CN115323379B - Environment-friendly zinc stripping agent and preparation method thereof - Google Patents

Environment-friendly zinc stripping agent and preparation method thereof Download PDF

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CN115323379B
CN115323379B CN202211017267.2A CN202211017267A CN115323379B CN 115323379 B CN115323379 B CN 115323379B CN 202211017267 A CN202211017267 A CN 202211017267A CN 115323379 B CN115323379 B CN 115323379B
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stripping agent
zinc stripping
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CN115323379A (en
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程海
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Shenzhen Has Surface Treatment Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)

Abstract

The invention relates to the technical field of zinc stripping agents, in particular to an environment-friendly zinc stripping agent and a preparation method thereof; the application discloses an environment-friendly zinc stripping agent, which comprises the following raw materials in parts by weight: 60-80g of sodium persulfate, 0.5g of corrosion inhibitor, 3mg of methanol, 30-50mg of sulfuric acid, 3-5g of malonic acid, 1mg of ethanol and the balance of water. The zinc stripping agent prepared by the invention can completely replace nitric acid by adding sodium persulfate, does not corrode aluminum, and has no pollutants such as ammonia nitrogen, so that the zinc stripping agent is environment-friendly and economical.

Description

Environment-friendly zinc stripping agent and preparation method thereof
Technical Field
The invention relates to the technical field of zinc stripping agents, in particular to an environment-friendly zinc stripping agent and a preparation method thereof.
Background
The process of zinc replacement of aluminum alloy is a replacement reaction, after zinc replacement treatment, a replacement layer composed of zinc, iron, nickel and the like is formed on the surface, but the replacement layer formed by the first zinc replacement is rough, the binding force of electroplating of a product is not guaranteed, fresh aluminum is exposed by removing acid, the second zinc replacement is carried out, the replacement layer of the second zinc replacement is compact, and the binding force of electroplating is not problematic.
Therefore, the process of dezincification needs strong acid medicament and has certain oxidizing property to ensure that aluminum cannot be corroded, so that the traditional process adopts 50% nitric acid by volume as a dezincification agent. However, the nitric acid is easy to generate smoke in the use process, ammonia nitrogen exceeds standard, and the nitric acid does not meet the environmental protection requirement, so that improvement is needed.
The invention provides an environment-friendly zinc stripping agent and a preparation method thereof, which are based on the aim of stripping zinc and achieving the environment protection.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the environment-friendly zinc stripping agent and the preparation method thereof, wherein the zinc stripping agent comprises sodium persulfate, and the oxidizing property of the sodium persulfate can completely replace nitric acid by adding the sodium persulfate, so that the zinc stripping agent does not corrode aluminum, and meanwhile, the zinc stripping agent has no pollutants such as ammonia nitrogen and the like, and is environment-friendly and economical.
The technical scheme adopted for solving the technical problems is as follows:
an environment-friendly zinc stripping agent comprises the following raw materials by weight per liter:
Figure BDA0003811281560000021
further, each liter of zinc stripping agent comprises the following raw materials by weight:
Figure BDA0003811281560000022
further, each liter of zinc stripping agent comprises the following raw materials by weight:
Figure BDA0003811281560000023
further, the slow release agent is aqueous silicone;
further, each liter of zinc stripping agent also comprises the following raw materials by weight:
phenylpropiotriazole 0.2g
Furthermore, each liter of zinc stripping agent also comprises the following raw materials by weight:
5-phenyl tetrazole 0.1g
Similarly, the invention also provides a preparation method of the environment-friendly zinc stripping agent, which comprises the following steps:
s1, preparing materials according to the composition of raw materials of a zinc stripping agent;
