CN111690920A - Modified silica sol chromium-free passivator for surface treatment of hot-dip galvanized steel sheet and preparation method and application thereof - Google Patents
Modified silica sol chromium-free passivator for surface treatment of hot-dip galvanized steel sheet and preparation method and application thereof Download PDFInfo
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- 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
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- 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
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- 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
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Abstract
The invention relates to the technical field of metal surface corrosion prevention, and particularly discloses a preparation method and application of a modified silica sol chromium-free passivator for surface treatment of a hot-dip galvanized steel sheet. The passivator is an environment-friendly chromium-free passivator and is mainly prepared from raw materials such as nano-material modified water-based resin, modified silica sol, phosphate aqueous solution, aqueous solution of zirconium-containing compound and the like. The passivator forms a layer of passive film on the surface of a hot-dip galvanized steel sheet in a blade coating mode, and shows excellent corrosion resistance, black resistance, yellowing resistance and coating property. And the production process of the passivator is simple, the cost is low, the stability is good, and the passivator has a very high industrial application value.
Description
Technical Field
The invention relates to the technical field of novel metal surface anticorrosion materials, in particular to a preparation method of a modified silica sol chromium-free passivator for surface treatment of a hot-dip galvanized steel sheet and application of the passivator in the aspects of metal corrosion resistance, blackening resistance, yellowing resistance and coating performance.
Background
The hot-dip galvanized steel sheet is one kind of galvanized steel sheet and is mainly applied to the fields of vehicles, ships, electromechanics, household appliances, building materials and the like. Since the zinc layer is easily corroded during the production, storage and use of the hot dip galvanized steel sheet, the usability and the aesthetic property of the hot dip galvanized steel sheet are seriously affected. Therefore, it is very important to perform an anticorrosive treatment on the surface of the hot-dip galvanized steel sheet. At present, the hot galvanizing steel factory mainly adopts chromate passivation treatment, and the main components of the treatment agent are trivalent chromium and hexavalent chromium. In the process of chromate passivation, hexavalent chromium is highly toxic and carcinogenic, causing serious harm to the human body and environment. In recent years, with the increasing environmental protection requirements of China, the chromate used for the corrosion prevention treatment of the surface of a hot-dip galvanized steel sheet is strictly controlled, and a chromium-free passivating agent which is harmless to the environment is required to be used. At present, related chromium-free passivator products appear on the market, but most of the products have the problems of poor corrosion resistance, black degeneration resistance, yellowing resistance and coating performance, and directly influence the later use of the hot-dip galvanized steel sheet. Therefore, the targeted development of the chromium-free passivator with environmental protection and excellent comprehensive performance is very urgent and important.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the modified silica sol chromium-free passivator for remarkably improving various properties (corrosion resistance, black degeneration resistance, yellowing resistance and coating property) of a chromium-free passivation film on the surface of a hot-dip galvanized steel sheet, and the modified silica sol chromium-free passivator can be used as an environment-friendly passivator product to be widely applied to hot-dip galvanized steel plants.
The second purpose of the invention is to provide a preparation method of the modified silica sol chromium-free passivator, which has the advantages of simple production process, low cost, good stability, contribution to expanded production and very high industrial application prospect.
The technical scheme adopted by the invention is as follows: a modified silica sol chromium-free passivator for surface treatment of a hot-dip galvanized steel sheet is prepared from the following raw materials in parts by mass: (A) 32-80 parts of nano material modified water-based resin, 30-60 parts of modified silica sol (B), 3-10 parts of phosphate aqueous solution (C), 2-10 parts of zirconium compound-containing aqueous solution (D) and 10-100 parts of deionized water (E).
The optimized scheme is that the modified silica sol chromium-free passivator for surface treatment of the hot-dip galvanized steel sheet is prepared from the following raw materials in parts by mass: (A) 45-60 parts of nano material modified water-based resin, (B) 35-45 parts of modified silica sol, (C) 3.5-5 parts of phosphate aqueous solution, (D) 2-3 parts of zirconium compound-containing aqueous solution and (E) 60-90 parts of deionized water.
Preferably, the nanomaterial-modified aqueous resin (a) is an aqueous cationic polyurethane resin, and is prepared by the following method: adding 100 parts of polypropylene glycol 400 and 70 parts of Hexamethylene Diisocyanate (HDI) into a reaction vessel, and heating to 85 ℃ for reaction for 2 hours; and then cooling to 60 ℃, adding 2.8 parts of pentaerythritol, 15 parts of Methyldiethanolamine (MDEA) and 90 parts of acetone, continuing to react for 2 hours at 60 ℃, cooling to 42 ℃, adding 12 parts of 3-aminopropyltriethoxysilane, stirring for 1 hour, adding 360 parts of deionized water under stirring, and finally adjusting the pH value to 5.0 by using acetic acid to obtain the nano material modified water-based resin.
In a preferred embodiment, the modified silica sol (B) is prepared by the following method: adding 60 parts of water, 1 part of acetic acid and 3.8 parts of titanium sulfate into a reaction kettle, and heating to 50 ℃; and then 6 parts of silane coupling agent is dripped, the reaction solution is kept at 50 ℃ for 1h after the dripping is finished, then the reaction solution is cooled to room temperature, and the pH value is adjusted to 4.5 by acetic acid, thus obtaining the modified silica sol.
Preferably, the silane coupling agent used in the preparation of the modified silica sol (B) is one or more selected from the group consisting of ethyltriethoxysilane, vinyltriethoxysilane and methylvinyldiethoxysilane.
In a preferred embodiment, the preparation method of the (C) aqueous phosphate solution comprises: preparing phosphate and deionized water according to the ratio of 0.03g/mL to 0.15g/mL to obtain the phosphate-deionized water; the phosphate is selected from sodium dihydrogen phosphate and/or zinc dihydrogen phosphate.
In a preferred embodiment, the method for preparing the aqueous solution of the zirconium-containing compound (D) comprises: preparing the zirconium-containing compound and deionized water according to the ratio of 0.05g/mL to 0.1g/mL to obtain the zirconium-containing compound; the zirconium-containing compound is selected from fluorozirconic acid and/or zirconium acetate.
Further, the parts are all parts by mass.
The preferable scheme is that the modified silica sol chromium-free passivator for the surface treatment of the hot-dip galvanized steel plate comprises the following specific preparation steps: adding the deionized water (E) into a reaction kettle, sequentially adding the nano material modified water-based resin (A) and the modified silica sol (B), and mixing and stirring uniformly; then adding the aqueous solution of the phosphate (C) into a reaction kettle, and stirring; and finally, adding the aqueous solution containing the zirconium compound (D) into a reaction kettle to ensure that the pH value of the whole reaction system is 2-6, and stirring the reaction solution at room temperature for 1h to obtain the chromium-free passivator.
In the modified silica sol chromium-free passivator of the invention, (a) nanomaterial-modified waterborne resin: the organic polyurethane resin is modified by the nano material, so that the composite effect of the resin and the inorganic salt can be improved; the modified resin has great improvement effect on film formation, and also has great improvement on the properties such as adhesive force of a film layer. (A) The nano material modified water-based resin mainly provides a film-forming framework for the passive film and endows the passive film with certain corrosion resistance and coating property.
In the modified silica sol chromium-free passivating agent of the invention, (B) the modified silica sol: the titanium salt is introduced into the passivating agent, can form sol together with organic silicon, and has an obvious effect of improving the corrosion resistance of the passivating agent. (B) The main functions of the modified silica sol are as follows: firstly, a silane coupling agent forms a compact three-dimensional network structure on the surface of a zinc coating, and can endow the film with good corrosion resistance and adhesion; secondly, a certain amount of titanium salt is introduced into the modified silica sol, and the titanium salt can be used as a filling material to provide guarantee for the corrosion resistance of the film.
In the modified silica sol chromium-free passivator disclosed by the invention, the phosphate (C) has the main function of adjusting the pH value of the passivator so as to ensure the stability of the passivator. Meanwhile, the phosphate can enhance the corrosion resistance and yellowing resistance of the film layer, so that the film layer does not yellow after the passivation film is baked at the high temperature of 240 ℃, and the usability of the passivation film is ensured.
In the modified silica sol chromium-free passivator of the invention, (D) the zirconium-containing compound mainly has the function of forming a chemically stable oxide conversion film on the surface of a zinc coating during film formation; the conversion film is firmly combined with the zinc coating by means of the zirconium compound, and simultaneously, other components in the passivation solution are strongly combined with the coating in a synergistic manner, so that the crosslinking degree of the passivation film layer is enhanced, and the high-performance chromium-free passivation film is obtained, and the passivation film achieves excellent black degeneration resistance and coating property.
