CN111945201A - Electrogalvanizing blue-white passivated titanium salt sealant and preparation method thereof - Google Patents
Electrogalvanizing blue-white passivated titanium salt sealant and preparation method thereof Download PDFInfo
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- CN111945201A CN111945201A CN202010841208.1A CN202010841208A CN111945201A CN 111945201 A CN111945201 A CN 111945201A CN 202010841208 A CN202010841208 A CN 202010841208A CN 111945201 A CN111945201 A CN 111945201A
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- 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 belongs to the field of metal surface treatment, and particularly relates to a titanium salt sealant after electrogalvanizing blue-white passivation and a preparation method thereof. The invention provides a titanium salt sealing agent after electrogalvanizing blue-white passivation, which comprises the following components in parts by weight: 16-20 parts of titanium trichloride, 1-2 parts of diethylenetriamine, 18-20 parts of doped polymer emulsion, 0.5-1 part of thiourea, 0.3-0.6 part of surfactant and 8-10 parts of zinc sulfate. The electrogalvanizing blue-white passivated titanium salt sealing agent provided by the invention has good film forming performance and sealing performance, strong salt spray resistance and good dispersion performance, and a film layer treated by the electrogalvanizing blue-white passivated titanium salt sealing agent is a blue-white film and is uniform and bright.
Description
Technical Field
The invention belongs to the field of metal surface treatment, and particularly relates to a titanium salt sealant after electrogalvanizing blue-white passivation and a preparation method thereof.
Background
Under the continuous development of science and technology, metal materials occupy an extremely important position in various modern industries, such as mechanical manufacturing, transportation and common daily life of people. Among them, metal materials such as steel and iron have abundant resources, low cost, simple recovery and excellent mechanical properties, so that the metal materials become the most widely applied materials among a large number of metal materials. However, the metal is inevitably subjected to the chemical action of oxygen and water vapor in the environment during the use process, thereby causing self corrosion. Corrosion refers to the destruction and deterioration of a metal material caused by a chemical reaction, an electrochemical reaction, or a simple physical dissolution of the metal material with a medium in the environment. The corrosion process is a spontaneous process, because the metal itself is in an unstable state, and tends to react with the surrounding medium to become metal ions, the process is irreversible, and causes great loss of national economy. The losses to humans from corrosion are enormous. According to the Chinese corrosion survey report, 1t of steel is corroded to rust every 90s in the world, metallic materials and equipment which are scrapped due to corrosion in the world are about 20% of the production quantity every year, and the economic loss of some developed countries caused by metal corrosion accounts for about 2-4% of the total value of national economy. The limited resources on the earth are increasingly exhausted, and with the development of global industry, besides direct loss, the problem of corrosion is becoming more and more serious. Although the work of pollution control and research is ongoing worldwide and corrosion protection technology is continuously developed to alleviate the corrosion problem, the corrosion of metals is still very serious in general.
Electrogalvanizing is indispensable in the field of metal material protection, forms a uniform, compact and well-combined zinc metal deposition layer on the surface of a steel workpiece by utilizing electrolysis, and separates the protected workpiece from a corrosive medium so as to achieve the anti-corrosion effect. However, if the zinc coating is not well post-treated, the coating quickly becomes dull and white corrosion products and even "red rust" appear successively, so that the effect of protecting the article is not achieved. Therefore, in order to improve the corrosion resistance of the product, passivation treatment is generally performed after zinc plating is finished, so that a layer of passivation film is formed on the surface of a plating layer; the blue-white passivation technology is simple and elegant in appearance, excellent in performance and deeply favored by the market, is one of the most main post-treatment technologies of galvanized parts, the treated galvanized parts are light blue and bright in appearance, the original color of the galvanized parts can be kept, the corrosion resistance of products is improved, and therefore the blue-white passivation technology is widely applied to various metal protection industries. However, the passivation film obtained by the existing passivation sealant technology has the technical problems of uneven distribution, unsatisfactory corrosion resistance effect and easy colorization of the passivation layer.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a titanium salt sealant after electrogalvanizing blue-white passivation and a preparation method thereof. The electrogalvanizing blue-white passivated titanium salt sealing agent provided by the invention has good film forming performance and sealing performance, strong salt spray resistance and good dispersion performance, and a film layer treated by the electrogalvanizing blue-white passivated titanium salt sealing agent is a blue-white film and is uniform and bright.
