CN111593380A - Acidic electro-galvanized iron alloy plating solution additive for high-iron-content plating layer and application method thereof - Google Patents

Acidic electro-galvanized iron alloy plating solution additive for high-iron-content plating layer and application method thereof Download PDF

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Publication number
CN111593380A
CN111593380A CN202010614953.2A CN202010614953A CN111593380A CN 111593380 A CN111593380 A CN 111593380A CN 202010614953 A CN202010614953 A CN 202010614953A CN 111593380 A CN111593380 A CN 111593380A
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China
Prior art keywords
acid
zinc
iron alloy
iron
additive
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Pending
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CN202010614953.2A
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Chinese (zh)
Inventor
黄道兵
蔡捷
冯冠文
陈莹莹
江鹤群
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Wuhan Iron and Steel Co Ltd
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Wuhan Iron and Steel Co Ltd
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Priority to CN202010614953.2A priority Critical patent/CN111593380A/en
Publication of CN111593380A publication Critical patent/CN111593380A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Abstract

The invention discloses an acidic electrogalvanizing ferroalloy plating solution additive with high iron content, which comprises 10-90% of organic acid and 10-90% of water or/and ethanol; the high-iron content means that the iron content in the zinc-iron alloy coating is 3-25%. The invention also discloses the application of the additive in zinc-iron alloy plating. Because the hydrophilic acid groups in the added organic acid are combined with the metal matrix, a uniform electroplating surface can be formed on the metal matrix, the uniform plating capacity of electroplating is improved, the crystal grains of the plating layer are refined, the crystallization of the plating layer is compact and fine, and the corrosion resistance, the brightness and the bonding force of the plating layer are improved. Meanwhile, the alkyl group of the aliphatic polycarboxylic acid deviates from the metal group, has hydrophobicity, can repel corrosive medium, improves the corrosion resistance of the coating and reduces the corrosion of electroplating equipment.