s2, dissolving sodium persulfate in water, slowly adding sulfuric acid, then adding malonic acid, and uniformly mixing to obtain a solution A;
s3, dissolving benzotriazole and 5-phenyl tetrazole in ethanol, and then adding the ethanol into the solution A to obtain a solution B;
s3, dissolving the corrosion inhibitor with methanol, adding the solution into the solution B, and finally, fixing the volume to obtain the zinc stripping agent.
The raw materials added in the invention have the functions and effects as follows:
sodium persulfate has stronger oxidizing property, can protect aluminum materials from being corroded by acid too quickly, and the product of the sodium persulfate reaction is sodium sulfate, so that the method is environment-friendly.
Since the acidity of sodium persulfate dissolved in water is not strong enough, the acidity can be improved by introducing sulfuric acid as an aid;
malonic acid is introduced as a complexing agent of nickel, so that metals such as zinc, nickel, iron and the like in the zinc substitution layer can be tightly complexed, and substitution reaction with aluminum can be carried out when a large amount of accumulation is avoided. Therefore, through the addition of malonic acid, even if the aluminum alloy is soaked for a long time, ash is not generated on the surface of the aluminum alloy;
the water-based silicone, the benzotriazole and the 5-phenyl tetrazole can be used as corrosion inhibitors, so that aluminum is ensured to be not corroded and ash is not suspended. The benzotriazole and the 5-phenyl tetrazole can be adsorbed on the surface of a metal matrix to prevent acid radicals from reacting with aluminum;
ethanol was used as a solvent for dissolving benzotriazol.
Methanol is used as a solvent for dissolving the aqueous silicone.
The beneficial effects of the invention are as follows:
1. according to the zinc stripping agent, the sodium persulfate is added, so that the oxidizing property of the sodium persulfate can completely replace nitric acid, the aluminum is not corroded, and meanwhile, pollutants such as ammonia nitrogen and the like are avoided, so that the zinc stripping agent is environment-friendly and economical;
2. through the addition of the corrosion inhibitor, the surface of the aluminum alloy is effectively ensured not to be excessively corroded, and ash is not hung.
Detailed Description
The conception, specific structure, and technical effects produced by the present invention will be clearly and completely described in connection with the embodiments below to fully understand the objects, features, and effects of the present invention.
Example 1
An environment-friendly zinc stripping agent comprises the following raw materials by weight per liter:
Figure BDA0003811281560000041
the preparation method of the environment-friendly zinc stripping agent comprises the following steps:
s1, preparing materials according to the composition of raw materials of a zinc stripping agent;
s2, dissolving sodium persulfate in water, slowly adding sulfuric acid, then adding malonic acid, and uniformly mixing to obtain a solution A;
s3, dissolving benzotriazole and 5-phenyl tetrazole in ethanol, and then adding the ethanol into the solution A to obtain a solution B;
s3, dissolving the water-based silicone with methanol, adding the dissolved water-based silicone into the solution B, and finally, fixing the volume (1L) to obtain the zinc stripping agent.
Example 2
An environment-friendly zinc stripping agent comprises the following raw materials by weight per liter:
Figure BDA0003811281560000051
the preparation method of the environment-friendly zinc stripping agent comprises the following steps:
s1, preparing materials according to the composition of raw materials of a zinc stripping agent;
s2, dissolving sodium persulfate in water, slowly adding sulfuric acid, then adding malonic acid, and uniformly mixing to obtain a solution A;
s3, dissolving benzotriazole and 5-phenyl tetrazole in ethanol, and then adding the ethanol into the solution A to obtain a solution B;
s3, dissolving the water-based silicone with methanol, adding the dissolved water-based silicone into the solution B, and finally, fixing the volume (1L) to obtain the zinc stripping agent.
Example 3
An environment-friendly zinc stripping agent comprises the following raw materials by weight per liter:
Figure BDA0003811281560000061
the preparation method of the environment-friendly zinc stripping agent comprises the following steps:
s1, preparing materials according to the composition of raw materials of a zinc stripping agent;