The invention also provides application of the passivator, and the passivator is applied to surface treatment of a hot-dip galvanized steel sheet.
According to the preferable scheme, the passivating agent has remarkable effects of improving the corrosion resistance, the black degeneration resistance, the yellowing resistance and the coating performance of the film layer.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the passivator disclosed by the invention has good film forming property, can obviously improve the corrosion resistance, black property resistance, yellowing resistance and coating property of a film, is excellent in comprehensive performance and has very high industrial application value.
The passivating agent has the advantages of simple production process, low cost and good stability, and is beneficial to industrial production.
Drawings
FIG. 1 is a graph of the surface treatment of a galvanized steel sheet with the passivating agent of examples 1-8 after 96 hours of salt spray resistance test; the galvanized steel sheets after the salt spray resistance tests of the embodiments 1 to 4 are sequentially arranged on the upper row of the plates from left to right; the galvanized steel sheets after the salt spray resistance tests of the embodiments 5 to 8 are sequentially arranged on the lower plate from left to right.
FIG. 2 is a graph of the surface treatment of the galvanized steel sheets with the passivator of examples 9-16 after 96 hours of salt spray resistance test; the galvanized steel sheets after the salt spray resistance tests of the embodiments 9 to 12 are sequentially arranged on the upper row of the plates from left to right; the galvanized steel sheets after the salt spray resistance tests of the embodiment 13 to the embodiment 16 are arranged on the lower plate row from left to right in sequence.
FIG. 3 is a coating morphology chart of the surface treated galvanized steel sheets treated by the passivator in examples 1-8; the galvanized steel sheets coated in the embodiments 1 to 4 are sequentially arranged on the upper row of the plates from left to right; the galvanized steel sheets coated in the embodiments 5 to 8 are arranged on the lower plate row from left to right in sequence.
FIG. 4 is a coating morphology chart of the passivator in examples 9-16 after the surface treatment of a galvanized steel sheet; the galvanized steel sheets coated in the examples 9 to 12 are sequentially arranged on the upper row of the plates from left to right; the galvanized steel sheets coated in the examples 13 to 16 are arranged on the lower plate row from left to right in sequence.
Detailed Description
In order to better explain the technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to the embodiments. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art without departing from the spirit of the invention.
In the following examples, "parts" means "parts by mass", and each "part" means 100 g.
In the following examples, the preparation method of the nanomaterial-modified water-based resin is as follows: adding 100 parts of polypropylene glycol 400 (mainly for improving the water solubility of resin) and 70 parts of hexamethylene diisocyanate into a reaction vessel, and heating to 85 ℃ for reaction for 2 hours; then cooling to 60 ℃, adding 2.8 parts of pentaerythritol, 15 parts of methyldiethanolamine and 90 parts of acetone, continuing to react for 2 hours at 60 ℃, cooling to 42 ℃, adding 12 parts of 3-aminopropyltriethoxysilane, stirring for 1 hour, adding 360 parts of deionized water under stirring, and finally adjusting the pH value to 5.0 by using acetic acid to obtain the nano material modified water-based resin, which is the nano material modified water-based cationic polyurethane resin.
The preparation method of the modified silica sol comprises the following steps: adding 60 parts of water, 1 part of acetic acid and 3.8 parts of titanium sulfate into a reaction kettle, and heating to 50 ℃; and then 6 parts of methyl vinyl diethoxy silane is dripped, the reaction solution is kept at 50 ℃ for 1h after the dripping is finished, then the reaction solution is cooled to room temperature, and the pH value is adjusted to 4.5 by acetic acid, thus obtaining the modified silica sol.
The aqueous solution of sodium dihydrogen phosphate and the aqueous solution of zinc dihydrogen phosphate are prepared by adding deionized water into sodium dihydrogen phosphate or zinc dihydrogen phosphate, and the concentration of the aqueous solution of sodium dihydrogen phosphate and the aqueous solution of zinc dihydrogen phosphate is 0.10 g/mL.
The aqueous solution of the fluozirconic acid is prepared by adding deionized water into the fluozirconic acid, and the concentration is 0.08 g/mL.
The aqueous solution of zirconium acetate is prepared by adding deionized water into zirconium acetate, and the concentration is 0.08 g/mL.