Description

Acidic electro-galvanized iron alloy plating solution additive for high-iron-content plating layer and application method thereof
Technical Field
The invention belongs to the technical field of electroplating, and particularly relates to an acidic electro-galvanized iron alloy plating solution additive for a high-iron-content plating layer and an application method thereof.
Background
The electro-galvanized plate has been widely used in the household and automobile industry due to its excellent corrosion resistance and high surface quality, but the pure zinc layer has poor corrosion resistance in harsh environments, such as acid, alkaline or humid environments containing salt substances. Therefore, zinc-based alloy electroplating processes with higher corrosion resistance have been researched and developed, wherein a zinc-iron alloy plating layer has better corrosion resistance, coating property, processability and weldability than a zinc plating layer, and is applied to household appliances and automobile industries.
The zinc-iron alloy plating solution applied at present mainly comprises: in a sulfate system, the iron content of the zinc-iron alloy coating is high and contains 3-25% of iron; the coating of the alkaline zincate system contains 0.4-0.9% of iron. Wherein the former can not be passivated by a conventional passivation mode due to high iron content to influence the corrosion resistance. The latter has low iron content and can be passivated by a conventional passivation process, so that the corrosion resistance can be greatly improved, and the neutral salt spray resistance test of a zinc-iron alloy coating with the thickness of 5 mu m can reach 2000 hours.
In general, in electroplating production, whether a high-brightness, uniform, fine and smooth coating can be obtained or not is very important in the use of the additive, but at present, the research and the use of the additive in the acidic zinc-iron alloy electroplating solution are not sufficiently paid attention, so that the research on the additive in the acidic zinc-iron alloy electroplating solution and the development of an economic and effective additive have very important meanings.
In the reports on additives of the plating solution of the electro-galvanized ferroalloy, the patent application with the application number of CN201110290891.5 discloses a brightener of zinc and a zinc-iron alloy, which is mainly used for preparing the additives of the steel parts, wires, strips and pipes for fast galvanizing and zinc-iron alloy, and comprises the following main components: the brightener is narrow in temperature range and has no corrosion inhibition effect on the acidic plating solution; patent application No. CN200910038328.1 discloses a bright corrosion-resistant zinc-iron alloy electroplating process, which adds complexing agent and ferrous ion into zincate plating solution, the zinc-iron alloy plating solution comprises the following components: zinc oxide, sodium hydroxide, triethanolamine, ferrous sulfate, a composition of dimethylamine and epichlorohydrin, ethylenediamine tetraacetic acid, vanillin, sodium dodecyl sulfate and zinc powder, the process can not solve the problem that the temperature range and the current density range of the zinc plating in the alkaline plating solution are narrow; the patent application with the application number of CN200710065899.5 discloses an additive mainly used for electroplating zinc and zinc-iron alloy on the surface of steel parts, wherein the electroplating brightener is an aqueous solution consisting of benzalacetone, surfactants (including nonionic surfactants and ionic surfactants), a condensation product of higher aliphatic alcohol and ethylene oxide, ethanol and water, the nonionic surfactants are any one of nonylphenol polyoxyethylene ether, polyethylene glycol and OP emulsifier, the ionic surfactants are any one of sodium dodecyl sulfate and sodium dodecyl sulfate, the brightener is an alkaline plating solution system, the electroplating temperature range is narrow, and the brightener has no corrosion inhibition effect on the alkaline plating solution.
Disclosure of Invention
The invention aims to provide an acid zinc-iron alloy electroplating solution additive with high iron content, which can ensure that the acid zinc-iron alloy electroplating solution can obtain a zinc-iron alloy electroplating layer with high surface performance in a wider temperature range and a larger current density range.
In order to solve the technical problems, the invention adopts the technical scheme that: an acid electrogalvanizing ferroalloy plating solution additive with high iron content comprises the following components in percentage by weight:
organic acid: 10-90%; water and/or ethanol: 10-90%;
the high-iron content means that the iron content in the zinc-iron alloy coating is 3-25%.
Further, the weight percentage content of the organic acid is 30-85%.
Further, the organic acid is a fatty acid polycarboxylic acid, and the fatty acid polycarboxylic acid is one or any combination of two or more of 1, 2-ethanedicarboxylic acid, 1,2, 3-propenetricarboxylic acid and 1,3, 6-hexanetricarboxylic acid.
Further, the organic acid further comprises at least one of 3-hydroxy-1, 3, 5-pentanedioic acid and phytic acid.
The invention also applies the acid zinc-iron alloy electroplating solution additive with high iron content to the acid zinc-iron alloy electroplating solutionThe electroplating is carried out by the specific method: the additive is directly added into the acidic zinc-iron alloy plating solution in an addition amount of 100-2000 ppm, and the solution passes through 1-10A/dm at the temperature of 0-50 DEG C2Electroplating is carried out by the current; the acid electro-galvanized iron alloy plating solution comprises the following components: 65-70 wt% of ferrous sulfate, 15 wt% of zinc sulfate, 10 wt% of potassium sulfate and 5-10 wt% of fluoroboric acid.
Compared with the prior art, the invention has the following advantages:
the added organic acid has hydrophilic acid groups, so that the organic acid has good dispersing capacity and covering capacity, can be effectively combined with a metal matrix, can form a uniform electroplating surface on the metal matrix, improves the uniform plating capacity of electroplating, improves the polarization of an electroplating cathode, makes the electrodeposition potential negative shift, refines coating grains, makes the coating crystal compact and fine, and improves the corrosion resistance, the brightness and the coating binding force of the coating. Meanwhile, the alkyl group of the aliphatic polycarboxylic acid deviates from the metal group, has hydrophobicity, can repel corrosive medium, improves the corrosion resistance of the coating, and simultaneously reduces the corrosion of electroplating equipment. Meanwhile, the additive is completely composed of organic compounds, so that the addition of impurity ions of inorganic additives is avoided, the codeposition of the impurity ions is reduced, the electroplating efficiency is improved, and the formed surface coating has excellent quality and small internal stress of the coating. The inventor finds that 1, 2-ethanedioic acid, 1,2, 3-propene tricarboxylic acid and 1,3, 6-hexane tricarboxylic acid can be used alone or in combination to refine grains and obtain a high-brightness, full, uniform and smooth coating with good corrosion resistance, and 3-hydroxy-1, 3, 5-pentanedioic acid and/or phytic acid can be added to obtain a brighter, finer and compact coating with good corrosion resistance, but the 3-hydroxy-1, 3, 5-pentanedioic acid and/or phytic acid can be used alone to obtain a coating with poor brightness and corrosion resistance.
