US20070199827A1 - Method for electroplating with tin-zinc alloy - Google Patents

Method for electroplating with tin-zinc alloy Download PDF

Info

Publication number
US20070199827A1
US20070199827A1 US11/704,805 US70480507A US2007199827A1 US 20070199827 A1 US20070199827 A1 US 20070199827A1 US 70480507 A US70480507 A US 70480507A US 2007199827 A1 US2007199827 A1 US 2007199827A1
Authority
US
United States
Prior art keywords
tin
plating bath
zinc alloy
acid
zinc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/704,805
Inventor
Satoshi Yuasa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dipsol Chemicals Co Ltd
Original Assignee
Dipsol Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dipsol Chemicals Co Ltd filed Critical Dipsol Chemicals Co Ltd
Assigned to DIPSOL CHEMICALS CO., LTD. reassignment DIPSOL CHEMICALS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YUASA, SATOSHI
Publication of US20070199827A1 publication Critical patent/US20070199827A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/10—Agitating of electrolytes; Moving of racks
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating

Definitions

  • the present invention relates to a method for electroplating with a tin-zinc alloy.
  • the systems that are still used include a rack system (maximum current density about 3 A/dm 2 ) in which the articles to be plated are treated upon mounting them on a jig and a barrel system (maximum current density 1 A/dm 2 ) in which the articles to be plated are treated in a barrel.
  • the present invention is based on a discovery that electroplating with a tin-zinc alloy can be carried out within a short interval by using a specific tin-zinc alloy plating bath at a plating bath temperature and plating bath stirring rate above the predetermined values.
  • the present invention provides a method for electroplating with a tin-zinc alloy that is performed under the following conditions: a plating bath temperature of 30 to 90° C., plating bath stirring rate of 5 to 300 m/min, and cathode current density of 5 to 200 A/dm 2 .
  • electroplating with a tin-lead alloy can be carried out within a short interval by using a specific tin-zinc alloy plating bath at a plating bath temperature and plating bath stirring rate above the predetermined values.
  • the temperature of the plating bath in the electroplating method in accordance with the present invention is 30 to 90° C., preferably 40 to 60° C., and the stirring rate of the plating solution is 5 to 300 m/min, preferably 10 to 100 m/min.
  • Stirring of the plating solution is specifically carried out by a plating apparatus of a jet flow system in which the solution is circulated with a pump or by a plating apparatus for steel sheets.
  • the plating apparatus can be made from any material, provided it has heat resistance and chemical resistance, and metals such as stainless steel and titanium or polyvinyl chloride, Teflon (registered trade name), and an ABS resin can be used.
  • a device enabling the stirring of the plating solution that is uniform with respect to the entire plated article is preferred from the standpoint of increasing the uniformity of the plated alloy composition and plated film thickness.
  • any plating bath well known to a person skilled in the art can be used as the bath for the tin-zinc alloy electroplating bath employed in the electroplating method in accordance with the present invention, but a plating bath comprising a hydroxycarboxylic acid or a salt thereof is preferred.
  • a compound having one or more hydroxyl groups and one or more carboxyl groups in a molecule is preferred as the hydroxycarboxylic acid.
  • hydroxycarboxylic acids include citric acid, tartaric acid, malic acid, glycolic acid, glyceric acid, lactic acid, ⁇ -hydroxypropionic acid, and gluconic acid.
  • citric acid, tartaric acid, malic acid, and gluconic acid are preferred among them.
  • hydroxycarboxylic acid salts include alkali metal salts (sodium, potassium, lithium salts) alkaline earth metal salts (magnesium, calcium, barium salts, and the like), divalent tin salts, zinc salts, ammonium salts, and organic amine salts (monomethylamine, dimethylamine, trimethylamine, methylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.) of the aforementioned hydroxycarboxylic acids.
  • alkali metal salts sodium, potassium, lithium salts
  • divalent tin salts alkaline earth metal salts (magnesium, calcium, barium salts, and the like
  • organic amine salts monomethylamine, dimethylamine, trimethylamine, methylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.
  • the preferred among them are sodium salts, potassium salts, lithium salts, divalent tin salts, and zinc salts of citric acid, tartaric
  • hydroxycarboxylic acids and salts thereof may be used individually or in a mixture of two or more thereof, and the concentration thereof in the plating bath is 0.25 to 3 mol/L, preferably 0.3 to 1.5 mol/L.
  • concentration thereof in the plating bath is 0.25 to 3 mol/L, preferably 0.3 to 1.5 mol/L.
  • the hydroxycarboxylic acid which is a counterion of the metal ions also constitutes part of the aforementioned concentration.
  • the pH of the plating bath comprising the hydroxycarboxylic acid or salt thereof is preferably 2 to 10, more preferably 3 to 9.
  • the pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate, or an acidic compound such as an inorganic acid or organic acid.
  • suitable compounds include alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water and acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
  • a plating bath comprising at least one species selected from the group consisting of amphoteric surfactants and water-soluble compounds obtained by a reaction of an aliphatic amine, an organic acid ester, and phthalic anhydride also can be utilized as the tin-zinc alloy electroplating bath used in the electroplating method in accordance with the present invention. More specifically, for example, a water-soluble compound can be used that is obtained by reacting 0.2 to 3 moles of an organic acid ester per 1 mole of an aliphatic amine for 10 to 60 min. at a temperature of 50 to 99° C. and then reacting phthalic anhydride with the obtained reactive product at a weight ratio of 0.1 to 1:1 for 30 to 180 min at a temperature of 60 to 130° C.
  • amphoteric surfactants include imidazoline-type, betaine-type, alanine-type, glycine-type, and amide-type surfactants.
  • aliphatic amines suitable for the reaction of the water-soluble compound include ethylenediamine, triethylenetetramine, isobutylamine, 3-methoxypropylamine, iminobispropylamine, diethylamine, hexamethylenetetramine, and dimethylaminopropylamine.
  • suitable organic acid esters include dimethyl manolate, diethyl succinate, diethyl maleate, dimethyl fumarate, diethyl tartarate, dimethyl malate, and diethyl tartronate.
  • These water-soluble compounds and amphoteric surfactants may be used individually or in a mixture of two or more thereof, and the content thereof in the plating bath is 0.00.1 to 50 g/L, preferably 0.01 to 30 g/L.
  • the pH of the plating bath comprising at least one species selected from the group consisting of amphoteric surfactants and water-soluble compounds obtained by a reaction of an aliphatic amine, an organic acid ester, and phthalic anhydride is preferably 2 to 10, more preferably 3 to 9.
  • the pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate, or an acidic compound such as an inorganic acid or organic acid.
  • suitable compounds include alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water and acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
  • alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water
  • acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
  • a plating bath comprising at least one species selected from the group consisting of tertiary amine compounds and quaternary amine compounds also can be used as the tin-zinc alloy electroplating bath employed in the electroplating method in accordance with the present invention.
  • tertiary amine compounds include imidazole compounds and aliphatic amine compounds
  • examples of quaternary amine compounds include reaction products of tertiary amine compounds and halogenated alkyls.
  • tertiary amine compounds include imidazole compounds, such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, 1-ethyl-2-methylimidazole, 1-oxymethylimidazole, 1-vinylimidazole, and 1, 5-dimethylimidazole, and aliphatic amines such as monoethanolamine, diethanolamine, triethanolamine, dimethylamine, ethylenediamine, diethylenetriamine, iminobispropylamine, triethylenetetramine, tetraethylenepentamine, and N,N-bis-(3-aminopropyl)ethylenediamine.
  • imidazole compounds such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, 1-ethyl-2-methylimidazole, 1-oxymethylimidazole, 1-vinylimidazole, and 1, 5-dimethylimidazole
