CN107488844B - Fluoride-free chromium-free passivation solution for tin-plated steel plate and use method thereof - Google Patents
Fluoride-free chromium-free passivation solution for tin-plated steel plate and use method thereof Download PDFInfo
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- CN107488844B CN107488844B CN201610405914.5A CN201610405914A CN107488844B CN 107488844 B CN107488844 B CN 107488844B CN 201610405914 A CN201610405914 A CN 201610405914A CN 107488844 B CN107488844 B CN 107488844B
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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
- 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
- C23C22/06—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 acidic solutions with pH less than 6
- C23C22/07—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 acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/10—Orthophosphates containing oxidants
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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
- 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
- C23C22/06—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 acidic solutions with pH less than 6
- C23C22/07—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 acidic solutions with pH less than 6 containing phosphates
Abstract
The invention discloses a fluoride-free chromium-free passivation solution for a tin-plated steel plate and a use method thereof. A fluoride-free chromium-free passivation solution for tin-plated steel plates comprises the following components in parts by weight: titanium salt, and the content of the titanium salt is 0.1-50 g/L; a phosphorus-containing compound in an amount of 0.1 to 50 g/L; an oxidant, and the content of the oxidant is 1-100 g/L; a complexing agent, wherein the content of the complexing agent is 1-100 g/L; the balance being water. The cold-rolled tin-plated steel plate treated by the fluoride-free chromium-free passivation solution has excellent corrosion resistance, vulcanization resistance and paint adhesion; the fluoride-free chromium-free passivation solution is directly sprayed, has obvious electricity saving compared with an electrolytic passivation process, does not generate waste liquid, and is environment-friendly.
Description
Technical Field
The invention relates to a passivation solution for passivation treatment of a tin-plated steel plate, in particular to a fluoride-free chromium-free passivation solution for a tin-plated steel plate and a use method thereof, belonging to the technical field of surface treatment of metal materials.
Background
In the production process of the cold-rolled tin-plated steel plate, after the steel plate is subjected to tin plating and reflow, in order to improve the corrosion resistance of the tin-plated steel plate, prevent the tin-plated layer from oxidizing and yellowing during storage or paint baking of the tin-plated steel plate, and improve the performances of the tin-plated steel plate such as resistance to sulfur blackening and the like, the tin-plated steel plate needs to be subjected to passivation treatment.
Currently, the most common passivation method is cathodic passivation with dichromate containing hexavalent chromium. The passivation film obtained after the passivation treatment by the dichromate is very thin, has good corrosion resistance and simple process, and is the most common passivation treatment method in factories for a long time. However, because of the use of dichromate or chromic anhydride as the main salt in the passivation process, the hexavalent chromium contained in dichromate is a highly toxic substance. Hexavalent chromium is a swallowable/inhalant poison, and skin contact may lead to allergies; the medicine is more likely to cause genetic gene defects, inhalation is likely to cause cancer, and long-term contact can cause symptoms of headache, coma, nasal mucosa atrophy, nasal perforation, skin ulcer, even various canceration and the like. The method has great harm to human health and has lasting danger to the environment. Particularly for the passivation treatment of tin plate in food and beverage industry, the harm to human body caused by adopting chromate passivation technology is not negligible. In addition, during the production of tin plates, some waste liquid is discharged, and the waste liquid also seriously pollutes the environment.
In recent years, more and more workers have been invested in the development of chromium-free passivation solutions, and some chromium-free passivation solution formulations have appeared. Chinese patent document CN1726304A discloses a treatment liquid for metal surface treatment and a surface treatment method, which contains 5 to 5000ppm of 1 or more compounds of zirconium or titanium, further contains 0.1 to 100ppm of free fluoride ions, and has a pH of 2 to 6.
Chinese patent document CN101535528A discloses a Zr/Ti-containing phosphating solution for passivating the surface of a metal composite material, wherein the composition of the solution is 5-50 g/L of phosphate ions, 0.3-3 g/L of zinc ions, 1-200 ppm of one or more water-soluble compounds of zirconium and/or titanium and 1-400 ppm of free fluoride ions.
Chinese patent document CN101631895A discloses a method for treating metal surfaces by treating with an oxidizing acidic pre-rinse followed by contact with one or more hydrofluoric acids comprising one or more elements selected from titanium, zirconium, hafnium, silicon, tin, germanium, aluminum and boron.