s2, dissolving sodium persulfate in water, slowly adding sulfuric acid, then adding malonic acid, and uniformly mixing to obtain a solution A;
s3, dissolving benzotriazole and 5-phenyl tetrazole in ethanol, and then adding the ethanol into the solution A to obtain a solution B;
s3, dissolving the water-based silicone with methanol, adding the dissolved water-based silicone into the solution B, and finally, fixing the volume (1L) to obtain the zinc stripping agent.
Example 4
An environment-friendly zinc stripping agent comprises the following raw materials by weight per liter:
Figure BDA0003811281560000062
Figure BDA0003811281560000071
the preparation method of the environment-friendly zinc stripping agent comprises the following steps:
s1, preparing materials according to the composition of raw materials of a zinc stripping agent;
s2, dissolving sodium persulfate in water, slowly adding sulfuric acid, then adding malonic acid, and uniformly mixing to obtain a solution A;
s3, dissolving benzotriazole and 5-phenyl tetrazole in ethanol, and then adding the ethanol into the solution A to obtain a solution B;
s3, dissolving the water-based silicone with methanol, adding the dissolved water-based silicone into the solution B, and finally, fixing the volume (1L) to obtain the zinc stripping agent.
Example 5
An environment-friendly zinc stripping agent comprises the following raw materials by weight per liter:
Figure BDA0003811281560000072
the preparation method of the environment-friendly zinc stripping agent comprises the following steps:
s1, preparing materials according to the composition of raw materials of a zinc stripping agent;
s2, dissolving sodium persulfate in water, slowly adding sulfuric acid, then adding malonic acid, and uniformly mixing to obtain a solution A;
s3, dissolving benzotriazole and 5-phenyl tetrazole in ethanol, and then adding the ethanol into the solution A to obtain a solution B;
s3, dissolving the water-based silicone with methanol, adding the dissolved water-based silicone into the solution B, and finally, fixing the volume (1L) to obtain the zinc stripping agent.
Comparative example 1
A zinc stripping agent contains 70g nitric acid (nitric acid content is 50%)
Comparative example 2
Zinc stripping agent, without acrylic acid, is the same as in example 1
Comparative example 3
A zinc stripping agent was prepared without adding aqueous silicone, and benzotriazole and 5-phenyltetrazole, and the other conditions were the same as in example 1.
And (3) testing: immersing an aluminum alloy into the zinc stripping agents of examples 1 to 5 and comparative examples 1 to 3, heating the zinc stripping agents to 90 ℃ and preserving heat for 1 hour, taking out, checking the surface condition of the immersed area of the aluminum alloy, and summarizing the results in the following table 1:
TABLE 1
Group of Surface condition of aluminum alloy
Example 1 The surface is not corroded and does not get dust
Example 2 The surface is not corroded and does not get dust
Example 3 The surface is not corroded and does not get dust
Example 4 The surface is not corroded and does not get dust
Comparative example 1 The surface is obviously corroded, black spots, yellow spots and ash are formed
Comparative example 2 The surface is not corroded, and the ash is obvious
Comparative example 3 Slightly corroded surface and a little dust is hung
From table 1 above, it can be seen that the zinc stripping agent prepared in examples 1 to 4 was used to soak aluminum alloy, the surface of the soaking area of aluminum alloy was not corroded and did not get dust, indicating that the zinc stripping agent did not cause excessive corrosion to aluminum alloy, and could be applied to the zinc stripping process.
Comparative example 1, aluminum alloy soaking area, surface over-corrosion was evident, black spots, macula lutea, and ash hanging; the addition of nitric acid can cause obvious over-corrosion of the surface of the aluminum alloy;
comparative example 2, aluminum alloy soaking area, surface corrosion is not excessive, and ash hanging is obvious; the method has the advantages that acrylic acid is not added, the surface of the aluminum alloy is not corroded, but the defect of obvious ash hanging exists;
comparative example 3, aluminum alloy immersed area, slightly corroded surface, and slightly ash-hanging; the specification does not add water-based siloxane ketone, benzotriazole and 5-phenyl tetrazole, which causes slight corrosion of the surface of an aluminum alloy soaking area and some ash hanging.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.

Claims (7)

1. The environment-friendly zinc stripping agent is characterized by comprising the following raw materials in parts by weight:
Figure QLYQS_1
the balance of water.
2. The environment-friendly zinc stripping agent as claimed in claim 1, wherein each liter of zinc stripping agent comprises the following raw materials by weight:
Figure QLYQS_2
the balance of water.
3. The environment-friendly zinc stripping agent as claimed in claim 2, wherein each liter of zinc stripping agent comprises the following raw materials by weight:
Figure QLYQS_3
Figure QLYQS_4
the balance of water.
4. The environmentally friendly zinc stripping agent according to claim 1, wherein the corrosion inhibitor is aqueous silicone.
5. The environment-friendly zinc stripping agent according to claim 1, wherein each liter of zinc stripping agent further comprises the following raw materials by weight:
0.2g of benzotriazol.
6. The environment-friendly zinc stripping agent according to claim 5, which is characterized by further comprising the following raw materials in parts by weight:
0.1g of 5-phenyltetrazole.
7. A method for preparing the environment-friendly zinc stripping agent as claimed in any one of claims 1 to 6, which comprises the following steps:
s1, preparing materials according to the composition of raw materials of a zinc stripping agent;
s2, dissolving sodium persulfate in water, slowly adding sulfuric acid, then adding malonic acid, and uniformly mixing to obtain a solution A;
s3, dissolving benzotriazole and 5-phenyl tetrazole in ethanol, and then adding the ethanol into the solution A to obtain a solution B;
s4, dissolving the corrosion inhibitor with methanol, adding the solution into the solution B, and finally, fixing the volume to obtain the zinc stripping agent.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173978A (en) * 2008-01-22 2009-08-06 Dipsol Chem Co Ltd Chemical conversion processing method for forming trivalent chromium chemically-processed coating film having excellent heat corrosion-resistance on zinc or zinc-alloy plating
CN101654798A (en) * 2008-08-21 2010-02-24 上村工业株式会社 Method of surface treatment for aluminum or aluminum alloy
JP2010121151A (en) * 2008-11-17 2010-06-03 Fuji Electric Systems Co Ltd Method for treating surface
JP2011137206A (en) * 2009-12-28 2011-07-14 Suzuki Motor Corp Plating pretreatment method of aluminum alloy
CN112725802A (en) * 2020-12-10 2021-04-30 昆山市板明电子科技有限公司 Novel environment-friendly tin stripping and hanging liquid and preparation method and use method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4538490B2 (en) * 2007-11-26 2010-09-08 上村工業株式会社 Metal substitution treatment liquid on aluminum or aluminum alloy and surface treatment method using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173978A (en) * 2008-01-22 2009-08-06 Dipsol Chem Co Ltd Chemical conversion processing method for forming trivalent chromium chemically-processed coating film having excellent heat corrosion-resistance on zinc or zinc-alloy plating
CN101654798A (en) * 2008-08-21 2010-02-24 上村工业株式会社 Method of surface treatment for aluminum or aluminum alloy
JP2010121151A (en) * 2008-11-17 2010-06-03 Fuji Electric Systems Co Ltd Method for treating surface
JP2011137206A (en) * 2009-12-28 2011-07-14 Suzuki Motor Corp Plating pretreatment method of aluminum alloy
CN112725802A (en) * 2020-12-10 2021-04-30 昆山市板明电子科技有限公司 Novel environment-friendly tin stripping and hanging liquid and preparation method and use method thereof

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* Cited by examiner, † Cited by third party
Title
环保退锌工艺在铝合金电镀前处理中的应用;容毅;伍炳杰;伍灿照;;电镀与精饰;第33卷(第12期);第5-8页 *

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