The technical scheme of the invention is as follows:
the electrogalvanizing blue-white passivated titanium salt sealant comprises the following components in parts by weight: 16-20 parts of titanium trichloride, 1-2 parts of diethylenetriamine, 18-20 parts of doped polymer emulsion, 0.5-1 part of thiourea, 0.3-0.6 part of surfactant and 8-10 parts of zinc sulfate.
Further, the electrogalvanizing blue-white passivated titanium salt sealing agent comprises the following components in parts by weight: 17 parts of titanium trichloride, 1.2 parts of diethylenetriamine, 19 parts of doped polymer emulsion, 0.6 part of thiourea, 0.4 part of surfactant and 9 parts of zinc sulfate.
Further, the doped polymer emulsion comprises the following components in parts by weight:
10-15 parts of polyvinyl alcohol, 5-10 parts of acrylic acid, 58-65 parts of itaconic acid, 2-3 parts of a doping agent, 0.3-0.5 part of an initiator, 0.1-0.3 part of sodium dodecyl sulfate, 1-3 parts of dodecafluoroheptyl propyl trimethoxy silane and 0.5-1 part of carnauba wax.
Further, the doped polymer emulsion comprises the following components in parts by weight:
13 parts of polyvinyl alcohol, 9 parts of acrylic acid, 62 parts of methylene succinic acid, 2.5 parts of a doping agent, 0.4 part of an initiator, 0.2 part of sodium dodecyl sulfate, 2 parts of dodecafluoroheptyl-propyl-trimethoxysilane and 0.7 part of carnauba wax.
Further, the molecular weight of the polyvinyl alcohol is 15000-25000.
Further, the molecular weight of the polyvinyl alcohol is 20000.
Further, the doping agent is composed of dodecenylsuccinic acid and sodium lignosulphonate according to the mass ratio of 8-12: 1-3.
Further, the doping agent is composed of dodecenylsuccinic acid and sodium lignosulphonate according to the mass ratio of 10: 3.
Further, the initiator is one of ammonium persulfate and sodium persulfate.
Further, the preparation method of the doped polymer emulsion comprises the following steps:
(1) mixing polyvinyl alcohol, acrylic acid, itaconic acid and lauryl sodium sulfate to obtain a mixture, adding water, wherein the adding amount of the water is 20-30 times of the mass of the mixture, and uniformly stirring to obtain a mixed material I;
(2) adding water into an initiator, wherein the adding amount of the water is 10-15 times of the mass of the initiator, and stirring for dissolving to obtain an initiator aqueous solution;
(3) adding carnauba wax into absolute ethyl alcohol, wherein the mass of the absolute ethyl alcohol is 20-30 times of that of the carnauba wax, heating to 90-100 ℃, keeping the temperature, heating for 10-20min, adding dodecafluoroheptyl-propyl-trimethoxysilane, keeping the temperature for 8-15min, and mixing the material II;
(4) adding the initiator aqueous solution and the doping agent obtained in the step (2) into the mixed material I obtained in the step (1) while stirring, heating to 50-55 ℃, performing ultrasonic treatment for 8-10min, keeping the temperature for 1-2h, continuously dropwise adding the mixed material II obtained in the step (3) by using a dropping funnel for 2-3h, heating to 60-70 ℃ after dropwise addition, reacting for 1-2h while keeping the temperature, and cooling to room temperature to obtain the catalyst.
Further, the surfactant is composed of sorbitan monooleate and triethanolamine oleate according to the mass ratio of 5-7: 1.
Further, the surfactant is composed of sorbitan monooleate and triethanolamine oleate according to the mass ratio of 6: 1.
The preparation method of the electrogalvanizing blue-white passivated titanium salt sealant comprises the following steps:
s1, mixing titanium trichloride and diethylenetriamine, adding water, wherein the addition amount of the water is 40-50 times of the total mass of the titanium trichloride and the diethylenetriamine, and uniformly stirring to obtain a premixed material;
s2, adding the doped polymer emulsion into the premix obtained in the step S1, stirring uniformly, placing in a constant-temperature water bath at 35-40 ℃ for heat preservation for 10-13h, discharging and cooling, adding thiourea, surfactant and zinc sulfate, stirring uniformly, and adjusting the pH value to 7.5-8.5 by using ammonia water to obtain the aqueous solution.
In the doped polymer emulsion added in the invention, acrylic acid and itaconic acid are used as monomers and are blended and modified with polyvinyl alcohol, so that good hardness and adhesion can be provided, the rust resistance and corrosion resistance of the product can be improved by adding a doping agent, silane dispersion liquid of carnauba wax is used as a solvent, polymerization is carried out under the action of an initiator, hydrolysis of dodecafluoroheptyl propyl trimethoxy silane is promoted in the polymerization process, and the obtained modified polymer emulsion is blended and cooperated with carnauba wax, so that the rust resistance and peeling resistance of the product can be enhanced.