  • tertiary amine compounds and quaternary amine compounds may be used individually or in a mixture of two or more thereof, and the content thereof in the plating bath is 0.1 to 30 g/L, preferably 0.2 to 20 g/L.
  • the pH of the plating bath comprising at least one species selected from the group consisting of tertiary amine compounds and quaternary amine compounds is preferably 10 to 14, more preferably 12 to 14.
  • the pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate.
  • suitable compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water.
  • the plating bath used in the electroplating method in accordance with the present invention can additionally contain at least one surfactant selected from the group consisting of a nonionic surfactant, anionic surfactant, and cationic surfactant. Introducing such surfactants into the plating bath enables denser precipitation at a high current density and, therefore, makes it possible to implement more smoothly the electroplating method in accordance with the present invention.
  • the divalent tin ion concentration is 1 to 100 g/L, preferably 5 to 80 g/L, and the zinc ion concentration is 0.2 to 80 g/L, preferably 1 to 50 g/L.
  • sources of such metal ions include various metal hydroxides, oxides, sulfates, chlorides, sulfamates, pyrophosphates, hydroxycarboxylates, sulfonates, and amino acid salts.
  • Various metal oxides, sulfates, chlorides, and hydroxides are preferred. Specific examples of hydroxycarboxylic acid salts are presented hereinabove.
  • sulfonates include alkanesulfonates, alkanolsulfonates, and phenolsulfonates.
  • alkanesulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, isopropanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, and hexanesulfonic acid.
  • alkanolsulfonic acids include 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, and 2-hydroxybutanesulfonic acid.
  • phenolsulfonic acids include phenolsulfonic acid, cresolsulfonic acid, and dimethylphenolsulfonic acid.
  • amino acids include glycine, glutamic acid, and alanine.
  • alkali metal salts sodium, potassium, lithium salts
  • alkaline earth metal salts magnesium, calcium, barium salts
  • ammonium salts and organic amine salts (monomethylamine, dimethylamine, trimethylamine, methylamine, ispropylamine, ethylenediamine, diethylenetriamine, etc.) of sulfuric acid, hydrochloric acid, sulfamic acid, pyrophosphoric acid, sulfonic acid, hydroxides and carbonates
  • sulfuric acid hydrochloric acid, sulfamic acid, pyrophosphoric acid, sulfonic acid, hydroxides and carbonates
  • salts include ammonium sulfate, ammonium chloride, sodium pyrophosphate, monomethyl sulfamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and among these especially preferred are ammonium sulfate, ammonium chloride, potassium hydroxide, and potassium carbonate.
  • the content of these salts is 10 to 300 g/L, preferably 50 to 200 g/L.
  • the plating bath used in the electroplating method in accordance with the present invention can contain water in addition to the above-described components and also can contain additives that have been used as a brightener for tin and zinc.
  • suitable additives include synthetic polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, and the like), ketones (benzalacetone, acetophenone, and the like), aliphatic aldehydes (formalin, acetaldehyde, crotonaldehyde, and the like), aromatic aldehydes (vanillin, salicylaldehyde, orthochlorobenzaldehyde, and the like), reaction products of unsaturated aliphatic aldehydes and amine compounds, sulfur compounds (thiourea, mercaptobenzimidazole, and the like), and also Cu, Ni, Mn, Bi, In, and the like.
  • additives are contained at 0.001 to 50 g/L, preferably 0.005 to 30 g/L.
  • hydroxyphenyl compounds such as catechol, pyrogallol, hydroquinone, sulfosalicylic acid, potassium dihydroxybenzenesulfonate and salts thereof and L-ascorbic acid, sorbitol and the like also can be used as oxidation preventing agents for tin.
  • the articles to be plated by the plating method in accordance with the present invention are metal materials such as Fe, Ni, Cu, or alloys based thereon, and the plating is carried out by using them as cathodes.
  • a carbon electrode and insoluble electrode obtained by plating Pt on a Ti material or tin-zinc alloy can be used as a counter electrode thereof.
  • the concentration of metals in the plating bath that is being used can be maintained by directly dissolving the aforementioned tin and zinc salts in the plating bath or by supplying an aqueous solution in which tin and zinc salts are dissolved into a high concentration.
  • the high-concentration aqueous solution of the metals may contain the above-described hydroxycarboxylic acid or salt thereof and an alkali hydroxide compound.
  • the cathode current density is 5 to 200 A/dm 2 , preferably 10 to 120 A/dm 2 .
  • the film thickness can be within a wide range, but is generally 0.5 to 500 ⁇ m, preferably 2 to 20 ⁇ m.
  • Tin-zinc alloy plating can be performed within a wide range of alloy compositions by changing the ratio of tin ions and zinc ions in the plating bath that is being used.
  • tin-zinc alloy coatings with a zinc content of 3 to 15% can be obtained on electronic components.
  • a tin-zinc alloy coating with a zinc content of 15 to 45% can be obtained.
  • a tin-zinc alloy coating with a zinc content of 50 to 90% can be produced.
  • the article to be plated is subjected to plating after a pretreatment conducted by the usual method. At least one operation selected from immersion degreasing, pickling, electrolytic washing, and activation is performed in the pretreatment process.
  • the film obtained may be washed with water and dried, or can be further coated by a chromating and conversion treatment, or with an inorganic or organic material by the usual method.
  • the present invention will be described below based on embodiments thereof, but the present invention is not limited to the embodiments, and the plating solution temperature, flow rate of the plating solution, and the composition of the plating bath can be freely changed according to the article to be plated.
  • a steel sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 50 m/min.
  • Tin (I) sulfate (as tin) 30 g/L
  • Zinc sulfate (as zinc) 25 g/L
  • Product obtained by reacting 1 mole 10 mL/L of ethylene diamine and 1 mole of dimethyl malonate for 60 mins. at 85° C. and then reacting phthalic anhydride with the obtained product at a weight ratio of 0.5:1 for 90 mins. at 95° C. pH 4 (adjusted with ammonia water)
  • a steel sheet was pretreated, Nymin NAG-1001 manufactured by Nippon Oils & Fats Co., Ltd. was added as a nonionic surfactant at 5 g/L to the plating solution of Embodiment 1, and electroplating was conducted under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 30 m/min.
  • a steel sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 30 m/min.
  • Potassium stannate (as tin) 55 g/L
  • Zinc oxide (as zinc) 5 g/L
  • Potassium hydroxide 80 g/L
  • Potassium carbonate 100 g/L
  • a phosphorus bronze sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 50° C. and a plating bath stirring rate of 60 m/min.
  • Product obtained by reacting 1 mole of 10 mL/L triethylene tetramine and 1.2 mole of diethyl succinate for 40 mins. at 80° C. and then reacting phthalic anhydride with the obtained product at a weight ratio of 0.7:1 for 120 mins. at 90° C.
  • a phosphorus bronze sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 60 m/min.
  • Tin methanesulfonate (as tin) 30 g/L
  • Zinc methanesulfonate (as zinc) 15 g/L
  • Sodium gluconate 150 g/L (0.69 mole/L)
  • Methanesulfonic acid 100 g/L
  • Product obtained by reacting 1 mole of 8 mL/L ethylene diamine and 1 mole of dimethyl maleate for 60 mins. at 90° C. and then reacting phthalic anhydride with the obtained product at a weight ratio of 0.5:1 for 150 mins. at 110° C.
  • a steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 1 under the conditions of a plating bath temperature of 23° C. and a plating bath stirring rate of 50 m/min.
  • a steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 1 under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 2 m/min.
  • a steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 3 under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 3 m/min.
  • Example 1 Example 2
  • Example 3 Plated Film Plated Film Plated Film precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness state (wt. %) time ( ⁇ m) state (wt. %) time ( ⁇ m) state (wt. %) time ( ⁇ m) state (wt.
  • Example 5 Plated Film Plated Film precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness state (wt. %) time ( ⁇ m) state (wt. %) time ( ⁇ m) 10 A/dm 2 ⁇ 88/12 120 9.4 ⁇ 85/15 120 9.0 20 A/dm 2 ⁇ 90/10 60 9.2 ⁇ 80/20 60 8.5 30 A/dm 2 ⁇ 90/10 40 9.2 ⁇ 80/20 40 8.5 40 A/dm 2 ⁇ 90/10 30 9.2 ⁇ 80/20 30 8.0 50 A/dm 2 ⁇ 90/10 25 9.0 ⁇ 80/20 25 7.9 60 A/dm 2 ⁇ 90/10 20 8.6 ⁇ 85/15 20 7.6 70 A/dm 2 ⁇ 91/9 17 7.2 ⁇ 84/16 17 7.3 80 A/dm 2 ⁇ 91/9 15 6.4 ⁇ 88/12 15 6.0 90 A/dm 2 x — 13 — ⁇ 90/10 13 5.4 100 A/dm 2 x — 12 —