Chinese patent document CN102373453A discloses a chromium-free passivation solution, wherein the raw material mixture of the chromium-free passivation solution contains a silane coupling agent and water, and further contains a titanium compound, an inorganic silicon compound, a water-soluble film forming agent, and tannic acid and/or phytic acid, wherein the titanium compound is one or more of hexafluorotitanic acid, ammonium hexafluorotitanate, potassium hexafluorotitanate, metatitanic acid or titanyl sulfate, and the inorganic silicon compound is one or more of nano silica powder, silica sol and sodium silicate.
Chinese patent document CN102027157A discloses a method for coating a metal surface with a passivating agent, the passivating agent and its use, the solution composition comprises at least one phosphate, at least 3g/L of at least one titanium or/and zirconium compound and at least one complexing agent, and also designs a corresponding aqueous composition, wherein the content of free fluoride contained in the complexing agent is 0.01-5 g/L.
Chinese patent document CN102066612A discloses an optimized Ti/Zr based passivation for metal surfaces, comprising in the reagent one or more water soluble compounds containing at least one atom selected from the elements titanium and/or zirconium, one or more water soluble compounds containing at least one fluorine atom.
Chinese patent document CN102851660A discloses a phosphorus-free and chromium-free passivation film-forming solution for steel surfaces and a using method thereof, wherein each liter of aqueous solution contains 1-20% of fluoride, 0.001-1% of titanium ions, 0.1-20% of oxidant, 0.001-1% of trivalent metal salt and 0.001-1% of surfactant.
Fluorine is widely present in natural water, and all tissues of a human body contain fluorine, but the fluorine is mainly accumulated in teeth and bone tendons, proper fluorine is necessary for the human body, and excessive fluorine is harmful to the human body. The lethal dose of sodium fluoride to human is 6-12 g, and high-level fluoride (10 mg/day) in long-term contact (about 10-20 years) can cause bone fluorosis, which is mainly manifested by arthralgia and sclerosis, ligament sclerosis and calcification, bone deformity, muscle weakness and nerve defect, so that bones become fragile.
Therefore, the development of the chromium-free fluorine-free green environment-friendly passivation solution has urgent need and has important significance for the production of tin-plated steel plates.
Disclosure of Invention
The invention aims to provide a fluoride-free chromium-free passivation solution for a tin-plated steel plate and a using method thereof, wherein the passivation solution does not contain chromium and fluorine, and solves the technical problems of chromium in the existing chromate passivation solution and fluorine in the chromium-free passivation solution; the cold-rolled tin-plated steel plate treated by the passivation solution has excellent corrosion resistance, vulcanization resistance and paint adhesion.
The technical scheme adopted by the invention is as follows: a fluoride-free chromium-free passivation solution for tin-plated steel plates comprises the following components in parts by weight: titanium salt, and the content of the titanium salt is 0.1-50 g/L; a phosphorus-containing compound in an amount of 0.1 to 50 g/L; an oxidant, and the content of the oxidant is 1-100 g/L; a complexing agent, wherein the content of the complexing agent is 1-100 g/L; the balance being water.
The titanium salt is soluble titanium salt and is one or more of potassium titanium oxalate, titanium sulfate, titanyl sulfate and titanium tetrachloride;
the compound containing phosphorus is one or more of soluble phosphoric acid, monohydrogen phosphate, dihydrogen phosphate and phosphate.
The oxidant is one or more of sodium peroxide, hydrogen peroxide, persulfate and sodium hypochlorite.
The complexing agent is an inorganic complexing agent or an organic complexing agent, and the complexing agent is an inorganic complexing agent and is one or more of bromide ions, chloride ions, nitrate ions, pyrophosphate ions and hydrogen peroxide; the complexing agent is organic complexing agent, and is one or more of malic acid, citric acid, tartaric acid, lactic acid, propionic acid, glycolic acid, triethanolamine and glycine.
The preparation method of the fluoride-free chromium-free passivation solution comprises the following steps:
1) respectively weighing or weighing titanium salt, a phosphorus-containing compound, an oxidant, a complexing agent and water according to the proportion;
2) putting titanium salt and water into a container, and uniformly mixing to ensure that the titanium salt is completely dissolved in the water; then adding a complexing agent into the water to fully complex the solution; sequentially adding an oxidant and a compound containing phosphorus into the solution; fully and uniformly stirring to obtain the finished product of the fluoride-free chromium-free passivation solution.
The titanium salt, the phosphorus-containing compound, the oxidant and the complexing agent in the step 1) are all analytically pure.
