CN111733433A - Alkaline electro-galvanized iron alloy plating solution additive for low-iron-content plating layer and application thereof - Google Patents
Alkaline electro-galvanized iron alloy plating solution additive for low-iron-content plating layer and application thereof Download PDFInfo
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- CN111733433A CN111733433A CN202010545064.5A CN202010545064A CN111733433A CN 111733433 A CN111733433 A CN 111733433A CN 202010545064 A CN202010545064 A CN 202010545064A CN 111733433 A CN111733433 A CN 111733433A
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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
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Abstract
The invention discloses an additive of alkaline electro-galvanized iron alloy plating solution of a low-iron-content plating layer and application thereof, wherein the additive comprises the following components in percentage by weight: 10-90% of heterocyclic organic amine and 10-90% of solvent. The heterocyclic organic amine is one or more of pyrazine, piperazine, pyridine, pyrimidine or pyrrole. The solvent is water or/and ethanol. The additive can improve the uniformity, corrosion resistance and binding property with a substrate of the zinc-iron alloy coating, and the zinc-iron alloy coating which is bright, fine, good in corrosion resistance and good in coating binding force is obtained.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to an alkaline electro-galvanized iron alloy plating solution additive for a low-iron-content plating layer and application 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 to 25 percent of iron; the alkaline zincate system contains 0.4-0.9% of iron in the coating. 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 alkaline zinc-iron alloy electroplating solution are not sufficiently paid attention, so that the research on the additive in the alkaline zinc-iron alloy electroplating solution and the development of an economic and effective additive have very important meanings.
In the report about the additive of the plating solution of the electro-galvanized ferroalloy, Chinese patent with application number CN201110290891.5 discloses a brightening agent of zinc and ferrozinc alloy, which is mainly used for preparing the additive of the rapid galvanizing and ferrozinc alloy on the surfaces of steel parts, wires, strips and pipes, and comprises the following main components: the brightener is complex in components, narrow in temperature range and free of corrosion inhibition on acidic plating solution; the Chinese patent with application number 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, ethylene diamine tetraacetic acid, vanillin, sodium dodecyl sulfate and zinc powder, the plating solution has complex components, and the process cannot solve the problem of narrow temperature range and narrow current density range in the alkaline plating solution for zinc plating; the Chinese invention patent with application number CN200710065899.5 discloses a zinc and zinc-iron alloy electroplating brightener, which is mainly used as an additive for electroplating zinc and zinc-iron alloy on the surface of steel parts, and 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, wherein the nonionic surfactants are any one of nonylphenol polyoxyethylene ether, polyethylene glycol and OP emulsifier, and the ionic surfactants are any one of sodium dodecyl sulfate and sodium dodecyl sulfate.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide the additive of the alkaline electro-galvanized iron alloy plating solution with the low-iron-content plating layer and the application thereof.
In order to achieve the aim, the invention provides an alkaline electro-galvanized iron alloy plating solution additive of a low-iron-content plating layer, which comprises the following components in percentage by weight:
10 to 90 percent of heterocyclic organic amine
10-90% of a solvent.
Further, the additive of the alkaline electro-galvanized iron alloy plating solution of the low-iron-content plating layer comprises the following components in percentage by weight:
50-80% of heterocyclic organic amine
20-50% of a solvent.
Further, the additive of the alkaline electro-galvanized iron alloy plating solution of the low-iron-content plating layer comprises the following components in percentage by weight:
50 percent of heterocyclic organic amine
50% of solvent.
Further, the heterocyclic organic amine is one or more of pyrazine, piperazine, pyridine, pyrimidine or pyrrole.
Further, the heterocyclic organic amine is formed by mixing pyrimidine and pyridine according to the weight ratio of 1: 1.
Further, the solvent is water or/and ethanol.
The invention also provides an application of the alkaline electro-galvanized iron alloy plating solution additive of the low-iron-content plating layer, wherein the alkaline electro-galvanized iron alloy plating solution additive of the low-iron-content plating layer is added into the alkaline zinc-iron alloy plating solution according to the addition amount of 50-1000 ppm for electroplating.
