CN110616422B - Chromium-free environment-friendly passivator for galvanized sheet and preparation and use method thereof - Google Patents
Chromium-free environment-friendly passivator for galvanized sheet and preparation and use method thereof Download PDFInfo
- Publication number
- CN110616422B CN110616422B CN201910950530.5A CN201910950530A CN110616422B CN 110616422 B CN110616422 B CN 110616422B CN 201910950530 A CN201910950530 A CN 201910950530A CN 110616422 B CN110616422 B CN 110616422B
- Authority
- CN
- China
- Prior art keywords
- chromium
- free environment
- passivator
- friendly
- galvanized
- 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.)
- Active
Links
Images
Classifications
-
- 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
- C23C22/00—Chemical 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
- C23C22/05—Chemical 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
- C23C22/68—Chemical 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 solutions with pH between 6 and 8
Abstract
The invention relates to a chromium-free environment-friendly passivator for a galvanized sheet and a preparation and use method thereof, wherein the passivator comprises the following components in parts by weight: 20-40 parts of latent curing type polyurethane emulsion; 5-20 parts of a zirconium coupling agent; organic compounds0.5-5 parts of zinc antirust agent; 1-8 parts of palm wax emulsion; 40-65 parts of pure water; the organic zinc antirust agent is ALCOPHOR; the pure water has a conductivity of less than 0.1 × 10‑6mΩ.cm‑1. The advantages are that: when the latent curing type polyurethane emulsion is used for curing, a film component is formed on a zinc plate through a cross-linking reaction, a zirconium coupling agent is organically complexed, corrosion of fluorine ions, sulfate ions and chloride ions is avoided, an organic zinc antirust agent, polyurethane and the coupling agent form an alternate cross-linking reaction, a firm passivation film is formed, and the latent curing type polyurethane emulsion has excellent corrosion prevention, wear resistance and lubrication effects.
Description
Technical Field
The invention relates to a chromium-free environment-friendly passivator for a galvanized sheet and a preparation and use method thereof.
Background
Galvanization is an effective method for improving the atmospheric corrosion resistance of steel, but in a humid environment, a galvanized layer is easy to corrode, white loose corrosion products are generated on the surface, dark gray products are sometimes generated, and the appearance and the performance of a steel plate are seriously affected, so that the galvanized plate needs to be passivated, and a protective film is covered on the surface of the galvanized plate. The passivating agent is a necessary product in the galvanizing processing process, the surface of a newly manufactured galvanized plate is very active, and the galvanized plate needs to be passivated before being packaged and stored in a warehouse so as to improve the antirust capacity in the storage and transportation processes. The action mechanism of the passivating agent is to seal micropores on the surface of the steel plate, and primary batteries are easily formed at the micropores to aggravate corrosion. The passivated steel plate has a smoother and more beautiful appearance, and does not influence subsequent processing such as welding, polishing and the like. The traditional passivation process adopts hexavalent chromic acid solution or sodium nitrite solution, and has self-repairing capability. Both of the above are carcinogenic substances, and the country has gradually abolished, especially exported products, and the use is forbidden. If the water discharged by European Union is not allowed to exceed 0.3mg/m3Some countries even propose no chromium (Cr) in wastewater6+) The ROHS directive of no hexavalent chromium is started to be implemented in 7 months in the European Union in 2006. Sodium nitrite is in contact with the skin for a long time, so that people can have serious skin allergy, and the taking of a few grams of sodium nitrite by mistake constitutes dangerous methemoglobinemia.
In recent years, the research on passivators is very active, more than 100 patent applications are already carried out in China, 50-60 passivators for galvanized plates are also available, and the passivators mainly focus on inorganic component passivators such as silicate, molybdate, titanate, zirconate and rare earth cerium lanthanum, but the antirust effect is not good when the protective film is too thin. The passivator composed of high polymer films such as conventional acrylic emulsion, polyurethane emulsion and the like has poor bonding strength with a metal matrix and also has unsatisfactory antirust effect. The third category is that the inorganic organic polymer composite passivator is improved compared with the two categories, but the adopted fluotitanate and fluozirconate assistants such as hydrogen fluoride, potassium fluoride, ammonium fluoride, sodium fluoride, fluosilicate and the like have obvious corrosion effect on the galvanized sheet; the adopted silane coupling agent and titanate coupling agent are easy to hydrolyze and have poor stability; the adopted anions of the rust inhibitors such as titanyl sulfate, lanthanum chloride, titanium trichloride and the like also have corrosion effect, and the high-grade chromium-free environment-friendly passivator which can be really used for industrial production is few.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a chromium-free environment-friendly passivator for a galvanized sheet and a preparation and use method thereof, which can meet the current environment-friendly requirement and can well protect a galvanized substrate.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a chromium-free environment-friendly passivator for a galvanized sheet comprises the following components in parts by weight:
the organic zinc antirust agent is ALCOPHOR.
