kHz or higher. The ultrasonic intensity at ultrasonic intensity measurement position B4 may be set to 40 kPa / kHz or lower, or 10 kPa / kHz or lower.

[0205] (Concentration of ionic surfactant: 0.10 mmol / L or more and 10 mmol / L or less) When cavitation of various sizes is generated in the ultrasonically irradiated plating bath B2, the ultrasonic energy is lost and easily attenuated. This becomes a problem when the substrate B3 is large and the electroplating bath B11 that accommodates it is also large. If the distance between the ultrasonic oscillating means B12 and the substrate B3 is large, the ultrasonic waves attenuate before reaching the substrate B3, making it difficult to keep the ultrasonic intensity within the aforementioned range across the entire substrate B3.

[0206] Therefore, an ionic surfactant is added to the plating bath B2. The ionic surfactant reduces the adverse effects of the diffusion layer, even in the large electroplating tank B11. The ionic surfactant controls the size of the cavitation generated by the ultrasound. This makes it possible to suppress energy loss due to unnecessary cavitation generation while mitigating the adverse effects of the diffusion layer near the surface of the substrate B3.

[0207] The concentration of the ionic surfactant in the plating bath should be between 0.10 mmol / L and 10 mmol / L. If the concentration of the ionic surfactant in the plating bath is too low, the above-mentioned effects will be insufficient. If the concentration of the ionic surfactant in the plating bath is too high, carbon derived from the ionic surfactant will be incorporated into the plating film, degrading the quality of the plating film. The concentration of the ionic surfactant may be 0.30 mmol / L or higher, or 0.50 mmol / L or higher. The concentration of the ionic surfactant may be 7 mmol / L or lower, or 5 mmol / L or lower.

[0208] In Comparative Example 1-1, shown in "Examples of Manufacturing Method B" described later, ultrasonic waves were irradiated onto a plating bath without the addition of a surfactant. Figure 9 shows the cavitation that occurred in Comparative Example 1-1. In Example 1-1, ultrasonic waves were irradiated onto a plating bath to which 1.0 mmol / L of sodium oleate had been added. Figure 10 shows the cavitation that occurred in Example 1-1.

[0209] The plating bath of Comparative Example 1-1, which did not contain a surfactant, contained cavitations of various sizes. Furthermore, the number of cavitations in the plating bath of Comparative Example 1-1 was small. This is presumed to be because energy was diverted to the generation of coarse cavitations.

[0210] On the other hand, in the plating bath of Example 1-1, in which an appropriate type of surfactant was added at an appropriate concentration, as shown in "Example of Manufacturing Method B" described later, the generation of coarse cavitation that causes energy loss was suppressed. Furthermore, the number of cavitation was also increased in the plating bath of Example 1-1. This is presumed to be because the ionic surfactant effectively controlled the diameter of the cavitation generated by ultrasound.

[0211] In this way, by adding the appropriate type of surfactant to the plating bath at the appropriate concentration and irradiating it with ultrasound, it is possible to obtain a beautiful plated film without causing plating discoloration, even under plating conditions where plating discoloration would occur with conventional techniques.

[0212] The surfactant added to the plating bath must be an ionic surfactant. Ionic surfactants are a general term for anionic surfactants, cationic surfactants, and amphoteric surfactants. Anionic surfactants are surfactants in which the part that ionizes in water and exhibits surface activity is an anion. Cationic surfactants are surfactants in which the part that ionizes in water and exhibits surface activity is a cation. Amphoteric surfactants are surfactants that have both a cationic active group and anionic active group within the same molecule and exhibit either anionic or cationic properties in water depending on the conditions.

[0213] In addition to ionic surfactants, there are also nonionic surfactants. Nonionic surfactants are commonly used in cleaning. However, when nonionic surfactants are used in the electroplating process and ultrasonic irradiation is applied, various adverse effects occur, such as precipitate formation, incorporation of nonionic surfactants into the film, and reduction of the process window. Therefore, preferably, the plating bath does not contain nonionic surfactants. However, it is permissible for the plating bath to contain a small amount of nonionic surfactant. For example, the concentration of nonionic surfactant in the plating bath may be 0 mmol / L or more and 0.10 mmol / L or less. The concentration of nonionic surfactant in the plating bath may be 0.090 mmol / L or less, 0.080 mmol / L or less, 0.050 mmol / L or less, or 0 mmol / L.

[0214] (HLB value of ionic surfactant: 3.0 to 8.0) In the manufacturing method of plated components, the ionic surfactant used has an HLB (Hydrophile-Lipophile Balance) value of 3.0 to 8.0 according to the Griffin method. The HLB value is an indicator of the lipophilicity and hydrophilicity of a surfactant. The HLB value determined by the Griffin method ranges from 0 to 20. The closer the HLB value of an ionic surfactant is to 0, the higher its lipophilicity. The closer the HLB value of an ionic surfactant is to 20, the higher its hydrophilicity.

[0215] When the HLB value of the ionic surfactant in the Griffin method is in the range of 3.0 to 8.0, the balance between the lipophilicity and hydrophilicity of the ionic surfactant is achieved, improving the affinity between the ionic surfactant and cavitation. This made it possible to further reduce the energy loss of ultrasound. The HLB value of the ionic surfactant in the Griffin method may be 3.5 or higher, 4.0 or higher, or 4.5 or higher. The HLB value of the ionic surfactant in the Griffin method may be 7.5 or lower, 7.0 or lower, or 6.0 or lower.

[0216] (Type of ionic surfactant: preferably anionic surfactant) The ionic surfactant used in the manufacturing method of plated components may also be an anionic surfactant. Although the principle is unclear, anionic surfactants have a stronger interaction with cavitation than cationic surfactants or amphoteric surfactants, and are able to reduce ultrasonic loss more effectively.

[0217] (Number of ultrasonic oscillators B12) The number of ultrasonic oscillating means B12 is not particularly limited. In Figure 8, the ultrasonic oscillating means B12 are mounted at regular intervals on both sides of the substrate B3 in the width direction. This allows ultrasonic waves to be applied to the substrate B3 from two or more directions during electroplating. Therefore, it becomes easier to apply ultrasonic waves to the entire surface of the substrate B3. On the other hand, if the substrate B3 is small, it is possible to use only one ultrasonic oscillating means B12. Various numbers can be selected depending on the shape and arrangement of the substrate B3.

[0218] (Capacity of electroplating tank B11) The capacity of the electroplating tank B11 refers to the maximum volume of the plating bath that can be safely accommodated in the electroplating tank B11. A larger electroplating tank B11 is preferable because it improves the efficiency of the electroplating work and increases the size of the substrate B3 that the electroplating apparatus B1 can electroplat. For example, the capacity of one electroplating tank B11 may be 500L or more, 1000L or more, 2000L or more, or 2500L or more. In other words, the volume of the plating bath used in the electroplating process may be 500L or more, 1000L or more, 2000L or more, or 2500L or more. In this case, the width of the substrate B3 may be 500mm or more, 750mm or more, or 1000mm or more.

[0219] In conventional plating apparatuses, if the capacity of the electroplating tank B11 is 500L or more, the attenuation of ultrasound near the center of the electroplating tank B11 becomes significant. As a result, the effect of ultrasonic irradiation is not obtained near the center of the electroplating tank B11. However, in the manufacturing method of electroplated members according to this embodiment, the attenuation of ultrasound is suppressed by an ionic surfactant. Therefore, the capacity of the electroplating tank B11 can be easily increased.

[0220] There is no specific upper limit specified for the capacity of the electroplating tank B11. For example, the capacity of the electroplating tank B11 may be 1500L or less, 1200L or less, or 1000L or less. In other words, the volume of the plating bath used in the electroplating process may be 1500L or less, 1200L or less, or 1000L or less.

[0221] (Spacing of ultrasonic oscillation means B12) When ultrasonic oscillating means B12 are arranged on both sides of the base material B3 in the width direction, it is preferable that the distance A between a pair of ultrasonic oscillating means B12 facing each other across the base material B3 is 500 mm or more. The distance A between a pair of ultrasonic oscillating means B12 facing each other across the base material B3 is the distance between the center of the oscillation surface of the ultrasonic oscillating means B12 provided at one end of the base material B3 and the center of the oscillation surface of the ultrasonic oscillating means B12 provided at the other end, as shown in Figure 15. When multiple ultrasonic oscillating means B12 are arranged on each side of the base material B3 in the width direction, the distance A between a pair of ultrasonic oscillating means B12 facing each other across the base material B3 is the minimum value of the distance A between a pair of ultrasonic oscillating means B12.

[0222] By setting the distance A between the pair of ultrasonic oscillating means B12 facing each other with the substrate B3 in between to 500 mm or more, the electroplating bath can be enlarged and the width dimension of the substrate B3 can be increased. The distance A between the pair of ultrasonic oscillating means B12 facing each other with the substrate B3 in between may be 550 mm or more, 600 mm or more, 800 mm or more, or 1000 mm or more.

[0223] In conventional plating apparatuses, if the distance A between the pair of ultrasonic oscillating means B12 is 500 mm or more, the attenuation of ultrasound near the center of the substrate B3 in the width direction becomes significant. As a result, the effect of ultrasonic irradiation cannot be obtained in the center of the substrate B3 in the width direction. However, in the manufacturing method of electroplated members according to this embodiment, the attenuation of ultrasound is suppressed by an ionic surfactant. Therefore, the distance A between the ultrasonic oscillating means B12 can be easily increased.

[0224] There is no particular upper limit specified for the distance A between a pair of ultrasonic oscillating means B12 facing each other with the substrate B3 in between. For example, the distance A between a pair of ultrasonic oscillating means B12 facing each other with the substrate B3 in between may be 2000 mm or less, 1800 mm or less, or 1500 mm or less.

[0225] (2. Electroplating equipment) The electroplating apparatus according to this embodiment comprises an electroplating tank B11 configured to accommodate a plating bath B2, an ultrasonic oscillating means B12 configured to emit ultrasonic waves inside the electroplating tank B11, substrate support means B13 and B131 configured to support a substrate B3 in the substrate placement area, and a counter electrode B14. The plating bath B2 contains an ionic surfactant at a concentration of 0.10 mmol / L to 10 mmol / L, the HLB value of the ionic surfactant in the Griffin method is 3.0 to 8.0, the frequency of the ultrasonic waves emitted by the ultrasonic oscillating means B12 is 15 kHz to 80 kHz, and the intensity of the ultrasonic waves at a location 5 cm away from the substrate placement area and at an intermediate location between the substrate placement area and the counter electrode B14, where the distance from the substrate placement area is closer, is 0.20 to 80 kPa / kHz.

[0226] The electroplating apparatus B1 according to this embodiment is suitable for carrying out the manufacturing method of the electroplated member according to this embodiment. The electroplating apparatus B1 according to this embodiment will be described below. Naturally, the embodiments of the manufacturing method of the electroplated member described above can be applied to the electroplating apparatus B1 according to this embodiment. Furthermore, the effects of the components of the electroplating apparatus B1 are as described with respect to the manufacturing method of the electroplated member.

[0227] (Electroplating tank) The electroplating apparatus has an electroplating tank. The electroplating tank is configured to accommodate a plating bath.

[0228] (Ultrasonic oscillation means) The electroplating apparatus further includes an ultrasonic oscillating means. The ultrasonic oscillating means is configured to emit ultrasonic waves inside the electroplating tank B11.

[0229] (Base material support means) The electroplating apparatus further includes a substrate support means. The substrate support means is configured to position the substrate at a predetermined location. In this disclosure, the position where the substrate is placed is referred to as the substrate placement area. The position and shape of the substrate placement area are not particularly limited. The position and shape of the substrate placement area can be determined according to the shape of the substrate and the position and shape of the counter electrode, which will be described later. In Figures 7, 8, and 11 to 15, the area where substrate B3 is placed is the substrate placement area.

[0230] (Opposite poles) The electroplating apparatus further includes a counter electrode. The counter electrode is positioned opposite the area where the substrate is to be placed. The counter electrode and the substrate supported in the area where the substrate is to be placed are energized during electroplating. The position and shape of the counter electrode are not particularly limited. The position and shape of the counter electrode can be determined according to the shape of the substrate to be electroplated and the position of the area where the substrate is to be placed.

[0231] (Plating bath and ultrasound) Plating bath B2 contains an ionic surfactant in a concentration of 0.10 mmol / L to 10 mmol / L. Furthermore, the HLB value of the ionic surfactant in the Griffin process is 3.0 to 8.0. Preferably, the ionic surfactant is an anionic surfactant.

[0232] The ultrasonic frequency emitted by the ultrasonic oscillating means B12 is between 15 kHz and 80 kHz. The ultrasonic intensity at a location 5 cm away from the planned substrate placement area, and at an intermediate location between the planned substrate placement area and the counter electrode B14, specifically at the location closest to the planned substrate placement area, is between 0.20 and 80 kPa / kHz.

[0233] By irradiating a plating bath containing a surfactant with ultrasound, the adverse effects of the diffusion layer near the surface of substrate B3 can be mitigated.

[0234] (Capacity of the electroplating tank) Preferably, the capacity of the electroplating tank is 500L or more. A larger electroplating tank B11 is preferable because it improves the efficiency of the electroplating work and increases the size of the substrate B3 that the electroplating apparatus B1 can electroplat. In conventional plating apparatuses, if the capacity of the electroplating tank B11 is 500L or more, the attenuation of ultrasound near the center of the electroplating tank B11 becomes significant. As a result, the effect of ultrasonic irradiation is not obtained near the center of the electroplating tank B11. However, in the manufacturing method of electroplated members according to this embodiment, the attenuation of ultrasound is suppressed by an ionic surfactant. Therefore, the capacity of the electroplating tank B11 can be easily increased. The preferred capacity of the electroplating tank B11 is as described above.

[0235] (Spacing of ultrasonic oscillation means) Preferably, the ultrasonic oscillating means are arranged on both sides in the width direction of the area where the substrate is to be placed. More preferably, the distance between a pair of ultrasonic oscillating means facing each other across the area where the substrate is to be placed is 500 mm or more. The distance A between a pair of ultrasonic oscillating means B12 facing each other across the area where the substrate is to be placed is the distance between the center of the oscillation surface of the ultrasonic oscillating means B12 provided at one end of the area where the substrate is to be placed and the center of the oscillation surface of the ultrasonic oscillating means B12 provided at the other end. When multiple ultrasonic oscillating means B12 are arranged on each side in the width direction of the area where the substrate is to be placed, the distance A between a pair of ultrasonic oscillating means B12 facing each other across the area where the substrate is to be placed is the minimum value of the distance A between a pair of ultrasonic oscillating means B12.

[0236] By setting the distance A between the pair of ultrasonic oscillating means B12 facing each other across the area where the substrate is to be placed to 500 mm or more, the electroplating tank can be enlarged, and the width of the area where the substrate is to be placed can be increased. The distance A between the pair of ultrasonic oscillating means B12 facing each other across the area where the substrate is to be placed may be 550 mm or more, 600 mm or more, 800 mm or more, or 1000 mm or more.

[0237] In conventional plating apparatuses, if the distance A between the pair of ultrasonic oscillating means B12 is 500 mm or more, the attenuation of ultrasound near the center in the width direction of the area where the substrate is to be placed becomes significant. As a result, the effect of ultrasonic irradiation cannot be obtained in the center in the width direction of the area where the substrate is to be placed. However, in the manufacturing method of electroplated members according to this embodiment, the attenuation of ultrasound is suppressed by an ionic surfactant. Therefore, the distance A between the ultrasonic oscillating means B12 can be easily increased.