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The object of the present invention is to provide an electroplating method that enables the high-speed treatment of articles to be plated that was difficult to achieve with the conventional tin-zinc electroplating. The present invention provides a method for electroplating with a tin-zinc alloy that is performed under the following conditions: plating bath temperature 30 to 90° C., plating bath stirring rate 5 to 300 m/min, and cathode current density 5 to 200 A/dm2. Preferably, in the tin-zinc alloy plating bath, the divalent tin ion concentration is 1 to 100 g/L and the zinc ion concentration is 0.2 to 80 g/L.

Description

    TECHNICAL FIELD
  • The present invention relates to a method for electroplating with a tin-zinc alloy.
    • BACKGROUND ART
  • Because electroplating with tin-zinc alloys produces coatings that excel in corrosion resistance, processability and solderability, this method has attracted attention and been widely applied to automobile parts and electronic components. Alkali cyan baths, pyrophosphoric acid baths, borofluoride baths, sulfonic acid baths and carboxylic acid baths have been suggested for use as plating baths in electroplating with tin-zinc alloys, and some of these baths have been practically used.
  • With the conventional methods using such electroplating baths, when the treatment is carried out at a high current density to shorten the treatment time, coarse precipitates, burns, and scorches appear in the plated layer and characteristics of the tin-zinc alloy coating are degraded. As a result, the practical use of high-speed electroplating is made difficult. The systems that are still used include a rack system (maximum current density about 3 A/dm2) in which the articles to be plated are treated upon mounting them on a jig and a barrel system (maximum current density 1 A/dm2) in which the articles to be plated are treated in a barrel. Further, when plating with a tin-zinc alloy is performed within a short interval, a method by which tin and zinc are electroplated separately and then alloyed and a melt plating method using a molten salt of a tin-zinc alloy are used.
    • DISCLOSURE OF THE INVENTION Problems That the Invention is to Solve
  • It is an object of the present invention to provide an electroplating method enabling the treatment of articles to be plated within a short interval that was difficult to achieve with the conventional methods for electroplating with tin-zinc alloys.
    • Means for the Solution of the Problems
  • The present invention is based on a discovery that electroplating with a tin-zinc alloy can be carried out within a short interval by using a specific tin-zinc alloy plating bath at a plating bath temperature and plating bath stirring rate above the predetermined values.
  • Thus, the present invention provides a method for electroplating with a tin-zinc alloy that is performed under the following conditions: a plating bath temperature of 30 to 90° C., plating bath stirring rate of 5 to 300 m/min, and cathode current density of 5 to 200 A/dm2.
    • Effect of the Invention
  • With the present invention, electroplating with a tin-lead alloy can be carried out within a short interval by using a specific tin-zinc alloy plating bath at a plating bath temperature and plating bath stirring rate above the predetermined values.
    • BEST MODE FOR CARRYING OUT THE INVENTION
  • The temperature of the plating bath in the electroplating method in accordance with the present invention is 30 to 90° C., preferably 40 to 60° C., and the stirring rate of the plating solution is 5 to 300 m/min, preferably 10 to 100 m/min. Stirring of the plating solution is specifically carried out by a plating apparatus of a jet flow system in which the solution is circulated with a pump or by a plating apparatus for steel sheets. The plating apparatus can be made from any material, provided it has heat resistance and chemical resistance, and metals such as stainless steel and titanium or polyvinyl chloride, Teflon (registered trade name), and an ABS resin can be used. Furthermore, a device enabling the stirring of the plating solution that is uniform with respect to the entire plated article is preferred from the standpoint of increasing the uniformity of the plated alloy composition and plated film thickness.
  • Any plating bath well known to a person skilled in the art can be used as the bath for the tin-zinc alloy electroplating bath employed in the electroplating method in accordance with the present invention, but a plating bath comprising a hydroxycarboxylic acid or a salt thereof is preferred.
  • A compound having one or more hydroxyl groups and one or more carboxyl groups in a molecule is preferred as the hydroxycarboxylic acid. Specific examples of such hydroxycarboxylic acids include citric acid, tartaric acid, malic acid, glycolic acid, glyceric acid, lactic acid, β-hydroxypropionic acid, and gluconic acid. The preferred among them are citric acid, tartaric acid, malic acid, and gluconic acid. Specific examples of hydroxycarboxylic acid salts include alkali metal salts (sodium, potassium, lithium salts) alkaline earth metal salts (magnesium, calcium, barium salts, and the like), divalent tin salts, zinc salts, ammonium salts, and organic amine salts (monomethylamine, dimethylamine, trimethylamine, methylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.) of the aforementioned hydroxycarboxylic acids. The preferred among them are sodium salts, potassium salts, lithium salts, divalent tin salts, and zinc salts of citric acid, tartaric acid, malic acid, and gluconic acid. These hydroxycarboxylic acids and salts thereof may be used individually or in a mixture of two or more thereof, and the concentration thereof in the plating bath is 0.25 to 3 mol/L, preferably 0.3 to 1.5 mol/L. When a hydroxycarboxylic acid salt is used as a divalent tin salt and/or zinc salt, the hydroxycarboxylic acid which is a counterion of the metal ions also constitutes part of the aforementioned concentration.
  • The pH of the plating bath comprising the hydroxycarboxylic acid or salt thereof is preferably 2 to 10, more preferably 3 to 9. The pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate, or an acidic compound such as an inorganic acid or organic acid. Specific examples of suitable compounds include alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water and acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