The pure water has an electric conductivity of less than 0.1 × 10-6mΩ.cm-1。
Latent curing polyurethane emulsion is used as main filming matter and has exposed and cured reaction group during high temperature stoving. Too much tends to cause microcracking in the film, and increases the cost, and too little protection becomes weak. Selecting latent curing type single-component polyurethane emulsion.
The zirconium coupling agent further crosslinks and cures the polymer film, and when the amount is less than 5 parts, the curing is slowed down.
The organic zinc rust inhibitor (trade name alcopor) is distributed in the film phase and reacts with the zinc surface further to play a role in rust prevention. When the content is too large, the crystalline particles become large to affect the integrity of the film. ALCOPHOR 827 available from Hangao or Hechuan chemical may be selected.
The palm wax emulsion can enable the film to have lubricity on the premise of not influencing the antirust capacity, is convenient for subsequent shearing processing precision, and has the characteristic of small corrosivity. Less than 1 part is preferable because lubricity will be lost and foaming will occur when too much is applied.
Pure water (conductivity less than 0.1X 10)-6mΩ.cm-1) High purity water is the basis and guarantee of rust prevention.
A preparation method of a chromium-free environment-friendly passivator for a galvanized sheet comprises the following steps:
1) uniformly mixing the latent curing type polyurethane emulsion and the zirconium coupling agent;
2) uniformly mixing an organic zinc antirust agent and pure water;
3) mixing the mixed solution obtained in the step 1) and the step 2), adding the palm wax emulsion, and grinding in a sand mill for more than 10min to obtain the uniform chromium-free environment-friendly passivator.
A using method of a chromium-free environment-friendly passivator for a galvanized sheet comprises the following steps:
1) degreasing, cleaning and drying the galvanized steel sheet;
2) the galvanized sheet is evenly coated with the chromium-free environment-friendly passivating agent on two sides through a roller coater, and the coating amount is 1.2-2.0g/m on one side2；
3) After being coated, the galvanized steel sheet is dried by hot air, and the temperature of the galvanized steel is controlled at 70-95 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the chromium-free environment-friendly passivator for the galvanized sheet utilizes cross-linking reaction on the galvanized sheet to form a membrane component when latent curing type polyurethane emulsion is cured, organically complexes a zirconium coupling agent to avoid corrosion of fluoride ions, sulfate ions and chloride ions, and forms a firm passivation membrane by the interpenetrating cross-linking reaction of an organic zinc antirust agent, polyurethane and the coupling agent, and has excellent corrosion prevention, wear resistance and lubrication effects. Under the condition of 85-95 ℃ of plate temperature, the drying speed is fast, the involucra has certain toughness, and the impact resistance is improved. The bonding strength, the rust resistance, the aging resistance and other key indexes are excellent, and white rust does not exist within 72 hours of a salt spray corrosion test.
Drawings
FIG. 1 is a first micrograph of a galvanized sheet treated with a chromium-free environmental passivation agent for galvanized sheets.
FIG. 2 is a second micrograph of a galvanized sheet treated with a chromium-free environmental passivation agent for galvanized sheets.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
A chromium-free environment-friendly passivator for a galvanized sheet comprises the following components in parts by weight:
the organic zinc antirust agent is ALCOPHOR. The pure water has a conductivity of less than 0.1 × 10-6mΩ.cm-1. The carnauba wax emulsion is preferably a carnauba wax emulsion.
Latent curing polyurethane emulsion is used as main filming matter and has exposed and cured reaction group during high temperature stoving. Too much tends to cause microcracking in the film, and increases the cost, and too little protection becomes weak. Selecting latent curing type single-component polyurethane emulsion.
The zirconium coupling agent further crosslinks and cures the polymer film, and when the amount is less than 5 parts, the curing is slowed down.
The organic zinc rust inhibitor (trade name alcopor) is distributed in the film phase and reacts with the zinc surface further to play a role in rust prevention. When the content is too large, the crystalline particles become large to affect the integrity of the film. ALCOPHOR 827 available from Hangao or Hechuan chemical may be selected.