The method for passivating the tin-plated steel plate by using the fluorine-free chromium-free passivation solution comprises the following steps of:
1) heating the fluorine-free chromium-free passivation solution to 30-50 ℃;
2) spraying the fluorine-free and chromium-free passivation solution on the surface of the reflowed tin-plated steel plate, and controlling the thickness of a wet film of the chromium-free passivation solution on the surface of the tin-plated steel plate to be 3-6 mu m;
3) drying the tin-plated steel plate obtained in the step 2) for 5-15 s under hot air at the temperature of 80-100 ℃.
Compared with the prior art, the invention has the following positive effects: 1. the chromium-free passivation solution disclosed by the invention solves the technical problems of chromium-containing in the existing chromate passivation solution and fluorine-containing in the chromium-free passivation solution, does not need electrolytic passivation in the passivation treatment of the chromium-free passivation solution disclosed by the invention, directly adopts spraying, has obvious electricity saving compared with an electrolytic passivation process, does not generate waste liquid, and is environment-friendly. 2. The salt spray resistance grade, porosity, sulfur resistance, adhesive force and the like of the tin-plated steel plate passivated by the fluorine-free chromium-free passivation solution reach or exceed the level of the tin-plated steel plate passivated by chromate.
Detailed Description
The present invention will be further illustrated below with reference to specific embodiments, which are to be understood as merely illustrative and not limitative of the scope of the present invention.
The passivated tin-plated steel sheets of examples 1-3 and comparative example 1 were named MRT4-CA, and the thickness of the steel sheets was 0.2mm and the thickness of the tin-plated steel sheets was 2.8g/m2。
Example 1, a fluoride-free chromium-free passivation solution for tin-plated steel plates, which comprises the following components in parts by weight: titanium sulfate, and the content of the titanium sulfate is 10 g/L; phosphoric acid, and the content of the phosphoric acid is 5 g/L; sodium persulfate, and the content of the sodium persulfate is 10 g/L; citric acid, and the content of the citric acid is 20 g/L; the balance being water
The method for passivating the tin-plated steel plate by using the fluorine-free chromium-free passivation solution comprises the following steps of:
1) heating the fluorine-free chromium-free passivation solution to 50 ℃;
2) spraying the fluorine-free and chromium-free passivation solution on the surface of the reflowed tin-plated steel plate, and controlling the thickness of a wet film of the chromium-free passivation solution on the surface of the tin-plated steel plate to be 5 mu m;
3) drying the tin-plated steel plate obtained in the step 2) for 10s at 80 ℃ in hot air.
The tin-plated steel sheets passivated according to the method of example 1 were tested as follows: carrying out salt spray resistance grade detection according to GB/T10125-2012 'Artificial atmosphere Corrosion test'; the porosity test is carried out according to GB/T17721-.
Embodiment 2, a fluoride-free chromium-free passivation solution for tin-plated steel plate, which comprises the following components in proportion: the content of the titanium potassium oxalate is 5 g/L; zinc dihydrogen phosphate, and the content of the zinc dihydrogen phosphate is 10 g/L; sodium hypochlorite with the content of 10 g/L; hydrochloric acid, and the content of the hydrochloric acid is 5 g/L; the balance being water
The method for passivating the tin-plated steel plate by using the fluorine-free chromium-free passivation solution comprises the following steps of:
1) heating the fluorine-free chromium-free passivation solution to 40 ℃;
2) spraying the fluorine-free and chromium-free passivation solution on the surface of the reflowed tin-plated steel plate, and controlling the thickness of a wet film of the chromium-free passivation solution on the surface of the tin-plated steel plate to be 4 mu m;
3) drying the tin-plated steel plate obtained in the step 2) for 15s at 90 ℃ in hot air.
The tin-plated steel plate passivated according to the method of example 2 was subjected to the salt spray resistance level, porosity, sulfur resistance and adhesion detection, the detection method was the same as that of example 1, and the detection results are shown in table 1.
Example 3, a fluoride-free chromium-free passivation solution for tin-plated steel plates, which comprises the following components in parts by weight: titanium tetrachloride, and the content of the titanium tetrachloride is 15 g/L; zinc monohydrogen phosphate, and the content of the zinc monohydrogen phosphate is 20 g/L; hydrogen peroxide, and the content of the hydrogen peroxide is 30 g/L; tartaric acid, and the content of the tartaric acid is 5 g/L; the balance being water
The method for passivating the tin-plated steel plate by using the fluorine-free chromium-free passivation solution comprises the following steps of:
1) heating the fluorine-free chromium-free passivation solution to 50 ℃;
2) spraying the fluorine-free and chromium-free passivation solution on the surface of the reflowed tin-plated steel plate, and controlling the thickness of a wet film of the chromium-free passivation solution on the surface of the tin-plated steel plate to be 6 mu m;
3) drying the tin-plated steel plate obtained in the step 2) for 8s at the temperature of 90 ℃ by hot air.