The acetic acid is glacial acetic acid.
Example 1
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, adding 3 parts of aqueous solution of fluozirconic acid into a reaction kettle, wherein the pH value of a reaction system is 4-5, and stirring the reaction solution for 1 hour at normal temperature to obtain the fluozirconic acid-fluorozirconate-aqueous solution.
Example 2
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of zinc dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, dripping 3 parts of aqueous solution of fluozirconic acid into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the fluozirconic acid-zirconium mixed solution.
Example 3
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, dripping 3 parts of aqueous solution of zirconium acetate into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the zirconium acetate.
Example 4
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of zinc dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, dripping 3 parts of aqueous solution of zirconium acetate into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the zirconium acetate.
Example 5
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 36 parts of modified silica sol, and uniformly mixing and stirring; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, dripping 3 parts of aqueous solution of fluozirconic acid into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the fluozirconic acid-zirconium mixed solution.
Example 6
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 44 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, dripping 3 parts of aqueous solution of fluozirconic acid into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the fluozirconic acid-zirconium mixed solution.
Example 7
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 4 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, dripping 3 parts of aqueous solution of fluozirconic acid into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the fluozirconic acid-zirconium mixed solution.
Example 8
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, dripping 2.5 parts of aqueous solution of fluozirconic acid into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the fluozirconic acid aqueous solution.
Example 9
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 30 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, dripping 3 parts of aqueous solution of fluozirconic acid into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the fluozirconic acid-zirconium mixed solution.
In the chromium-free passivator prepared by the embodiment, as the main function of the nano-material modified water-based resin is to provide a film-forming skeleton, the using amount is reduced, the film-forming property is poor, and groups provided by the resin and combined with a coating film layer are reduced, which shows that the coating property is poor; also, the salt fogging property is deteriorated.
Example 10
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 28 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, dripping 3 parts of aqueous solution of fluozirconic acid into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the fluozirconic acid-zirconium mixed solution.
The chromium-free passivator prepared by the embodiment has the main effect of improving the crosslinking degree of the passivation film by the modified silica sol so as to ensure the corrosion resistance and the blackening resistance of the film; meanwhile, due to the structural characteristics of the silica sol, the adhesive force between the passivation film and the paint film can be enhanced, and the coating property of the film layer is further improved; the silica sol of the invention introduces a certain amount of titanium salt, which provides guarantee for the corrosion resistance of the film. Therefore, when the amount of the modified silica sol is too small, the silica sol film layer becomes sparse, the bonding force with the metal becomes poor, the porosity becomes large, the degree of crosslinking becomes low, and the corrosion resistance, blackening resistance, and paintability become poor.
Example 11
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 2.5 parts of sodium dihydrogen phosphate aqueous solution into the reaction kettle, and stirring; and finally, dripping 3 parts of aqueous solution of fluozirconic acid into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the fluozirconic acid-zirconium mixed solution.
The chromium-free passivator prepared by the embodiment has the main effect of adjusting the pH value of the passivator to ensure the stability of the passivator; meanwhile, the phosphate can enhance the corrosion resistance and yellowing resistance of the film. Thus, a corresponding performance deficiency results due to the reduced amount of phosphate.
Example 12
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, dripping 1.5 parts of aqueous solution of fluozirconic acid into the reaction kettle, wherein the pH value of the reaction system is 4-5, and stirring the reaction solution at room temperature for 1 hour to obtain the fluozirconic acid-fluorozirconate-aqueous solution.
The chromium-free passivator prepared by the embodiment has the advantages that the amount of fluozirconic acid is reduced, a formed zirconium salt conversion film is not compact enough in the film forming process, the bonding force between a passivation film and a galvanized base material is reduced, the compactness of a coating is influenced, and the blackening resistance and the coating performance are reduced.
Example 13
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 82 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, adding 3 parts of aqueous solution of fluozirconic acid into a reaction kettle, wherein the pH value of a reaction system is 4-5, and stirring the reaction solution for 1 hour at normal temperature to obtain the fluozirconic acid-fluorozirconate-aqueous solution.
According to the chromium-free passivator prepared by the embodiment, due to the fact that the consumption of the nano material modified water-based resin is too much, organic matters in a passivator system are increased, and the high temperature resistance and yellowing phenomenon are caused when the passivator is subjected to high temperature yellowing at 240 ℃.