[0238] There is no particular upper limit specified for the distance A between a pair of ultrasonic oscillating means B12 facing each other across the area where the substrate is to be placed. For example, the distance A between a pair of ultrasonic oscillating means B12 facing each other across the area where the substrate is to be placed may be 2000 mm or less, 1800 mm or less, or 1500 mm or less.

[0239] (Other embodiments) While embodiments of this disclosure have been described above, this disclosure is not limited thereto and can be modified as appropriate without departing from the technical concept of the disclosure. Modifications of this disclosure are described below.

[0240] The ultrasonic oscillation means B12 may be capable of pulse oscillation, which switches ultrasonic oscillation on and off at a constant period, or sweep oscillation, which vibrates at a frequency in the range of several kHz. By performing pulse oscillation or sweep oscillation, the state of the ultrasonic waves inside the electroplating bath B11 changes, making it less likely for standing waves to occur, thereby further improving the quality of the plated film.

[0241] The counter electrode B14 may be a soluble anode or an insoluble anode. A soluble anode dissolves during electroplating, replenishing the plating metal in the plating bath B2. An insoluble anode does not dissolve during electroplating. Regardless of which counter electrode B14 is used, the method for manufacturing the electroplated member according to this embodiment can be carried out without any problems.

[0242] The temperature of the plating bath B2 can vary depending on the type of plating bath. In the example, a temperature of 30°C to 60°C is selected, but even if a temperature other than that in the example is selected, the method for manufacturing the electroplated member according to this embodiment can be carried out without any problems.

[0243] (Regarding the analysis of the plating bath components) The type and concentration of surfactants contained in the plating bath can be determined by high-performance liquid chromatography. (Embodiment of Manufacturing Method B)

[0244] (Embodiment of manufacturing method C)

[0245] The inventors have diligently studied an electroplating method that can form a good electroplated nickel without substantially using boric acid-based pH buffers, which have a high environmental impact, and organic carboxylic acid-based pH buffers, which increase the carbon content in the electroplated nickel. The inventors have found that by irradiating the cathode (base material) with ultrasound during the electroplating process, pH fluctuations can be suppressed very effectively. This is presumed to be because the cavitation phenomenon caused by ultrasound locally agitates the electroplated nickel bath near the cathode, efficiently destroying the diffusion layer that creates a concentration gradient.

[0246] The ability to disrupt the diffusion layer around the cathode using ultrasound in electroplating of nickel has not been previously reported. Based on this new finding, the inventors hypothesized that the addition of a pH buffer to the electroplating bath could be substantially eliminated. The inventors then conducted further investigations into the ultrasonic irradiation conditions and, as a result, completed an electroplating method that can form a good electroplated nickel coating without using a pH buffer.

[0247] Figure 16 shows a photograph of a plated steel sheet obtained by plating with nickel sulfate as the nickel salt, from a bath without a pH buffer, while irradiating with ultrasound (Example 1 shown in "Example of Manufacturing Method C" later). Figure 17 shows a photograph of a plated steel sheet obtained by plating with nickel sulfate as the nickel salt, from a bath without a pH buffer, without irradiating with ultrasound (Comparative Example 1 shown in "Example of Manufacturing Method C" later). As shown in Figure 17, according to the conventional technique, it is difficult to form good electroplated nickel without a pH buffer. However, by irradiating with ultrasound under predetermined conditions, it was possible to form extremely good electroplated nickel as shown in Figure 16.

[0248] (1. Electroplating method for nickel) The electroplating method according to one embodiment of the present disclosure, obtained through the above process, comprises a step of electroplating a base material using an electroplating nickel bath containing a nickel salt, wherein the concentration of the pH buffer in the electroplating nickel bath is 0.10 mol / L or less, and in the electroplating process, the base material is irradiated with ultrasound, the frequency of the ultrasound is 15 kHz or more and 180 kHz or less, and the intensity of the ultrasound at a distance of 5 cm from the surface of the base material is 0.20 to 80 kPa / kHz. The electroplating method according to this embodiment will now be described in detail.

[0249] The electroplating method according to this embodiment includes a step of electroplating a base material using an electroplating bath containing a nickel salt. The base material and the apparatus for performing the electroplating are not particularly limited. For example, if the base material is a steel strip, it is preferable to electroplat the base material using a continuous plating apparatus. On the other hand, the plating apparatus may be a batch processing apparatus.

[0250] An example of a continuous plating apparatus is shown in Figure 18. The continuous plating apparatus comprises an electroplating tank C5, a counter electrode C2, and a sheet feed roller C6. The electroplating tank C5 houses an electroplated nickel plating bath C4. The sheet feed roller C6 supports the base material C1 in the electroplated nickel plating bath C4. The sheet feed roller C6 also rotates to move the base material C1. The arrows on the sheet feed roller C6 indicate the direction of rotation of the sheet feed roller C6. The arrows along the base material C1 indicate the direction of movement of the base material C1. The sheet feed roller C6 immerses the base material C1 in the electroplated nickel plating bath C4 and then lifts it out. The counter electrode C2 is positioned opposite the base material C1. The counter electrode C2 is connected to a power supply (not shown).

[0251] Hereafter, the left-right direction in Figure 18 will be referred to as the X direction, and the up-down direction as the Y direction. The direction perpendicular to the X and Y directions will be referred to as the Z direction. The width direction of the base material C1 is the Z direction.

[0252] The electroplated nickel bath C4 contains a nickel salt. The type of nickel salt is not particularly limited. Preferred examples of nickel salts are described later.

[0253] In electroplating, the base material C1 is used as the cathode and the counter electrode C2 is used as the anode, and current is passed through both the base material C1 and the counter electrode C2. As a result, nickel is electrochemically deposited on the surface of the base material C1, forming a nickel plating layer.

[0254] (Concentration of pH buffer in an electroplated nickel bath) The concentration of the pH buffer in the electroplated nickel bath should be 0.10 mol / L or less. This reduces the environmental impact of the electroplated nickel bath. A lower concentration of pH buffer is preferable. Therefore, the concentration of the pH buffer may be 0.08 mol / L or less, 0.05 mol / L or less, or 0.01 mol / L or less. The electroplated nickel bath may be substantially free of pH buffer. In this disclosure, substantially free of pH buffer means that the concentration of pH buffer is so low that it does not exhibit buffering capacity. When the pH buffer does not exhibit buffering capacity, it means that when neutralization titration is performed on the plating bath using a base, a neutralization point cannot be confirmed. Furthermore, no pH buffer may be added to the electroplated nickel bath at all, and its concentration may be 0 mol / L.

[0255] In the electroplating nickel method according to this embodiment, ultrasonic waves are used instead of a pH buffer to suppress pH fluctuations near the cathode. Therefore, ultrasonic waves are irradiated onto the base material during the electroplating process.

[0256] The means for irradiating with ultrasonic waves C8 are not particularly limited. An example of a means for irradiating with ultrasonic waves C8 when the plating apparatus is the continuous plating apparatus shown in Figure 18 is shown in Figure 19. Figure 19 is a schematic diagram of the base material C1 around the counter electrode C2. The left-right direction in Figure 19 is the Z direction, i.e., the width direction of the base material C1. The up-down direction in Figure 19 is the Y direction. The arrows in Figure 19 indicate the direction of movement of the base material C1.

[0257] The continuous plating apparatus in Figure 19 has multiple ultrasonic emitting means C7. The ultrasonic emitting means C7 are attached to the electroplating bath C5. The ultrasonic emitting means C7 irradiate both ends of the base material C1 with ultrasonic waves C8. The ultrasonic waves C8 irradiate the nickel in the electroplating bath C4 near the surface of the base material C1. 2+ Eliminate the concentration gradient.

[0258] (Ultrasonic frequency: 15kHz to 180kHz) The ultrasonic frequency must be between 15 kHz and 180 kHz. Experiments conducted by the inventors showed that pH fluctuations were most efficiently suppressed when the ultrasonic frequency was between 15 kHz and 180 kHz. Lower ultrasonic frequencies generate larger cavitation, but the frequency of cavitation generation decreases. At frequencies below 15 kHz, cavitation that causes strong agitation is generated, but the frequency is low, and sufficient agitation is not achieved. On the other hand, at frequencies above 180 kHz, cavitation is generated at a high frequency, but the generated cavitation is small, resulting in weak agitation and insufficient agitation. The ultrasonic frequency may also be 20 kHz or higher, 30 kHz or higher, or 50 kHz or higher. The ultrasonic frequency may also be 160 kHz or lower, 130 kHz or lower, or 80 kHz or lower.

[0259] (Ultrasonic intensity: 0.20 kPa / kHz to 80 kPa / kHz) Furthermore, the ultrasonic intensity must be between 0.20 and 80 kPa / kHz. The ultrasonic intensity is the value obtained by dividing the sound pressure (kPa) of the ultrasonic wave at the predetermined ultrasonic intensity measurement position C3 by the ultrasonic frequency (kHz).

[0260] The ultrasonic intensity measurement position C3 is the location that is closest to the center of the base material in the width direction among (a) and (b) below. (a) A point 5 cm away from the center of the width of the base material C1 (b) The midpoint between the center of the base material C1 in the width direction and the opposite electrode C2 The details of the ultrasonic intensity measurement position C3 will be explained below with reference to Figures 20 to 23. Figures 20 to 23 are top views of the base material C1 and counter electrode C2 in the continuous plating apparatus shown in Figure 18. The vertical direction in Figures 20 to 23 is the Z direction, i.e., the width direction of the base material C1. The horizontal direction in Figures 20 to 23 is the X direction.

[0261] In the continuous plating apparatus shown in Figure 20, both the base material C1 and the counter electrode C2 are flat and are arranged parallel to each other. The distance D between the center surface of the base material C1 in the width direction and the counter electrode C2 is 10 cm or more. In the continuous plating apparatus shown in Figure 20, the ultrasonic intensity measurement position C3 is located 5 cm away from the center surface of the base material C1 in the width direction.

[0262] In the continuous plating apparatus shown in Figure 21, both the base material C1 and the counter electrode C2 are flat and are arranged parallel to each other. The distance D between the center surface of the base material C1 in the width direction and the counter electrode C2 is less than 10 cm. In the continuous plating apparatus shown in Figure 21, the ultrasonic intensity measurement position C3 is set to a point midway between the center of the base material C1 in the width direction and the counter electrode C2.

[0263] In the continuous plating apparatus shown in Figure 22, the base material C1 is curved, while the counter electrode C2 is flat. The base material C1 and the counter electrode C2 are not parallel. The distance D between the center surface of the base material C1 in the width direction and the counter electrode C2 is 10 cm or more. In the continuous plating apparatus shown in Figure 22, the ultrasonic intensity measurement position C3 is set 5 cm away from the center surface of the base material C1 in the width direction.

[0264] In the continuous plating apparatus shown in Figure 23, the base material C1 is curved, while the counter electrode C2 is flat. The base material C1 and the counter electrode C2 are not parallel. The distance D between the center surface of the base material C1 in the width direction and the counter electrode C2 is less than 10 cm. In the continuous plating apparatus shown in Figure 23, the ultrasonic intensity measurement position C3 is set to a point midway between the center of the base material C1 in the width direction and the counter electrode C2.

[0265] When the ultrasonic intensity is less than 0.20 kPa / kHz, local agitation around the base material is unlikely to occur, and it is thought that the diffusion layer that creates a hydrogen ion concentration gradient cannot be sufficiently broken down.

[0266] Furthermore, from the perspective of suppressing pH fluctuations, there is no upper limit to the ultrasonic intensity. However, if the ultrasonic intensity exceeds 80 kPa / kHz, its effect may saturate, potentially causing unnecessary equipment load and deterioration of the working environment. Therefore, the ultrasonic intensity should be kept below 80 kPa / kHz. The ultrasonic intensity may also be 0.40 kPa / kHz or higher, 1.2 kPa / kHz or higher, or 4.0 kPa / kHz or higher. The ultrasonic intensity may also be 40 kPa / kHz or lower, 20 kPa / kHz or lower, or 10 kPa / kHz or lower.

[0267] In order to keep the ultrasonic intensity at ultrasonic intensity measurement position C3 within the above range, the plating apparatus should be configured to satisfy, for example, the following three requirements. (Requirement 1) The ultrasonic oscillating means C7 are arranged on both sides in the width direction of the base material C1. (Requirement 2) The output of the ultrasonic oscillator C7 should be 800 W / m 3 That concludes this section. (Requirement 3) The distance between the ultrasonic oscillating means C7 and the closest ultrasonic oscillating means C7 facing it across the base material C1 shall be 500 mm or more and 2000 mm or less.

[0268] For example, as shown in Figure 19, the ultrasonic oscillating means C7 are installed on both sides of the base material C1 in the width direction (i.e., the Z direction). The output of all ultrasonic oscillating means C7 is set to the range described above. In addition, the distance between the upper left ultrasonic oscillating means and the upper right ultrasonic oscillating means in Figure 19 is set to the range described above. Furthermore, the distance between the lower left ultrasonic oscillating means and the lower right ultrasonic oscillating means in Figure 19 is set to the range described above. This makes it possible to set the ultrasonic intensity at the ultrasonic intensity measurement position C3 to the range described above.

[0269] As long as the above requirements are met, the conditions for the electroplating process are not particularly limited. A more preferred example of the electroplating process is described below.

[0270] For example, the nickel salt contained in the electroplated nickel bath may include a salt of one or more substances selected from the group consisting of nickel sulfate, nickel sulfamate, nickel chloride, and nickel bromide. By using these nickel salts, the quality of Ni plating can be further improved. Particularly preferably, the nickel salt includes a salt of one or more substances selected from the group consisting of nickel sulfate and nickel sulfamate.

[0271] The temperature of the electroplated nickel bath is preferably between 30°C and 70°C. Maintaining a temperature of 30°C or higher ensures the efficiency of the electroplating process. Furthermore, maintaining a temperature of 70°C or lower suppresses concentration fluctuations due to evaporation of the electroplated nickel bath.

[0272] The cathode current density in electroplating is 1 A / dm 2 More than 100A / dm 2 The following is preferable: Cathode current density of 1 A / dm 2 By doing so, the efficiency of the electroplating process can be ensured. The cathode current density is 100 A / dm². 2 By doing the following, the stability of the electroplating process can be ensured.

[0273] The amount of electricity used in electroplating is 2C / dm 2 More than 1200C / dm 2 The following is preferable: Current flow rate 2C / dm 2 By doing so, the stability of the electroplating process can be ensured. Current flow rate: 100C / dm 2 Above, 500C / dm 2 Above, or 800C / dm 2 The above is also acceptable. On the other hand, the amount of electricity supplied is 1200 C / dm 2 By doing the following, the occurrence of warping in Ni plating can be suppressed. The amount of Ni plating formed by electroplating generally depends on the amount of electricity applied. For example, the amount of Ni plating can be 1.0 g / m². 2 More than 1.5g / m 2 Above, or 2.0 g / m 2 It is preferable to keep the above in place.

