CN112030151A - No-clean chromium-free conversion agent for continuous coil unit and preparation method thereof - Google Patents

No-clean chromium-free conversion agent for continuous coil unit and preparation method thereof Download PDF

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Publication number
CN112030151A
CN112030151A CN202010889174.3A CN202010889174A CN112030151A CN 112030151 A CN112030151 A CN 112030151A CN 202010889174 A CN202010889174 A CN 202010889174A CN 112030151 A CN112030151 A CN 112030151A
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China
Prior art keywords
acid
conversion agent
chromium
free
coil unit
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CN202010889174.3A
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Inventor
章衍
程玉伟
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Hefei Langyi Surface Treatment Co ltd
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Hefei Langyi Surface Treatment Co ltd
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Priority to CN202010889174.3A priority Critical patent/CN112030151A/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The invention discloses a no-clean chromium-free conversion agent for a continuous coil unit and a preparation method thereof, and is characterized in that the conversion agent comprises the following components in percentage by mass: 5-25% of phosphoric acid, 1.5-5.5% of nitric acid, 2.5-10.5% of citric acid, 1.5-5.5% of gluconic acid, 1.5-5.5% of fluotitanic acid, 1.5-5.5% of fluozirconic acid, 1.0-15% of manganese carbonate, 1.0-10% of film forming promoter, 0.2-5.0% of thickening agent and the balance of deionized water. The conversion agent is a chromium-free and cleaning-free green environment-friendly product; can process various materials such as aluminum coils, steel coils, hot-dip galvanized coils, electrogalvanized steel plate coils, alloys and the like; the generated conversion film layer has strong binding force and corrosion resistance; the method is suitable for the technologies of continuous production, roller coating, dipping, spraying and the like of a coil machine set; the passivation time by using the conversion agent is short, the cost is low and the efficiency is high.