  • A plating bath comprising at least one species selected from the group consisting of amphoteric surfactants and water-soluble compounds obtained by a reaction of an aliphatic amine, an organic acid ester, and phthalic anhydride also can be utilized as the tin-zinc alloy electroplating bath used in the electroplating method in accordance with the present invention. More specifically, for example, a water-soluble compound can be used that is obtained by reacting 0.2 to 3 moles of an organic acid ester per 1 mole of an aliphatic amine for 10 to 60 min. at a temperature of 50 to 99° C. and then reacting phthalic anhydride with the obtained reactive product at a weight ratio of 0.1 to 1:1 for 30 to 180 min at a temperature of 60 to 130° C. Examples of suitable amphoteric surfactants include imidazoline-type, betaine-type, alanine-type, glycine-type, and amide-type surfactants. Examples of aliphatic amines suitable for the reaction of the water-soluble compound include ethylenediamine, triethylenetetramine, isobutylamine, 3-methoxypropylamine, iminobispropylamine, diethylamine, hexamethylenetetramine, and dimethylaminopropylamine. Examples of suitable organic acid esters include dimethyl manolate, diethyl succinate, diethyl maleate, dimethyl fumarate, diethyl tartarate, dimethyl malate, and diethyl tartronate. These water-soluble compounds and amphoteric surfactants may be used individually or in a mixture of two or more thereof, and the content thereof in the plating bath is 0.00.1 to 50 g/L, preferably 0.01 to 30 g/L.
  • The pH of the plating bath comprising at least one species selected from the group consisting of amphoteric surfactants and water-soluble compounds obtained by a reaction of an aliphatic amine, an organic acid ester, and phthalic anhydride is preferably 2 to 10, more preferably 3 to 9. The pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate, or an acidic compound such as an inorganic acid or organic acid. Specific examples of suitable compounds include alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water and acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
  • Further, a plating bath comprising at least one species selected from the group consisting of tertiary amine compounds and quaternary amine compounds also can be used as the tin-zinc alloy electroplating bath employed in the electroplating method in accordance with the present invention. Examples of tertiary amine compounds include imidazole compounds and aliphatic amine compounds, and examples of quaternary amine compounds include reaction products of tertiary amine compounds and halogenated alkyls. Specific examples of tertiary amine compounds include imidazole compounds, such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, 1-ethyl-2-methylimidazole, 1-oxymethylimidazole, 1-vinylimidazole, and 1, 5-dimethylimidazole, and aliphatic amines such as monoethanolamine, diethanolamine, triethanolamine, dimethylamine, ethylenediamine, diethylenetriamine, iminobispropylamine, triethylenetetramine, tetraethylenepentamine, and N,N-bis-(3-aminopropyl)ethylenediamine. Further, specific examples of halogenated alkyls that can be reacted with tertiary amine compounds include monochloroacetic acid, benzyl chloride, chloroacetamide, 3-aminobenzylchloride, allyl chloride, dichlorethane, monochloropropane, dichloroglycerin, ethylene chlorohydrine, and epichlorohydrine. These tertiary amine compounds and quaternary amine compounds may be used individually or in a mixture of two or more thereof, and the content thereof in the plating bath is 0.1 to 30 g/L, preferably 0.2 to 20 g/L.
  • The pH of the plating bath comprising at least one species selected from the group consisting of tertiary amine compounds and quaternary amine compounds is preferably 10 to 14, more preferably 12 to 14. The pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate. Specific examples of suitable compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water.
  • The plating bath used in the electroplating method in accordance with the present invention can additionally contain at least one surfactant selected from the group consisting of a nonionic surfactant, anionic surfactant, and cationic surfactant. Introducing such surfactants into the plating bath enables denser precipitation at a high current density and, therefore, makes it possible to implement more smoothly the electroplating method in accordance with the present invention.
  • In the plating bath used in the plating method in accordance with the present invention, the divalent tin ion concentration is 1 to 100 g/L, preferably 5 to 80 g/L, and the zinc ion concentration is 0.2 to 80 g/L, preferably 1 to 50 g/L. Examples of sources of such metal ions include various metal hydroxides, oxides, sulfates, chlorides, sulfamates, pyrophosphates, hydroxycarboxylates, sulfonates, and amino acid salts. Various metal oxides, sulfates, chlorides, and hydroxides are preferred. Specific examples of hydroxycarboxylic acid salts are presented hereinabove. Specific examples of sulfonates include alkanesulfonates, alkanolsulfonates, and phenolsulfonates. Specific examples of alkanesulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, isopropanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, and hexanesulfonic acid. Specific examples of alkanolsulfonic acids include 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, and 2-hydroxybutanesulfonic acid. Specific examples of phenolsulfonic acids include phenolsulfonic acid, cresolsulfonic acid, and dimethylphenolsulfonic acid. Specific examples of amino acids include glycine, glutamic acid, and alanine.
  • In order to improve electric conduction during plating, alkali metal salts (sodium, potassium, lithium salts), alkaline earth metal salts (magnesium, calcium, barium salts), ammonium salts, and organic amine salts (monomethylamine, dimethylamine, trimethylamine, methylamine, ispropylamine, ethylenediamine, diethylenetriamine, etc.) of sulfuric acid, hydrochloric acid, sulfamic acid, pyrophosphoric acid, sulfonic acid, hydroxides and carbonates can be introduced in the plating bath used in the electroplating method in accordance with the present invention. Specific examples of such salts include ammonium sulfate, ammonium chloride, sodium pyrophosphate, monomethyl sulfamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and among these especially preferred are ammonium sulfate, ammonium chloride, potassium hydroxide, and potassium carbonate. The content of these salts is 10 to 300 g/L, preferably 50 to 200 g/L.
  • The plating bath used in the electroplating method in accordance with the present invention can contain water in addition to the above-described components and also can contain additives that have been used as a brightener for tin and zinc. Examples of suitable additives include synthetic polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, and the like), ketones (benzalacetone, acetophenone, and the like), aliphatic aldehydes (formalin, acetaldehyde, crotonaldehyde, and the like), aromatic aldehydes (vanillin, salicylaldehyde, orthochlorobenzaldehyde, and the like), reaction products of unsaturated aliphatic aldehydes and amine compounds, sulfur compounds (thiourea, mercaptobenzimidazole, and the like), and also Cu, Ni, Mn, Bi, In, and the like. These additives are contained at 0.001 to 50 g/L, preferably 0.005 to 30 g/L. Furthermore, hydroxyphenyl compounds such as catechol, pyrogallol, hydroquinone, sulfosalicylic acid, potassium dihydroxybenzenesulfonate and salts thereof and L-ascorbic acid, sorbitol and the like also can be used as oxidation preventing agents for tin.