The tin-plated steel plate passivated according to the method of example 3 was subjected to the salt spray resistance level, porosity, sulfur resistance and adhesion detection, the detection method was the same as that of example 1, and the detection results are shown in table 1.
In the comparative example 1,carrying out passivation treatment on the tin-plated steel plate by using a chromate passivation solution, wherein the concentration of a sodium dichromate solution is 25g/L, the pH value is 4.5, and the cathode electrolytic passivation current density is 0.8A/m2The electrifying time is 5s, and the thickness of the passivation film is 5.0mg/m2。
The tin-plated steel plate passivated according to the method of the comparative example 1 is respectively subjected to salt spray resistance level, porosity, sulfur resistance and adhesion detection, the detection method is the same as that of the example 1, and the detection results are shown in the table 1.
TABLE 1 Performance parameters after passivation treatment of tin-plated steel sheets according to examples of the present invention
The foregoing is only a preferred embodiment of the present invention, and other embodiments of the present invention are possible in addition to the above-described embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (3)
1. A fluoride-free chromium-free passivation solution for tin-plated steel plates is characterized by comprising the following components in parts by weight: titanium salt, and the content of the titanium salt is 0.1-50 g/L; a phosphorus-containing compound in an amount of 0.1 to 50 g/L; an oxidant, and the content of the oxidant is 1-100 g/L; a complexing agent, wherein the content of the complexing agent is 1-100 g/L; the balance of water; the titanium salt is soluble titanium salt and is one or more of potassium titanium oxalate, titanium sulfate, titanyl sulfate and titanium tetrachloride; the compound containing phosphorus is one or more of soluble phosphoric acid and soluble phosphate; the oxidant is one or more of sodium peroxide, hydrogen peroxide, persulfate and sodium hypochlorite; the complexing agent is an inorganic complexing agent or an organic complexing agent, and the complexing agent is an inorganic complexing agent and is one or more of bromide ions, chloride ions, pyrophosphate ions and hydrogen peroxide; the complexing agent is organic complexing agent, and is one or more of malic acid, citric acid, tartaric acid, lactic acid, propionic acid, glycolic acid, triethanolamine and glycine.
2. A method of making the fluorine-free chromium-free passivation solution of claim 1, comprising the steps of:
1) respectively weighing or weighing titanium salt, a compound containing phosphorus, an oxidant, a complexing agent and water according to a ratio, wherein the titanium salt, the compound containing phosphorus, the oxidant and the complexing agent are analytically pure;
2) putting titanium salt and water into a container, and uniformly mixing to ensure that the titanium salt is completely dissolved in the water; then adding a complexing agent into the water to fully complex the solution; sequentially adding an oxidant and a compound containing phosphorus into the solution; fully and uniformly stirring to obtain the finished product of the fluoride-free chromium-free passivation solution.
3. A method for passivating a tin-plated steel sheet using the fluorine-free chromium-free passivation solution of claim 1, comprising the steps of:
1) heating the fluorine-free chromium-free passivation solution to 30-50 ℃;
2) spraying the fluorine-free and chromium-free passivation solution on the surface of the reflowed tin-plated steel plate, and controlling the thickness of a wet film of the chromium-free passivation solution on the surface of the tin-plated steel plate to be 3-6 mu m;
3) drying the tin-plated steel plate obtained in the step 2) for 5-15 s under hot air at the temperature of 80-100 ℃.
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| WO2019006608A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市宏昌发科技有限公司 | Passivator, method of surface passivation for metal-plated part and metal workpiece |
| CN110551997B (en) * | 2018-06-04 | 2022-03-15 | 上海梅山钢铁股份有限公司 | Chromium-free passivation solution for electrotinning steel plate and use method thereof |
| CN115074714A (en) * | 2022-06-16 | 2022-09-20 | 广州三孚新材料科技股份有限公司 | Composite conversion coating treatment solution for surface of tinned plate and process for preparing conversion coating by using treatment solution |
| CN115786894A (en) * | 2023-01-06 | 2023-03-14 | 广东腐蚀科学与技术创新研究院 | Vanadium-containing treatment fluid and preparation method thereof |
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