Description

No-clean chromium-free conversion agent for continuous coil unit and preparation method thereof
Technical Field
The invention relates to the technical field of metal surface treatment, mainly relates to a non-cleaning chromium-free environment-friendly conversion agent, and is particularly suitable for generating high-quality conversion film layers of different metals in a continuous coil unit process.
Background
The metal is subjected to surface treatment to form a conversion coating, so that the service life of the metal can be effectively prolonged, and the purpose of corrosion resistance is achieved. At present, the traditional chromate oxidation process is still widely used, and although the method is simple to operate, low in cost and excellent in performance of a generated conversion film, hexavalent chromium or trivalent chromium is related to a highly toxic substance, has carcinogenicity and seriously affects human health. With the continuous improvement of the environmental protection requirement of China, the chromium ion tolerance in the wastewater discharge is zero. Therefore, the development of a surface passivation technology with no toxicity, no harm, environmental friendliness, high efficiency and low energy consumption becomes a current research hotspot.
Although many researches on chromium-free passivators are carried out, most of the current passivators require post-cleaning treatment, such as a self-repairing anti-corrosion conversion coating on the surface of aluminum and aluminum alloy and a preparation method thereof (CN 103184447A), and the conversion coating prepared by the method needs a subsequent water washing process. Meanwhile, most of the existing passivators are only suitable for dipping or spraying processes, for example, an environment-friendly process (CN 1614090A) for forming a conversion coating on the surface of aluminum and aluminum alloy, and the passivators are only suitable for dipping or spraying; a composite chromium-free slow-release passivator and preparation and application thereof (CN 111074253A), wherein the passivator is only used for dipping or spraying treatment. In addition, most of the existing passivators only aim at a single metal type, and cannot simultaneously meet the surface treatment requirements of different types of metals, for example, an environment-friendly process (CN 1614090A) for forming a conversion coating on the surface of aluminum and aluminum alloy is only suitable for the surface treatment of aluminum and aluminum alloy; a galvanized sheet chromium-free environment-friendly passivator and a preparation and use method (CN 110616422A), which are only suitable for surface treatment of galvanized sheets. Up to now, there is no clean-free, chromium-free conversion agent that can be applied to high quality conversion coating of different kinds of metals in continuous coil assembly process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a cleaning-free chromium-free conversion agent for a continuous coil unit and a preparation method thereof, and the specific technical scheme is as follows:
a no-clean chromium-free conversion agent for a continuous coil unit and a preparation method thereof are characterized in that the conversion agent comprises the following components by mass percent: 5-25% of phosphoric acid, 1.5-5.5% of nitric acid, 2.5-10.5% of citric acid, 1.5-5.5% of gluconic acid, 1.5-5.5% of fluotitanic acid, 1.5-5.5% of fluozirconic acid, 1.0-15% of manganese carbonate, 1.0-10% of film forming promoter, 0.2-5.0% of thickening agent and the balance of deionized water.
The film forming promoter is one or a mixture of a plurality of fluoboric acid and fluosilicic acid.
The thickener is one or more of methylcellulose, sodium carboxymethylcellulose, sodium polyacrylate, polyoxyethylene, and polyvinylpyrrolidone.
The material suitable for the conversion agent is various materials such as aluminum coils, steel coils, hot-dip galvanized coils, electrogalvanized steel coils, alloys and the like.
The preparation method of the conversion agent comprises the following steps:
(1) according to the formula composition of raw materials, phosphoric acid, nitric acid, fluotitanic acid, fluozirconic acid and deionized water are fully stirred to prepare a solution A;
(2) dissolving citric acid, gluconic acid, manganese carbonate, a film forming promoter, a thickening agent and the like in a proper amount of deionized water, and fully stirring until the citric acid, the gluconic acid, the manganese carbonate, the film forming promoter, the thickening agent and the like are dissolved to prepare a solution B;
(3) and slowly adding the solution A into the solution B, and fully stirring to prepare the cleaning-free chromium-free conversion agent.
The invention has the beneficial effects that:
(1) the conversion agent is a chromium-free and cleaning-free green environment-friendly product;
(2) the conversion agent can be used for treating various materials such as aluminum coils, steel coils, hot-dip galvanized coils, electrogalvanized steel coils, alloys and the like;
(3) the conversion film layer generated by the conversion agent has strong binding force and corrosion resistance;
(4) the conversion agent is suitable for the processes of continuous production of a coil machine set, roller coating, dipping, spraying and the like;
(5) the conversion agent has the advantages of short passivation time, low cost and high efficiency.
Detailed Description
Example 1
A no-clean chromium-free conversion agent for a continuous coil unit comprises the following components in percentage by weight: 10% of phosphoric acid, 3% of nitric acid, 5% of citric acid, 3% of gluconic acid, 3% of fluotitanic acid, 3% of fluozirconic acid, 5% of manganese carbonate, 5% of film forming promoter, 0.5% of thickening agent and the balance of deionized water.
The film forming accelerant is as follows: 5% of fluoboric acid;
the thickening agent is as follows: 0.5 percent of methyl cellulose.
The preparation method of the conversion agent comprises the following steps:
(1) according to the formula composition of raw materials, phosphoric acid, nitric acid, fluotitanic acid, fluozirconic acid and deionized water are fully stirred to prepare a solution A;
(2) dissolving citric acid, gluconic acid, manganese carbonate, fluoroboric acid, methyl cellulose and the like in a proper amount of deionized water, and fully stirring until the citric acid, the gluconic acid, the manganese carbonate, the fluoroboric acid, the methyl cellulose and the like are dissolved to prepare a solution B;
(3) and slowly adding the solution A into the solution B, and fully stirring to prepare the cleaning-free chromium-free conversion agent.