The electrogalvanizing blue-white passivated titanium salt sealing agent provided by the invention has the advantages of good dispersibility, high corrosion resistance, strong film adhesion and good film forming property, and neutral salt spray tests prove that the time of white rust on a workpiece treated by the electrogalvanizing blue-white passivated titanium salt sealing agent is up to 144h, so that the electroplating quality of the workpiece is remarkably improved.
The doping agent which is added in the invention and consists of dodecenylsuccinic acid and sodium lignosulphonate according to a certain mass ratio can form a firm oil film on the surface of metal to protect the metal from being rusted and corroded, so that the rust resistance and corrosion resistance of the film layer are improved, and the bonding force between the film layer and the metal and the adhesion force of the film layer are improved.
The polyvinyl alcohol with specific molecular weight added in the invention can not only enhance the film-forming property of the product, but also improve the stability of the doped polymer emulsion, thereby being beneficial to the uniformity of film formation.
The surfactant which is composed of sorbitan monooleate and triethanolamine oleate in a certain mass ratio is added in the invention, which is beneficial to maintaining the stability of the whole system, thereby ensuring the color uniformity and film forming uniformity of the product.
Compared with the prior art, the invention has the following advantages:
(1) the electrogalvanizing blue-white passivated titanium salt sealant provided by the invention has good film forming performance and sealing performance and strong salt spray resistance.
(2) The electrogalvanizing blue-white passivated titanium salt sealing agent provided by the invention has good dispersibility and good film forming property, and a film layer treated by the electrogalvanizing blue-white passivated titanium salt sealing agent is uniformly distributed.
(3) The film treated by the electrogalvanizing blue-white passivated titanium salt sealing agent has excellent corrosion resistance and strong film adhesion; neutral salt spray tests prove that the time of white rust of the workpiece treated by the electrogalvanizing blue-white passivated titanium salt sealing agent is up to 144h, and the electroplating quality of the workpiece is obviously improved.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention.
Example 1 titanium salt sealant after electrogalvanizing blue-white passivation
The electrogalvanizing blue-white passivated titanium salt sealing agent comprises the following components in parts by weight: 16 parts of titanium trichloride, 1 part of diethylenetriamine, 18 parts of doped polymer emulsion, 0.5 part of thiourea, 0.3 part of surfactant and 8 parts of zinc sulfate; the surfactant is composed of sorbitan monooleate and triethanolamine oleate according to the mass ratio of 5: 1.
The doped polymer emulsion comprises the following components in parts by weight:
10 parts of polyvinyl alcohol with the molecular weight of 15000, 5 parts of acrylic acid, 58 parts of itaconic acid, 2 parts of a doping agent, 0.3 part of an initiator, 0.1 part of sodium dodecyl sulfate, 1 part of dodecafluoroheptyl-propyl-trimethoxy silane and 0.5 part of carnauba wax; the dopant consists of dodecenylsuccinic acid and sodium lignosulphonate according to the mass ratio of 8: 3; the initiator is ammonium persulfate.
The preparation method of the doped polymer emulsion comprises the following steps:
(1) mixing polyvinyl alcohol, acrylic acid, itaconic acid and lauryl sodium sulfate to obtain a mixture, adding water, wherein the adding amount of the water is 20 times of the mass of the mixture, and uniformly stirring to obtain a mixed material I;
(2) adding water into an initiator, wherein the adding amount of the water is 10 times of the mass of the initiator, and stirring for dissolving to obtain an initiator aqueous solution;
(3) adding carnauba wax into absolute ethyl alcohol, wherein the mass of the absolute ethyl alcohol is 20 times of that of the carnauba wax, heating to 90 ℃, keeping the temperature, heating for 10min, adding dodecafluoroheptyl-propyl-trimethoxy silane, keeping the temperature for 8min, and mixing a material II;
(4) adding the initiator aqueous solution and the doping agent obtained in the step (2) into the mixed material I obtained in the step (1) while stirring, heating to 50 ℃, performing ultrasonic treatment for 8min, preserving heat for 1h, continuously dropwise adding the mixed material II obtained in the step (3) by using a dropping funnel for 2h, heating to 60 ℃ after dropwise adding, preserving heat for 1h, and cooling to room temperature to obtain the catalyst.
The preparation method of the electrogalvanizing blue-white passivated titanium salt sealant comprises the following steps:
s1, mixing titanium trichloride and diethylenetriamine, adding water, wherein the addition amount of the water is 40 times of the total mass of the titanium trichloride and the diethylenetriamine, and uniformly stirring to obtain a premixed material;
s2, adding the doped polymer emulsion into the premix obtained in the step S1, stirring uniformly, placing in a constant-temperature water bath at 35 ℃ for heat preservation for 10 hours, discharging and cooling, adding thiourea, surfactant and zinc sulfate, stirring uniformly, and adjusting the pH to 7.5 by using ammonia water to obtain the aqueous solution.
Example 2 titanium salt sealant after electrogalvanizing blue-white passivation
The electrogalvanizing blue-white passivated titanium salt sealing agent comprises the following components in parts by weight: 20 parts of titanium trichloride, 2 parts of diethylenetriamine, 20 parts of doped polymer emulsion, 1 part of thiourea, 0.6 part of surfactant and 10 parts of zinc sulfate; the surfactant is composed of sorbitan monooleate and triethanolamine oleate according to the mass ratio of 7: 1.
The doped polymer emulsion comprises the following components in parts by weight:
15 parts of polyvinyl alcohol with the molecular weight of 25000, 10 parts of acrylic acid, 65 parts of itaconic acid, 3 parts of a doping agent, 0.5 part of an initiator, 0.3 part of sodium dodecyl sulfate, 3 parts of dodecafluoroheptyl-propyl-trimethoxy silane and 1 part of carnauba wax; the dopant consists of dodecenylsuccinic acid and sodium lignosulphonate according to the mass ratio of 12: 1; the initiator is sodium persulfate.
The preparation method of the doped polymer emulsion comprises the following steps:
(1) mixing polyvinyl alcohol, acrylic acid, itaconic acid and lauryl sodium sulfate to obtain a mixture, adding water, wherein the adding amount of the water is 30 times of the mass of the mixture, and uniformly stirring to obtain a mixed material I;
(2) adding water into an initiator, wherein the adding amount of the water is 15 times of the mass of the initiator, and stirring for dissolving to obtain an initiator aqueous solution;
(3) adding carnauba wax into absolute ethyl alcohol, wherein the mass of the absolute ethyl alcohol is 30 times that of the carnauba wax, heating to 100 ℃, keeping the temperature, heating for 20min, adding dodecafluoroheptyl-propyl-trimethoxysilane, keeping the temperature for 15min, and mixing the material II;
(4) adding the initiator aqueous solution and the doping agent obtained in the step (2) into the mixed material I obtained in the step (1) while stirring, heating to 55 ℃, performing ultrasonic treatment for 10min, preserving heat for 2h, continuously dropwise adding the mixed material II obtained in the step (3) by using a dropping funnel for 3h, heating to 70 ℃ after dropwise adding, preserving heat for 2h, and cooling to room temperature to obtain the catalyst.
The preparation method of the electrogalvanizing blue-white passivated titanium salt sealant comprises the following steps:
s1, mixing titanium trichloride and diethylenetriamine, adding water, wherein the addition amount of the water is 50 times of the total mass of the titanium trichloride and the diethylenetriamine, and uniformly stirring to obtain a premixed material;
s2, adding the doped polymer emulsion into the premix obtained in the step S1, stirring uniformly, placing in a constant-temperature water bath at 40 ℃ for heat preservation for 13 hours, discharging and cooling, adding thiourea, surfactant and zinc sulfate, stirring uniformly, and adjusting the pH to 8.5 by using ammonia water to obtain the aqueous solution.
Example 3 titanium salt sealant after electrogalvanizing blue-white passivation
The electrogalvanizing blue-white passivated titanium salt sealing agent comprises the following components in parts by weight: 17 parts of titanium trichloride, 1.2 parts of diethylenetriamine, 19 parts of doped polymer emulsion, 0.6 part of thiourea, 0.4 part of surfactant and 9 parts of zinc sulfate; the surfactant is composed of sorbitan monooleate and triethanolamine oleate according to the mass ratio of 6: 1.
The doped polymer emulsion comprises the following components in parts by weight:
13 parts of polyvinyl alcohol with the molecular weight of 20000, 9 parts of acrylic acid, 62 parts of methylene succinic acid, 2.5 parts of doping agent, 0.4 part of initiator, 0.2 part of sodium dodecyl sulfate, 2 parts of dodecafluoroheptyl propyl trimethoxy silane and 0.7 part of carnauba wax; the dopant consists of dodecenylsuccinic acid and sodium lignosulphonate according to the mass ratio of 10: 3; the initiator is sodium persulfate.
The preparation method of the doped polymer emulsion comprises the following steps:
(1) mixing polyvinyl alcohol, acrylic acid, itaconic acid and lauryl sodium sulfate to obtain a mixture, adding water, wherein the adding amount of the water is 28 times of the mass of the mixture, and uniformly stirring to obtain a mixed material I;
(2) adding water into an initiator, wherein the adding amount of the water is 12 times of the mass of the initiator, and stirring for dissolving to obtain an initiator aqueous solution;
(3) adding carnauba wax into absolute ethyl alcohol, wherein the mass of the absolute ethyl alcohol is 25 times that of the carnauba wax, heating to 95 ℃, keeping the temperature, heating for 12min, adding dodecafluoroheptyl-propyl-trimethoxy silane, keeping the temperature for 10min, and mixing the material II;
(4) adding the initiator aqueous solution and the doping agent obtained in the step (2) into the mixed material I obtained in the step (1) while stirring, heating to 52 ℃, performing ultrasonic treatment for 9min, preserving heat for 1.5h, continuously dropwise adding the mixed material II obtained in the step (3) by using a dropping funnel for 2.5h, heating to 65 ℃ after dropwise adding, preserving heat for reaction for 1.5h, and cooling to room temperature to obtain the material.
The preparation method of the electrogalvanizing blue-white passivated titanium salt sealant comprises the following steps:
s1, mixing titanium trichloride and diethylenetriamine, adding water, wherein the addition amount of the water is 48 times of the total mass of the titanium trichloride and the diethylenetriamine, and uniformly stirring to obtain a premixed material;
s2, adding the doped polymer emulsion into the premix obtained in the step S1, stirring uniformly, placing in a thermostatic water bath at 37 ℃ for heat preservation for 11 hours, discharging and cooling, adding thiourea, surfactant and zinc sulfate, stirring uniformly, and adjusting the pH to 8 by using ammonia water to obtain the aqueous solution.
Comparative example 1 titanium salt sealant after electrogalvanizing blue-white passivation
The electrogalvanizing blue-white passivated titanium salt sealing agent comprises the following components in parts by weight: 17 parts of titanium trichloride, 1.2 parts of diethylenetriamine, 19 parts of doped polymer emulsion, 0.6 part of thiourea, 0.4 part of surfactant and 9 parts of zinc sulfate; the surfactant is composed of sorbitan monooleate and triethanolamine oleate according to the mass ratio of 1: 1.
The doped polymer emulsion comprises the following components in parts by weight:
13 parts of polyvinyl alcohol with the molecular weight of 20000, 9 parts of acrylic acid, 62 parts of methylene succinic acid, 2.5 parts of doping agent, 0.4 part of initiator, 0.2 part of sodium dodecyl sulfate, 2 parts of dodecafluoroheptyl propyl trimethoxy silane and 0.7 part of carnauba wax; the dopant consists of dodecenylsuccinic acid and sodium lignosulphonate according to the mass ratio of 10: 3; the initiator is sodium persulfate.
The preparation methods of the doped polymer emulsion and the titanium salt sealant after electrogalvanizing blue-white passivation are similar to those in example 3.
The difference from example 3 is that the surfactant consists of sorbitan monooleate and triethanolamine oleate in a mass ratio of 1: 1.
Comparative example 2, titanium salt sealant after electrogalvanizing blue-white passivation
The electrogalvanizing blue-white passivated titanium salt sealing agent comprises the following components in parts by weight: 17 parts of titanium trichloride, 1.2 parts of diethylenetriamine, 19 parts of doped polymer emulsion, 0.6 part of thiourea, 0.4 part of surfactant and 9 parts of zinc sulfate; the surfactant is sorbitan monooleate.
The doped polymer emulsion comprises the following components in parts by weight:
13 parts of polyvinyl alcohol with the molecular weight of 20000, 9 parts of acrylic acid, 62 parts of methylene succinic acid, 2.5 parts of doping agent, 0.4 part of initiator, 0.2 part of sodium dodecyl sulfate, 2 parts of dodecafluoroheptyl propyl trimethoxy silane and 0.7 part of carnauba wax; the dopant consists of dodecenylsuccinic acid and sodium lignosulphonate according to the mass ratio of 10: 3; the initiator is sodium persulfate.
The preparation methods of the doped polymer emulsion and the titanium salt sealant after electrogalvanizing blue-white passivation are similar to those in example 3.
The difference from example 3 is that triethanolamine oleate is not added to the surfactant.
Comparative example 3, titanium salt sealant after electrogalvanizing blue-white passivation
The electrogalvanizing blue-white passivated titanium salt sealing agent comprises the following components in parts by weight: 17 parts of titanium trichloride, 1.2 parts of diethylenetriamine, 19 parts of doped polymer emulsion, 0.6 part of thiourea, 0.4 part of surfactant and 9 parts of zinc sulfate; the surfactant is composed of sorbitan monooleate and triethanolamine oleate according to the mass ratio of 6: 1.
The doped polymer emulsion comprises the following components in parts by weight:
13 parts of polyvinyl alcohol with the molecular weight of 20000, 9 parts of acrylic acid, 62 parts of methylene succinic acid, 2.5 parts of doping agent, 0.4 part of initiator, 0.2 part of sodium dodecyl sulfate, 2 parts of dodecafluoroheptyl propyl trimethoxy silane and 0.7 part of carnauba wax; the dopant consists of dodecenylsuccinic acid and sodium lignosulphonate according to the mass ratio of 1: 1; the initiator is sodium persulfate.
The preparation methods of the doped polymer emulsion and the titanium salt sealant after electrogalvanizing blue-white passivation are similar to those in example 3.
The difference from example 3 is that the dopant consists of dodecenylsuccinic acid and sodium lignosulfonate in a mass ratio of 1: 1.
Comparative example 4, titanium salt sealant after electrogalvanizing blue-white passivation
The electrogalvanizing blue-white passivated titanium salt sealing agent comprises the following components in parts by weight: 17 parts of titanium trichloride, 1.2 parts of diethylenetriamine, 19 parts of doped polymer emulsion, 0.6 part of thiourea, 0.4 part of surfactant and 9 parts of zinc sulfate; the surfactant is composed of sorbitan monooleate and triethanolamine oleate according to the mass ratio of 6: 1.
The doped polymer emulsion comprises the following components in parts by weight:
13 parts of polyvinyl alcohol with the molecular weight of 20000, 9 parts of acrylic acid, 62 parts of methylene succinic acid, 2.5 parts of doping agent, 0.4 part of initiator, 0.2 part of sodium dodecyl sulfate, 2 parts of dodecafluoroheptyl propyl trimethoxy silane and 0.7 part of carnauba wax; the dopant is dodecenylsuccinic acid; the initiator is sodium persulfate.
The preparation methods of the doped polymer emulsion and the titanium salt sealant after electrogalvanizing blue-white passivation are similar to those in example 3.
The difference from example 3 is that sodium lignosulfonate was not added to the dopant.
Comparative example 5 titanium salt sealant after electrogalvanizing blue-white passivation
The electrogalvanizing blue-white passivated titanium salt sealing agent comprises the following components in parts by weight: 17 parts of titanium trichloride, 1.2 parts of diethylenetriamine, 19 parts of doped polymer emulsion, 0.6 part of thiourea, 0.4 part of surfactant and 9 parts of zinc sulfate; the surfactant is composed of sorbitan monooleate and triethanolamine oleate according to the mass ratio of 6: 1.
The doped polymer emulsion comprises the following components in parts by weight:
13 parts of polyvinyl alcohol with the molecular weight of 30000, 9 parts of acrylic acid, 62 parts of methylene succinic acid, 2.5 parts of doping agent, 0.4 part of initiator, 0.2 part of sodium dodecyl sulfate, 2 parts of dodecafluoroheptyl propyl trimethoxy silane and 0.7 part of carnauba wax; the dopant consists of dodecenylsuccinic acid and sodium lignosulphonate according to the mass ratio of 10: 3; the initiator is sodium persulfate.
The preparation methods of the doped polymer emulsion and the titanium salt sealant after electrogalvanizing blue-white passivation are similar to those in example 3.
The difference from example 3 is that the molecular weight of the polyvinyl alcohol in the doped polymer emulsion is 30000.
Comparative example 6, titanium salt sealant after electrogalvanizing blue-white passivation
The electrogalvanizing blue-white passivated titanium salt sealing agent comprises the following components in parts by weight: 17 parts of titanium trichloride, 1.2 parts of diethylenetriamine, 19 parts of doped polymer emulsion, 0.6 part of thiourea, 0.4 part of surfactant and 9 parts of zinc sulfate; the surfactant is composed of sorbitan monooleate and triethanolamine oleate according to the mass ratio of 6: 1.
The doped polymer emulsion comprises the following components in parts by weight:
9 parts of acrylic acid, 62 parts of methylene succinic acid, 2.5 parts of a doping agent, 0.4 part of an initiator, 0.2 part of sodium dodecyl sulfate, 2 parts of dodecafluoroheptyl-propyl-trimethoxy silane and 0.7 part of carnauba wax; the dopant consists of dodecenylsuccinic acid and sodium lignosulphonate according to the mass ratio of 10: 3; the initiator is sodium persulfate.
The preparation methods of the doped polymer emulsion and the titanium salt sealant after electrogalvanizing blue-white passivation are similar to those in example 3.
The difference from example 3 is that no polyvinyl alcohol was added to the doped polymer emulsion.
Test example I, neutral salt spray Corrosion test
1. Test samples: the electrogalvanizing titanium salt sealant prepared in the embodiment 1, the embodiment 2, the embodiment 3, the comparative embodiment 3 and the comparative embodiment 4 is passivated with blue and white.
2. The test method comprises the following steps:
2.1, a process flow: workpiece → oil and rust removal → cleaning → galvanizing → blue and white passivation → sealing → drying
2.2, neutral salt spray corrosion test:
the steel plates after oil and rust removal, cleaning, galvanizing and blue and white passivation are respectively immersed in the electrogalvanizing blue and white passivation titanium salt sealing agent prepared in the examples 1, 2, 3 and 4 for sealing treatment, the sealing time is 25S, the temperature is 25 ℃, and cold air is blown to dry; drying the sealed test piece at 60 deg.C for 15min, and performing neutral salt spray corrosion test.
The neutral salt spray resistance time is tested by referring to GBT10125-1997 salt spray test for artificial atmosphere corrosion test, and the grade evaluation is carried out by referring to GB/T6461-2002 rating of samples and test pieces after corrosion tests of metals and other inorganic coatings on metal substrates. In addition, a neutral salt spray corrosion test was performed using a steel plate without sealing treatment as a control.
3. The test results are shown in table 1.
Table 1: neutral salt spray corrosion test result
As can be seen from Table 1, the workpiece subjected to sealing treatment by the electrogalvanizing blue-white passivated titanium salt sealing agent provided by the invention has white rust occurrence time of not less than 120h and protection level of not less than 8, which is obviously superior to the contrast, wherein the neutral salt spray resistant time of the embodiment 3 is longest, and the protection level is highest, which is the best embodiment of the invention; compared with comparative examples 3-4, the workpiece subjected to sealing treatment by the electrogalvanizing blue-white passivated titanium salt sealing agent has longer neutral salt spray resistance time and better protection level.
Test example two, film appearance test
1. Test samples: the titanium salt sealant after the blue and white passivation of the electroplating zinc prepared by the embodiment 3, the comparative example 1, the comparative example 2, the comparative example 5 and the comparative example 6.
2. The test method comprises the following steps:
2.1, a process flow: workpiece → oil and rust removal → cleaning → galvanizing → blue and white passivation → sealing → drying
The steel plates after oil and rust removal, cleaning, galvanizing and blue and white passivation are respectively immersed in the electrogalvanizing blue and white passivation titanium salt sealing agent prepared in the embodiment 3, the comparative example 1, the comparative example 2, the comparative example 5 and the comparative example 6 for sealing treatment, the sealing time is 25S, the temperature is 25 ℃, and the steel plates are dried by cold air; the sealed test piece was dried at 60 ℃ for 15min, and the appearance of the film was observed.
3. The test results are shown in table 2.
Table 2: film appearance results
As can be seen from Table 2, after the electrogalvanizing blue-white passivated titanium salt sealant provided by the invention is used for sealing, the film appearance is a blue-white film, the color is bright, the color is uniform, and the film is formed uniformly, while the problems of poor film forming uniformity and the like are caused after the electrogalvanizing blue-white passivated titanium salt sealant of comparative examples 1-2 and 5-6 is used for sealing. Therefore, the electrogalvanizing blue-white passivated titanium salt sealing agent prepared by the invention has good dispersibility, and the uniformity of film distribution is improved.
Test example three, adhesion test
1. Test samples: the electrogalvanizing blue-white passivated titanium salt sealing agent prepared in the embodiment 3, the comparative example 3 and the comparative example 4.
2. The test method comprises the following steps:
2.1, a process flow: workpiece → oil and rust removal → cleaning → galvanizing → blue and white passivation → sealing → drying
The steel plates after oil and rust removal, cleaning, galvanizing and blue and white passivation are respectively immersed in the electrogalvanizing blue and white passivation titanium salt sealing agent prepared in the embodiment 3, the comparative example 3 and the comparative example 4 for sealing treatment, the sealing time is 25S, the temperature is 25 ℃, and cold air is blown to dry; and drying the sealed test piece at the temperature of 60 ℃ for 15min, and carrying out an adhesion test experiment.
The sand-free rubber is held by hand, the passive film is rubbed back and forth for more than ten times, and the passive film is not separated, does not fade and is intact, so the bonding force of the passive film is qualified.
3. The test results are shown in table 3.
Table 3: adhesion test results
| Item | Example 3 | Comparative example 3 | Comparative example 4 |
| Adhesion test (second time) | 20 | 16 | 12 |
As can be seen from Table 3, the adhesion test frequency of the workpiece subjected to sealing treatment by the electrogalvanizing blue-white passivated titanium salt sealing agent provided by the invention is the largest, which shows that the bonding force of the film is good. Compared with comparative examples 3-4, the film adhesion of the workpiece subjected to sealing treatment by the electrogalvanizing blue-white passivated titanium salt sealing agent is strong.
Claims (10)
1. The electrogalvanizing blue-white passivated titanium salt sealant is characterized by comprising the following components in parts by weight: 16-20 parts of titanium trichloride, 1-2 parts of diethylenetriamine, 18-20 parts of doped polymer emulsion, 0.5-1 part of thiourea, 0.3-0.6 part of surfactant and 8-10 parts of zinc sulfate.
2. The electrogalvanizing blue-white passivated titanium salt sealant as claimed in claim 1, which comprises the following components in parts by weight: 17 parts of titanium trichloride, 1.2 parts of diethylenetriamine, 19 parts of doped polymer emulsion, 0.6 part of thiourea, 0.4 part of surfactant and 9 parts of zinc sulfate.
3. The electrogalvanizing titanium salt sealant after blue and white passivation according to claim 1 or 2, wherein the doped polymer emulsion comprises the following components in parts by weight:
10-15 parts of polyvinyl alcohol, 5-10 parts of acrylic acid, 58-65 parts of itaconic acid, 2-3 parts of a doping agent, 0.3-0.5 part of an initiator, 0.1-0.3 part of sodium dodecyl sulfate, 1-3 parts of dodecafluoroheptyl propyl trimethoxy silane and 0.5-1 part of carnauba wax.
4. The electrogalvanizing blue-white passivated titanium salt sealant as claimed in claim 3, wherein the doped polymer emulsion is composed of the following components in parts by mass:
13 parts of polyvinyl alcohol, 9 parts of acrylic acid, 62 parts of methylene succinic acid, 2.5 parts of a doping agent, 0.4 part of an initiator, 0.2 part of sodium dodecyl sulfate, 2 parts of dodecafluoroheptyl-propyl-trimethoxysilane and 0.7 part of carnauba wax.
5. The electrogalvanized blue-white post-passivation titanium salt blocking agent as claimed in claim 3, wherein the molecular weight of the polyvinyl alcohol is 15000-25000.
6. The electrogalvanized blue-white passivated titanium salt sealant according to claim 3, wherein the dopant consists of dodecenylsuccinic acid and sodium lignosulfonate in a mass ratio of 8-12: 1-3.
7. The electrogalvanized blue-white passivated titanium salt sealant according to claim 6, wherein the dopant consists of dodecenylsuccinic acid and sodium lignosulfonate in a mass ratio of 10: 3.
8. The electrogalvanized zinc blue-white passivated titanium salt blocking agent according to claim 1 or 2, wherein the surfactant consists of sorbitan monooleate and triethanolamine oleate in a mass ratio of 5-7: 1.
9. The electrogalvanized blue-white post-passivation titanium salt sealant according to claim 8, wherein the surfactant consists of sorbitan monooleate and triethanolamine oleate in a mass ratio of 6: 1.
10. The method for preparing the titanium salt sealant after electrogalvanizing blue-white passivation according to any one of claims 1 to 9, comprising the following steps:
s1, mixing titanium trichloride and diethylenetriamine, adding water, wherein the addition amount of the water is 40-50 times of the total mass of the titanium trichloride and the diethylenetriamine, and uniformly stirring to obtain a premixed material;
s2, adding the doped polymer emulsion into the premix obtained in the step S1, stirring uniformly, placing in a constant-temperature water bath at 35-40 ℃ for heat preservation for 10-13h, discharging and cooling, adding thiourea, surfactant and zinc sulfate, stirring uniformly, and adjusting the pH value to 7.5-8.5 by using ammonia water to obtain the aqueous solution.
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