CN110699678A - Corrosion-resistant passivator and preparation method thereof - Google Patents
Corrosion-resistant passivator and preparation method thereof Download PDFInfo
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- CN110699678A CN110699678A CN201911140619.1A CN201911140619A CN110699678A CN 110699678 A CN110699678 A CN 110699678A CN 201911140619 A CN201911140619 A CN 201911140619A CN 110699678 A CN110699678 A CN 110699678A
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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
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Abstract
The invention relates to a corrosion-resistant passivator which comprises the following components in parts by weight: 200-250 parts of trivalent chromium salt, 50-100 parts of complexing agent, 10-50 parts of stabilizing agent and 80-160 parts of metal salt, wherein the stabilizing agent is prepared from methyl cellulose and high polymer, and the high polymer is at least one of gelatin and glycine. The passivation film layer obtained by the corrosion-resistant passivator has higher hardness and better corrosion-resistant stabilizer.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a corrosion-resistant passivator and a preparation method thereof.
Background
Zinc is a metal with active chemical properties, and if the post-treatment is not carried out well after the electrogalvanizing, a zinc coating is easy to oxidize and darken in the atmosphere, and finally corrosion is generated. To reduce the chemical activity of zinc, passivation is often performed using a passivating agent.
The hexavalent chromium passivator is widely used in the traditional zinc-plating passivator, because the hexavalent chromium passivator has fast film formation and good corrosion resistance, the hexavalent chromium can cause serious pollution to water quality. Therefore, the passivator starts to develop from high chromium to medium chromium and low chromium. Among them, the trivalent chromium passivator is concerned by people, because the trivalent passivator can replace hexavalent chromium passivator, and strong acid is not used when preparing the passivator, the passive film obtained by using the passivator has uniform color, but still has some obvious defects, such as slow film forming speed, reduced corrosion resistance after passivation of a zinc coating, reduced scratch resistance of the passivation layer and the like. Thus, the trivalent chromium passivators obtained using conventional techniques are not used for some galvanized components which are exposed to complex acid gases or to environments susceptible to corrosive contamination for long periods of time.
Disclosure of Invention
Based on the passivation agent, the passivation layer formed on the zinc coating by using the passivation agent has good corrosion resistance stability and scratch resistance.
The specific technical scheme is as follows:
the corrosion-resistant passivator comprises the following components in parts by weight: 200-250 parts of trivalent chromium salt, 50-100 parts of complexing agent, 10-50 parts of stabilizing agent and 80-160 parts of metal salt, wherein the stabilizing agent is prepared from raw materials including methyl cellulose and high polymer, and the high polymer is at least one of gelatin and glycine.
In one embodiment, the composition comprises the following components in parts by weight: 220-250 parts of trivalent chromium salt, 60-90 parts of complexing agent, 10-30 parts of stabilizer and 100-150 parts of metal salt.
In one embodiment, the trivalent chromium salt is at least one of basic chromium sulfate, chromium nitrate and chromium chloride.
In one embodiment, the complexing agent is at least two of ammonium bifluoride, malonic acid, oxalic acid, citric acid and malic acid.
In one embodiment, the metal salt is at least one of cobalt sulfate, magnesium sulfate, sodium nitrate, cobalt nitrate, and lanthanum nitrate.
In one embodiment, the mass ratio of the methyl cellulose to the high polymer in the stabilizer is 1 (3-5).
In one embodiment, the preparation of the stabilizer comprises the steps of: and dissolving the methyl cellulose in pure water at the temperature of 90-100 ℃, adding the high polymer, and stirring and fully dissolving to obtain the stabilizer.
In one embodiment, the high polymer is a mixture of the gelatin and the glycine.
The preparation method of the corrosion-resistant passivator is characterized by comprising the following steps;
adding trivalent chromium salt into pure water at 60-100 ℃, and stirring and dissolving to obtain a first mixed solution;
adding a complexing agent and a stabilizing agent into the first mixed solution, stirring and dissolving, and standing at a constant temperature of 70-100 ℃ for 2-5 hours to obtain a second mixed solution;
and adding metal salt into the second mixed solution, stirring and dissolving to obtain the corrosion-resistant passivator.
In one embodiment, the pure water is at a temperature of 90-100 ℃; and/or the presence of a gas in the gas,
the constant temperature is 80-100 ℃.