Further, the electroplating process is carried out at the temperature of 10-50 ℃ and the passing speed of 1-7A/dm2Electroplating is performed by the current of (1).
Furthermore, the alkaline zinc-iron alloy plating solution comprises the following components in percentage by weight: 50% of potassium pyrophosphate, 20% of sodium dihydrogen phosphate, 10% of ferrous chloride and 20% of zinc oxide.
Compared with the prior art, the invention has the following advantages:
firstly, the additive improves the corrosion resistance, the brightness and the coating binding force of the zinc-iron alloy coating, has good dispersion capacity and covering capacity, can obtain the high-surface-performance electroplated zinc-iron alloy coating in a wider temperature range by adding the additive into the plating solution, improves the uniform plating capacity of the coating process, and simultaneously reduces the corrosion of alkaline plating solution to electroplating equipment.
Secondly, the additive of the invention is completely composed of organic compounds, avoids some inherent defects of inorganic additives, and has the advantages of small dosage, high efficiency, simple and convenient manufacture, low cost, no toxicity or peculiar smell, complete water solubility, wide application range and the like.
Thirdly, the application method of the additive is simple, 50-1000 ppm of the additive is directly added into the alkaline electro-galvanized iron alloy plating solution for electroplating, an electro-galvanized iron alloy layer with good surface performance, small internal stress of the plating layer and high corrosion resistance can be obtained, and the treatment time is short.
Fourthly, the additive liquid of the invention is not only green and environment-friendly, pollution-free, but also has wide application range, small dosage, no toxicity and peculiar smell, complete water solubility, easy obtaining and low cost. And the steel surface treated by the additive can obtain an electroplated zinc-iron alloy layer with excellent surface quality, brightness, compactness, good surface performance, high corrosion resistance and good bonding force with a substrate, so that the brightness and the surface appearance quality of a zinc layer are improved.
Detailed Description
The following describes the embodiments of the present invention in detail with reference to the embodiments, but they are not intended to limit the present invention and are only examples. While the advantages of the invention will be apparent and readily appreciated by the description.
Example 1
Mixing 50% of pyrazine and 50% of distilled water according to the weight percentage, and uniformly stirring to prepare the additive of the electro-galvanized iron alloy plating solution; the additive is added into alkaline zinc-iron alloy plating solution according to the addition of 500ppm, and the alkaline zinc-iron alloy plating solution comprises the following components in percentage by weight: potassium pyrophosphate 50%, sodium dihydrogen phosphate 20%, ferrous chloride 10% and zinc oxide 20%, using carbon steel as cathode at 25 deg.C, passing through 5A/dm2Current processing of 30 s; the obtained electroplated zinc-iron alloy layer with the surface coating of more than 60 mu m is bright, full and uniform, the coating is bent at 180 degrees and does not fall off, the rust area on the surface in a salt spray experiment for 72 hours is less than 0.5 percent, and meanwhile, the corrosion effect of alkaline plating solution on equipment is obviously reduced.
Example 2
Mixing 40% of pyrazine, 40% of pyrrole, 5% of ethanol and 15% of distilled water according to the weight percentage, and uniformly stirring to prepare the additive of the electro-galvanized iron alloy plating solution; the additive is added into alkaline zinc-iron alloy plating solution according to the addition of 100ppm, and the alkaline zinc-iron alloy plating solution comprises the following components in percentage by weight: potassium pyrophosphate 50%, sodium dihydrogen phosphate 20%, ferrous chloride 10% and zinc oxide 20%, using carbon steel as cathode at 35 deg.C, passing through 1A/dm2Current treatment of 20 s; the obtained electroplated zinc-iron alloy layer with the surface coating of more than 20 microns is bright, full and uniform, the coating is bent at 180 degrees and does not fall off, the rust area on the surface in a salt spray experiment for 72 hours is less than 1 percent, and meanwhile, the corrosion effect of alkaline plating solution on equipment is obviously reduced.
Example 3
Mixing 25% of pyrrole, 25% of piperazine and 50% of distilled water according to the weight percentage, and uniformly stirring to prepare the additive of the electro-galvanized iron alloy plating solution; the additive is added into an alkaline zinc-iron alloy plating solution in an addition amount of 200ppm, and the alkaline zinc-iron alloy plating solution comprises the following components in percentage by weight: potassium pyrophosphate 50%, sodium dihydrogen phosphate 20%, ferrous chloride 10% and zinc oxide 20%, using carbon steel as cathode at 50 deg.C, passing through 4A/dm2Current processing of 50 s; the obtained electroplated zinc-iron alloy layer with the surface coating of more than 50 microns is bright, full and uniform, the coating is bent at 180 degrees and does not fall off, the rust area on the surface in a salt spray experiment for 72 hours is less than 0.5 percent, and meanwhile, the corrosion effect of alkaline plating solution on equipment is obviously reduced.
Example 4
Mixing 25% of pyrimidine, 25% of pyridine and 50% of distilled water according to the weight percentage, and uniformly stirring to prepare the additive of the electro-galvanized iron alloy plating solution; the additive is added into an alkaline zinc-iron alloy plating solution according to the addition of 1000ppm, and the alkaline zinc-iron alloy plating solution comprises the following components in percentage by weight: potassium pyrophosphate 50%, sodium dihydrogen phosphate 20%, ferrous chloride 10% and zinc oxide 20%, using carbon steel as cathode at 10 deg.C, passing through 2A/dm2Current processing of (5) for 60 s; the obtained electroplated zinc-iron alloy layer with the surface coating of more than 35 mu m is bright, full and uniform, the coating is bent at 180 degrees and does not fall off, the rust area on the surface in a salt spray experiment for 72 hours is less than 0.5 percent, and meanwhile, the corrosion effect of alkaline plating solution on equipment is obviously reduced.
Example 5
Mixing 5% of pyrimidine, 5% of pyridine, 45% of distilled water and 45% of ethanol according to the weight percentage, and uniformly stirring to prepare the additive of the electro-galvanized iron alloy plating solution; the additive is added into alkaline zinc-iron alloy plating at the addition of 1000ppmIn the solution, the alkaline zinc-iron alloy plating solution consists of the following components in percentage by weight: potassium pyrophosphate 50%, sodium dihydrogen phosphate 20%, ferrous chloride 10% and zinc oxide 20%, using carbon steel as cathode at 10 deg.C, passing through 2A/dm2Current processing of (5) for 60 s; the obtained electroplated zinc-iron alloy layer with the surface coating of more than 35 mu m is bright, full and uniform, the coating is bent at 180 degrees and does not fall off, the rust area on the surface in a salt spray experiment for 72 hours is less than 1 percent, and meanwhile, the corrosion effect of alkaline plating solution on equipment is obviously reduced.
Example 6
Mixing 45% of pyrimidine, 45% of pyridine and 10% of distilled water according to the weight percentage, and uniformly stirring to prepare the additive of the electro-galvanized iron alloy plating solution; the additive is added into alkaline zinc-iron alloy plating solution in an addition amount of 50ppm, and the alkaline zinc-iron alloy plating solution comprises the following components in percentage by weight: potassium pyrophosphate 50%, sodium dihydrogen phosphate 20%, ferrous chloride 10% and zinc oxide 20%, using carbon steel as cathode at 10 deg.C, passing through 7A/dm2Current processing of (5) for 60 s; the obtained electroplated zinc-iron alloy layer with the surface coating of more than 35 mu m is bright, full and uniform, the coating is bent at 180 degrees and does not fall off, the rust area on the surface in a salt spray experiment for 72 hours is less than 1 percent, and meanwhile, the corrosion effect of alkaline plating solution on equipment is obviously reduced.