The carnauba wax emulsion can enable the film to have lubricity on the premise of not influencing the antirust capacity, and is convenient for subsequent shearing processing precision. Less than 1 part is preferable because lubricity will be lost and foaming will occur when too much is applied.
Pure water (conductivity less than 0.1X 10)-6mΩ.cm-1) High purity water is the basis and guarantee of rust prevention.
A preparation method of a chromium-free environment-friendly passivator for a galvanized sheet comprises the following steps:
1) uniformly mixing the latent curing type polyurethane emulsion and the zirconium coupling agent;
2) uniformly mixing an organic zinc antirust agent and pure water;
3) mixing the mixed solution obtained in the step 1) and the step 2), adding the carnauba wax emulsion, and grinding in a sand mill for more than 10min to obtain the uniform chromium-free environment-friendly passivator.
A using method of a chromium-free environment-friendly passivator for a galvanized sheet comprises the following steps:
1) degreasing the galvanized steel sheet, cleaning with pure water, and drying with hot air;
2) the galvanized sheet is evenly coated with the chromium-free environment-friendly passivating agent on two sides through a roller coater, and the coating amount is 1.2-2.0g/m on one side2；
3) After being coated, the galvanized steel sheet is dried by hot air, and the temperature of the galvanized steel is controlled to be 85-95 ℃.
The chromium-free environment-friendly passivator for the galvanized sheet comprises the following components in percentage by weight:
| example one | Example two | EXAMPLE III | Example four | |
| Latent curing polyurethane emulsion (unit:%) | 30 | 40 | 20 | 20 |
| Zirconium coupling agent (Unit:%) | 10 | 5 | 20 | 8 |
| Organic zinc antirust agent (unit:%) | 1.5 | 5 | 5 | 1 |
| Carnauba wax emulsion (unit:%) | 4 | 4 | 1 | 7 |
| Pure water (unit:%) | 54.5 | 46 | 54 | 64 |
The galvanized sheet chromium-free environment-friendly passivator has the following treatment effects:
the galvanized sheet chromium-free environment-friendly passivating agent can protect the corrosion resistance of the substrate after being coated on the galvanized sheet and has excellent binding force.
Claims (2)
1. The chromium-free environment-friendly passivator for the galvanized sheet is characterized by comprising the following components in parts by weight:
the organic zinc antirust agent is ALCOPHOR;
the preparation method of the chromium-free environment-friendly passivator for the galvanized sheet comprises the following steps:
1) uniformly mixing the latent curing type polyurethane emulsion and the zirconium coupling agent;
2) uniformly mixing an organic zinc antirust agent and pure water;
3) mixing the mixed solution obtained in the step 1) and the step 2), adding the carnauba wax emulsion, and grinding in a sand mill for more than 10min to obtain a uniform chromium-free environment-friendly passivator;
the passivator is applied to galvanized steel sheets, white rust does not exist within 72 hours of a salt spray corrosion test, and the breakage rate after being scratched by a hundred-grid knife is 0; the use method of the chromium-free environment-friendly passivator for the galvanized sheet is characterized by comprising the following steps:
1) degreasing, cleaning and drying the galvanized steel sheet;
2) the galvanized sheet is evenly coated with the chromium-free environment-friendly passivating agent on two sides through a roller coater, and the coating amount is 1.2-2.0g/m on one side2；
3) After being coated, the galvanized steel sheet is dried by hot air, and the temperature of the galvanized steel is controlled at 70-95 ℃; the formed passive film has excellent corrosion resistance, abrasion resistance and lubrication; under the condition of 85-95 ℃ of plate temperature, the drying speed is fast, the involucra has certain toughness, and the impact resistance is improved.