[0274] The type of base material is not particularly limited, and any material capable of forming electroplated nickel can be used as the base material. Examples of base materials include metal substrates (steel plates, plated steel plates, copper plates, wires, etc.) and conductive substrates (carbon fibers, conductive resins, etc.). The base material can be either porous or non-porous. However, if a porous base material is used, ultrasonic waves do not propagate well within the minute pores, making it difficult for cavitation to occur, and thus little effect from the ultrasound is expected to be obtained. Furthermore, there are no particular limitations on the sound source used to irradiate the ultrasound. For example, a point-shaped sound source may be placed and ultrasonic waves may be irradiated radially toward the base material. Alternatively, the sound source may be placed in a planar manner to cover the base material and ultrasonic waves may be irradiated uniformly across the entire base material. Examples of sound sources include horn type (the point-shaped sound source mentioned above), immersion type (a sound source of about several tens of centimeters square is placed inside the tank), anode oscillation type (the counter electrode (anode) itself is used as the sound source), and plating tank type (the planar sound source mentioned above).

[0275] (2. Method for manufacturing nickel-plated components) Another embodiment of the present disclosure provides a method for manufacturing a nickel-plated member, comprising the electro-nickel plating method according to this embodiment. The electro-nickel plating method according to this embodiment can form a good electro-nickel plating without substantially using a pH buffer. Therefore, in the nickel-plated member obtained by the manufacturing method according to this embodiment, carbon from the pH buffer is not incorporated into the plating film, and the properties of the plating film are expected to be much improved compared to conventional methods. Furthermore, the manufacturing method according to this embodiment can reduce the cost of wastewater treatment.

[0276] (Regarding the analysis of the plating bath components) The type and concentration of pH buffering agent in the plating bath can be measured by ICP emission spectrometry or high-performance liquid chromatography. The type of nickel salt in the plating bath can also be measured by high-performance liquid chromatography.

[0277] (3. Electroplating equipment) The electroplating apparatus according to this embodiment comprises an electroplating tank C5 configured to accommodate an electroplating nickel bath C4 containing a nickel salt, an ultrasonic oscillating means C7 configured to emit ultrasonic waves inside the electroplating tank C5, a base material support means configured to support a base material C1 in a base material placement area, and a counter electrode C2. In the electroplating nickel bath C4, the concentration of the pH buffering agent is 0.10 mol / L or less, the frequency of the ultrasonic waves emitted by the ultrasonic oscillating means C7 is 15 kHz or more and 80 kHz or less, and the intensity of the ultrasonic waves is 0.20 to 80 kPa / kHz at a location 5 cm away from the center in the width direction of the base material placement area, and at a location midway between the center in the width direction of the base material placement area and the counter electrode C2, where the distance from the base material placement area is even closer.

[0278] The electroplating apparatus according to this embodiment is suitable for carrying out the manufacturing method of the electroplated member according to this embodiment. The electroplating apparatus according to this embodiment will be described below. Naturally, the embodiments of the manufacturing method of the electroplated member described above can be applied to the electroplating apparatus according to this embodiment. Furthermore, the effects of the components of the electroplating apparatus are as described in relation to the manufacturing method of the electroplated member.

[0279] (Electroplating tank C5) The electroplating apparatus has an electroplating tank C5. The electroplating tank C5 is configured to accommodate an electroplated nickel plating bath C4.

[0280] (Ultrasonic oscillation means C7) The electroplating apparatus further includes an ultrasonic oscillator C7. The ultrasonic oscillator C7 is configured to emit ultrasonic waves inside the electroplating tank C5.

[0281] (Base material support means) The electroplating apparatus further includes a base material support means. An example of a base material support means is the plate-feeding roller C6 described above. The base material support means is configured to position the base material C1 at a predetermined location. In this disclosure, the position where the base material C1 is placed is referred to as the base material placement area. The position and shape of the base material placement area are not particularly limited. The position and shape of the base material placement area can be determined according to the shape of the base material C1 and the position and shape of the counter electrode C2, which will be described later. In Figures 18 to 23, the location where the base material C1 is placed is the base material placement area.

[0282] (Opposite poles) The electroplating apparatus further includes a counter electrode C2. The counter electrode C2 is positioned opposite the area where the base material is to be placed. The counter electrode C2 and the sheet feed roller C6, which is positioned outside the electro-nickel plating bath C4, are connected to a power source (not shown). The counter electrode C2 and the base material C1 supported in the area where the base material is to be placed are energized during electroplating. The position and shape of the counter electrode C2 are not particularly limited. The position and shape of the counter electrode C2 can be determined according to the shape of the base material C1 to be electroplated and the position of the area where the base material is to be placed.

[0283] (Electro-nickel plating bath C4 and ultrasound) The plating bath is an electro-nickel plating bath C4 containing nickel salts. The concentration of the pH buffer in the electro-nickel plating bath C4 is set to 0.10 mol / L or less.

[0284] The ultrasonic frequency emitted by the ultrasonic oscillating means C7 is between 15 kHz and 80 kHz. The ultrasonic intensity at a point 5 cm away from the center in the width direction of the area where the base material is to be placed, and at a point midway between the center in the width direction of the area where the base material is to be placed and the counter electrode, where the distance from the area where the base material is to be placed is even closer, is between 0.20 and 80 kPa / kHz.

[0285] The electroplating apparatus according to this embodiment irradiates the base material C1 with ultrasonic waves having a predetermined frequency and intensity. Therefore, the electroplating apparatus according to this embodiment can mitigate the adverse effects of the diffusion layer near the surface of the base material C1 and form a good coating even from an electroplated nickel plating bath C4 that substantially does not contain a pH buffer. (Embodiment of manufacturing method C)

[0286] (Embodiment of Manufacturing Method D) The inventors of this invention have developed a low Ni 2+ Using a nickel plating bath with a concentration of 5 g / m² 2 We have diligently studied methods for manufacturing nickel-plated components that can form a good coating with the above nickel deposition amount. The inventors have found that by irradiating the substrate (the cathode) with ultrasound during the electroplating process, the formation of granular precipitates and the occurrence of plating discoloration can be suppressed very effectively. This is presumed to be because the cavitation phenomenon caused by ultrasound locally agitates the electroplated nickel bath near the cathode, efficiently destroying the diffusion layer that creates the concentration gradient.

[0287] In electroplating nickel, the ability to destroy the diffusion layer around the cathode using ultrasound has not been previously reported. Based on this new finding, the inventors believe that low Ni 2+ In a nickel plating bath with a concentration of 5 g / m², 2 We thought that it might be possible to form a coating with the above amount of adhesion and a good appearance. The inventors then conducted further investigations into the ultrasonic irradiation conditions, and as a result, low Ni 2+ In a nickel plating bath with a concentration of 5 g / m², 2 We have successfully completed a method for manufacturing plated components that can form a good coating with the above amount of adhesion.

[0288] Furthermore, Patent Document 7 discloses an electroplating method using ultrasound in electroplating nickel. However, in that technology, the role of ultrasound is to arrange fine particles at the nodes of the standing wave to perform composite plating. The technology disclosed in Patent Document 7 differs from this disclosure in both its problems and effects.

[0289] Figures 24 and 25 show photographs of examples of plated steel sheets. The manufacturing conditions for these plated steel sheets were as described in the table below. The ultrasonic intensity was measured at the location shown in Figure 28, i.e., 5 cm away from the center of the substrate surface in the width direction. The theoretical deposition amounts listed in the table are calculated using the following formula. Theoretical adhesion amount = k × I × t k: Electrochemical equivalent of the deposited metal (g / C) I: Electrolytic current (A) t: Electrolysis time (seconds) The current efficiency listed in the table is calculated using the following formula. Current efficiency = amount of deposit ÷ theoretical amount of deposit × 100

[0290] [Table 1]

[0291] In the plated steel sheet shown in Figure 25, significant discoloration and unevenness occurred on the plated surface. On the other hand, in the plated steel sheet shown in Figure 24, neither unevenness nor discoloration occurred on the plated surface. As shown in Figure 25, in the conventional technology, Ni 2+ It is difficult to form good electroplated nickel from a bath with a concentration of 0.3 mol / L. However, by irradiating with ultrasound under predetermined conditions, it was possible to form electroplated nickel with an extremely good appearance, as shown in Figure 24.

[0292] (1. Method for manufacturing nickel-plated components) The method for manufacturing a nickel-plated member according to one aspect of the present disclosure, obtained through the above process, comprises a step of electroplating a substrate D1 using an electro-nickel plating bath D4 containing a nickel salt, wherein in the electro-nickel plating bath D4, Ni 2+The concentration C (mol / L) is set to 0.10 mol / L or more and 0.80 mol / L or less. In the electroplating process, ultrasonic waves D8 are irradiated onto the substrate D1, with the frequency of ultrasonic waves D8 being 15 kHz or more and 180 kHz or less. The intensity of ultrasonic waves D8 at a location 5 cm away from the center of the substrate D1 in the width direction, or at a location midway between the center of the substrate D1 in the width direction and the counter electrode D2, where the distance from the center of the substrate D1 in the width direction is closer (ultrasonic intensity measurement position D3), is set to 0.20 to 80 kPa / kHz. The method for manufacturing the nickel-plated member according to this embodiment will now be described in detail.

[0293] (Electroplating treatment) In the method for manufacturing a nickel-plated member according to this embodiment, the substrate is electroplated. The substrate and the apparatus for performing the electroplating are not particularly limited. For example, if the substrate is a steel strip, it is preferable to electroplat the substrate using a continuous plating apparatus. On the other hand, the plating apparatus may be a batch processing apparatus.

[0294] An example of a continuous plating apparatus is shown in Figure 26. The continuous plating apparatus comprises an electroplating tank D5, a counter electrode D2, and sheet feed rollers D6 and D61. The electroplating tank D5 houses an electroplated nickel plating bath D4. Sheet feed rollers D6 and D61 support the substrate D1 in the electroplated nickel plating bath D4. Sheet feed rollers D6 and D61 also rotate to move the substrate D1. The arrows on sheet feed rollers D6 and D61 indicate the direction of rotation of sheet feed rollers D6 and D61. The arrows along the substrate D1 indicate the direction of movement of the substrate D1. Sheet feed roller D6 immerses the substrate D1 in the electroplated nickel plating bath D4 and then pulls it out. The counter electrode D2 is positioned opposite the substrate D1. The substrate D1 and the counter electrode D2 are connected to a power supply (not shown). Note that the sheet feed rollers D6 may be used to connect the substrate D1 to the power supply.

[0295] Hereinafter, the left-right direction in Figure 26 will be referred to as the X direction, and the up-down direction as the Y direction. The direction perpendicular to the X and Y directions will be referred to as the Z direction. The width direction of the substrate D1 is the Z direction. The width direction is the direction parallel to the normal extending from the vibration plane of the ultrasonic emitting means on the surface of the substrate D1. If multiple ultrasonic emitting means are installed in orientations where the normal directions extending from their vibration planes are not parallel, the width direction should be set for each normal, and it is sufficient if the required ultrasonic intensity is obtained at any of the ultrasonic intensity measurement positions D3.

[0296] The electroplated nickel bath D4 contains a nickel salt. The type of nickel salt is not particularly limited. Preferred examples of nickel salts are described later.

[0297] In the electroplating process, the substrate D1 is used as the cathode and the counter electrode D2 is used as the anode, and current is passed through both the substrate D1 and the counter electrode D2. As a result, nickel is electrochemically deposited on the surface of the substrate D1, forming a nickel plating layer.

[0298] (Ni in an electroplated nickel bath 2+ Concentration: 0.10mol / L or more and 0.80mol / L or less) The method for manufacturing a nickel-plated member according to this embodiment includes a step of electroplating a substrate using an electroplated nickel plating bath containing a nickel salt. 2+ The concentration C (mol / L) shall be between 0.10 mol / L and 0.80 mol / L.

[0299] Ni 2+ When the concentration C (mol / L) is less than 0.10 mol / L, even with localized ultrasonic stirring, a sufficient amount of Ni can be transferred to the substrate surface. 2+ It is not possible to supply Ni in the electro-nickel plating bath, and a good coating cannot be obtained. Therefore, Ni 2+ The concentration should be 0.10 mol / L or higher. Ni in the electroplated nickel bath. 2+ The concentration may be set to 0.15 mol / L or higher, 0.20 mol / L or higher, or 0.30 mol / L or higher.

[0300] From the perspective of obtaining a good coating, Ni 2+ There is no upper limit to the concentration. However, Ni 2+ If the concentration exceeds 0.80 mol / L, the cost of supplying the plating bath due to liquid removal will increase, and Ni will be present in the waste liquid. 2+ An increase in wastewater treatment costs may result from the increase. Therefore, in the manufacturing method of nickel-plated members according to this embodiment, the Ni in the electro-nickel plating bath is used. 2+ The concentration should be 0.80 mol / L or less. Ni 2+ A lower concentration is preferable. Therefore, Ni 2+ The concentration may be 0.70 mol / L or less, 0.60 mol / L or less, or 0.40 mol / L or less.

[0301] (Ultrasound irradiation) In the method for manufacturing a nickel-plated member according to this embodiment, ultrasonic waves are used to bring Ni near the cathode. 2+ To facilitate supply, ultrasonic waves D8 are irradiated onto the substrate D1 during the electroplating process.

[0302] The means for irradiating with ultrasonic waves D8 are not particularly limited. An example of the means for irradiating with ultrasonic waves D8 when the plating apparatus is the continuous plating apparatus shown in Figure 26 is shown in Figure 27. Figure 27 is a schematic diagram of the substrate D1 around the counter electrode D2. The left-right direction in Figure 27 is the Z direction, i.e., the width direction of the substrate D1. The up-down direction in Figure 27 is the Y direction. The arrows in Figure 27 indicate the direction of movement of the substrate D1.

[0303] The continuous plating apparatus in Figure 27 has multiple ultrasonic emitting means D7. The ultrasonic emitting means D7 are attached to the electroplating bath D5. The ultrasonic emitting means D7 irradiate both ends of the substrate D1 with ultrasonic waves D8. The ultrasonic waves D8 irradiate the nickel in the electroplating bath D4 near the surface of the substrate D1. 2+The concentration gradient is eliminated. The ultrasonic oscillating means D7 attached to both ends of the base material D1 may be attached in an alternating manner. In order to obtain sufficient ultrasonic intensity on the base material D1, it is preferable to place the ultrasonic oscillating means D7 at both ends of the base material D1 and attach them so that the distance between the closest opposing ultrasonic oscillating means D7 is between 500 mm and 2000 mm.

[0304] (Ultrasonic frequency: 15kHz to 180kHz) The ultrasonic frequency must be between 15 kHz and 180 kHz. Our experiments have shown that when the ultrasonic frequency is between 15 kHz and 180 kHz, Ni, which is impossible to plate under conditions without ultrasonic irradiation, can be plated. 2+ Plating became possible even at higher concentrations. The reason for this is not yet clear, but it is thought that the above-mentioned frequencies are the ones that most easily cause cavitation around the substrate and have the strongest stirring effect due to cavitation. The ultrasonic frequency may be 20kHz or higher, 30kHz or higher, or 50kHz or higher. The ultrasonic frequency may also be 160kHz or lower, 130kHz or lower, or 80kHz or lower.

[0305] (Ultrasonic intensity: 0.20 kPa / kHz to 80 kPa / kHz) Furthermore, the ultrasonic intensity must be between 0.20 kPa / kHz and 80 kPa / kHz. The ultrasonic intensity is the value obtained by dividing the sound pressure (kPa) of the ultrasonic wave at the predetermined ultrasonic intensity measurement position D3 by the ultrasonic frequency (kHz).

[0306] The ultrasonic intensity measurement position D3 is the location among (a) and (b) below that is closest to the center of the substrate in the width direction. (a) A point 5 cm away from the center of the surface in the width direction of base material D1 (b) The midpoint between the center of the base material D1 in the width direction and the counter electrode D2 The details of the ultrasonic intensity measurement position D3 will be explained below with reference to Figures 28 to 31. Figures 28 to 31 are top views of the substrate D1 and counter electrode D2 in the continuous plating apparatus shown in Figure 26. The vertical direction in Figures 28 to 31 is the Z direction, i.e., the width direction of the substrate D1. The horizontal direction in Figures 28 to 31 is the X direction.

[0307] In the continuous plating apparatus shown in Figure 28, both the substrate D1 and the counter electrode D2 are flat and are arranged parallel to each other. The distance D between the center surface of the substrate D1 in the width direction and the counter electrode D2 is 10 cm or more. In the continuous plating apparatus shown in Figure 28, the ultrasonic intensity measurement position D3 is located 5 cm away from the center surface of the substrate D1 in the width direction.

[0308] In the continuous plating apparatus shown in Figure 29, both the substrate D1 and the counter electrode D2 are flat and are arranged parallel to each other. The distance D between the center surface of the substrate D1 in the width direction and the counter electrode D2 is less than 10 cm. In the continuous plating apparatus shown in Figure 29, the ultrasonic intensity measurement position D3 is set to a point midway between the center of the substrate D1 in the width direction and the counter electrode D2.

[0309] In the continuous plating apparatus shown in Figure 30, the substrate D1 is curved, while the counter electrode D2 is flat. The substrate D1 and the counter electrode D2 are not parallel. The distance D between the center surface of the substrate D1 in the width direction and the counter electrode D2 is 10 cm or more. In the continuous plating apparatus shown in Figure 30, the ultrasonic intensity measurement position D3 is set to a location 5 cm away from the center surface of the substrate D1 in the width direction.

[0310] In the continuous plating apparatus shown in Figure 31, the substrate D1 is curved, while the counter electrode D2 is flat. The substrate D1 and the counter electrode D2 are not parallel. The distance D between the center surface of the substrate D1 in the width direction and the counter electrode D2 is less than 10 cm. In the continuous plating apparatus shown in Figure 31, the ultrasonic intensity measurement position D3 is set to a point midway between the center of the substrate D1 in the width direction and the counter electrode D2.

[0311] When the ultrasonic intensity is less than 0.20 kPa / kHz, local agitation around the substrate is unlikely to occur, and it is thought that the diffusion layer that creates the concentration gradient cannot be sufficiently broken down.

[0312] Note, 2+ From the perspective of reducing the concentration of the substance, there is no upper limit to the intensity of the ultrasound. However, if the intensity of the ultrasound exceeds 80 kPa / kHz, its effect may saturate, potentially unnecessarily increasing the load on the device. Therefore, the intensity of the ultrasound should be kept below 80 kPa / kHz.

[0313] The ultrasonic intensity may be 0.40 kPa / kHz or higher, 1.2 kPa / kHz or higher, or 4.0 kPa / kHz or higher. The ultrasonic intensity may also be 40 kPa / kHz or lower, 20 kPa / kHz or lower, or 10 kPa / kHz or lower.

[0314] In order to keep the ultrasonic intensity at ultrasonic intensity measurement position D3 within the above range, the plating apparatus should be configured to satisfy, for example, the following two requirements. (Requirement 1) The ultrasonic oscillating means D7 are arranged on both sides in the width direction of the base material D1. (Requirement 2) The output of the ultrasonic oscillator D7 should be 800 W / m 3 That concludes this section. (Requirement 3) The distance between the ultrasonic oscillating means D7 and the closest ultrasonic oscillating means D7 facing it across the substrate D1 shall be 500 mm or more and 2000 mm or less.

[0315] For example, as shown in Figure 27, the ultrasonic oscillating means D7 are installed on both sides of the substrate D1 in the width direction (i.e., the Z direction). The output of all ultrasonic oscillating means D7 is set to the range described above. In addition, the distance between the upper left ultrasonic oscillating means and the upper right ultrasonic oscillating means in Figure 27 is set to the range described above. Furthermore, the distance between the lower left ultrasonic oscillating means and the lower right ultrasonic oscillating means in Figure 27 is set to the range described above. This makes it possible to set the ultrasonic intensity at the ultrasonic intensity measurement position D3 to the range described above.

[0316] As long as the above requirements are met, the conditions for the electroplating process are not particularly limited. The method for manufacturing the nickel-plated member according to this embodiment physically destroys the diffusion layer that creates a concentration gradient. Therefore, there are no particular restrictions on the components of the electroplated nickel bath and other plating conditions, and they can be broadly selected according to the purpose. A more preferred example of the electroplating process is described below.

[0317] (Ni 2+ (Relationship between concentration and cathode current density) For example, Ni in an electroplated nickel bath 2+ Concentration C (mol / L) and the cathode current density i (A / dm²) of the electroplating process. 2 ) and may also be values ​​that satisfy equation D1. Formula D1 20C≦i≦20C+80 Cathode current density i(A / dm²) in electroplating process 2 By setting the cathode current density (i) to 20C or higher, the efficiency of the electroplating process can be ensured. 2 By setting the temperature to 20C + 80 or lower, the stability of the electroplating process can be ensured.

[0318] Within the limits that do not compromise economic efficiency, the cathode current density i(A / dm) of the electroplating process is... 2 A lower value for the cathode current density i(A / dm²) of the electroplating process is preferable. 2 ) may also be a value that satisfies equation D2. Formula D2 20C≦i≦20C+40

[0319] (Types of nickel salts) The nickel salts contained in the electroplated nickel bath may include salts of one or more substances selected from the group consisting of nickel sulfate, nickel sulfamate, nickel chloride, and nickel bromide. By using these nickel salts, the quality of Ni plating can be further improved.

[0320] (Temperature of the electroplated nickel bath) The temperature of the electroplated nickel bath is preferably between 30°C and 70°C. Maintaining a temperature of 30°C or higher ensures the efficiency of the electroplating process. Furthermore, maintaining a temperature of 70°C or lower suppresses concentration fluctuations due to evaporation of the electroplated nickel bath.

[0321] (Plating adhesion amount) The amount of plating deposited in the electroplating process is 5 g / m². 2 More than 50g / m 2 The following is preferable: Plating adhesion amount of 5 g / m 2 By doing so, the corrosion resistance required for the components of various parts such as battery cans and fuel tanks can be ensured. Plating adhesion amount: 50 g / m² 2 By doing the following, the occurrence of warping in Ni plating can be suppressed.

[0322] (base material) The type of substrate is not particularly limited, and any material capable of forming electroplated nickel can be used as a substrate. Examples of substrates include metal substrates (steel sheets, plated steel sheets, copper sheets, wires, etc.) and conductive substrates (carbon fibers, conductive resins, etc.). When the substrate is in the form of a plate, the thickness of the substrate is preferably 0.10 mm or more, 0.50 mm or more, or 1.0 mm or more.

[0323] (Ultrasonic oscillation means) Furthermore, there are no particular limitations on the sound source used to irradiate the ultrasonic waves. For example, a point-shaped sound source may be arranged to irradiate the substrate radially with ultrasonic waves. Alternatively, a sound source may be arranged in a planar manner to cover the substrate and irradiate the entire substrate uniformly with ultrasonic waves. Examples of sound sources include a horn type (the point-shaped sound source described above), a submersible type (a sound source approximately several tens of centimeters square is installed inside the tank), an anode oscillator type (the counter electrode (anode) itself is used as the sound source), and a plating tank type (the planar sound source described above).

[0324] [Analysis of plating bath components and nickel deposition amount] The concentration of nickel ions in the plating bath can be measured by ICP emission spectrometry.

[0325] (2. Electroplating equipment) Another aspect of the present disclosure is an electroplating apparatus comprising: an electroplating tank D5 configured to accommodate an electro-nickel plating bath D4 containing a nickel salt; an ultrasonic oscillating means D7 configured to emit ultrasonic waves D8 inside the electroplating tank D5; a substrate support means configured to support a substrate D1 in a substrate placement area; and a counter electrode D2, wherein the electro-nickel plating bath D4 contains Ni 2+ The concentration C (mol / L) is between 0.10 mol / L and 0.80 mol / L, the frequency of the ultrasonic waves D8 emitted by the ultrasonic wave emitting means D7 is between 15 kHz and 180 kHz, and the intensity of the ultrasonic waves D8 is between 0.20 and 80 kPa / kHz at a point 5 cm away from the center of the widthwise surface of the area to be placed on the substrate, and at the point between the center of the widthwise surface of the area to be placed on the substrate and the counter electrode D2, whichever is closer to the area to be placed on the substrate.

[0326] The electroplating apparatus according to this embodiment is suitable for carrying out the manufacturing method of the electroplated nickel member according to this embodiment. The electroplating apparatus according to this embodiment will be described below. Naturally, the embodiments of the manufacturing method of the electroplated nickel member described above can be applied to the electroplating apparatus according to this embodiment. Furthermore, the effects of the components of the electroplating apparatus are as described in the manufacturing method of the electroplated nickel member.

[0327] (Electroplating tank D5) The electroplating apparatus has an electroplating tank D5. The electroplating tank D5 is configured to accommodate an electro-nickel plating bath D4 containing nickel salts. Ni in the electro-nickel plating bath D4 2+ The concentration C (mol / L) is between 0.10 mol / L and 0.80 mol / L.

[0328] (Ultrasonic oscillation means D7) The electroplating apparatus further includes an ultrasonic oscillator D7. The ultrasonic oscillator D7 is configured to emit ultrasonic waves D8 inside the electroplating tank D5.

[0329] (Base material support means) The electroplating apparatus further includes a substrate support means. The substrate support means is configured to position the substrate D1 at a predetermined location. In this disclosure, the position where the substrate D1 is placed is referred to as the substrate placement area. The position and shape of the substrate placement area are not particularly limited. The position and shape of the substrate placement area can be determined according to the shape of the substrate D1 and the position and shape of the counter electrode D2, which will be described later. In Figures 26 to 31, the area where the substrate D1 is placed is the substrate placement area.

[0330] (Opposite pole D2) The electroplating apparatus further includes a counter electrode D2. The counter electrode D2 is positioned opposite the area where the substrate is to be placed. The counter electrode D2 and the substrate D1 supported in the area where the substrate is to be placed are energized during electroplating. The position and shape of the counter electrode D2 are not particularly limited. The position and shape of the counter electrode D2 can be determined according to the shape of the substrate D1 to be electroplated and the position of the area where the substrate is to be placed.

[0331] The frequency of the ultrasonic waves D8 emitted by the ultrasonic wave emitting means D7 is between 15 kHz and 80 kHz. The intensity of the ultrasonic waves D8 at a location 5 cm away from the planned substrate placement area, and at an intermediate location between the planned substrate placement area and the counter electrode D2, where the distance from the planned substrate placement area is closer, is between 0.20 and 80 kPa / kHz.

[0332] Preferably, Ni in the electro-nickel plating bath D4 2+ Concentration C (mol / L) and the cathode current density i (A / dm²) of the electroplating process. 2 ) and are values ​​that satisfy equation D1. Formula D1 20C≦i≦20C+80 (Embodiment of Manufacturing Method D)

[0333] (Embodiment of manufacturing method E) The reason why the dissolution reaction of a soluble anode does not proceed in an electroplating nickel bath with a low chloride ion concentration is the concentration gradient formed in the electroplating nickel bath near the surface of the soluble anode. Within the concentration gradient, the diffusion of chloride ions is restricted. Therefore, the concentration gradient inhibits the dissolution reaction of the soluble anode. To combine a soluble anode with an electroplating nickel bath with a low chloride ion concentration, it is necessary to eliminate the concentration gradient. However, it is impossible to eliminate the concentration gradient that occurs in an electroplating nickel bath by stirring the plating solution.

[0334] The inventors of this invention have diligently studied methods for manufacturing nickel-plated components that can maintain the dissolution reaction of the soluble anode even when using an electroplated nickel plating bath with a low chloride ion concentration. The inventors have found that by irradiating the soluble anode with ultrasound during the electroplating process, it is possible to maintain the dissolution reaction of the soluble anode very effectively, even in an electroplated nickel plating bath with a low chloride ion concentration. This is presumed to be because the cavitation phenomenon caused by ultrasound locally agitates the electroplated nickel plating bath near the soluble anode, efficiently destroying the diffusion layer that creates a concentration gradient.

[0335] The ability to disrupt the diffusion layer around the soluble anode using ultrasound in electroplated nickel has not been previously reported. Based on this new finding, the inventors hypothesized that it might be possible to maintain the dissolution reaction of the soluble anode even when using an electroplated nickel plating bath with a low chloride ion concentration. The inventors then conducted further investigations into the ultrasonic irradiation conditions. As a result, they successfully developed a method for manufacturing nickel-plated components that can maintain the dissolution reaction of the soluble anode even when using an electroplated nickel plating bath with a low chloride ion concentration.

[0336] Furthermore, Patent Document 7 discloses an electroplating method using ultrasound in electroplating nickel. However, the role of ultrasound in that technology is to arrange fine particles at the nodes of the standing wave and perform composite plating. This technology addresses a different problem than that of this disclosure. In addition, the effect of ultrasound in that technology also differs from that of this disclosure.

[0337] Figure 32 shows graphs of the current efficiency of the dissolution reaction of the soluble anode in electroplating of nickel under various conditions. In these examples, a watt bath was used as the electroplating nickel bath. 2+ The concentration is set to 1.6 mol / L, the chloride ion concentration to 0.01-0.30 mol / L, and the cathode current density to 20 A / dm². 2 In some cases, plating was performed while irradiating the soluble anode with ultrasound. In other cases, plating was performed without irradiating the soluble anode with ultrasound. The relationship between the current efficiency of the dissolution reaction and the chloride ion concentration in the soluble anode for each example is plotted in the graph of Figure 32. In the graph of Figure 32, the chloride ion concentration is on the horizontal axis and the current efficiency of the dissolution reaction in the soluble anode is on the vertical axis. These examples are Examples 1 to 3 and Comparative Examples 1 to 5, which are shown in "Examples of Manufacturing Method E" described later.

[0338] As shown in Figure 32, under normal conditions without ultrasonic irradiation, the current efficiency of the dissolution reaction at the soluble anode decreases when the chloride ion concentration falls below 0.3 mol / L. However, by irradiating the soluble anode with ultrasonic waves under predetermined conditions, the current efficiency of the dissolution reaction at the soluble anode could be maintained even when the chloride ion concentration was below 0.3 mol / L.

[0339] The method for manufacturing a nickel-plated member according to one embodiment of the present disclosure, obtained through the above process, comprises a step of electroplating a substrate using an electroplated nickel bath containing a nickel salt and chloride ions and a soluble anode, wherein the chloride ion concentration C (mol / L) is 0.05 mol / L or more and 0.30 mol / L or less, and in the electroplating process, ultrasonic waves are irradiated onto the soluble anode, the frequency of the ultrasonic waves is 15 kHz or more and 180 kHz or less, and the intensity of the ultrasonic waves at a location 5 cm away from the surface of the soluble anode, or at an intermediate location between the soluble anode and the substrate, which is closer to the soluble anode, is set to 0.20 to 80 kPa / kHz. The method for manufacturing a nickel-plated member according to this embodiment will now be described in detail.

[0340] The method for manufacturing a nickel-plated member according to this embodiment includes a step of electroplating a substrate using an electroplated nickel plating bath containing a nickel salt and chloride ions and a soluble anode.

[0341] (Nickel-plated material) A nickel-plated member is a member comprising a base and a nickel-plated film disposed on the surface of the base. The base of the nickel-plated member may have a substrate and a base coating disposed on the surface of the substrate. That is, the base coating may be disposed between the nickel-plated film and the substrate. On the other hand, naturally, the base coating does not have to be provided on the nickel-plated member. That is, the nickel-plated film may be directly disposed on the surface of the substrate. In this case, the term "base" becomes synonymous with "substrate."

[0342] (base material) The substrate is the material for the nickel-plated component. After electro-nickel plating, the substrate becomes the base for the nickel-plated component. The substrate may have a base material and an undercoat applied to the surface of the base material. On the other hand, naturally, the substrate does not have to have an undercoat. The shape and material of the substrate are not particularly limited. Preferred examples of the substrate will be described later.

[0343] (Soluble anode) A soluble anode is an anode that releases metal ions into the electrolyte during electrolysis. In the manufacturing method of nickel-plated components, the soluble anode contains nickel. The nickel in the soluble anode dissolves, replenishing nickel ions in the electroplated nickel bath. Preferred examples of soluble anodes will be described later.

[0344] (Electro-nickel plating bath) The electroplated nickel bath contains a nickel salt. The type of nickel salt is not particularly limited. Preferred examples of nickel salts are described later.

[0345] The electroplated nickel bath also contains chloride ions (Cl - ) is included. The chloride ion concentration C (mol / L) in the electroplated nickel bath shall be between 0.05 mol / L and 0.30 mol / L. If the chloride ion concentration C (mol / L) is less than 0.05 mol / L, the dissolution reaction at the soluble anode will be limited even with localized stirring by ultrasound.

[0346] Furthermore, from the viewpoint of maintaining the dissolution reaction at the soluble anode, there is no upper limit to the chloride ion concentration. However, if the chloride ion concentration exceeds 0.30 mol / L, the risk of corrosion of the plating equipment due to chloride ions increases. For this reason, in this disclosure, the chloride ion concentration is set to 0.3 mol / L or less. A lower chloride ion concentration is preferable. Accordingly, the chloride ion concentration may be 0.25 mol / L or less, 0.20 mol / L or less, or 0.10 mol / L or less.

[0347] (Ultrasound) In the method for manufacturing nickel-plated members according to this embodiment, ultrasound is used to promote the dissolution of the soluble anode. Therefore, ultrasound is irradiated onto the soluble anode during the electroplating process.

[0348] The ultrasonic frequency should be between 15 kHz and 180 kHz. Our experiments have shown that when the ultrasonic frequency is between 15 kHz and 180 kHz, it is possible to maintain the dissolution reaction of the soluble anode, even at chloride ion concentrations where the dissolution reaction is restricted under conditions without ultrasonic irradiation. While the reason for this is not yet clear, it is thought that the above frequency is the one that most easily induces cavitation around the soluble anode and provides the strongest stirring effect due to cavitation. The ultrasonic frequency may also be between 20 kHz and 30 kHz, or 50 kHz. Alternatively, the ultrasonic frequency may be between 160 kHz and 130 kHz, or 80 kHz.

[0349] Furthermore, the ultrasonic intensity at the designated ultrasonic intensity measurement location shall be between 0.20 kPa / kHz and 80 kPa / kHz. The designated ultrasonic intensity measurement location is the location that is closest to the soluble anode among (a) and (b) below. (a) A location approximately 5 cm away from the surface of the soluble anode (b) Intermediate portion between the soluble anode and the cathode (i.e., the substrate) Furthermore, ultrasonic intensity is the value obtained by dividing the ultrasonic sound pressure (kPa) by the ultrasonic frequency (kHz). The details of the ultrasonic intensity measurement position E3 will be explained below with reference to Figures 33 to 36. Figures 33 to 36 are side views of the opposing plate-shaped soluble anode E1 and substrate E2.

[0350] In the configuration illustrated in Figure 33, both the soluble anode E1 and the substrate E2 are flat and are arranged parallel to each other. The distance D between the center surface of the soluble anode E1 in the width direction and the substrate E2 is 10 cm or more. In the configuration illustrated in Figure 33, the ultrasonic intensity measurement position E3 is located 5 cm away from the center surface of the soluble anode E1 in the width direction.

[0351] In the configuration illustrated in Figure 34, both the soluble anode E1 and the substrate E2 are flat and are arranged parallel to each other. The distance D between the center surface of the soluble anode E1 in the width direction and the substrate E2 is less than 10 cm. In the configuration illustrated in Figure 34, the ultrasonic intensity measurement position E3 is located midway between the center of the soluble anode E1 in the width direction and the substrate E2.

[0352] In the configuration illustrated in Figure 35, the soluble anode E1 is curved, while the substrate E2 is flat. The soluble anode E1 and the substrate E2 are not parallel. The distance D between the center surface of the soluble anode E1 in the width direction and the substrate E2 is 10 cm or more. In the configuration illustrated in Figure 35, the ultrasonic intensity measurement position E3 is 5 cm away from the center surface of the soluble anode E1 in the width direction.

[0353] In the continuous plating apparatus shown in Figure 36, the soluble anode E1 is curved, while the substrate E2 is flat. The soluble anode E1 and the substrate E2 are not parallel. The distance D between the center surface of the soluble anode E1 in the width direction and the substrate E2 is less than 10 cm. In the configuration illustrated in Figure 36, the ultrasonic intensity measurement position E3 is set to a point midway between the center of the soluble anode E1 in the width direction and the substrate E2.

[0354] The ultrasonic intensity at the specified ultrasonic intensity measurement position described above shall be between 0.20 kPa / kHz and 80 kPa / kHz. If the ultrasonic intensity is less than 0.20 kPa / kHz, local agitation around the soluble anode is unlikely to occur, and it is considered that the diffusion layer that creates the concentration gradient cannot be sufficiently broken down.

[0355] Furthermore, from the perspective of reducing chloride ion concentration, there is no upper limit to the ultrasonic intensity. However, if the ultrasonic intensity exceeds 80 kPa / kHz, its effect may saturate, potentially causing unnecessary equipment load and deterioration of the working environment. Therefore, the ultrasonic intensity should be kept below 80 kPa / kHz. The ultrasonic intensity may also be 0.40 kPa / kHz or higher, 1.2 kPa / kHz or higher, or 4.0 kPa / kHz or higher. The ultrasonic intensity may also be 40 kPa / kHz or lower, 20 kPa / kHz or lower, or 10 kPa / kHz or lower.

[0356] In order to keep the ultrasonic intensity at ultrasonic intensity measurement position E3 within the above-mentioned range, the plating apparatus should be configured to satisfy, for example, the following requirements. (Requirement 1) The output of the ultrasonic oscillator E4 should be 800 W / m 3 That concludes this section. (Requirement 2) Degas the electroplated nickel bath. (Requirement 3) The ultrasonic oscillating means E4 are arranged on both sides in the width direction of the soluble anode E1, and the distance between the ultrasonic oscillating means E4 and the closest ultrasonic oscillating means E4 facing it across the soluble anode E1 is 500 mm or more and 2000 mm or less.

[0357] For example, as shown in Figure 37, ultrasonic oscillators E4 installed in the electroplating bath E5 are placed on both sides of the width direction of the soluble anode E1. The output of all ultrasonic oscillators E4 is set within the range described above. The distance between the upper left ultrasonic oscillator E4 and the upper right ultrasonic oscillator E4 in Figure 37 is also set within the range described above. Furthermore, the distance between the lower left ultrasonic oscillator E4 and the lower right ultrasonic oscillator E4 in Figure 37 is also set within the range described above. In addition, the electroplated nickel bath is degassed. Degassing removes bubbles from the electroplated nickel bath that cause attenuation of the ultrasonic waves E6. This makes it possible to set the intensity of the ultrasonic waves E6 at the ultrasonic intensity measurement position E3 within the range described above.

[0358] As long as the above requirements are met, the conditions for the electroplating process are not particularly limited. The method for manufacturing the nickel-plated member according to this embodiment physically destroys the diffusion layer that creates a concentration gradient. Therefore, there are no particular restrictions on the components of the electroplated nickel bath and other plating conditions, and they can be broadly selected according to the purpose. A more preferred example of the electroplating process is described below.

[0359] (Ni in an electroplated nickel bath 2+ concentration) For example, Ni in an electroplated nickel bath 2+ The concentration c (mol / L) may be between 0.1 mol / L and 2.0 mol / L. Ni in the electroplated nickel bath 2+ By setting the concentration c (mol / L) to 0.1 mol / L or higher, the deposition efficiency of nickel at the cathode can be ensured. Also, Ni in the electro-nickel plating bath 2+ By keeping the concentration c (mol / L) below 2.0 mol / L, nickel loss due to liquid extrusion can be suppressed.

[0360] Within the limits that do not impair the nickel deposition efficiency at the cathode, Ni in the electro-nickel plating bath 2+ The concentration c (mol / L) is preferable as it works favorably in the dissolution reaction at the soluble anode. Therefore, Ni in the electroplated nickel bath 2+ The concentration c (mol / L) may be 0.8 mol / L or less, or 0.4 mol / L or less.

[0361] (Types of nickel salts) The nickel salts contained in the electroplated nickel bath may include salts of one or more substances selected from the group consisting of nickel sulfate, nickel sulfamate, nickel chloride, and nickel bromide. By using these nickel salts, the quality of nickel plating can be improved.

[0362] Particularly preferably, the nickel salt added to the electroplated nickel bath contains nickel sulfate. In this case, it is preferable that the following formula is satisfied during the process of electroplating the substrate. 0.8 ≤ SO4 2- Concentration / Ni 2+ concentration SO4 2- Concentration and Ni 2+ The concentration refers to the sulfate ion concentration and nickel ion concentration of the electroplated nickel bath, and the unit is mol / L. Preferably, the above formula is always filled while current is being passed through the soluble anode and substrate for the electroplating process. This improves the current efficiency of the electroplating reaction at the cathode.

[0363] (Temperature of the electroplated nickel bath) The temperature of the electroplated nickel bath is preferably between 30°C and 70°C. Maintaining a temperature of 30°C or higher ensures the efficiency of the electroplating process. Furthermore, maintaining a temperature of 70°C or lower suppresses concentration fluctuations due to evaporation of the electroplated nickel bath.

[0364] (Soluble anode configuration) The configuration of the soluble anode is not particularly limited. Examples of soluble anodes include nickel plates and insoluble baskets containing granular nickel. When the soluble anode is a nickel plate, the nickel plate dissolves during electroplating. When the soluble anode has an insoluble basket and granular nickel filled therein, the granular nickel dissolves during electroplating. On the other hand, the insoluble basket does not dissolve. The material of the insoluble basket is, for example, titanium. When the soluble anode has an insoluble basket and granular nickel filled therein, the outer surface of the insoluble basket is considered the surface of the soluble anode when determining the ultrasonic intensity measurement position.

[0365] (Composition of the base material) The composition of the substrate is not particularly limited. Any material capable of forming electroplated nickel on its surface can be used as the substrate. Examples of substrates include metal substrates (steel sheets, plated steel sheets, copper sheets, wires, etc.) and conductive substrates (carbon fibers, conductive resins, etc.).

[0366] (Ultrasonic oscillation means) Furthermore, there are no particular limitations on the sound source used for irradiating with ultrasound. For example, a point-shaped sound source may be placed in the plating apparatus and ultrasound may be irradiated radially toward the soluble anode. Alternatively, the sound source may be placed in a planar manner to cover the soluble anode and ultrasound may be irradiated uniformly over the entire soluble anode. Examples of sound sources include a horn type (the point-shaped sound source described above), a submersible type (a sound source approximately several tens of centimeters square installed inside the tank), and a plating tank type (the planar sound source described above).

[0367] (Analysis of the components of the electroplated nickel bath) The concentration of nickel ions in an electroplated nickel bath can be measured by ICP emission spectrometry. Quantitative analysis is performed by creating a calibration curve using elemental standard solutions of known concentrations and then measuring the plating solution. The concentrations of chloride and sulfate ions in the electroplated nickel bath can be measured by high-performance liquid chromatography.

[0368] (Electroplating equipment) An electroplating apparatus according to another aspect of the present disclosure comprises an electroplating tank configured to accommodate an electroplating nickel bath containing a nickel salt and chloride ions, an ultrasonic oscillating means configured to emit ultrasonic waves inside the electroplating tank, a substrate support means configured to support a substrate in a substrate placement area, and a soluble anode, wherein the chloride ion concentration C (mol / L) in the electroplating nickel bath is 0.05 mol / L or more and 0.30 mol / L or less, the frequency of the ultrasonic waves emitted by the ultrasonic oscillating means is 15 kHz or more and 80 kHz or less, and the ultrasonic intensity at a location 5 cm away from the center of the soluble anode in the width direction, or at a location midway between the center of the soluble anode in the width direction and the substrate placement area, which is closer to the soluble anode, is 0.20 to 80 kPa / kHz.

[0369] The electroplating apparatus according to this embodiment is suitable for carrying out the manufacturing method of the electroplated member according to this embodiment. The electroplating apparatus according to this embodiment will be described below. Naturally, the embodiments of the manufacturing method of the electroplated member described above can be applied to the electroplating apparatus according to this embodiment. Furthermore, the effects of the components of the electroplating apparatus are as described in relation to the manufacturing method of the electroplated member.

[0370] (Electroplating tank) The electroplating apparatus has an electroplating tank. The electroplating tank is configured to accommodate an electroplated zinc bath.

[0371] (Ultrasonic oscillation means) The electroplating apparatus further includes an ultrasonic oscillating means. The ultrasonic oscillating means is configured to emit ultrasonic waves inside the electroplating tank.

[0372] (Base material support means) The electroplating apparatus further includes a substrate support means. The substrate support means is configured to position the substrate at a predetermined location. In this disclosure, the position where the substrate is placed is referred to as the substrate placement area. The position and shape of the substrate placement area are not particularly limited. The position and shape of the substrate placement area can be determined according to the shape of the substrate and the position and shape of the counter electrode, which will be described later. In Figures 33 to 36, the location where the substrate E2 is placed is the substrate placement area.

[0373] (Soluble anode) The electroplating apparatus further includes a soluble anode. The soluble anode is positioned opposite the area where the substrate is to be placed. The soluble anode and the substrate supported in the area where the substrate is to be placed are energized during electroplating. The position and shape of the soluble anode are not particularly limited. The position and shape of the soluble anode can be determined according to the shape of the substrate to be electroplated and the position of the area where the substrate is to be placed.

[0374] (Electrogalvanizing bath and ultrasound) The plating bath is an electroplated nickel plating bath containing nickel salts and chloride ions. The chloride ion concentration C (mol / L) in the electroplated nickel plating bath is 0.05 mol / L or more and 0.30 mol / L or less. Preferably, the chloride ion concentration C (mol / L) in the electroplated nickel plating bath is 0.05 mol / L or more and 0.25 mol / L or less.

[0375] The ultrasonic frequency emitted by the ultrasonic oscillating means is between 15 kHz and 80 kHz. The ultrasonic intensity at a point 5 cm away from the center of the soluble anode in the width direction, and at a point midway between the center of the soluble anode in the width direction and the planned substrate placement area, where the distance from the soluble anode is closer, is between 0.20 and 80 kPa / kHz.

[0376] The means for setting the ultrasonic intensity within the above-mentioned range are not particularly limited. For example, the ultrasonic intensity can be set within the above-mentioned range by adjusting the output, arrangement, etc., of the ultrasonic oscillating means according to the arrangement and shape of the soluble anode and the planned substrate placement area.

[0377] The following are suitable examples for setting the ultrasonic intensity within the above range. Preferably, the electroplating apparatus further includes a degassing means. Examples of degassing means include, for example, a degassing pump for liquids, or a buffer tank or piping configured to be connectable to a degassing pump. More preferably, the output of the ultrasonic oscillating means of the electroplating apparatus is 800 W / m². 3 That concludes the explanation. More preferably, the distance between the ultrasonic oscillating means and the nearest ultrasonic oscillating means facing it across the soluble anode is 500 mm to 2000 mm. These means make it possible to set the intensity of the ultrasonic waves E6 at the ultrasonic intensity measurement position E3 within the above range.

[0378] The electroplating apparatus according to this embodiment is capable of irradiating the substrate with ultrasound having a predetermined frequency and intensity. Therefore, the electroplating apparatus according to this embodiment can mitigate the adverse effects of the diffusion layer near the surface of the substrate and maintain the dissolution reaction of the soluble anode even when using an electroplating nickel bath with a low chloride ion concentration.

[0379] (Ni in the electroplated nickel bath) 2+ concentration) Preferably, Ni in the electroplated nickel 2+ The concentration c (mol / L) is between 0.1 mol / L and 2.0 mol / L. Ni in an electroplated nickel bath. 2+ By setting the concentration c (mol / L) to 0.1 mol / L or higher, the deposition efficiency of nickel at the cathode can be ensured. Also, Ni in the electro-nickel plating bath 2+ By keeping the concentration c (mol / L) below 2.0 mol / L, nickel loss due to liquid extrusion can be suppressed.

[0380] (SO4 in an electroplated nickel bath) 2- Concentration / Ni 2+ concentration) The nickel salts contained in the electroplated nickel bath may include salts of one or more substances selected from the group consisting of nickel sulfate, nickel sulfamate, nickel chloride, and nickel bromide. Using these nickel salts can improve the quality of nickel plating. Particularly preferred is that the nickel salt added to the electroplated nickel bath contains nickel sulfate. In this case, it is preferable that the following formula is satisfied during the process of electroplating the substrate. 0.8 ≤ SO4 2- Concentration / Ni 2+ concentration SO4 2- Concentration and Ni 2+ The concentration refers to the sulfate ion concentration and nickel ion concentration of the electroplated nickel bath, and the unit is mol / L. Preferably, the above formula is always filled while current is being passed through the soluble anode and substrate for the electroplating process. This improves the current efficiency of the electroplating reaction at the cathode. (Embodiment of manufacturing method E)

[0381] (Embodiment of manufacturing method F) When a substrate is immersed in an electroplating bath and a voltage is applied between the substrate and the electroplating bath, a chemical reaction occurs that forms tin plating on the surface of the substrate. Then, in the electroplating bath around the substrate, Sn 2+ Sn is consumed. As a result, Sn is directed toward the plated surface. 2+ This results in a concentration gradient.

[0382] Sn in electroplated tin bath 2+ The lower limit of the concentration is restricted by this concentration gradient. 2+ To achieve plating in an electroplating bath with an even lower concentration, it is necessary to eliminate the concentration gradient. However, it has been considered impossible to eliminate the concentration gradient that occurs in an electroplating bath by stirring the plating solution. Therefore, in known electroplating conditions, in order to use a phenol sulfonic acid bath, a concentration of 15 g / L (0.126 mol / L) or more of Sn is required. 2+Using an electroplating bath with the appropriate concentration is essential.

[0383] The inventors of this invention have found that low Sn 2+ We have diligently studied methods for manufacturing tin-plated components that can form a good coating in an electroplating bath of a certain concentration. The inventors have found that irradiating the cathode (substrate) with ultrasound during the electroplating process can very effectively suppress the decrease in current efficiency. This is presumed to be because the cavitation phenomenon caused by the ultrasound locally agitates the electroplating bath near the cathode, efficiently destroying the diffusion layer that creates the concentration gradient.

[0384] In electroplating, the ability to disrupt the diffusion layer around the cathode using ultrasound has not been previously reported. Based on this new finding, the inventors believe that low Sn 2+ We hypothesized that a good coating could be formed using an electroplating bath with a certain concentration of tin. The inventors then conducted further investigations into the ultrasonic irradiation conditions. As a result, we found that low Sn 2+ We have successfully developed a method for manufacturing tin-plated components that can form a good coating in an electroplating bath of a certain concentration.

[0385] Furthermore, Patent Document 4 discloses an electroplating method using ultrasound in electroplating of tin. However, the Sn assumed in Patent Document 4 2+ The concentration is high, at 30 g / L or more. Furthermore, the role of ultrasound in the technology described in Patent Document 4 is to increase the current density of the electro-tin plating process. Therefore, the technology described in Patent Document 4 and the technology disclosed here differ in both their problems and effects.

[0386] Figure 38 shows that the electroplating bath is a phenol sulfonic acid bath, and the Sn of the electroplating bath 2+ The concentration is set to 0.08 mol / L, and the cathode current density is set to 5 A / dm². 2 The image shows a plated steel sheet obtained by plating while irradiating the substrate with ultrasound under the specified conditions. This plated steel sheet corresponds to Example 1 in Table 22. According to the prior art, Sn 2+When plating is performed using an electroplating bath with a concentration of 0.08 mol / L, the current efficiency decreases significantly. See, for example, Comparative Example 1 in Table 22. However, by irradiating with ultrasound under predetermined conditions, it was possible to form good electroplating with high current efficiency, as shown in Example 1 and Figure 38.

[0387] The method for manufacturing a tin-plated member according to one aspect of the present disclosure, obtained through the above process, comprises a step of electroplating a substrate F1 using an electroplated tin bath F4 containing a tin salt, wherein the Sn of the electroplated tin bath F4 2+ The concentration C (mol / L) is set to 0.020 mol / L or higher and 0.120 mol / L or lower, and the phenolsulfonic acid concentration of the electroplated tin bath F4 is set to Sn 2+ The concentration C (mol / L) is set to 1 to 5 times the normal level. In the electroplating process, ultrasonic waves F8 are irradiated onto the substrate F1, with the frequency of ultrasonic waves F8 being between 15 kHz and 180 kHz, and the intensity of ultrasonic waves F8 at a predetermined ultrasonic intensity measurement position F3 being between 0.20 kPa / kHz and 80 kPa / kHz. The ultrasonic intensity measurement position F3 is the location that is closer to the center of the substrate F1 in the width direction of the following two locations. (A) A point 5 cm away from the center of the surface in the width direction of base material F1 (B) Midway between the center of the base material F1 in the width direction and the opposite electrode The electroplating method according to this embodiment will be described in detail below.

[0388] (Electroplating treatment) In the method for manufacturing a tin-plated member according to this embodiment, a base material F1 is electroplated. The base material F1 and the apparatus for performing the electroplating are not particularly limited. For example, if the base material F1 is a steel strip, it is preferable to electroplat the base material F1 using a continuous plating apparatus. On the other hand, the plating apparatus may be a batch processing apparatus.

[0389] An example of a continuous plating apparatus is shown in Figure 39. The continuous plating apparatus comprises an electroplating tank F5, a counter electrode F2, and a sheet feed roller F6. The electroplating tank F5 houses an electro-tin plating bath F4. The sheet feed roller F6 supports the substrate F1 in the electro-tin plating bath F4. The sheet feed roller F6 also rotates to move the substrate F1. The arrows on the sheet feed roller F6 indicate the direction of rotation of the sheet feed roller F6. The arrows along the substrate F1 indicate the direction of movement of the substrate F1. The sheet feed roller F6 immerses the substrate F1 in the electro-tin plating bath F4 and then lifts it out. The counter electrode F2 is positioned opposite the substrate F1. The counter electrode F2 is connected to a power supply (not shown).

[0390] Hereafter, the left-right direction in Figure 39 will be referred to as the X direction, and the up-down direction as the Y direction. The direction perpendicular to the X and Y directions will be referred to as the Z direction. The width direction of the base material F1 is the Z direction.

[0391] The electroplating bath F4 contains a tin salt. The type of tin salt is not particularly limited. Preferred examples of tin salts are described later.

[0392] In the electroplating process, the substrate F1 is used as the cathode and the counter electrode F2 is used as the anode, and current is passed through the substrate F1 and the counter electrode F2. As a result, tin is electrochemically deposited on the surface of the substrate F1, forming a tin plating layer.

[0393] (Sn of electroplated tin bath F4) 2+ Concentration C: 0.020mol / L or more and 0.120mol / L or less) The electroplating method according to this embodiment includes a step of electroplating a substrate F1 using an electroplating bath F4 containing tin salts. 2+ The concentration C (mol / L) shall be between 0.020 mol / L and 0.120 mol / L.

[0394] Sn 2+ If the concentration C (mol / L) is less than 0.020 mol / L, even with localized ultrasonic stirring, a sufficient amount of Sn will not reach the surface of the substrate F1. 2+It is not possible to supply Sn in the electro-tin plating bath F4, and a good coating cannot be obtained. 2+ The concentration should be 0.020 mol / L or higher. Preferably, the Sn of the electroplating bath F4. 2+ The concentration shall be 0.030 mol / L or higher, 0.040 mol / L or higher, or 0.060 mol / L or higher.

[0395] Furthermore, from the perspective of obtaining a good coating, Sn 2+ There is no upper limit to the concentration. However, Sn 2+ If the concentration exceeds 0.120 mol / L, increased costs may occur due to the removal of the plating solution. Removal of the plating solution refers to the phenomenon in which the plating solution adheres to the substrate and is removed from the plating bath. Therefore, in the manufacturing method of the tin-plated member according to this embodiment, the Sn of the electro-tin plating bath F4 2+ The concentration should be 0.120 mol / L or less. Sn 2+ A lower concentration is preferable. Therefore, Sn 2+ The concentration may be 0.100 mol / L or less, 0.080 mol / L or less, or 0.060 mol / L.

[0396] (Phenol sulfonic acid concentration in electroplating bath F4: Sn 2+ (Concentration C (mol / L) is between 1 and 5 times the original concentration) The phenol sulfonic acid concentration in electroplated tin bath F4 is equal to the Sn concentration in electroplated tin bath F4. 2+ The concentration should be between 1 and 5 times the concentration C (mol / L). The phenolsulfonic acid concentration is Sn 2+ If the concentration C is less than 1, then the Sn of the electrotin plating bath F4 2+ It is oxidized, and sludge is formed.

[0397] Furthermore, from the perspective of obtaining a good coating, there is no upper limit to the phenolsulfonic acid concentration. However, if the phenolsulfonic acid concentration is Sn 2+ If the concentration exceeds five times that of C, the effect saturates, leading to increased costs. Therefore, in the manufacturing method of the tin-plated member according to this embodiment, the phenolsulfonic acid concentration is set to Sn 2+ The concentration should be no more than 5 times that of concentration C.

[0398] In the electroplating method according to this embodiment, ultrasonic waves F8 are used to atomize Sn near the cathode. 2+ To facilitate supply, ultrasonic waves F8 are irradiated onto the substrate F1 during the electroplating process.

[0399] The means for irradiating with ultrasonic waves F8 are not particularly limited. An example of a means for irradiating with ultrasonic waves F8 when the plating apparatus is a continuous plating apparatus as shown in Figure 39 is shown in Figure 40. Figure 40 is a schematic diagram of the substrate F1 around the counter electrode F2. The left-right direction in Figure 40 is the Z direction, i.e., the width direction of the substrate F1. The up-down direction in Figure 40 is the Y direction. The arrows in Figure 40 indicate the direction of movement of the substrate F1.

[0400] The continuous plating apparatus in Figure 40 has multiple ultrasonic oscillating means F7. The ultrasonic oscillating means F7 are attached to the electroplating bath F5. The ultrasonic oscillating means F7 irradiate both ends of the substrate F1 with ultrasonic waves F8. The ultrasonic waves F8 eliminate the diffusion layer of the electroplating bath F4 near the surface of the substrate F1.

[0401] (Frequency of ultrasonic wave F8: 15kHz to 180kHz) The frequency of ultrasonic wave F8 must be between 15 kHz and 180 kHz. Our experiments have shown that when the frequency of ultrasonic wave F8 is between 15 kHz and 180 kHz, in particular, Sn, which cannot be plated under conditions without ultrasonic wave F8 irradiation, can be plated. 2+ Plating became possible even at higher concentrations. The reason for this is not yet clear, but it is thought that the above-mentioned frequencies are the ones that most easily cause cavitation around the substrate F1 and have the strongest stirring effect due to cavitation. The frequency of ultrasonic wave F8 may be 20 kHz or higher, 30 kHz or higher, or 50 kHz or higher. The frequency of ultrasonic wave F8 may be 160 kHz or lower, 130 kHz or lower, or 80 kHz or lower.

[0402] (Ultrasonic F8 intensity: 0.20 kPa / kHz to 80 kPa / kHz) Furthermore, the intensity of ultrasonic wave F8 must be between 0.20 kPa / kHz and 80 kPa / kHz. The intensity of ultrasonic wave F8 is the value obtained by dividing the sound pressure (kPa) of ultrasonic wave F8 at a predetermined ultrasonic wave intensity measurement position F3 by the frequency (kHz) of ultrasonic wave F8.

[0403] The ultrasonic intensity measurement position F3 is the location that is closest to the center of the substrate F1 in the width direction among (a) and (b) below. (a) A point 5 cm away from the center of the surface in the width direction of the base material F1 (b) The midpoint between the center of the substrate F1 in the width direction and the counter electrode F2 The details of the ultrasonic intensity measurement position F3 will be explained below with reference to Figures 41 to 44. Figures 41 to 44 are top views of the substrate F1 and counter electrode F2 in the continuous plating apparatus shown in Figure 39. The vertical direction in Figures 41 to 44 is the Z direction, i.e., the width direction of the substrate F1. The horizontal direction in Figures 41 to 44 is the X direction.

[0404] In the continuous plating apparatus shown in Figure 41, both the substrate F1 and the counter electrode F2 are flat and are arranged parallel to each other. The distance D between the center surface of the substrate F1 in the width direction and the counter electrode F2 is 10 cm or more. In the continuous plating apparatus shown in Figure 41, the ultrasonic intensity measurement position F3 is set 5 cm away from the center surface of the substrate F1 in the width direction.

[0405] In the continuous plating apparatus shown in Figure 42, both the substrate F1 and the counter electrode F2 are flat and are arranged parallel to each other. The distance D between the center surface of the substrate F1 in the width direction and the counter electrode F2 is less than 10 cm. In the continuous plating apparatus shown in Figure 42, the ultrasonic intensity measurement position F3 is set to a point midway between the center of the substrate F1 in the width direction and the counter electrode F2.

[0406] In the continuous plating apparatus shown in Figure 43, the substrate F1 is curved, while the counter electrode F2 is flat. The substrate F1 and the counter electrode F2 are not parallel. The distance D between the center surface of the substrate F1 in the width direction and the counter electrode F2 is 10 cm or more. In the continuous plating apparatus shown in Figure 43, the ultrasonic intensity measurement position F3 is set to a location 5 cm away from the center surface of the substrate F1 in the width direction.

[0407] In the continuous plating apparatus shown in Figure 44, the substrate F1 is curved, while the counter electrode F2 is flat. The substrate F1 and the counter electrode F2 are not parallel. The distance D between the center surface of the substrate F1 in the width direction and the counter electrode F2 is less than 10 cm. In the continuous plating apparatus shown in Figure 44, the ultrasonic intensity measurement position F3 is set to a point midway between the center of the substrate F1 in the width direction and the counter electrode F2.

[0408] If the intensity of the ultrasonic wave F8 is less than 0.20 kPa / kHz, it is thought that local agitation is unlikely to occur around the substrate F1, and the diffusion layer that creates the concentration gradient cannot be sufficiently broken down.

[0409] Note that Sn 2+ From the perspective of reducing the concentration of the substance, there is no upper limit to the intensity of ultrasonic F8. However, if the intensity of ultrasonic F8 exceeds 80 kPa / kHz, its effect may saturate, potentially leading to unnecessary deterioration of the equipment load and working environment. Therefore, the intensity of ultrasonic F8 should be kept below 80 kPa / kHz.

[0410] The intensity of ultrasonic wave F8 may be 0.40 kPa / kHz or higher, 1.2 kPa / kHz or higher, or 4.0 kPa / kHz or higher. The intensity of ultrasonic wave F8 may be 40 kPa / kHz or lower, 20 kPa / kHz or lower, or 10 kPa / kHz or lower.

[0411] In order to keep the intensity of the ultrasonic wave F8 at the ultrasonic intensity measurement position F3 within the above range, the plating apparatus is configured to satisfy, for example, the following two requirements. (Requirement 1) The ultrasonic oscillating means F7 is arranged on both sides of the base material F1 in the width direction. (Requirement 2) The output of the ultrasonic oscillator F7 should be 800 W / m 3 That concludes this section. (Requirement 3) The distance between the ultrasonic oscillating means F7 and the closest ultrasonic oscillating means F7 facing it across the substrate F1 shall be 500 mm or more and 2000 mm or less.

[0412] For example, as shown in Figure 40, the ultrasonic oscillating means F7 are installed on both sides of the substrate F1 in the width direction (i.e., the Z direction). The output of all ultrasonic oscillating means F7 is set to the range described above. In addition, the distance between the upper left ultrasonic oscillating means F7 and the upper right ultrasonic oscillating means F7 in Figure 40 is set to the range described above. Furthermore, the distance between the lower left ultrasonic oscillating means F7 and the lower right ultrasonic oscillating means F7 in Figure 40 is set to the range described above. This makes it possible to set the ultrasonic intensity at the ultrasonic intensity measurement position F3 to the range described above.

[0413] As long as the above requirements are met, the conditions for the electroplating process are not particularly limited. The electroplating method according to this embodiment physically destroys the diffusion layer that creates a concentration gradient. Therefore, there are no particular restrictions on the components of the electroplated tin bath F4 and other plating conditions, and they can be broadly selected according to the purpose. A more preferred example of a method for manufacturing a tin-plated member is described below.

[0414] (Sn 2+ (Relationship between concentration and cathode current density) For example, Sn in electroplated tin bath F4 2+ Concentration C (mol / L) and the cathode current density i (A / dm²) of the electroplating process. 2 ) and may also be values ​​that satisfy equation F1. Formula F1 30C+6.0 <i≦30C+35.0 Cathode current density i(A / dm²) in electroplating process 2 By setting the cathode current density (F1) to 30C+6.0 or higher, the efficiency of the electroplating process can be ensured. The lower limit value of the cathode current density i specified in formula F1, "30C+6.0", corresponds to approximately 50% of the limit current density when electroplating is performed without ultrasonic irradiation. The term "limit current density" is defined in JIS H 0400:1998 "Terminology for Electroplating and Related Processes" as "the maximum value of the current density at which the supply of ions by diffusion reaches its limit and the current density no longer increases even if the voltage is increased." In the manufacturing method of the tin-plated member according to this embodiment, the limit current density is increased by ultrasonic waves. Therefore, the cathode current density can be increased as defined in formula F1.

[0415] Furthermore, the cathode current density i(A / dm) of the electroplating process. 2 By setting the temperature to 30C + 35.0 or less, the current efficiency of the electroplating process can be increased to 90% or more.

[0416] Within the limits that do not compromise economic efficiency, the cathode current density i(A / dm) of the electroplating process is... 2 A lower value for the cathode current density i(A / dm²) of the electroplating process is preferable. 2 ) may also be a value that satisfies equation F2. Formula F2 30C+17.5≦i≦30C+35.0 The lower limit of the cathode current density i specified in formula F2, "30C + 17.5", corresponds to approximately 50% of the limiting current density when electroplating is performed while irradiating with ultrasound.

[0417] (Types of metal salts) The tin salt contained in the electroplating bath F4 is preferably tin sulfate. By using tin sulfate, the quality of the plating can be further improved.

[0418] (Temperature of electroplated tin bath F4) The temperature of the electroplating bath F4 is preferably between 30°C and 70°C. Maintaining a temperature of 30°C or higher ensures the efficiency of the electroplating process. Furthermore, maintaining a temperature of 70°C or lower suppresses concentration fluctuations due to evaporation of the electroplating bath F4.

[0419] (Plating adhesion amount) The amount of plating deposited in the electroplating process is 10 g / m². 2 More than 50g / m 2 The following is preferable: Plating adhesion amount of 10 g / m 2 By doing so, the corrosion resistance and workability required for various components such as electrical equipment, office equipment, and steel furniture can be ensured. Plating adhesion amount: 50g / m² 2By doing the following, the occurrence of warping in the plated material can be suppressed.

[0420] (Gloss agent) It is preferable that the electroplating bath F4 contains a brightener. By using a brightener, a smooth plated film can be obtained. Suitable examples of brighteners for acidic plating baths are ethoxylated α-naphthol, ethoxylated α-naphthol sulfonic acid, polyethylene glycol, and alkylene oxide compounds. The appropriate amount range varies depending on the type of brightener and the current density, but the range of 0.01 to 10 g / L is common. The lower limit of the appropriate amount range of brightener is determined by the smoothness of the plated film. The upper limit of the appropriate amount range of brightener is determined by the maximum current density and cost.

[0421] (Base material F1) The type of substrate F1 is not particularly limited. Any material capable of forming electroplating can be used as the substrate F1. Examples of substrate F1 include metal substrates (steel sheets, plated steel sheets, copper sheets, wires, etc.) and conductive substrates (carbon fibers, conductive resins, etc.).

[0422] (Ultrasonic oscillation means F7) Furthermore, there are no particular limitations on the sound source used to irradiate the ultrasonic waves F8. For example, a point-shaped sound source may be arranged to irradiate the substrate F1 radially. Alternatively, the sound source may be arranged in a planar manner to cover the substrate F1 and irradiate the entire substrate F1 uniformly with ultrasonic waves. Examples of sound sources include a horn type (the point-shaped sound source described above), a submersible type (a sound source approximately several tens of centimeters square is installed inside the tank), an anode oscillator type (the counter electrode (anode) itself is used as the sound source), and a plating tank type (the planar sound source described above).

[0423] (Analysis of the components of electroplated tin bath F4) Sn in electroplated tin bath F4 2+ The concentration C can be measured by ICP emission spectrometry. After creating a calibration curve using elemental standard solutions of known concentrations, quantitative analysis is performed by measuring the electroplated tin bath F4.

[0424] The electroplating apparatus according to this embodiment comprises an electroplating tank F5 configured to accommodate an electroplating bath F4 containing tin salts, an ultrasonic oscillating means F7 configured to emit ultrasonic waves F8 inside the electroplating tank F5, a substrate support means configured to support a substrate F1 in a substrate placement area, and a counter electrode F2, wherein the electroplating bath F4 contains Sn 2+ The concentration C (mol / L) is between 0.020 mol / L and 0.120 mol / L, and the phenolsulfonic acid concentration in the electroplating bath F4 is Sn 2+ The concentration C (mol / L) is between 1 and 5 times, the frequency of the ultrasonic waves F8 emitted by the ultrasonic wave oscillating means F7 is between 15 kHz and 80 kHz, and the intensity of the ultrasonic waves F8 is between 0.20 and 80 kPa / kHz at a point 5 cm away from the center in the width direction of the area where the substrate is to be placed, and at a point midway between the center in the width direction of the area where the substrate is to be placed and the counter electrode F2, where the distance from the area where the substrate is to be placed is even closer.

[0425] The electroplating apparatus according to this embodiment is suitable for carrying out the manufacturing method of the electroplated member according to this embodiment. The electroplating apparatus according to this embodiment will be described below. Naturally, the aspects of the manufacturing method of the tin-plated member described above can be applied to the electroplating apparatus according to this embodiment. Furthermore, the effects of the components of the electroplating apparatus are as described in relation to the manufacturing method of the tin-plated member.

[0426] (Electroplating tank F5) The electroplating apparatus has an electroplating tank F5. The electroplating tank F5 is configured to accommodate an electro-tin plating bath F4.

[0427] (Ultrasonic oscillation means F7) The electroplating apparatus further includes an ultrasonic oscillator F7. The ultrasonic oscillator F7 is configured to emit ultrasonic waves F8 inside the electroplating tank F5.

[0428] (Base material support means) The electroplating apparatus further includes a substrate support means. The substrate support means is configured to position the substrate F1 at a predetermined location. In this disclosure, the position where the substrate F1 is placed is referred to as the substrate placement area. The position and shape of the substrate placement area are not particularly limited. The position and shape of the substrate placement area can be determined according to the shape of the substrate F1 and the position and shape of the counter electrode, which will be described later. In Figures 39 to 44, the location where the substrate F1 is placed is the substrate placement area.

[0429] (Opposite poles) The electroplating apparatus further includes a counter electrode F2. The counter electrode F2 is positioned opposite the substrate placement area or the substrate F1. The counter electrode F2 and the substrate F1 supported in the substrate placement area are energized during electroplating. The position and shape of the counter electrode F2 are not particularly limited. The position and shape of the counter electrode F2 can be determined according to the shape of the substrate F1 to be electroplated and the position of the substrate placement area.

[0430] (Electroplating bath F4 and ultrasonic F8) The plating bath is an electroplated tin bath F4 containing tin salts. 2+ The concentration C (mol / L) shall be between 0.020 mol / L and 0.120 mol / L.

[0431] The frequency of the ultrasonic waves F8 emitted by the ultrasonic oscillating means F7 is between 15 kHz and 80 kHz. The intensity of the ultrasonic waves F8 at a point 5 cm away from the center in the width direction of the area where the substrate is to be placed, and at a point midway between the center in the width direction of the area where the substrate is to be placed and the counter electrode, where the distance from the area where the substrate is to be placed is closer, is between 0.20 and 80 kPa / kHz.

[0432] The electroplating apparatus according to this embodiment irradiates the substrate F1 with ultrasonic waves F8 having a predetermined frequency and intensity. Therefore, the electroplating apparatus according to this embodiment mitigates the adverse effects of the diffusion layer near the surface of the substrate F1, resulting in low Sn 2+ Even with an electroplating bath of concentration F4, a good coating can be formed.

[0433] Preferably, the Sn of the electro-tin plating bath F4. 2+ Concentration C (mol / L) and cathode current density i (A / dm²) 2 ) and are values ​​that satisfy equation F1. Formula F1 30C+6.0 <i≦30C+35.0 Cathode current density i(A / dm²) in electroplating process 2 By setting the cathode current density (i) to 30C + 6.0 or higher, the efficiency of the electroplating process can be ensured. 2 By setting the temperature to 30C + 35.0, the stability of the electroplating process can be ensured. (Embodiment of manufacturing method F)

[0434] (Embodiment of manufacturing method G) When a substrate is immersed in an electrogalvanizing bath and a voltage is applied between the substrate and the electrogalvanizing bath, a chemical reaction occurs that forms a zinc plating. Then, the Zn in the electrogalvanizing bath around the substrate... 2+ This is consumed. As a result, in the electro-zinc plating bath, Zn is directed toward the plating surface. 2+ This results in a concentration gradient.

[0435] Zn in electroplated zinc bath 2+ The lower limit of the concentration is restricted by this concentration gradient. 2+ To achieve electro-galvanizing at specific concentrations, it is necessary to eliminate concentration gradients.

[0436] However, it has been considered impossible to eliminate the concentration gradient that occurs in an electro-zinc plating bath by stirring the plating solution. Therefore, under known electro-zinc plating conditions, Zn 2+ It is practically essential to maintain a concentration of over 0.80 mol / L.

[0437] The inventors have developed a low-Zn 2+We have diligently studied methods for manufacturing zinc-plated components that can form a good coating using a high-concentration zinc plating bath. The inventors have discovered that by irradiating the substrate (the cathode) with ultrasound during the electroplating process, the decrease in current efficiency can be suppressed very effectively. This is presumed to be because the cavitation phenomenon caused by ultrasound locally agitates the electroplated zinc bath near the cathode, efficiently destroying the diffusion layer that creates the concentration gradient.

[0438] In electrogalvanizing, the ability to disrupt the diffusion layer around the cathode using ultrasound has not been previously reported. Based on this new finding, the inventors believe that low Zn 2+ We hypothesized that a good coating could be formed using an electroplating bath with a certain concentration of zinc. The inventors then conducted further investigations into the ultrasonic irradiation conditions. As a result, we found that low Zn... 2+ We have successfully developed a method for manufacturing zinc-plated components that can form a good coating in an electro-zinc plating bath of a certain concentration.

[0439] Figure 45 shows a photograph of a plated steel sheet obtained by plating the substrate while irradiating it with ultrasonic waves (Example 1 shown in "Example of Manufacturing Method G" described later). The electro-zinc plating bath was a sulfuric acid bath, and the Zn in the electro-zinc plating bath was 2+ The concentration is set to 0.4 mol / L, and the cathode current density is set to 60 A / dm². 2 That's what I decided.

[0440] Conventional technology uses Zn 2+ Plating from a bath with a concentration of 0.4 mol / L results in a significant decrease in current efficiency (see Comparative Example 1 shown in "Example of Manufacturing Method G" below). However, by irradiating with ultrasound under predetermined conditions, it was possible to form good electroplated zinc with high current efficiency, as shown in Example 1 and Figure 45.

[0441] The method for manufacturing a zinc-plated member according to one aspect of the present disclosure, obtained through the above process, comprises a step of electroplating a substrate G1 using an electro-zinc plating bath G4 containing a zinc salt, wherein the electro-zinc plating bath G4 contains Zn 2+ The concentration C (mol / L) is between 0.10 mol / L and 0.80 mol / L. In the electroplating process, the substrate G1 is irradiated with ultrasonic waves G8, the frequency of ultrasonic waves G8 is between 15 kHz and 180 kHz, and the intensity of ultrasonic waves G8 at a predetermined ultrasonic intensity measurement position G3 is between 0.20 kPa / kHz and 80 kPa / kHz. The ultrasonic intensity measurement position G3 is the location that is closer to the center of the substrate G1 in the width direction of the following two locations. (A) A point 5 cm away from the center of the surface in the width direction of base material G1 (B) The midpoint between the center of the base material G1 in the width direction and the counter electrode G2 The method for manufacturing the zinc-plated member according to this embodiment will be described in detail below.

[0442] (Electroplating treatment) In the method for manufacturing a zinc-plated member according to this embodiment, the substrate is electroplated. The substrate and the apparatus for performing the electroplating are not particularly limited. For example, if the substrate is a steel strip, it is preferable to electroplat the substrate using a continuous plating apparatus. On the other hand, the plating apparatus may be a batch processing apparatus.

[0443] An example of a continuous plating apparatus is shown in Figure 46. The continuous plating apparatus comprises an electroplating tank G5, a counter electrode G2, and a sheet feed roller G6. The electroplating tank G5 houses an electrogalvanizing bath G4. The sheet feed roller G6 supports the substrate G1 in the electrogalvanizing bath G4. The sheet feed roller G6 also rotates to move the substrate G1. The arrows on the sheet feed roller G6 indicate the direction of rotation of the sheet feed roller G6. The arrows along the substrate G1 indicate the direction of movement of the substrate G1. The sheet feed roller G6 immerses the substrate G1 in the electrogalvanizing bath G4 and then lifts it out. The counter electrode G2 is positioned opposite the substrate G1. The counter electrode G2 is connected to a power supply (not shown).

[0444] Hereafter, the left-right direction in Figure 46 will be referred to as the X direction, and the up-down direction as the Y direction. The direction perpendicular to the X and Y directions will be referred to as the Z direction. The width direction of the base material G1 is the Z direction.

[0445] The electro-zinc plating bath G4 contains a zinc salt. The type of zinc salt is not particularly limited. Preferred examples of zinc salts are described later.

[0446] In electroplating, the substrate G1 is used as the cathode and the counter electrode G2 is used as the anode, and current is passed through both the substrate G1 and the counter electrode G2. As a result, zinc is electrochemically deposited on the surface of the substrate G1, forming a zinc plating layer.

[0447] (Zn in the electroplating bath) 2+ Concentration: 0.10mol / L or more and 0.80mol / L or less) The method for manufacturing a zinc-plated member according to this embodiment includes a step of electroplating a substrate using an electro-zinc plating bath containing zinc salts. 2+ The concentration C (mol / L) shall be between 0.10 mol / L and 0.80 mol / L.

[0448] Zn 2+ When the concentration C (mol / L) is less than 0.10 mol / L, even with localized ultrasonic stirring, a sufficient amount of Zn can be absorbed onto the substrate surface. 2+ It is not possible to supply Zn in the electro-zinc plating bath, and a good coating cannot be obtained. 2+ The concentration should be 0.10 mol / L or higher. Ni in the electroplated zinc bath. 2+ The concentration may be set to 0.15 mol / L or higher, 0.20 mol / L or higher, or 0.30 mol / L or higher.

[0449] Furthermore, from the perspective of obtaining a good coating, Zn 2+ There is no upper limit to the concentration. However, Zn 2+ If the concentration exceeds 0.80 mol / L, the cost associated with removing the liquid will increase, and the Zn in the waste liquid will also increase. 2+An increase in the amount of Zn may result in an increase in environmental burden. Therefore, in the method for manufacturing zinc-plated members according to this embodiment, the Zn of the electro-zinc plating bath 2+ The concentration should be 0.80 mol / L or less. Zn 2+ A lower concentration is preferable. Therefore, Zn 2+ The concentration may be 0.60 mol / L or less, or 0.40 mol / L.

[0450] (Ultrasound irradiation) In the method for manufacturing a zinc-plated member according to this embodiment, ultrasonic waves are used to control the Zn near the cathode. 2+ To facilitate supply, ultrasonic waves G8 are irradiated onto the substrate G1 during the electroplating process.

[0451] The means for irradiating with ultrasonic waves G8 are not particularly limited. An example of a means for irradiating with ultrasonic waves G8 when the plating apparatus is a continuous plating apparatus as shown in Figure 46 is shown in Figure 47. Figure 47 is a schematic diagram of the substrate G1 around the counter electrode G2. The left-right direction in Figure 47 is the Z direction, i.e., the width direction of the substrate G1. The up-down direction in Figure 47 is the Y direction. The arrows in Figure 47 indicate the direction of movement of the substrate G1.

[0452] The continuous plating apparatus in Figure 47 has multiple ultrasonic emitting means G7. The ultrasonic emitting means G7 are attached to the electroplating bath G5. The ultrasonic emitting means G7 irradiate both ends of the substrate G1 with ultrasonic waves G8. The ultrasonic waves G8 irradiate the nickel in the electroplated zinc bath G4 near the surface of the substrate G1. 2+ Eliminate the concentration gradient.

[0453] (Ultrasonic frequency: 15kHz to 180kHz) The ultrasonic frequency must be between 15 kHz and 180 kHz. Our experiments have shown that when the ultrasonic frequency is between 15 kHz and 180 kHz, Zn, which is impossible to plate under conditions without ultrasonic irradiation, can be plated. 2+Plating became possible even at higher concentrations. The reason for this is not yet clear, but it is thought that the above-mentioned frequencies are the ones that most easily cause cavitation around the substrate and have the strongest stirring effect due to cavitation. The ultrasonic frequency may be 20kHz or higher, 30kHz or higher, or 50kHz or higher. The ultrasonic frequency may also be 170kHz or lower, 160kHz or lower, 130kHz or lower, or 80kHz or lower.

[0454] (Ultrasonic intensity: 0.20 kPa / kHz to 80 kPa / kHz) Furthermore, the ultrasonic intensity must be between 0.20 kPa / kHz and 80 kPa / kHz. The ultrasonic intensity is the value obtained by dividing the sound pressure (kPa) of the ultrasonic wave at the designated ultrasonic intensity measurement position G3 by the ultrasonic frequency (kHz).

[0455] The ultrasonic intensity measurement position G3 is the location among (a) and (b) below that is closest to the center of the substrate in the width direction. (a) A point 5 cm away from the center of the surface in the width direction of base material G1 (b) The midpoint between the center of the base material G1 in the width direction and the counter electrode G2 The details of the ultrasonic intensity measurement position G3 will be explained below with reference to Figures 48 to 51. Figures 48 to 51 are top views of the substrate G1 and counter electrode G2 in the continuous plating apparatus shown in Figure 46. The vertical direction in Figures 48 to 51 is the Z direction, i.e., the width direction of the substrate G1. The horizontal direction in Figures 48 to 51 is the X direction.

[0456] In the continuous plating apparatus shown in Figure 48, both the substrate G1 and the counter electrode G2 are flat and are arranged parallel to each other. The distance D between the center surface of the substrate G1 in the width direction and the counter electrode G2 is 10 cm or more. In the continuous plating apparatus shown in Figure 48, the ultrasonic intensity measurement position G3 is located 5 cm away from the center surface of the substrate G1 in the width direction.

[0457] In the continuous plating apparatus shown in Figure 49, both the substrate G1 and the counter electrode G2 are flat and are arranged parallel to each other. The distance D between the center surface of the substrate G1 in the width direction and the counter electrode G2 is less than 10 cm. In the continuous plating apparatus shown in Figure 49, the ultrasonic intensity measurement position G3 is set midway between the center of the substrate G1 in the width direction and the counter electrode G2.

[0458] In the continuous plating apparatus shown in Figure 50, the substrate G1 is curved, while the counter electrode G2 is flat. The substrate G1 and the counter electrode G2 are not parallel. The distance D between the center surface of the substrate G1 in the width direction and the counter electrode G2 is 10 cm or more. In the continuous plating apparatus shown in Figure 50, the ultrasonic intensity measurement position G3 is set 5 cm away from the center surface of the substrate G1 in the width direction.

[0459] In the continuous plating apparatus shown in Figure 51, the substrate G1 is curved, while the counter electrode G2 is flat. The substrate G1 and the counter electrode G2 are not parallel. The distance D between the center surface of the substrate G1 in the width direction and the counter electrode G2 is less than 10 cm. In the continuous plating apparatus shown in Figure 51, the ultrasonic intensity measurement position G3 is set to a point midway between the center of the substrate G1 in the width direction and the counter electrode G2.

[0460] When the ultrasonic intensity is less than 0.20 kPa / kHz, local agitation around the substrate is unlikely to occur, and it is thought that the diffusion layer that creates the concentration gradient cannot be sufficiently broken down.

[0461] Note that Zn 2+ From the perspective of reducing the concentration of radioactive materials, there is no upper limit to the intensity of the ultrasound. However, if the intensity of the ultrasound exceeds 80 kPa / kHz, its effect may saturate, potentially causing unnecessary equipment load and deterioration of the working environment. Therefore, the intensity of the ultrasound should be kept below 80 kPa / kHz.

[0462] The ultrasonic intensity may be 0.40 kPa / kHz or higher, 1.2 kPa / kHz or higher, or 4.0 kPa / kHz or higher. The ultrasonic intensity may also be 40 kPa / kHz or lower, 20 kPa / kHz or lower, or 10 kPa / kHz or lower.

[0463] In order to keep the ultrasonic intensity at ultrasonic intensity measurement position G3 within the above range, the plating apparatus should be configured to satisfy, for example, the following two requirements. (Requirement 1) The ultrasonic oscillating means G7 are arranged on both sides in the width direction of the base material G1. (Requirement 2) The output of the ultrasonic oscillator G7 should be 800 W / m 3 That concludes this section. (Requirement 3) The distance between the ultrasonic oscillating means G7 and the closest ultrasonic oscillating means G7 facing it across the substrate G1 shall be 500 mm or more and 2000 mm or less.

[0464] For example, as shown in Figure 47, the ultrasonic oscillating means G7 are installed on both sides of the substrate G1 in the width direction (i.e., the Z direction). The output of all ultrasonic oscillating means G7 is set to the range described above. In addition, the distance between the upper left ultrasonic oscillating means and the upper right ultrasonic oscillating means in Figure 47 is set to the range described above. Furthermore, the distance between the lower left ultrasonic oscillating means and the lower right ultrasonic oscillating means in Figure 47 is set to the range described above. This makes it possible to set the ultrasonic intensity at the ultrasonic intensity measurement position G3 to the range described above.

[0465] As long as the above requirements are met, the conditions for the electroplating process are not particularly limited. The method for manufacturing a zinc-plated member according to this embodiment physically destroys the diffusion layer that creates a concentration gradient. Therefore, there are no particular restrictions on the components of the electroplated zinc bath and other plating conditions, and they can be broadly selected according to the purpose. A more preferred example of the electroplating process is described below.

[0466] (Zn 2+ (Relationship between concentration and cathode current density) For example, Zn in an electroplated zinc bath 2+ Concentration C (mol / L) and the cathode current density i (A / dm²) of the electroplating process. 2 ) and may also be values ​​that satisfy equation G1. Formula G1 100C≦i≦300C+60 Cathode current density i(A / dm²) in electroplating process 2By setting the cathode current density (i) to 100C or higher, the efficiency of the electroplating process can be ensured. 2 By setting the temperature to 300C+60 or lower, the stability of the electroplating process can be ensured.

[0467] Within the limits that do not compromise economic efficiency, the cathode current density i(A / dm) of the electroplating process is... 2 A lower value for the cathode current density i(A / dm²) of the electroplating process is preferable. 2 ) may also be a value that satisfies equation G2. Formula G2 100C ≦i≦200C+30

[0468] (Types of metal salts) The zinc salt contained in the electroplated zinc bath is preferably zinc sulfate. By using zinc sulfate, the quality of the zinc plating film can be further improved.

[0469] The electroplating bath may contain salts of metals other than zinc. This allows for the formation of a zinc alloy plating film. In this case, it is preferable that the concentration of all metal ions in the electroplating bath be within the range of 0.10 mol / L to 0.80 mol / L. Furthermore, in the electroplating bath, the proportion of Zn in the molar amount of all metal ions is... 2+ It is preferable that the molar proportion of is greater than 50%, 60% or more, 70% or more, 80% or more, 90% or more, or 98% or more.

[0470] (Temperature of the electrogalvanizing bath) The temperature of the electrogalvanizing bath is preferably between 30°C and 70°C. Maintaining a temperature of 30°C or higher ensures the efficiency of the electrogalvanizing process. Furthermore, maintaining a temperature of 70°C or lower suppresses concentration fluctuations due to evaporation of the electrogalvanizing bath.

[0471] (Plating adhesion amount) The amount of plating deposited in the electroplating process is 10 g / m².2 More than 50g / m 2 The following is preferable: Plating adhesion amount of 10 g / m 2 By doing so, the corrosion resistance and workability required for various components such as electrical equipment, office equipment, and steel furniture can be ensured. Plating adhesion amount: 50g / m² 2 By doing the following, the occurrence of warping in the zinc-plated member can be suppressed.

[0472] (base material) The type of substrate is not particularly limited, and any material capable of forming electroplating can be used as a substrate. Examples of substrates include metal substrates (steel sheets, plated steel sheets, copper sheets, wires, etc.) and conductive substrates (carbon fibers, conductive resins, etc.).

[0473] (Ultrasonic oscillation means) Furthermore, there are no particular limitations on the sound source used to irradiate the ultrasonic waves. For example, a point-shaped sound source may be arranged to irradiate the substrate radially with ultrasonic waves. Alternatively, a sound source may be arranged in a planar manner to cover the substrate and irradiate the entire substrate uniformly with ultrasonic waves. Examples of sound sources include a horn type (the point-shaped sound source described above), a submersible type (a sound source approximately several tens of centimeters square is installed inside the tank), an anode oscillator type (the counter electrode (anode) itself is used as the sound source), and a plating tank type (the planar sound source described above).

[0474] (Analysis of electroplated zinc bath components) Zn contained in the electroplated zinc bath 2+ The concentration of C can be measured by ICP emission spectrometry. After creating a calibration curve using elemental standard solutions of known concentrations, quantitative analysis is performed by measuring the electro-zinc plating solution.

[0475] The electroplating apparatus according to this embodiment comprises an electroplating tank G5 configured to accommodate an electroplating bath G4 containing zinc salts, an ultrasonic oscillating means G7 configured to emit ultrasonic waves G8 inside the electroplating tank G5, a substrate support means configured to support a substrate G1 in a substrate placement area, and a counter electrode G2, wherein the electroplating bath G4 contains Zn 2+The concentration C (mol / L) is between 0.10 mol / L and 0.80 mol / L, the frequency of the ultrasonic waves G8 emitted by the ultrasonic wave oscil...

Claims

[Claim 1] The process includes a step of electroplating a substrate using a plating bath containing additives, In the electroplating process described above, ultrasonic waves are irradiated onto the substrate, The additive comprises either or both a water-soluble, aliphatic monohydric alcohol, or a water-soluble, aliphatic carboxylic acid. A method for manufacturing electroplated components.

Images