The above description is only an embodiment of the present invention, and it should be noted that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention, and the rest that is not described in detail is the prior art.
Claims (9)
1. An additive of alkaline electro-galvanized iron alloy plating solution with a low-iron-content plating layer is characterized in that: the composition comprises the following components in percentage by weight:
10 to 90 percent of heterocyclic organic amine
10-90% of a solvent.
2. The additive for alkaline electro-galvanized iron alloy plating solution of low iron content plating according to claim 1, characterized in that: the composition comprises the following components in percentage by weight:
50-80% of heterocyclic organic amine
20-50% of a solvent.
3. The additive for alkaline electro-galvanized iron alloy plating solution of low iron content plating according to claim 1, characterized in that: the composition comprises the following components in percentage by weight:
50 percent of heterocyclic organic amine
50% of solvent.
4. The additive for alkaline electrogalvanized iron alloy plating baths with low iron content plating according to claim 1, 2 or 3, characterized in that: the heterocyclic organic amine is one or more of pyrazine, piperazine, pyridine, pyrimidine or pyrrole.
5. The additive for alkaline electrogalvanized iron alloy plating baths with low iron content plating according to claim 1, 2 or 3, characterized in that: the heterocyclic organic amine is formed by mixing pyrimidine and pyridine according to the weight ratio of 1: 1.
6. The additive for alkaline electrogalvanized iron alloy plating baths with low iron content plating according to claim 1, 2 or 3, characterized in that: the solvent is water or/and ethanol.
7. The use of the additive for the alkaline electro-galvanized iron alloy plating solution with low iron content according to any one of claims 1 to 6, which is characterized in that: and adding the additive of the alkaline electro-galvanized iron alloy plating solution of the low-iron-content plating layer into the alkaline zinc-iron alloy plating solution according to the addition amount of 50-1000 ppm for electroplating.
8. Use according to claim 7, characterized in that: the electroplating process is carried out at the temperature of 10-50 ℃ and the passing speed of 1-7A/dm2Electroplating is performed by the current of (1).
9. Use according to claim 7, characterized in that: the alkaline zinc-iron alloy plating solution comprises the following components in percentage by weight: 50% of potassium pyrophosphate, 20% of sodium dihydrogen phosphate, 10% of ferrous chloride and 20% of zinc oxide.
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| CN202010545064.5A CN111733433A (en) | 2020-06-15 | 2020-06-15 | Alkaline electro-galvanized iron alloy plating solution additive for low-iron-content plating layer and application thereof |
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| CN202010545064.5A CN111733433A (en) | 2020-06-15 | 2020-06-15 | Alkaline electro-galvanized iron alloy plating solution additive for low-iron-content plating layer and application thereof |
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Citations (7)
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|---|---|---|---|---|
| US4581110A (en) * | 1984-02-27 | 1986-04-08 | Nippon Surface Treatment Chemicals Co. Ltd. | Method for electroplating a zinc-iron alloy from an alkaline bath |
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| US6652728B1 (en) * | 1998-09-02 | 2003-11-25 | Atotech Deutschland Gmbh | Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings |
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2020
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|---|---|---|---|---|
| US4581110A (en) * | 1984-02-27 | 1986-04-08 | Nippon Surface Treatment Chemicals Co. Ltd. | Method for electroplating a zinc-iron alloy from an alkaline bath |
| US4717458A (en) * | 1986-10-20 | 1988-01-05 | Omi International Corporation | Zinc and zinc alloy electrolyte and process |
| US6652728B1 (en) * | 1998-09-02 | 2003-11-25 | Atotech Deutschland Gmbh | Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings |
| CN104164686A (en) * | 2014-07-22 | 2014-11-26 | 武汉钢铁(集团)公司 | Acidic electrolytic zinc plating solution additive and application method thereof |
| CN106086956A (en) * | 2016-07-30 | 2016-11-09 | 哈尔滨工业大学 | Alkaline non-cyanide electrodepositing zinc-nickel alloy additive and application thereof |
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Application publication date: 20201002 |