The zinc coating trivalent chromium environment-friendly corrosion-resistant passivator and the preparation method thereof have the following advantages and beneficial effects:
the inventor of the invention discovers through a large amount of creative experimental researches that the hardness of the passivation film layer is enhanced by adding the corrosion-resistant stabilizer into the prepared corrosion-resistant passivator to participate in the reaction, and the corrosion resistance of the passivation film layer is also obviously improved.
The corrosion-resistant passivator has the advantages of high stability, wide application range and lower production cost.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a corrosion-resistant passivator which comprises the following components in parts by weight: 200-250 parts of trivalent chromium salt, 50-100 parts of complexing agent, 10-50 parts of stabilizing agent and 80-160 parts of metal salt, wherein the stabilizing agent is prepared from raw materials including methyl cellulose and high polymer, and the high polymer is at least one of gelatin and glycine.
In one specific example, the composition comprises the following components in parts by weight: 220-250 parts of trivalent chromium salt, 60-90 parts of complexing agent, 10-30 parts of stabilizer and 100-150 parts of metal salt.
In one specific example, the trivalent chromium salt is at least one of basic chromium sulfate, chromium nitrate, and chromium chloride.
In one specific example, the complexing agent is at least two of ammonium bifluoride, malonic acid, oxalic acid, citric acid, and malic acid.
In one specific example, the metal salt is at least one of cobalt sulfate, magnesium sulfate, sodium nitrate, cobalt nitrate, and lanthanum nitrate.
In a specific example, the mass ratio of the methyl cellulose to the high polymer in the stabilizer is 1 (3-5).
In one specific example, the preparation of the stabilizer comprises the steps of: dissolving methyl cellulose in pure water at 90-100 ℃, adding high polymer, and stirring to fully dissolve to obtain the stabilizer.
The methyl cellulose has the effects of thickening and enhancing the surface activity of the compound, is more beneficial to the film formation of the passivating agent, and further has the function of enhancing the physical and mechanical properties of a stabilizer obtained by compounding with a high polymer, meanwhile, a high molecular active group rich in the stabilizer and trivalent chromium ions can perform a complexing reaction, and the corrosion resistance effect of the passivating agent can be further improved by the complexing reaction combination.
In one particular example, the high polymer is a mixture of gelatin and glycine.
The preparation method of the corrosion-resistant passivator comprises the following steps;
adding trivalent chromium salt into pure water at 60-100 ℃, and stirring and dissolving to obtain a first mixed solution;
adding a complexing agent and a stabilizing agent into the first mixed solution, stirring and dissolving, and standing at a constant temperature of 70-100 ℃ for 2-5 hours to obtain a second mixed solution;
and adding metal salt into the second mixed solution, stirring and dissolving to obtain the corrosion-resistant passivator.
In one specific example, the pure water temperature is 90 ℃ to 100 ℃.
In one specific example, the constant temperature is 80 ℃ to 100 ℃.
In the following examples, all the starting materials were commercially available unless otherwise specified.
Preparation of the stabilizer: dissolving 5g of methylcellulose in 98 ℃ pure water, adding 20g of gelatin or 15g of glycine, stirring to fully dissolve, and supplementing pure water to 1L to obtain the stabilizer. All the stabilizers used in the following examples are the stabilizers prepared according to the present invention.
Example 1
Raw materials:
trivalent chromium salt: 160g of basic chromium sulfate and 90g of chromium nitrate;
complexing agent: 30g of ammonium bifluoride and 50g of citric acid;
a stabilizer: 10g of a mixture;
metal salt: 50g of sodium nitrate and 50g of cobalt nitrate.
Preparation of the corrosion-resistant passivator:
adding trivalent chromium salt into pure water with the temperature of 98 ℃, and stirring and dissolving to obtain a first mixed solution;
adding a complexing agent and a stabilizing agent into the first mixed solution, stirring for dissolving, standing at the constant temperature of 80 ℃ for 2 hours, and naturally cooling to obtain a second mixed solution;
and adding metal salt into the second mixed solution, stirring and dissolving to obtain the corrosion-resistant passivator.
Example 2
Raw materials:
trivalent chromium salt: 150g of basic chromium sulfate and 80g of chromium chloride;
complexing agent: 30g of ammonium bifluoride and 40g of malic acid;
a stabilizer: 20g of the total weight of the mixture;
metal salt: 100g of sodium nitrate and 50g of cobalt nitrate.
Preparation of the corrosion-resistant passivator:
adding trivalent chromium salt into pure water with the temperature of 98 ℃, and stirring and dissolving to obtain a first mixed solution;
adding a complexing agent and a stabilizing agent into the first mixed solution, stirring for dissolving, standing at the constant temperature of 80 ℃ for 2 hours, and naturally cooling to obtain a second mixed solution;
and adding metal salt into the second mixed solution, stirring and dissolving to obtain the corrosion-resistant passivator.
Example 3
Raw materials:
trivalent chromium salt: 150g of chromium nitrate and 80g of chromium chloride;
complexing agent: 30g of ammonium bifluoride and 35g of malonic acid;
a stabilizer: 25g of the total weight of the mixture;
metal salt: 50g of sodium nitrate and 50g of cobalt nitrate.
Preparation of the corrosion-resistant passivator:
adding trivalent chromium salt into pure water with the temperature of 98 ℃, and stirring and dissolving to obtain a first mixed solution;
adding a complexing agent and a stabilizing agent into the first mixed solution, stirring for dissolving, standing at the constant temperature of 80 ℃ for 2 hours, and naturally cooling to obtain a second mixed solution;
and adding metal salt into the second mixed solution, stirring and dissolving to obtain the corrosion-resistant passivator.
Example 4
Raw materials:
trivalent chromium salt: 150g of chromium nitrate and 80g of chromium chloride;
complexing agent: 5g of ammonium bifluoride and 5g of malonic acid;
a stabilizer: 25g of the total weight of the mixture;
metal salt: 50g of sodium nitrate and 50g of cobalt nitrate.
Preparation of the corrosion-resistant passivator:
adding trivalent chromium salt into pure water with the temperature of 98 ℃, and stirring and dissolving to obtain a first mixed solution;
adding a complexing agent and a stabilizing agent into the first mixed solution, stirring for dissolving, standing at the constant temperature of 80 ℃ for 2 hours, and naturally cooling to obtain a second mixed solution;
and adding metal salt into the second mixed solution, stirring and dissolving to obtain the corrosion-resistant passivator.
Example 5
Raw materials:
trivalent chromium salt: 50g of chromium nitrate and 20g of chromium chloride;
complexing agent: 30g of ammonium bifluoride and 35g of malonic acid;
a stabilizer: 25g of the total weight of the mixture;
metal salt: 50g of sodium nitrate and 50g of cobalt nitrate.
Preparation of the corrosion-resistant passivator:
adding trivalent chromium salt into pure water with the temperature of 98 ℃, and stirring and dissolving to obtain a first mixed solution;
adding a complexing agent and a stabilizing agent into the first mixed solution, stirring for dissolving, standing at the constant temperature of 80 ℃ for 2 hours, and naturally cooling to obtain a second mixed solution;
and adding metal salt into the second mixed solution, stirring and dissolving to obtain the corrosion-resistant passivator.
Comparative example 1
Raw materials:
trivalent chromium salt: 150g of basic chromium sulfate and 100g of chromium chloride;
complexing agent: 30g of ammonium bifluoride and 50g of malic acid;
metal salt: 100g of sodium nitrate and 50g of cobalt nitrate.
Preparation of the corrosion-resistant passivator:
adding trivalent chromium salt into pure water with the temperature of 98 ℃, and stirring and dissolving to obtain a first mixed solution;
adding a complexing agent into the first mixed solution, stirring for dissolving, standing at a constant temperature of 80 ℃ for 2 hours, and naturally cooling to obtain a second mixed solution;
and adding metal salt into the second mixed solution, stirring and dissolving to obtain the corrosion-resistant passivator.
Comparative example 2
Raw materials:
trivalent chromium salt: 150g of basic chromium sulfate and 100g of chromium chloride;
a stabilizer: 25g of the total weight of the mixture;
metal salt: 100g of sodium nitrate and 50g of cobalt nitrate.
The preparation of the zinc coating trivalent chromium environment-friendly corrosion-resistant passivator comprises the following steps:
adding trivalent chromium salt into pure water with the temperature of 98 ℃, and stirring and dissolving to obtain a first mixed solution;
adding a stabilizer into the first mixed solution, stirring for dissolving, standing at the constant temperature of 80 ℃ for 2 hours, and naturally cooling to obtain a second mixed solution;
and adding metal salt into the second mixed solution, stirring and dissolving to obtain the corrosion-resistant passivator.
Test examples
The galvanized sheet is subjected to immersion passivation by using the passivators prepared in the above examples and comparative examples under the same environment, after a stable passivation film is formed, the film layer is subjected to a neutral salt spray test and a scratch resistance test according to the GB/T6461-2002 standard, and the test results are shown in tables 1 and 2:
table 1: neutral salt spray test results
Table 2: scratch resistance test results
The performance analysis of the galvanized sheet dipped and passivated film layer by different passivators in the above test examples shows that the results are shown in table 1 and table 2. The results of the examples 1 to 3 show that the corrosion resistance of the passivated film layer of the passivator prepared in the formula proportioning range is obviously improved, the stability is higher, and correspondingly, the scratch resistance is also improved to a certain extent. As can be seen from example 3 and comparative example 1, the stabilizer has a remarkable accelerating effect on the corrosion resistance of the passivation film formed by the passivation agent and the stability maintained under the long-term salt spray environment. It can be seen from examples 3 and 4 and comparative example 2 that the corrosion resistance and scratch resistance of the passivator obtained when the trivalent chromium salt and the complexing agent deviate from the ratio range of the invention are reduced.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The corrosion-resistant passivator is characterized by comprising the following components in parts by weight: 200-250 parts of trivalent chromium salt, 50-100 parts of complexing agent, 10-50 parts of stabilizing agent and 80-160 parts of metal salt, wherein the stabilizing agent is prepared from raw materials including methyl cellulose and high polymer, and the high polymer is at least one of gelatin and glycine.
2. The corrosion-resistant passivator of claim 1 comprising the following components in parts by weight: 220-250 parts of trivalent chromium salt, 60-90 parts of complexing agent, 10-30 parts of stabilizer and 100-150 parts of metal salt.
3. A corrosion resistant passivating agent according to claim 1 or 2, wherein the trivalent chromium salt is at least one of basic chromium sulfate, chromium nitrate and chromium chloride.
4. A corrosion resistant passivating agent according to claim 1 or 2, wherein the complexing agent is at least two of ammonium bifluoride, malonic acid, oxalic acid, citric acid and malic acid.
5. A corrosion resistant passivating agent according to claim 1 or 2, wherein the metal salt is at least one of cobalt sulfate, magnesium sulfate, sodium nitrate, cobalt nitrate and lanthanum nitrate.
6. The corrosion-resistant passivator according to claim 1 or 2, wherein the mass ratio of the methyl cellulose to the high polymer in the stabilizer is 1 (3-5).
7. The corrosion-resistant passivating agent according to claim 1, wherein the preparation of the stabilizing agent comprises the steps of: and dissolving the methyl cellulose in pure water at the temperature of 90-100 ℃, adding the high polymer, and stirring and fully dissolving to obtain the stabilizer.
8. A corrosion resistant passivating agent according to claim 1, 2 or 7, wherein the high polymer is a mixture of the gelatin and the glycine.
9. A method of preparing a corrosion resistant passivating agent according to any of claims 1 to 8, comprising the steps of;
adding trivalent chromium salt into pure water at 60-100 ℃, and stirring and dissolving to obtain a first mixed solution;
adding a complexing agent and a stabilizing agent into the first mixed solution, stirring and dissolving, and standing at a constant temperature of 70-100 ℃ for 2-5 hours to obtain a second mixed solution;
and adding metal salt into the second mixed solution, stirring and dissolving to obtain the corrosion-resistant passivator.
10. The preparation method of the corrosion-resistant passivator according to claim 9, wherein the pure water temperature is 90 ℃ to 100 ℃; and/or the presence of a gas in the gas,
the constant temperature is 80-100 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111996522A (en) * | 2020-08-03 | 2020-11-27 | 鞍钢股份有限公司 | Zinc-aluminum-magnesium steel plate environment-friendly passivator and preparation and use method thereof |
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| CN103993304A (en) * | 2013-02-17 | 2014-08-20 | 武汉风帆电镀技术股份有限公司 | Trivalent-chromium pretreatment solution for aluminium and aluminium alloy |
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