Detailed Description
Example 1
Mixing 40% of 1, 2-ethanedioic acid and 60% of distilled water, and uniformly stirring to prepare the additive of the electro-galvanized iron alloy plating solution; the additive was added to an acidic zinc-iron alloy plating solution (70 wt% ferrous sulfate, 15 wt% zinc sulfate, 10 wt% sulfur) in an amount of 1000ppmPotassium and 5 wt% fluoroboric acid), at 35 ℃ with carbon steel as the cathode, passing through 7A/dm2Current treatment of (2) for 10 s; the obtained electroplated zinc-iron alloy coating has bright, full and uniform surface coating, and the iron content of the coating is 20%. The plating layer has good binding force, the plating layer is bent at 180 degrees without falling off, the corrosion resistance of the plating layer is good, the rust area of the surface in a salt spray experiment for 72 hours is less than 1 percent, and meanwhile, the corrosion effect of the acid plating solution on equipment is obviously reduced.
Example 2
Mixing 30% of 1,2, 3-propylene tricarboxylic acid, 10% of phytic acid, 10% of ethanol and 50% of distilled water, and uniformly stirring to prepare the additive of the electroplating zinc-iron alloy plating solution; the additive is added into an acidic zinc-iron alloy plating solution with the addition amount of 100ppm, wherein the iron sulfate with the concentration of 65wt percent, the zinc sulfate with the concentration of 15wt percent, the potassium sulfate with the concentration of 10wt percent and the fluoroboric acid with the concentration of 10wt percent pass through a cathode made of carbon steel with the temperature of 10 DEG C2Current processing of 4 s; the obtained electroplated zinc-iron alloy coating is brighter, closer, finer, fuller and more uniform than that of the electroplated zinc-iron alloy coating obtained in the embodiment 1, the coating has good smoothness, and the iron content of the coating is 14%. The coating has good ductility, good binding force, no shedding of 180-degree bent coating, good corrosion resistance, rust area of the surface less than 0.5% in 72-hour salt spray experiment, and obviously reduced corrosion effect of acid plating solution on equipment.
Example 3
Mixing 15% of 1,3, 6-hexanetricarboxylic acid, 15% of phytic acid and 70% of distilled water, and uniformly stirring to prepare the additive of the electro-galvanized iron alloy plating solution; adding the additive into acid zinc-iron alloy plating solution with the addition amount of 2000ppm, wherein 68 wt% ferrous sulfate, 15 wt% zinc sulfate, 10 wt% potassium sulfate and 7 wt% fluoroboric acid pass through a cathode made of carbon steel at 50 ℃ and 1A/dm2Current treatment of 20 s; the obtained electroplated zinc-iron alloy coating is brighter, closer, finer, fuller and more uniform than that of the electroplated zinc-iron alloy coating obtained in the embodiment 1, the coating has good smoothness, and the iron content of the coating is 17%. The coating has good ductility and binding force, the coating is not dropped off after being bent for 180 degrees, the corrosion resistance of the coating is excellent, the rust area of the surface is less than 0.5 percent in a salt spray experiment for 72 hours, and meanwhile, the corrosion effect of the acid plating solution on equipment is obviously reduced.
Example 4
Mixing 25% of 1, 2-ethanedioic acid, 10% of 3-hydroxy-1, 3, 5-pentanedioic acid, 50% of distilled water and 15% of ethanol, and stirring uniformly to obtain the additive for the electroplating zinc-iron alloy plating solution; adding the additive into an acidic zinc-iron alloy plating solution at an addition amount of 900ppm, wherein the acidic zinc-iron alloy plating solution comprises 70 wt% of ferrous sulfate, 15 wt% of zinc sulfate, 10 wt% of potassium sulfate and 5 wt% of fluoroboric acid, and carbon steel is used as a cathode at 0 ℃ to pass through the solution at a speed of 8A/dm2Current processing of 30 s; the obtained electroplated zinc-iron alloy coating is brighter, fuller, compact, fine and uniform than that of the electroplated iron alloy coating in the embodiment 1, the coating has good smoothness, and the iron content of the coating is 20%. The coating has good ductility, good binding force, no shedding of 180-degree bent coating, good corrosion resistance, rust area of the surface less than 0.5% in 72-hour salt spray experiment, and obviously reduced corrosion effect of acid plating solution on equipment.
Example 5
Mixing 35% of 3-hydroxy-1, 3, 5-pentanedioic acid, 50% of distilled water and 15% of ethanol, and stirring uniformly to obtain the additive for the electro-galvanized iron alloy plating solution; adding the additive into an acidic zinc-iron alloy plating solution at an addition amount of 900ppm, wherein the acidic zinc-iron alloy plating solution comprises 70 wt% of ferrous sulfate, 15 wt% of zinc sulfate, 10 wt% of potassium sulfate and 5 wt% of fluoroboric acid, and carbon steel is used as a cathode at 0 ℃ to pass through the solution at a speed of 8A/dm2Current processing of 30 s; obtaining the zinc-iron alloy coating with the iron content of 20%. The plating layer has coarse crystallization, dull surface, poor brightness, large internal stress of the plating layer and poor binding force, and the plating layer partially falls off after being bent for 180 degrees; the corrosion resistance is poor, and the rust area on the surface is more than 6 percent in a salt spray experiment in 72 hours.
Example 6
Mixing 30% phytic acid and 70% distilled water, and stirring to obtain the additive for the electro-galvanized iron alloy plating solution; adding the additive into acid zinc-iron alloy plating solution with the addition amount of 2000ppm, wherein 68 wt% ferrous sulfate, 15 wt% zinc sulfate, 10 wt% potassium sulfate and 7 wt% fluoroboric acid pass through a cathode made of carbon steel at 50 ℃ and 1A/dm2Current treatment of 20 s; obtaining a zinc-iron alloy coating with the iron content of 17 percent. The coating has coarse grains, dull surface coating, poor brightness, brittle coating and microcracks. The coating has poor bonding forceThe plating layer is partially peeled off after being bent for 180 degrees, and the substrate is partially exposed; the corrosion resistance is poor, and the rust area on the surface is more than 7 percent in a salt spray experiment in 72 hours.
Since modifications and variations in the above-described and other embodiments of the invention may occur to persons skilled in the art, it is not intended to limit the invention to the precise form or embodiments disclosed.

Claims (5)

1. An acid electrogalvanizing ferroalloy plating solution additive with high iron content is characterized in that: the additive comprises the following components in percentage by weight:
organic acid: 10-90%; water and/or ethanol: 10-90%;
the high-iron content means that the iron content in the zinc-iron alloy coating is 3-25%.
2. The acidic electrogalvanized iron alloy plating bath additive with high iron content according to claim 1, characterized in that: the organic acid accounts for 30-85% by weight.
3. The acidic electrogalvanized iron alloy plating bath additive with high iron content according to claim 1 or 2, characterized in that: the organic acid is fatty acid polycarboxylic acid, and the fatty acid polycarboxylic acid is one or any combination of more than two of 1, 2-ethanedicarboxylic acid, 1,2, 3-propene tricarboxylic acid and 1,3, 6-hexane tricarboxylic acid.
4. The acidic electrogalvanized iron alloy plating bath additive with high iron content according to claim 1 or 2, characterized in that: the organic acid also comprises at least one of 3-hydroxy-1, 3, 5-pentanedioic acid and phytic acid.
5. Use of the acidic electrogalvanized zinc-iron alloy plating bath additive with high iron content according to any one of claims 1 to 4 in zinc-iron alloy plating, characterized in that: the additive is directly added into the acidic zinc-iron alloy plating solution in an addition amount of 100-2000 ppm, and the solution passes through 1-10A/dm at the temperature of 0-50 DEG C2By the current ofElectroplating; the acid electro-galvanized iron alloy plating solution comprises the following components: 65-70 wt% of ferrous sulfate, 15 wt% of zinc sulfate, 10 wt% of potassium sulfate and 5-10 wt% of fluoroboric acid.
CN202010614953.2A 2020-06-30 2020-06-30 Acidic electro-galvanized iron alloy plating solution additive for high-iron-content plating layer and application method thereof Pending CN111593380A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061911A1 (en) * 1981-03-26 1982-10-06 Nippon Paint Co., Ltd. Process and composition for treating phosphated metal surfaces
EP0151235A1 (en) * 1983-12-03 1985-08-14 Kawasaki Steel Corporation Process for preparing Zn-Fe base alloy electroplated steel strips
CN101063216A (en) * 2007-05-22 2007-10-31 昆明理工大学 Zinc and Zn-Fe alloy electroplating bright technique
CN101545125A (en) * 2009-03-31 2009-09-30 华南理工大学 Bright corrosion resisting zinc-iron alloy plating process
CN101922028A (en) * 2009-06-16 2010-12-22 武汉奥化表面工程有限公司 Galvanized iron (vanadium) alloy process of acid system
JP2012025978A (en) * 2010-07-20 2012-02-09 Nippon Hyomen Kagaku Kk Zinc-iron alloy plating solution
CN104955990A (en) * 2013-02-05 2015-09-30 不二商事株式会社 Method for regenerating plating solution

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061911A1 (en) * 1981-03-26 1982-10-06 Nippon Paint Co., Ltd. Process and composition for treating phosphated metal surfaces
EP0151235A1 (en) * 1983-12-03 1985-08-14 Kawasaki Steel Corporation Process for preparing Zn-Fe base alloy electroplated steel strips
CN101063216A (en) * 2007-05-22 2007-10-31 昆明理工大学 Zinc and Zn-Fe alloy electroplating bright technique
CN101545125A (en) * 2009-03-31 2009-09-30 华南理工大学 Bright corrosion resisting zinc-iron alloy plating process
CN101922028A (en) * 2009-06-16 2010-12-22 武汉奥化表面工程有限公司 Galvanized iron (vanadium) alloy process of acid system
JP2012025978A (en) * 2010-07-20 2012-02-09 Nippon Hyomen Kagaku Kk Zinc-iron alloy plating solution
CN104955990A (en) * 2013-02-05 2015-09-30 不二商事株式会社 Method for regenerating plating solution

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