2. The galvanized sheet chromium-free environment-friendly passivator according to claim 1, wherein the conductivity of pure water is less than 0.1 x 10-6mΩ.cm-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910950530.5A CN110616422B (en) | 2019-10-08 | 2019-10-08 | Chromium-free environment-friendly passivator for galvanized sheet and preparation and use method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910950530.5A CN110616422B (en) | 2019-10-08 | 2019-10-08 | Chromium-free environment-friendly passivator for galvanized sheet and preparation and use method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110616422A CN110616422A (en) | 2019-12-27 |
| CN110616422B true CN110616422B (en) | 2022-03-22 |
Family
ID=68925514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910950530.5A Active CN110616422B (en) | 2019-10-08 | 2019-10-08 | Chromium-free environment-friendly passivator for galvanized sheet and preparation and use method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110616422B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114951933A (en) * | 2022-04-06 | 2022-08-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Spot welding method for environment-friendly passivated galvanized plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508767A (en) * | 1982-12-28 | 1985-04-02 | Dai Nippon Tokyo Co., Ltd | Process for forming a corrosion resistant coating |
| WO2017016455A1 (en) * | 2015-07-27 | 2017-02-02 | 宝山钢铁股份有限公司 | Environmentally friendly surface treating agent for galvanized steel sheet, galvanized steel sheet, and manufacturing method for galvanized steel sheet |
| WO2017028438A1 (en) * | 2015-08-14 | 2017-02-23 | 尤为 | Chromium-free passivator with hydrophobic surface property for plated metal |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010070730A1 (en) * | 2008-12-16 | 2010-06-24 | 日本パーカライジング株式会社 | Surface treating agent for galvanized steel sheet |
| CN104497841B (en) * | 2014-12-15 | 2016-08-24 | 中国钢研科技集团有限公司 | A kind of galvanized steel sheet surface aqueous chromium-free lubricated agent and using method thereof |
| CN104947098A (en) * | 2015-05-29 | 2015-09-30 | 焦占付 | Hot galvanizing chromium-free passivation agent and preparation method thereof |
-
2019
- 2019-10-08 CN CN201910950530.5A patent/CN110616422B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508767A (en) * | 1982-12-28 | 1985-04-02 | Dai Nippon Tokyo Co., Ltd | Process for forming a corrosion resistant coating |
| WO2017016455A1 (en) * | 2015-07-27 | 2017-02-02 | 宝山钢铁股份有限公司 | Environmentally friendly surface treating agent for galvanized steel sheet, galvanized steel sheet, and manufacturing method for galvanized steel sheet |
| WO2017028438A1 (en) * | 2015-08-14 | 2017-02-23 | 尤为 | Chromium-free passivator with hydrophobic surface property for plated metal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110616422A (en) | 2019-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100735595B1 (en) | Nonchromate metallic surface treating agent for pcm use, method for pcm surface treatment, and treated pcm steel panel | |
| EP1902157B1 (en) | Chrome-free composition of low temperature curing for treating a metal surface and a metal sheet using the same | |
| TWI457468B (en) | Hot-dip galvanized steel sheet and manufacturing method therefor | |
| CN100510177C (en) | Composition and method for surface treatment of metal materials | |
| CN102602079B (en) | Anti-stain and anti-fingerprint stainless steel plate and preparation method thereof | |
| CN101435078B (en) | Non-chrome resin composition, method for processing steel plate surface and steel plate | |
| WO1999018256A1 (en) | Surface treatment composition for metallic material and method for treatment | |
| JP2005120469A (en) | Composition for treating surface of metallic material, and surface treatment method | |
| WO1999046342A1 (en) | Surface treatment composition for metallic material and method of treatment | |
| CN102634785A (en) | Method for passivation of zinc and zinc alloy and chromium-free passivation solution | |
| CN108165968B (en) | A kind of metal surface treatment process | |
| CN104498925B (en) | A kind of metal surface treating liquid and application based on polyfunctional group alkyl phosphate | |
| CN105088208A (en) | Trivalent chrome complex for hot dip aluminum-zinc plate and preparation method of trivalent chrome complex | |
| CN106756945A (en) | A kind of plated steel sheet chromium-free passivation liquid | |
| JP2007002330A (en) | Surface treatment agent for zinc or zinc alloy galvanized steel sheet, and surface treated zinc or zinc alloy galvanized steel sheet | |
| CN110616422B (en) | Chromium-free environment-friendly passivator for galvanized sheet and preparation and use method thereof | |
| AU2012321711A1 (en) | Paint pretreatment agent for coating-type paint, and coating-type painting method | |
| CN109112518B (en) | Hot galvanizing chromium-free passivator | |
| EP0624182A1 (en) | Autodeposition coating composition | |
| CN105386025B (en) | A kind of hot galvanized layer chrome-free tanning agent and its preparation method | |
| EP2880108B1 (en) | Organic-inorganic hybrid coating solution composition and organic-inorganic hybrid coated steel sheet | |
| CN105296998A (en) | Control method of surface cracks of passivated membrane of chromium-free passivated galvanized plate | |
| JP3993729B2 (en) | Metal plate material excellent in corrosion resistance, paintability, fingerprint resistance and workability, and manufacturing method thereof | |
| CN112481574A (en) | High-corrosion-resistance hot galvanizing passivation solution and preparation method thereof | |
| CN105695971A (en) | Washing-free chromizing passivator for aluminum and aluminum alloy and use method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |