CN112481575A - Hot galvanizing passivation solution and preparation method thereof - Google Patents
Hot galvanizing passivation solution and preparation method thereof Download PDFInfo
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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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
- C23C22/34—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 fluorides or complex fluorides
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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
- C23C22/46—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 oxalates
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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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention discloses a hot galvanizing passivation solution and a preparation method thereof, belonging to the technical field of hot galvanizing. The hot galvanizing passivation solution comprises the following components in parts by weight: 5-15 parts of trivalent chromium compound, 10-15 parts of acidic reagent, 0.5-5 parts of vanadium-containing compound, 10-15 parts of organic resin, 5-15 parts of silane coupling agent and 5-15 parts of complexing agent. The product takes a trivalent chromium compound as a chromium source, avoids the toxicity of a hexavalent chromium source in the traditional passivation solution, is matched with a vanadium-containing compound, a complex and resin, and is high in film forming speed and short in passivation time, and the obtained passivation layer is fine, smooth, compact, attractive in film appearance and excellent in corrosion resistance. The invention also provides a preparation method of the hot galvanizing passivation solution, which has simple operation steps and can realize large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of hot galvanizing, in particular to a hot galvanizing passivation solution and a preparation method thereof.
Background
With the rapid development of industries such as automobiles, buildings, hardware and the like, the demand of hot dip products is increased year by year, and hot dip galvanizing has the advantages of excellent corrosion resistance, beautiful appearance, easy processing, relatively low cost and the like, and is well received by the majority of users. Zinc is a reactive metal, and if subsequent treatment is not carried out after galvanization, the galvanization can become dark quickly and lose the protection function. In order to reduce the activity of zinc, chromate treatment is a cheap and effective method for inhibiting the generation of white rust on a zinc layer, has the advantages of simple process, good film binding force, good corrosion resistance and the like, and is widely used for galvanized products, however, hexavalent chromium is easy to dissolve in water, chromate solution contains toxic hexavalent chromium compounds, treatment solution and chromium-containing cleaning wastewater in the production process can cause serious pollution to the environment, the use of passivation solution containing hexavalent chromium is forbidden, passivation solution on the market generally adopts trivalent chromium for treatment at present, the toxicity of the passivation solution is lower than that of hexavalent chromium, but the existing trivalent chromium passivation solution has the following obvious defects: (1) the passivation time is long, and the passivation time of the prior trivalent chromium is 20-60 s; (2) the trivalent chromium passivation film has no automatic repair capability, the corrosion resistance is to be improved, the neutral salt spray time of the post-treatment is up to 48 hours for white rust, the red rust time is not more than 120 hours, the neutral salt spray time can meet the requirement for common hot-dip galvanized products, but the neutral salt spray time is difficult to meet the requirement for harsh products or products exposed outdoors.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide the hot galvanizing passivation solution which does not contain hexavalent chromium, has the advantages of high film forming speed, beautiful appearance, short passivation time, high corrosion resistance of a passivation film and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a hot galvanizing passivation solution comprises the following components in parts by weight: 5-15 parts of trivalent chromium compound, 10-15 parts of acidic reagent, 0.5-5 parts of vanadium-containing compound, 10-15 parts of organic resin, 5-15 parts of silane coupling agent and 5-15 parts of complexing agent.
The hot galvanizing passivation solution provided by the invention takes the trivalent chromium compound as the chromium source, avoids the toxicity of the hexavalent chromium source in the traditional passivation solution, is matched with the vanadium-containing compound, the complex and the resin, and has the advantages of high film forming speed, capability of forming a passivation film with fineness, high mechanical strength and strong corrosion resistance in a short time, capability of achieving an ideal hot galvanizing protection effect without subsequent treatment, convenience in use and operation, and attractive and beautiful appearance.
Preferably, the trivalent chromium compound includes at least one of chromium chloride, chromium nitrate, chromium sulfate, chromium phosphate, chromium oxalate, and chromium carbonate.
Preferably, the acidic reagent is at least one of an organic acid reagent or an inorganic acid reagent.
More preferably, the acidic agent is at least one of sulfuric acid, nitric acid, hydrofluoric acid, acetic acid, hydrochloric acid, sulfurous acid, fluorosilicic acid, citric acid, and gluconic acid. The acidic reagent participates in accelerating the formation of a passive film, changes the performance of the film and improves the transparency and the binding force of the film. Organic acid or inorganic acid is related to the growth of the film, if the product is added too much, the product has stronger dissolving capacity on a zinc coating, a formed passive film is thinner, and the corrosion resistance is general; if the amount of the additive is too small, the formed passivation film is thick, the passivation solution is unstable, the film layer is rough, and the binding force is poor.
Preferably, the vanadium-containing compound includes at least one of vanadium sulfate, vanadium nitrate, sodium vanadate, ammonium vanadate, manganese vanadate, and potassium vanadate. The oxide or hydroxide generated by the reaction of the vanadate compound and other vanadium-containing compounds in the passivation solution can be uniformly deposited on the surface of the hot galvanizing, and the dissolution of the anode coating is hindered, so that the corrosion resistance of the hot galvanizing is remarkably improved. In the hot galvanizing passivation solution, if the vanadium-containing compound is added too much, the vanadium-containing compound reacts to generate oxide and hydroxide which are deposited on the hot galvanizing surface unevenly, the binding force is poor, and the passivation solution is unstable and is easy to precipitate; if the amount of the catalyst is too small, the reaction is less likely to generate oxides and hydroxides, and the corrosion resistance is lowered.
Preferably, the organic resin is a cationic urethane resin or a nonionic acrylic resin, and the cationic amino group includes at least one of a primary amino group, a tertiary amino group, and a quaternary amino group. The organic resin can be cross-linked and strengthened into a uniform glass state protective layer in the using and drying process of the product, and the protective layer is filled in the gaps of the passive film, so that the passive film is compact and low in porosity, and the corrosion resistance of the passive film is excellent finally.
Preferably, the silane coupling agent is a silane coupling agent containing an active hydrogen functional group including at least one of an active hydrogen-containing amino group, an epoxy group, a mercapto group, and a methacryloxy group. The silane coupling agent is used as a silicon compound with a unique structure, has better bonding strength to inorganic matters and organic matters, can form molecular bridging between interfaces of various inorganic materials and organic material components of hot galvanizing passivation solution, connects two materials with different properties, effectively improves the bonding strength of the interface layer, and improves the bonding force and the corrosion resistance of the materials.
Preferably, the complexing agent comprises at least one of malic acid, gluconic acid, sodium tartrate, sodium citrate, sodium gluconate, potassium tartrate, potassium citrate, potassium gluconate, ammonium tartrate, ammonium malate, ammonium citrate, ammonium gluconate, monoethanolamine, triethylenetetramine and tetraethylenetetramine. The complexing agent has strong chelating ability, stable property and difficult precipitation, and can ensure that the prepared hot galvanizing passivation solution has good storage and use stability.
Preferably, the hot galvanizing passivation solution further comprises 80-120 parts of distilled water.
Preferably, the hot galvanizing passivation solution comprises the following components in parts by weight: 100 parts of distilled water, 10 parts of trivalent chromium compound, 2 parts of vanadium-containing compound, 12 parts of acidic reagent, 12 parts of organic resin, 9 parts of silane coupling agent and 8 parts of complexing agent. In the hot galvanizing passivation solution prepared according to the component proportion, the trivalent chromium compound can form a passivation film with bright color on a zinc coating, and with the addition of the vanadium-containing compound and the auxiliary film forming agent, the formation of the film can be further accelerated, the passivation time is shortened, and meanwhile, the formed passivation film has the characteristics of fineness, uniformity, transparency, compactness and excellent bonding force; the addition of the complexing agent can effectively complex heavy metal impurities in the passivation solution, so that the passivation solution is stable. The silane coupling agent can be used for erecting a molecular bridge between the interfaces of the inorganic material and the organic material to connect the two materials with different properties, so that the bonding strength of the interface layer is effectively improved, and the bonding force and the corrosion resistance of the materials are improved. The organic resin can be cross-linked and strengthened into a uniform glass state protective layer in the drying process, and the protective layer is filled in the gaps of the passive film, so that the passive film is compact and has low porosity, and the corrosion resistance of the passive film is excellent.
The invention also aims to provide a preparation method of the hot galvanizing passivation solution, which comprises the following steps:
(1) adding a trivalent chromium compound into distilled water, heating and reacting to obtain a mixed solution A;
(2) adding a vanadium-containing compound into the mixed solution A obtained in the step (1), stirring and mixing, and adding an acidic reagent to obtain a mixed solution B;
(3) and (3) sequentially adding a complexing agent and a silane coupling agent into the mixed solution B obtained in the step (2) under stirring, uniformly mixing, adding an organic resin, and stirring for 25-35 min to obtain the hot galvanizing passivation solution.
The preparation method of the hot galvanizing passivation solution provided by the invention has simple operation steps and can realize large-scale industrial production.
Preferably, the heating temperature in the step (1) is 25-35 ℃, and the reaction time is 25-35 min.
Preferably, the stirring and mixing time in the step (2) is 10-20 min.
The components are mixed and reacted more fully and uniformly under the optimized technical parameters.
The invention has the beneficial effects that: the invention provides a hot galvanizing passivation solution, which takes a trivalent chromium compound as a chromium source, avoids the toxicity of a hexavalent chromium source in the traditional passivation solution, is matched with a vanadium-containing compound, a complex and resin, and has the advantages of high film forming speed, short passivation time, fine and compact passivation layer, beautiful film layer, effective resistance to various external environments and excellent corrosion resistance. The invention also provides a preparation method of the hot galvanizing passivation solution, which has simple operation steps and can realize large-scale industrial production.
Detailed Description
For better illustrating the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples, which are intended to be understood in detail, but not intended to limit the present invention.
Example 1
In an embodiment of the hot galvanizing passivation solution of the present invention, the hot galvanizing passivation solution includes the following components in parts by weight: 10 parts of trivalent chromium compound, 12 parts of acidic reagent, 2 parts of vanadium-containing compound, 12 parts of organic resin, 9 parts of silane coupling agent and 8 parts of complexing agent; the trivalent chromium compound is chromium chloride; the acid reagent is a 15% hydrochloric acid aqueous solution; the vanadium-containing compound is sodium vanadate; the organic resin is a primary amino-contained ethyl formate resin; the silane coupling agent is a HYDROSIL product produced by Guangzhou firm chemical import and export company; the hot galvanizing passivation solution also comprises 100 parts of distilled water.
The preparation method of the hot galvanizing passivation solution comprises the following steps:
(1) adding a trivalent chromium compound into distilled water, heating to 30 ℃, and reacting for 30min to obtain a mixed solution A;
(2) adding a vanadium-containing compound into the mixed solution A obtained in the step (1), stirring and mixing for 15min, and adding an acidic reagent to obtain a mixed solution B;
(3) and (3) sequentially and slowly adding the complexing agent and the silane coupling agent into the mixed solution B obtained in the step (2) under stirring, uniformly mixing, keeping the temperature for 10min, adding the organic resin, and stirring for 30min to obtain the hot galvanizing passivation solution.
Example 2
The difference between the embodiment and the embodiment 1 is that the hot galvanizing passivation solution of the embodiment comprises the following components in parts by weight: 8 parts of trivalent chromium compound, 15 parts of acidic reagent, 5 parts of vanadium-containing compound, 10 parts of organic resin, 8 parts of silane coupling agent and 5 parts of complexing agent; the trivalent chromium compound is chromium nitrate; the acid reagent is a nitric acid aqueous solution with the concentration of 30 percent; the vanadium-containing compound is vanadium nitrate; the organic resin is tertiary-urethane-containing resin; the silane coupling agent is a HYDROSIL product produced by Guangzhou firm chemical import and export company; the complexing agent is gluconic acid.
Example 3
The difference between the embodiment and the embodiment 1 is that the hot galvanizing passivation solution of the embodiment comprises the following components in parts by weight: 12 parts of trivalent chromium compound, 10 parts of acidic reagent, 1 part of vanadium-containing compound, 15 parts of organic resin, 12 parts of silane coupling agent and 15 parts of complexing agent; the trivalent chromium compound is chromium sulfate; the acid reagent is a sulfuric acid solution with the concentration of 10 percent; the vanadium-containing compound is vanadium sulfate; the organic resin is a primary amino-contained ethyl formate resin; the silane coupling agent is a HYDROSIL product produced by Guangzhou firm chemical import and export company; the complexing agent is malic acid.
Comparative example 1
The difference between the comparative example and the comparative example 1 is that the hot galvanizing passivation solution of the comparative example comprises the following components in parts by weight: 10 parts of trivalent chromium compound, 12 parts of acidic reagent, 0.1 part of vanadium-containing compound, 12 parts of organic resin, 9 parts of silane coupling agent and 8 parts of complexing agent.
Comparative example 2
The difference between the comparative example and the comparative example 1 is that the hot galvanizing passivation solution of the comparative example comprises the following components in parts by weight: 10 parts of trivalent chromium compound, 12 parts of acidic reagent, 6 parts of vanadium-containing compound, 12 parts of organic resin, 9 parts of silane coupling agent and 8 parts of complexing agent.
Comparative example 3
The difference between the comparative example and the comparative example 1 is that the hot galvanizing passivation solution of the comparative example comprises the following components in parts by weight: 10 parts of trivalent chromium compound, 9 parts of acidic reagent, 2 parts of vanadium-containing compound, 12 parts of organic resin, 9 parts of silane coupling agent and 8 parts of complexing agent.
Comparative example 4
The difference between the comparative example and the comparative example 1 is that the hot galvanizing passivation solution of the comparative example comprises the following components in parts by weight: 10 parts of trivalent chromium compound, 16 parts of acidic reagent, 2 parts of vanadium-containing compound, 12 parts of organic resin, 9 parts of silane coupling agent and 8 parts of complexing agent.
Comparative example 5
The difference between the comparative example and the comparative example 1 is that the hot galvanizing passivation solution of the comparative example comprises the following components in parts by weight: 10 parts of trivalent chromium compound, 12 parts of acidic reagent, 2 parts of vanadium-containing compound, 12 parts of organic resin, 4 parts of silane coupling agent and 8 parts of complexing agent.
Comparative example 6
The difference between the comparative example and the comparative example 1 is that the hot galvanizing passivation solution of the comparative example comprises the following components in parts by weight: 10 parts of trivalent chromium compound, 12 parts of acidic reagent, 2 parts of vanadium-containing compound, 12 parts of organic resin, 9 parts of silane coupling agent and 4 parts of complexing agent.
Comparative example 7
The comparative example differs from comparative example 1 only in that the acidic agent is phosphoric acid.
Comparative example 8
The comparative example differs from comparative example 1 only in that the sodium vanadate is replaced with potassium titanate. Can be used for
In order to verify the service performance of the hot galvanizing passivation solution, the hot galvanizing passivation solution products obtained in examples 1-3 and the products obtained in comparative examples 1-8 are subjected to passivation tests and salt water spraying experiment tests, wherein the passivation tests are to coat the products at 25 ℃, the coating thickness is 10 microns, the forming time of a passivation film layer is recorded, and the test results are shown in table 1; the salt spray test uses the GB/T10125-2012 standard test method, and the test results are shown in Table 2.
TABLE 1
| Item | Passivation time/s |
| Example 1 | 3 |
| Example 2 | 4 |
| Example 3 | 4 |
| Comparative example 1 | 6 |
| Comparative example 2 | 6 |
| Comparative example 3 | 7 |
| Comparative example 4 | 9 |
| Comparative example 5 | 8 |
| Comparative example 6 | 9 |
| Comparative example 7 | 12 |
| Comparative example 8 | 7 |
TABLE 2
As can be seen from tables 1 and 2, compared with products obtained in comparative examples 1-8, the hot galvanizing passivation solution provided by the invention has a faster passivation film formation rate and better corrosion resistance, the time of red rust of the product is longer than 600h, white rust does not occur, and the performance of the hot galvanizing passivation solution is far better than that of the existing passivation solution products.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The hot galvanizing passivation solution is characterized by comprising the following components in parts by weight: 5-15 parts of trivalent chromium compound, 10-15 parts of acidic reagent, 0.5-5 parts of vanadium-containing compound, 10-15 parts of organic resin, 5-15 parts of silane coupling agent and 5-15 parts of complexing agent.
2. The hot galvanizing passivation solution of claim 1, wherein the trivalent chromium compound comprises at least one of chromium chloride, chromium nitrate, chromium sulfate, chromium phosphate, chromium oxalate and chromium carbonate.
3. The hot galvanizing passivation solution according to claim 1, characterized in that the acidic reagent is at least one of an organic acid reagent and an inorganic acid reagent; preferably, the acidic reagent is at least one of sulfuric acid, nitric acid, hydrofluoric acid, acetic acid, hydrochloric acid, sulfurous acid, fluosilicic acid, citric acid and gluconic acid.
4. The hot galvanizing passivation solution of claim 1, wherein the vanadium-containing compound comprises at least one of vanadium sulfate, vanadium nitrate, sodium vanadate, ammonium vanadate, manganese vanadate and potassium vanadate.
5. The hot dip galvanizing passivation solution of claim 1, wherein the organic resin is a cationic urethane resin or a nonionic acrylic resin, and the cationic amino group includes at least one of a primary amino group, a tertiary amino group, and a quaternary amino group.
6. The hot galvanizing passivation solution of claim 1, wherein the silane coupling agent is a silane coupling agent containing active hydrogen functional groups, and the active hydrogen functional groups comprise at least one of amino groups, epoxy groups, mercapto groups and methacryloxy groups containing active hydrogen.
7. The hot dip galvanizing passivation solution of claim 1, wherein the complexing agent includes at least one of malic acid, gluconic acid, sodium tartrate, sodium citrate, sodium gluconate, potassium tartrate, potassium citrate, potassium gluconate, ammonium tartrate, ammonium malate, ammonium citrate, ammonium gluconate, monoethanolamine, triethylenetetramine, and tetraethylenetetramine.
8. The hot galvanizing passivation solution of claim 1, which comprises the following components in parts by weight: 100 parts of distilled water, 10 parts of trivalent chromium compound, 2 parts of vanadium-containing compound, 12 parts of acidic reagent, 12 parts of organic resin, 9 parts of silane coupling agent and 8 parts of complexing agent.
9. The preparation method of the hot galvanizing passivation solution according to any one of claims 1 to 8, characterized by comprising the following steps:
(1) adding a trivalent chromium compound into distilled water, heating and reacting to obtain a mixed solution A;
(2) adding a vanadium-containing compound into the mixed solution A obtained in the step (1), stirring and mixing, and adding an acidic reagent to obtain a mixed solution B;
(3) and (3) sequentially adding a complexing agent and a silane coupling agent into the mixed solution B obtained in the step (2) under stirring, uniformly mixing, adding an organic resin, and stirring for 25-35 min to obtain the hot galvanizing passivation solution.
10. The preparation method of the hot galvanizing passivation solution according to claim 9, characterized in that the heating temperature in the step (1) is 25-35 ℃, and the reaction time is 25-35 min; and (3) stirring and mixing for 10-20 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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