  • The articles to be plated by the plating method in accordance with the present invention are metal materials such as Fe, Ni, Cu, or alloys based thereon, and the plating is carried out by using them as cathodes. A carbon electrode and insoluble electrode obtained by plating Pt on a Ti material or tin-zinc alloy can be used as a counter electrode thereof. When an insoluble anode is used, the concentration of metals in the plating bath that is being used can be maintained by directly dissolving the aforementioned tin and zinc salts in the plating bath or by supplying an aqueous solution in which tin and zinc salts are dissolved into a high concentration. The high-concentration aqueous solution of the metals may contain the above-described hydroxycarboxylic acid or salt thereof and an alkali hydroxide compound.
  • The cathode current density is 5 to 200 A/dm2, preferably 10 to 120 A/dm2. The film thickness can be within a wide range, but is generally 0.5 to 500 μm, preferably 2 to 20 μm.
  • Tin-zinc alloy plating can be performed within a wide range of alloy compositions by changing the ratio of tin ions and zinc ions in the plating bath that is being used. For example, tin-zinc alloy coatings with a zinc content of 3 to 15% can be obtained on electronic components. When resistance to salt water or corrosion resistance is to be improved, a tin-zinc alloy coating with a zinc content of 15 to 45% can be obtained. Furthermore, when a film with high corrosion resistance that is to be exposed to the atmosphere is obtained, a tin-zinc alloy coating with a zinc content of 50 to 90% can be produced.
  • With the plating method in accordance with the present invention, the article to be plated is subjected to plating after a pretreatment conducted by the usual method. At least one operation selected from immersion degreasing, pickling, electrolytic washing, and activation is performed in the pretreatment process. After the plating, the film obtained may be washed with water and dried, or can be further coated by a chromating and conversion treatment, or with an inorganic or organic material by the usual method.
  • The present invention will be described below based on embodiments thereof, but the present invention is not limited to the embodiments, and the plating solution temperature, flow rate of the plating solution, and the composition of the plating bath can be freely changed according to the article to be plated.
    • EXAMPLES Example 1
  • A steel sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 50 m/min.
    Tin (I) sulfate (as tin) 30 g/L
    Zinc sulfate (as zinc) 25 g/L
    Citric acid 150 g/L
    (0.71 mole/L)
    Ammonium sulfate 100 g/L
    Product obtained by reacting 1 mole 10 mL/L
    of ethylene diamine and 1 mole of
    dimethyl malonate for 60 mins. at 85° C.
    and then reacting phthalic anhydride
    with the obtained product at a weight
    ratio of 0.5:1 for 90 mins. at 95° C.
    pH 4 (adjusted with ammonia water)
    • Example 2
  • A steel sheet was pretreated, Nymin NAG-1001 manufactured by Nippon Oils & Fats Co., Ltd. was added as a nonionic surfactant at 5 g/L to the plating solution of Embodiment 1, and electroplating was conducted under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 30 m/min.
    • Example 3
  • A steel sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 30 m/min.
    Potassium stannate (as tin) 55 g/L
    Zinc oxide (as zinc) 5 g/L
    Potassium hydroxide 80 g/L
    Potassium carbonate 100 g/L
    Product obtained by reacting 1 mole of 1 g/L
    1-methyl imidazole and 1 mole of
    benzyl chloride for 180 mins. at 85° C.
    Product obtained by reacting 1 mole of 1 g/L
    diethylene triamine and 1 mole of
    ethylene chlorhydrine for 90 mins. at 100° C.
    pH 14
    • Example 4
  • A phosphorus bronze sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 50° C. and a plating bath stirring rate of 60 m/min.
    Tin (I) sulfate (as tin) 20 g/L
    Zinc sulfate (as zinc) 7 g/L
    Citric acid 120 g/L
    (0.57 mole/L)
    Ammonium sulfate 80 g/L
    Product obtained by reacting 1 mole of 10 mL/L
    triethylene tetramine and 1.2 mole of
    diethyl succinate for 40 mins. at 80° C.
    and then reacting phthalic anhydride
    with the obtained product at a weight
    ratio of 0.7:1 for 120 mins. at 90° C.
    Coconut oil alkyl-N-carboxyethyl-N- 5 g/L
    hydroxyethyl imidazolium betaine sodium
    pH 5.5 (adjusted with sodium hydroxide)
    • Example 5
  • A phosphorus bronze sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 60 m/min.
    Tin methanesulfonate (as tin) 30 g/L
    Zinc methanesulfonate (as zinc) 15 g/L
    Sodium gluconate 150 g/L
    (0.69 mole/L)
    Methanesulfonic acid 100 g/L
    Product obtained by reacting 1 mole of 8 mL/L
    ethylene diamine and 1 mole of
    dimethyl maleate for 60 mins. at 90° C.
    and then reacting phthalic anhydride
    with the obtained product at a weight
    ratio of 0.5:1 for 150 mins. at 110° C.
    Salicylaldehyde 0.05 g/L
    pH 6.2 (adjusted with sodium hydroxide)
    • Comparative Example 1
  • A steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 1 under the conditions of a plating bath temperature of 23° C. and a plating bath stirring rate of 50 m/min.
    • Comparative Example 2
  • A steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 1 under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 2 m/min.
    • Comparative Example 3
  • A steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 3 under the conditions of a plating bath temperature of 60° C. and a plating bath stirring rate of 3 m/min.
  • The plated precipitate state, alloy composition (wt.%) of the precipitated film, treatment time, and film thickness in Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Tables 1 to 2.
    TABLE 1
    Example 1 Example 2 Example 3
    Plated Film Plated Film Plated Film
    precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness
    state (wt. %) time (μm) state (wt. %) time (μm) state (wt. %) time (μm)
    10 A/dm2 0 70/30 120  8.8 ∘ 70/30 120  8.8 ∘ 45/55 240  7.0
    20 A/dm2 ∘ 70/30 60 8.8 ∘ 70/30 60 8.8 ∘ 45/55 120  6.5
    30 A/dm2 ∘ 70/30 40 8.8 ∘ 70/30 40 8.8 ∘ 40/60 80 4.9
    40 A/dm2 ∘ 72/28 30 8.9 ∘ 70/30 30 8.8 Δ 40/60 60 3.5
    50 A/dm2 ∘ 72/28 25 8.9 ∘ 70/30 25 8.7 x — 48 —
    60 A/dm2 ∘ 75/25 20 8.0 ∘ 75/25 20 8.1 x — 40 —
    70 A/dm2 ∘ 75/25 17 7.8 ∘ 75/25 17 8.0 x — 34 —
    80 A/dm2 ∘ 75/25 15 7.6 ∘ 75/25 15 7.8 x — 30 —
    90 A/dm2 Δ 85/15 13 7.4 ∘ 82/18 13 7.6 x — 27 —
    100 A/dm2  Δ 85/15 12 6.9 ∘ 82/18 12 7.2 x — 24 —

    The treatment time is measured in seconds in all the above cases.

    ∘: dense and smooth precipitate

    Δ: local occurrence of coarse precipitate

    x: powder-like coarse precipitate
  • TABLE 2
    Example 4 Example 5
    Plated Film Plated Film
    precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness
    state (wt. %) time (μm) state (wt. %) time (μm)
    10 A/dm2 ∘ 88/12 120  9.4 ∘ 85/15 120  9.0
    20 A/dm2 ∘ 90/10 60 9.2 ∘ 80/20 60 8.5
    30 A/dm2 ∘ 90/10 40 9.2 ∘ 80/20 40 8.5
    40 A/dm2 ∘ 90/10 30 9.2 ∘ 80/20 30 8.0
    50 A/dm2 ∘ 90/10 25 9.0 ∘ 80/20 25 7.9
    60 A/dm2 ∘ 90/10 20 8.6 ∘ 85/15 20 7.6
    70 A/dm2 Δ 91/9  17 7.2 ∘ 84/16 17 7.3
    80 A/dm2 Δ 91/9  15 6.4 ∘ 88/12 15 6.0
    90 A/dm2 x — 13 — ∘ 90/10 13 5.4
    100 A/dm2  x — 12 — Δ 95/5 12 4.2

    The treatment time is measured in seconds in all the above cases.