Example 14
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 65 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, adding 3 parts of aqueous solution of fluozirconic acid into a reaction kettle, wherein the pH value of a reaction system is 4-5, and stirring the reaction solution for 1 hour at normal temperature to obtain the fluozirconic acid-fluorozirconate-aqueous solution.
The chromium-free passivator prepared by the embodiment has the advantages that the use amount of the modified silica sol is too large, so that the inorganic filler particles in a passivator system are increased, the adhesive force of a film layer is easily influenced after the film is formed, and the coating effect is poor.
Example 15
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 11 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, adding 3 parts of aqueous solution of fluozirconic acid into a reaction kettle, wherein the pH value of a reaction system is 4-5, and stirring the reaction solution for 1 hour at normal temperature to obtain the fluozirconic acid-fluorozirconate-aqueous solution.
The chromium-free passivator prepared by the embodiment has the advantages that the acid value in a passivator system can be increased due to excessive sodium dihydrogen phosphate, so that a galvanized sheet is easily excessively corroded in a film forming process, and a passivated sheet is more easily darkened and has poor blackening resistance in a blackening resistance experiment.
Example 16
A preparation method of a chromium-free passivator comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 60 parts of nano material modified water-based resin and 40 parts of modified silica sol, and mixing and stirring uniformly; then adding 5 parts of sodium dihydrogen phosphate aqueous solution into a reaction kettle, and stirring; and finally, adding 11 parts of aqueous solution of fluozirconic acid into a reaction kettle, wherein the pH value of a reaction system is 4-5, and stirring the reaction solution for 1 hour at normal temperature to obtain the fluozirconic acid-fluorozirconate-aqueous solution.
The chromium-free passivator prepared by the embodiment has the advantages that the consumption of fluozirconic acid is too high, the cross-linking degree of a passivator system is too high, sample gel is easily caused, the stability is damaged, and a film layer is easily cracked after film formation, so that the corrosion resistance is reduced.
The performance of the chromium-free passivators prepared in examples 1-16 was evaluated by the following specific method:
test substrates: unpassivated oiled galvanized sheet provided by martial Steel.
Preparing a passivation film:
(1) degreasing, deoiling and cleaning the galvanized plate, and drying the galvanized plate by using a blower for later use;
(2) spreading the passivator on hot-dip galvanized plate with 8um wire rod, and controlling the thickness of the film to be 0.8-1.2g/m2；
(3) And (3) placing the coated hot-galvanized plate in an oven at the temperature of 180 ℃, taking out the hot-galvanized plate when the temperature of the hot-galvanized plate reaches 80-100 ℃, placing the hot-galvanized plate at room temperature for 24 hours, observing the appearance, and then testing the salt spray resistance, the yellowing resistance and the blackening resistance.
The evaluation method comprises the following steps:
(1) appearance of the passivated sheet: visually, evaluation was carried out according to the following criteria.
V: the film layer is uniform and has metallic luster;
x: non-uniform film or fogging of the film.
(2) Corrosion resistance: the corrosion resistance test of the passivated board adopts a neutral salt fog accelerated corrosion test, adopts a JH-60 type salt fog corrosion test box and is executed according to GB/T10125-2012 salt fog test of artificial atmosphere corrosion test; test medium: chemically pure NaCl deionized water solution with medium concentration of 50g/L and pH value of 6.5; test temperature: 35 +/-2 ℃; the settling amount of the salt spray: 1-2 mL/h 80cm2(ii) a Placing a sample: the experimental surface and the vertical direction form an angle of 30 degrees; continuously spraying in a cycle of 24h in each period,opening the box to check the sample once before each period is finished, wherein the checking time is not more than 30 min. The corrosion area of the passivated panel was evaluated and evaluated according to the following criteria.
V: the corrosion area of the film layer is 0-5%;
x: the corrosion area of the film layer is more than 5 percent.
(3) Black degeneration resistance: and (3) placing the passivated board in a constant temperature and humidity box with the temperature of 80 ℃ and the RH of 80 percent, taking out and drying after 120h, observing the surface condition of the sample board, measuring the color difference value delta E before and after measurement, recording and evaluating according to the following standard.
V: the color difference value delta E is less than or equal to 3;
x: color difference value, Δ E > 3.