The conversion agent prepared in the embodiment is used for carrying out continuous coil machine set process treatment on the surfaces of 4032 aluminum alloy and 3003 aluminum alloy respectively, the converted film layers after treatment are flat, compact and uniform in color, and are subjected to corrosion and wear resistance experiments (a neutral salt spray resistance experiment is carried out on the converted film layers for a time required for a phenomenon of white erosion or bubbling under a sodium chloride atmosphere of 4%; a solvent resistance experiment is carried out on the converted film layers for a time required for a phenomenon of white erosion or bubbling under a neutral salt spray condition after being soaked in a 95% ethanol solution for 15 minutes, and a yellowing resistance experiment is carried out on the converted film layers for a time required for a phenomenon of white erosion or bubbling under a neutral salt spray condition after being kept for 15 minutes under an atmospheric environment at 300 ℃), and the obtained data are as follows:
4032 aluminium alloy 3003 aluminum alloy 4032 aluminum alloy (commercially available chromate treatment) 3003 aluminum alloy (commercially available chromate passivator treatment)
Neutral salt fog resistant (hour) 95 92 79 76
Solvent resistance (hours) 78 76 63 60
Yellowing resistance (hour) 46 42 35 32
Example 2
A no-clean chromium-free conversion agent for a continuous coil unit comprises the following components in percentage by weight: 8% of phosphoric acid, 4% of nitric acid, 4.5% of citric acid, 3.5% of gluconic acid, 3% of fluotitanic acid, 3% of fluozirconic acid, 4.5% of manganese carbonate, 6% of film forming accelerant, 0.6% of thickening agent and the balance of deionized water.
The film forming accelerant is as follows: 3% of fluoboric acid and 3% of fluosilicic acid;
the thickening agent is as follows: 0.3 percent of sodium polyacrylate and 0.3 percent of polyoxyethylene.
The preparation method of the conversion agent comprises the following steps:
(1) according to the formula composition of raw materials, phosphoric acid, nitric acid, fluotitanic acid, fluozirconic acid and deionized water are fully stirred to prepare a solution A;
(2) dissolving citric acid, gluconic acid, manganese carbonate, fluoroboric acid, fluosilicic acid, sodium polyacrylate, polyoxyethylene and the like in a proper amount of deionized water, and fully stirring until the solution is dissolved to prepare a solution B;
(3) and slowly adding the solution A into the solution B, and fully stirring to prepare the cleaning-free chromium-free conversion agent.
The conversion agent prepared in the embodiment is used for respectively carrying out continuous coil unit process treatment on the surfaces of ZG10Cr13 steel, ASTMA526 galvanized plates and ASTMA642 galvanized plates, the treated conversion film layer is flat and compact and has uniform color, and an anticorrosion and wear-resistant experiment (the time required for the phenomenon of white corrosion or blistering under a sodium chloride atmosphere with the neutral salt spray resistance experiment of 4 percent, the time required for the phenomenon of white corrosion or blistering under a neutral salt spray condition after being soaked in a 95 percent ethanol solution for 15 minutes in a solvent-resistant experiment, the time required for the phenomenon of white corrosion or blistering under an atmospheric environment at 300 ℃ for 15 minutes and then under a neutral salt spray condition in a yellowing-resistant experiment) is carried out, and the measured data are as follows:
ZG10Cr13 steel ASTMA526 galvanized sheet ZG10Cr13 Steel (commercial chromium salt passivator treatment) ASTMA526 galvanized sheet (commercial chromium salt passivator treatment)
Neutral salt fog resistant (hour) 88.5 86 69.5 67
Solvent resistance (hours) 75 73.5 59 56
Yellowing resistance (hour) 45 41.5 32 30
Example 3
A no-clean chromium-free conversion agent suitable for a continuous coil unit comprises the following components in percentage by weight: 10% of phosphoric acid, 2% of nitric acid, 3.5% of citric acid, 4.5% of gluconic acid, 3% of fluotitanic acid, 3% of fluozirconic acid, 4.5% of manganese carbonate, 7% of film forming accelerant, 0.8% of thickening agent and the balance of deionized water.
The film forming accelerant is as follows: 4% of fluoboric acid and 3% of fluosilicic acid;
the thickening agent is as follows: 0.2 percent of sodium carboxymethylcellulose, 0.3 percent of sodium polyacrylate and 0.3 percent of polyvinylpyrrolidone.
The preparation method of the conversion agent comprises the following steps:
(1) according to the formula composition of raw materials, phosphoric acid, nitric acid, fluotitanic acid, fluozirconic acid and deionized water are fully stirred to prepare a solution A;
(2) according to the formula of the raw materials, citric acid, gluconic acid, manganese carbonate, fluoroboric acid, fluosilicic acid, sodium carboxymethylcellulose, sodium polyacrylate, polyvinylpyrrolidone and the like are dissolved in a proper amount of deionized water, and the solution B is prepared after the solution is fully stirred and dissolved;
(3) and slowly adding the solution A into the solution B, and fully stirring to prepare the cleaning-free chromium-free conversion agent.
The conversion agent prepared in this example is used for performing an immersion process on the surfaces of HT100 steel and astm a642 galvanized sheet for 3 minutes, the converted film after the treatment is flat and compact, has uniform color and luster, and is subjected to an anticorrosion and wear-resistant test (a neutral salt spray test is performed on the conversion agent, wherein the neutral salt spray test is performed on the conversion agent, the time required for the occurrence of white corrosion or blistering occurs in a sodium chloride atmosphere with a concentration of 4%; a solvent resistance test is performed on the conversion agent, the time required for the occurrence of white corrosion or blistering occurs after the conversion agent is soaked in a 95% ethanol solution for 15 minutes and then placed under a neutral salt spray condition, and a yellowing resistance test is performed on the conversion agent, the time required for the occurrence of white corrosion or blistering occurs after the conversion agent is:
HT100 steel ASTMA642 galvanized sheet HT100 Steel (commercially available chromium salt passivator treatment) ASTMA642 galvanized sheet (commercially available chromium salt passivator treatment)
Neutral salt fog resistant (hour) 85 82 66 63
Solvent resistance (hours) 71.5 68 53 51
Yellowing resistance (hour) 41 38 30 28.5