    ∘: dense and smooth precipitate

    Δ: local occurrence of coarse precipitate

    x: powder-like coarse precipitate
  • TABLE 3
    Comparative Example 1 Comparative Example 2 Comparative Example 3
    Plated Film Plated Film Plated Film
    precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness precipitate Sn/Zn Treatment thickness
    state (wt. %) time (μm) state (wt. %) time (μm) state (wt. %) time (μm)
    10 A/dm2 ∘ 48/52 120  5.6 ∘ 66/34 120  4.2 Δ 45/55 120  3.2
    20 A/dm2 ∘ 52/48 60 4.2 x — 60 — x — 60 —
    30 A/dm2 Δ 52/48 40 2.9 x — 40 — x — 40 —
    40 A/dm2 x — 30 — x — 30 — x — 30 —
    50 A/dm2 x — 25 — x — 25 — x — 25 —
    60 A/dm2 x — 20 — x — 20 — x — 20 —
    70 A/dm2 x — 17 — x — 17 — x — 17 —
    80 A/dm2 x — 15 — x — 15 — x — 15 —
    90 A/dm2 x — 13 — x — 13 — x — 13 —
    100 A/dm2  x — 12 — x — 12 — x — 12 —

    The treatment time is measured in seconds in all the above cases.

    ∘: dense and smooth precipitate

    ≢: local occurrence of coarse precipitate

    x: powder-like coarse precipitate

Claims (6)

1. A method for electroplating with a tin-zinc alloy performed under the following conditions:
plating bath temperature: 30 to 90° C.;
plating bath stirring rate: 5 to 300 m/min; and
cathode current density: 5 to 200 A/dm2.
2. The method according to claim 1, wherein the tin-zinc alloy plating bath comprises a hydroxycarboxylic acid or a salt thereof, and a pH of the tin-zinc alloy plating bath is 2 to 10.
3. The method according to claim 1, wherein the tin-zinc alloy plating bath comprises at least one species selected from the group consisting of amphoteric surfactants and water-soluble compounds obtained by a reaction of an aliphatic amine, an organic acid ester, and a phthalic anhydride, and a pH of the tin-zinc alloy plating bath is 2 to 10.
4. The method according to claim 1, wherein the tin-zinc alloy plating bath comprises at least one species selected from the group consisting of tertiary amine compounds and quaternary amine compounds, and a pH of the tin-zinc alloy plating bath is 10 to 14.
5. The method according to claim 1, wherein the tin-zinc alloy plating bath comprises at least one species selected from the group consisting of nonionic surfactants, anionic surfactants, and cationic surfactants.
6. The method according to claim 1, wherein in the tin-zinc alloy plating bath, the divalent tin ion concentration is 1 to 100 g/L and the zinc ion concentration is 0.2 to 80 g/L.
US11/704,805 2004-08-10 2007-02-09 Method for electroplating with tin-zinc alloy Abandoned US20070199827A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2004233633A JP4594672B2 (en) 2004-08-10 2004-08-10 Tin-zinc alloy electroplating method
JP2004-233633 2004-08-10
PCT/JP2005/014648 WO2006016603A1 (en) 2004-08-10 2005-08-10 Tin-zinc alloy electroplating method

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/014648 Continuation WO2006016603A1 (en) 2004-08-10 2005-08-10 Tin-zinc alloy electroplating method

Publications (1)

Publication Number Publication Date
US20070199827A1 true US20070199827A1 (en) 2007-08-30

Family

ID=35839372

Family Applications (1)

Application Number Title Priority Date Filing Date
US11/704,805 Abandoned US20070199827A1 (en) 2004-08-10 2007-02-09 Method for electroplating with tin-zinc alloy

Country Status (8)

Country Link
US (1) US20070199827A1 (en)
EP (1) EP1811063B1 (en)
JP (1) JP4594672B2 (en)
KR (1) KR100929761B1 (en)
CN (1) CN101001982B (en)
BR (1) BRPI0514210B1 (en)
ES (1) ES2526430T3 (en)
WO (1) WO2006016603A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105002526A (en) * 2015-06-30 2015-10-28 安徽飞达新材料科技股份有限公司 Cold-rolled steel plate brightener
CN111188069A (en) * 2019-12-31 2020-05-22 大连长丰实业总公司 Tin-plated bismuth alloy solution and preparation method thereof
CN111394734A (en) * 2020-05-06 2020-07-10 苏州清飙科技有限公司 Stripping polishing solution for die-casting zinc alloy and preparation method thereof

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102634827B (en) * 2012-05-07 2015-04-08 东莞市闻誉实业有限公司 Tin-zinc alloy electroplating method
CN102690975B (en) * 2012-06-11 2014-12-03 东莞市闻誉实业有限公司 Ternary tin-zinc alloy and electroplating method thereof
CN104213159A (en) * 2014-09-17 2014-12-17 朱忠良 Electroplating liquid and electroplating method
CN104357884A (en) * 2014-11-14 2015-02-18 无锡伊佩克科技有限公司 Method for plating zinc-tin alloy on ferrous material
CN105350056B (en) * 2015-11-24 2017-12-01 安徽天思朴超精密模具股份有限公司 The preparation method and application of wear-resistant electroplate liquid material compositions and wear-resistant electroplate liquid
KR101678013B1 (en) * 2016-02-15 2016-11-21 주식회사 베프스 A plating solution with concentration-detecting indicators for determing supplement time of metal component and plating method of therewith
KR102621912B1 (en) * 2018-12-24 2024-01-05 현대자동차주식회사 Excellent activation whisker resistant zinc coating method for electrical and electronic components
CN114927677B (en) * 2022-05-31 2024-05-24 山东大学 Flexible sodium battery anode material and green preparation method and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5175632A (en) * 1974-12-27 1976-06-30 Dipsol Chem Kotakusuzu aengokindenkimetsukyotenkabutsu
US4183799A (en) * 1978-08-31 1980-01-15 Production Machinery Corporation Apparatus for plating a layer onto a metal strip
US4749626A (en) * 1985-08-05 1988-06-07 Olin Corporation Whisker resistant tin coatings and baths and methods for making such coatings
US5618402A (en) * 1992-09-25 1997-04-08 Dipsol Chemicals Co., Ltd. Tin-zinc alloy electroplating bath and method for electroplating using the same
US5650238A (en) * 1994-08-01 1997-07-22 Nkk Corporation Zinc-electroplated steel sheet
US5985106A (en) * 1995-07-14 1999-11-16 Velasquez; Geronimo Z. Continuous rack plater
JP2000026991A (en) * 1998-07-10 2000-01-25 Daiwa Kasei Kenkyusho:Kk Tin and tin alloy plating bath
EP1138805A2 (en) * 2000-03-31 2001-10-04 Shipley Company LLC Tin electolyte
WO2004065663A1 (en) * 2003-01-24 2004-08-05 Ishihara Chemical Co., Ltd. Tin-containing plating bath