(4) Yellowing resistance: and (3) placing the passivated board in a hot air furnace at 240 ℃, baking for 20 minutes, naturally cooling to room temperature, repeating the operation for 4 times, observing the surface condition of the steel plate, measuring the color difference value delta E of the sample before and after baking by using a color difference meter, recording, and evaluating according to the following standard.
V: the color difference value delta E is less than or equal to 3;
x: color difference value, Δ E > 3.
(5) Coating property: degreasing the passivated board by using a degreasing agent, phosphating the passivated board by using a phosphating solution, washing and drying the passivated board by water, spraying the passivated board by using electrostatic powder, and then baking the passivated board. The plates were made in hundreds of cells and recorded for evaluation according to the following criteria.
V: the coating has no cracking and shedding phenomenon;
x: the coating is cracked and peeled off.
Table 1: results of Performance evaluation
As can be seen from the above table: after the passivating agent is applied to surface treatment of a hot-dip galvanized steel sheet, the appearance of a formed film, corrosion resistance, black-stain resistance, yellowing resistance and coating performance are obviously enhanced. The appearance patterns of the galvanized steel sheets treated by the passivators in the examples 1-16 after 96 hours of salt spray resistance test are shown in the figures 1-2; the appearance of the paintability of the surface-treated galvanized steel sheets treated by the passivators in examples 1-16 is shown in FIGS. 3-4. The passivating agent has good stability, does not cause the problems of product deterioration and the like after being placed for a long time in the industrial use process, and can be popularized and used in hot galvanizing steel plants.
Claims (7)
1. The modified silica sol chromium-free passivator for surface treatment of a hot-dip galvanized steel sheet is characterized by being prepared from the following raw materials in parts by mass: 32-80 parts of nano material modified water-based resin, 30-60 parts of modified silica sol, 3-10 parts of phosphate aqueous solution, 2-10 parts of zirconium compound-containing aqueous solution and 10-100 parts of deionized water.
2. The modified silica sol chromium-free passivator according to claim 1, wherein the passivator is prepared from the following raw materials in parts by mass: 45-60 parts of nano material modified water-based resin, 35-45 parts of modified silica sol, 3.5-5 parts of phosphate aqueous solution, 2-3 parts of zirconium compound-containing aqueous solution and 60-90 parts of deionized water.
3. The modified silica sol chromium-free passivator according to claim 1 or 2, wherein the nanomaterial-modified aqueous resin is prepared by the following method, wherein the raw materials are in parts by mass: adding 100 parts of polypropylene glycol 400 and 70 parts of hexamethylene diisocyanate into a reaction vessel, and heating to 85 ℃ for reaction for 2 hours; and then cooling to 60 ℃, adding 2.8 parts of pentaerythritol, 15 parts of methyldiethanolamine and 90 parts of acetone, continuing to react for 2 hours at 60 ℃, cooling to 42 ℃, adding 12 parts of 3-aminopropyltriethoxysilane, stirring for 1 hour, adding 360 parts of deionized water under stirring, and finally adjusting the pH value to 5.0 by using acetic acid to obtain the nano material modified water-based resin.
4. The modified silica sol chromium-free passivator according to claim 1 or 2, wherein the modified silica sol is prepared by the following method, wherein the raw materials are calculated by mass portion: adding 60 parts of water, 1 part of acetic acid and 3.8 parts of titanium sulfate into a reaction kettle, and heating to 50 ℃; and then 6 parts of silane coupling agent is dripped, the reaction solution is kept at 50 ℃ for 1h after the dripping is finished, then the reaction solution is cooled to room temperature, and the pH value is adjusted to 4.5 by acetic acid, thus obtaining the modified silica sol.
5. The modified silica sol chromium-free passivating agent of claim 4, wherein the silane coupling agent is selected from one or more of ethyltriethoxysilane, vinyltriethoxysilane, and methylvinyldiethoxysilane.
6. The modified silica sol chromium-free passivating agent according to claim 1 or 2, wherein the concentration of the aqueous phosphate solution is 0.03g/mL to 0.15g/mL, and the phosphate is sodium dihydrogen phosphate and/or zinc dihydrogen phosphate.
7. The modified silica sol chromium-free passivating agent according to claim 1 or 2, wherein the concentration of the aqueous solution containing the zirconium compound is 0.05g/mL to 0.1g/mL, and the zirconium compound is fluorozirconic acid and/or zirconium acetate.
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