Claims (5)

1. A no-clean chromium-free conversion agent for a continuous coil unit and a preparation method thereof are characterized in that the conversion agent comprises the following components by mass percent:
5-25% of phosphoric acid, 1.5-5.5% of nitric acid, 2.5-10.5% of citric acid, 1.5-5.5% of gluconic acid, 1.5-5.5% of fluotitanic acid, 1.5-5.5% of fluozirconic acid, 1.0-15% of manganese carbonate, 1.0-10% of film forming promoter, 0.2-5.0% of thickening agent and the balance of deionized water.
2. The no-clean chromium-free conversion agent for the continuous coil unit as claimed in claim 1, wherein the film-forming promoter is one or more of fluoboric acid and fluosilicic acid.
3. The no-clean chromium-free conversion agent for the continuous coil unit as claimed in claim 1, wherein the thickener is one or more of methylcellulose, sodium carboxymethylcellulose, sodium polyacrylate, polyoxyethylene and polyvinylpyrrolidone.
4. The no-clean chromium-free conversion agent for continuous coil unit as claimed in claim 1, wherein the material is selected from aluminum coil, steel coil, hot-dip galvanized coil, electrogalvanized steel coil and alloy.
5. The no-clean chromium-free conversion agent for the continuous coil unit and the preparation method thereof according to claim 1 are characterized by comprising the following steps:
(1) according to the formula composition of raw materials, phosphoric acid, nitric acid, fluotitanic acid, fluozirconic acid and deionized water are fully stirred to prepare a solution A;
(2) dissolving citric acid, gluconic acid, manganese carbonate, a film forming promoter, a thickening agent and the like in a proper amount of deionized water, and fully stirring until the citric acid, the gluconic acid, the manganese carbonate, the film forming promoter, the thickening agent and the like are dissolved to prepare a solution B;
(3) and slowly adding the solution A into the solution B, and fully stirring to prepare the cleaning-free chromium-free conversion agent.
CN202010889174.3A 2020-08-29 2020-08-29 No-clean chromium-free conversion agent for continuous coil unit and preparation method thereof Pending CN112030151A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112501599A (en) * 2020-12-31 2021-03-16 合肥朗逸表面处理有限公司 Multipurpose chromium-free metal surface conversion agent and preparation method thereof
CN112593221A (en) * 2020-12-09 2021-04-02 苏州帝航防护设施有限公司 Anti-oxidation aluminum alloy surface treating agent

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CN101967633A (en) * 2010-09-16 2011-02-09 华南理工大学 Treatment liquid and method or preparing Ti/Zr-containing yellow passive film on surface of aluminum alloy
CN103668157A (en) * 2013-12-13 2014-03-26 三达奥克化学股份有限公司 Low-cost environmental-friendly silane vitrification treatment agent for steel and iron workpieces
CN106756933A (en) * 2016-12-28 2017-05-31 河南恒润昌环保科技有限公司 A kind of aluminium alloy chrome-free tanning agent and preparation method thereof
CN107675154A (en) * 2017-11-18 2018-02-09 安徽省万帮新型建材科技有限公司 A kind of inactivating treatment liquid for aluminum alloy materials
CN108149232A (en) * 2017-12-24 2018-06-12 无锡市恒利弘实业有限公司 A kind of aluminium or seven line aluminium alloys environmentally friendly passivating solution and preparation method thereof and treatment process
CN110607522A (en) * 2019-10-12 2019-12-24 佛山市湾厦新材料科技有限公司 Vitrification agent and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101967633A (en) * 2010-09-16 2011-02-09 华南理工大学 Treatment liquid and method or preparing Ti/Zr-containing yellow passive film on surface of aluminum alloy
CN103668157A (en) * 2013-12-13 2014-03-26 三达奥克化学股份有限公司 Low-cost environmental-friendly silane vitrification treatment agent for steel and iron workpieces
CN106756933A (en) * 2016-12-28 2017-05-31 河南恒润昌环保科技有限公司 A kind of aluminium alloy chrome-free tanning agent and preparation method thereof
CN107675154A (en) * 2017-11-18 2018-02-09 安徽省万帮新型建材科技有限公司 A kind of inactivating treatment liquid for aluminum alloy materials
CN108149232A (en) * 2017-12-24 2018-06-12 无锡市恒利弘实业有限公司 A kind of aluminium or seven line aluminium alloys environmentally friendly passivating solution and preparation method thereof and treatment process
CN110607522A (en) * 2019-10-12 2019-12-24 佛山市湾厦新材料科技有限公司 Vitrification agent and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112593221A (en) * 2020-12-09 2021-04-02 苏州帝航防护设施有限公司 Anti-oxidation aluminum alloy surface treating agent
CN112501599A (en) * 2020-12-31 2021-03-16 合肥朗逸表面处理有限公司 Multipurpose chromium-free metal surface conversion agent and preparation method thereof

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Application publication date: 20201204