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5175633A (en) * 1974-12-27 1976-06-30 Dipsol Chem Suzu aengokinmetsukyoku
JPH02175894A (en) * 1988-12-28 1990-07-09 Kosaku:Kk Method and device for tin or tin alloy electroplating
JPH06228786A (en) * 1993-01-29 1994-08-16 Deitsupusoole Kk Tin-zinc alloy plating bath and plating method using this bath
JP3609565B2 (en) * 1996-12-09 2005-01-12 株式会社大和化成研究所 Tin-zinc alloy plating bath
JP3366851B2 (en) * 1997-12-18 2003-01-14 株式会社ジャパンエナジー Tin alloy electroplating solution and plating method
JP2002275678A (en) * 2001-01-11 2002-09-25 Nikko Materials Co Ltd Whisker-free tin and tin alloy plating solution, printing film and plating object

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5175632A (en) * 1974-12-27 1976-06-30 Dipsol Chem Kotakusuzu aengokindenkimetsukyotenkabutsu
US4183799A (en) * 1978-08-31 1980-01-15 Production Machinery Corporation Apparatus for plating a layer onto a metal strip
US4749626A (en) * 1985-08-05 1988-06-07 Olin Corporation Whisker resistant tin coatings and baths and methods for making such coatings
US5618402A (en) * 1992-09-25 1997-04-08 Dipsol Chemicals Co., Ltd. Tin-zinc alloy electroplating bath and method for electroplating using the same
US5650238A (en) * 1994-08-01 1997-07-22 Nkk Corporation Zinc-electroplated steel sheet
US5985106A (en) * 1995-07-14 1999-11-16 Velasquez; Geronimo Z. Continuous rack plater
JP2000026991A (en) * 1998-07-10 2000-01-25 Daiwa Kasei Kenkyusho:Kk Tin and tin alloy plating bath
EP1138805A2 (en) * 2000-03-31 2001-10-04 Shipley Company LLC Tin electolyte
WO2004065663A1 (en) * 2003-01-24 2004-08-05 Ishihara Chemical Co., Ltd. Tin-containing plating bath
EP1591563A1 (en) * 2003-01-24 2005-11-02 Ishihara Chemical Co., Ltd. Tin-containing plating bath

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105002526A (en) * 2015-06-30 2015-10-28 安徽飞达新材料科技股份有限公司 Cold-rolled steel plate brightener
CN111188069A (en) * 2019-12-31 2020-05-22 大连长丰实业总公司 Tin-plated bismuth alloy solution and preparation method thereof
CN111394734A (en) * 2020-05-06 2020-07-10 苏州清飙科技有限公司 Stripping polishing solution for die-casting zinc alloy and preparation method thereof

Also Published As

Publication number Publication date
JP2006052431A (en) 2006-02-23
KR20070031442A (en) 2007-03-19
CN101001982A (en) 2007-07-18
ES2526430T3 (en) 2015-01-12
CN101001982B (en) 2010-09-08
EP1811063B1 (en) 2014-12-03
EP1811063A1 (en) 2007-07-25
KR100929761B1 (en) 2009-12-03
EP1811063A4 (en) 2009-03-04
JP4594672B2 (en) 2010-12-08
BRPI0514210B1 (en) 2016-05-03
BRPI0514210A2 (en) 2009-04-28
WO2006016603A1 (en) 2006-02-16

Similar Documents

Publication Publication Date Title
US20070199827A1 (en) Method for electroplating with tin-zinc alloy
JP4249438B2 (en) Pyrophosphate bath for copper-tin alloy plating
US4889602A (en) Electroplating bath and method for forming zinc-nickel alloy coating
RU2610183C1 (en) Electroplating with zinc alloy
EP0770711B1 (en) Sn-Bi alloy-plating bath and method for forming plated Sn-Bi alloy film
US6129830A (en) Process for the electrolytic deposition of copper layers
US5169514A (en) Plating compositions and processes
US5674374A (en) Sn-Bi alloy-plating bath and plating method using the same
TWI439580B (en) Pyrophosphate-based bath for plating of tin alloy layers
KR20110022558A (en) Pyrophosphate-containing bath for cyanide-free deposition of copper-tin alloys
KR20110011613A (en) Modified copper-tin electrolyte and process for the deposition of bronze layers
US6755960B1 (en) Zinc-nickel electroplating
EP1292724B2 (en) Zinc-nickel electroplating
EP2350355B1 (en) Zinc alloy electroplating baths and processes
EP0663460B1 (en) Tin-zinc alloy electroplating bath and method for electroplating using the same
KR20130098304A (en) Electrolyte and process for the deposition of copper-tin alloy layers
EP1639155B1 (en) Zinc and zinc-alloy electroplating
WO2000068464A2 (en) Alloy plating
US20070023280A1 (en) Zinc and zinc-alloy electroplating
CN103806046A (en) Method for increasing deposition rate of electroplated layer by applying magnetic field
CN112513337A (en) Tin alloy electroplating bath and plating method using the same
JPS6319600B2 (en)
JPH04259393A (en) Zinc-nickel alloy coating bath and method for preventing precipitation of black on material to be coated

Legal Events

Date Code Title Description
AS Assignment

Owner name: DIPSOL CHEMICALS CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:YUASA, SATOSHI;REEL/FRAME:019279/0822

Effective date: 20070410

STCV Information on status: appeal procedure

Free format text: ON APPEAL -- AWAITING DECISION BY THE BOARD OF APPEALS

STCV Information on status: appeal procedure

Free format text: BOARD OF APPEALS DECISION RENDERED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION