CN115449243A - Oriented silicon steel insulating coating liquid and preparation method thereof - Google Patents
Oriented silicon steel insulating coating liquid and preparation method thereof Download PDFInfo
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- CN115449243A CN115449243A CN202211191173.7A CN202211191173A CN115449243A CN 115449243 A CN115449243 A CN 115449243A CN 202211191173 A CN202211191173 A CN 202211191173A CN 115449243 A CN115449243 A CN 115449243A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention provides an oriented silicon steel insulating coating liquid and a preparation method thereof, belonging to the technical field of oriented silicon steel insulating coating preparation. When the coating composite liquid is applied to the surface of the oriented silicon steel, the prepared insulating coating for the oriented silicon steel has good heat resistance, adhesiveness, insulativity, moisture absorption resistance and corrosion resistance.
Description
Technical Field
The application relates to the technical field of preparation of oriented silicon steel insulating coatings, in particular to oriented silicon steel insulating coating liquid and a preparation method thereof.
Background
Oriented silicon steel is a soft magnetic alloy widely applied to the power and electrician industry and is mainly used for manufacturing transformer cores. The oriented silicon steel pursues high magnetic induction and low iron loss, and MgO is coated on the surface of the oriented silicon steel plate, so that the iron loss of the oriented silicon steel can be reduced. However, for medium and large transformers, the insulation and corrosion resistance of the magnesium silicate coating on the surface of the laminated core cannot meet the requirements of the transformer. Therefore, in order to further improve the insulation performance and corrosion resistance of the silicon steel sheet, an insulation coating needs to be further coated on the magnesium silicate base layer.
At present, inorganic insulating coatings are the development trend of oriented silicon steel insulating coatings, and two types of chromate and phosphate are more applied to the inorganic insulating coatings. At present, the most used chromium-containing phosphate insulating coatings are chromium-containing phosphate insulating coatings with excellent comprehensive performance, but the toxicity of chromic anhydride to human bodies and the environment cannot be ignored.
Disclosure of Invention
The embodiment of the application provides an oriented silicon steel insulating coating liquid and a preparation method thereof, and aims to solve the technical problem that the existing chromium-containing phosphate insulating coating has toxicity to human bodies and the environment.
In a first aspect, the embodiment of the application provides an oriented silicon steel insulating coating liquid, which comprises the following components: phosphate, silica sol, chromic anhydride, manganese salt and water.
Further, the weight ratio of the phosphate, the silica sol, the chromic anhydride, the manganese salt and the water is (20-35): (25-40): (1-6): (0.5-5): (14-53.5).
Further, the phosphate is at least one of aluminum phosphate, magnesium phosphate, zinc phosphate, calcium phosphate, strontium phosphate, cobalt phosphate, and nickel phosphate.
Further, the pH value of the silica sol is 7-10, siO 2 20-40 wt% of Na 2 The O content is less than or equal to 0.3 weight percent, and the grain diameter is 5-20 nm.
In a second aspect, embodiments of the present application provide a method for preparing the oriented silicon steel insulating coating liquid of the first aspect, where the method includes:
preparing a phosphate solution;
adding chromic anhydride into the phosphate solution to obtain a first mixed solution;
adding manganese salt into the mixed solution I to obtain a mixed solution II;
and adding silica sol into the second mixed solution to obtain the oriented silicon steel insulating coating solution.
In a third aspect, embodiments of the present application provide an insulating coating formed from the oriented silicon steel insulating coating liquid of the first aspect.
In a fourth aspect, embodiments of the present application provide a method for preparing the insulating coating according to the third aspect, where the method for preparing the insulating coating includes:
covering the surface of the steel body with the oriented silicon steel insulating coating liquid, drying at 350-450 ℃ for 25-35 s, and then preserving heat at 780-820 ℃ for 25-35 s to obtain the insulating coating.
In a fifth aspect, embodiments of the present application provide an oriented silicon steel including an oriented silicon steel substrate and an insulating coating adhered to at least a portion of a surface of the oriented silicon steel substrate;
the insulating coating is the insulating coating of the third aspect.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
the embodiment of the application provides a coating composite liquid which comprises five components of phosphate, silica sol, chromic anhydride, manganese salt and water, wherein the manganese salt is adopted to partially replace the chromic anhydride, so that the consumption of the chromic anhydride is reduced, and the coating composite liquid is beneficial to environmental protection. Therefore, the coating composite liquid provided by the embodiment of the application can improve the environmental protection property of the chromium-containing phosphate insulating coating.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
Fig. 1 is a scanning electron microscope image of an oriented silicon steel insulating coating provided in example 1 of the present application;
FIG. 2 is a scanning electron microscope image of an insulating coating of oriented silicon steel provided in comparative example 1 of the present application;
fig. 3 is a schematic flow chart of a preparation method of a coating composite liquid provided in an embodiment of the present application.
Detailed Description
The present invention will be specifically explained below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, 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. If there is a conflict, the present specification will control.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention may be commercially available or may be prepared by existing methods.
Oriented silicon steel is a soft magnetic alloy widely applied to the power and electrician industry and is mainly used for manufacturing transformer cores. The oriented silicon steel pursues high magnetic induction and low iron loss, and MgO is coated on the surface of the oriented silicon steel plate, so that the iron loss of the oriented silicon steel can be reduced. However, for medium-sized and large-sized transformers, the insulation and corrosion resistance of the magnesium silicate coating on the surface of the laminated core cannot meet the requirements of the transformer. Therefore, in order to further improve the insulation performance and corrosion resistance of the silicon steel sheet, an insulation coating needs to be further coated on the magnesium silicate base layer.
At present, inorganic insulating coatings are the development trend of oriented silicon steel insulating coatings, and two types of chromate and phosphate are more applied to the inorganic insulating coatings. At present, the most used chromium-containing phosphate insulating coatings are chromium-containing phosphate insulating coatings with excellent comprehensive performance, but the toxicity of chromic anhydride to human bodies and the environment cannot be ignored.
In order to solve the technical problems, the embodiment of the invention provides the following general ideas:
in a first aspect, the embodiment of the application provides an oriented silicon steel insulating coating liquid, which comprises the following components: phosphate, silica sol, chromic anhydride, manganese salt and water.
The embodiment of the application provides an oriented silicon steel insulating coating liquid, the coating composite liquid comprises five components of phosphate, silica sol, chromic anhydride, manganese salt and water, the manganese salt is adopted to partially replace the chromic anhydride, the consumption of the chromic anhydride is reduced, and the environment protection is facilitated. The manganese salt and the chromic anhydride both have strong oxidizing property, can enhance the hygroscopicity when the water-soluble oriented silicon steel insulating coating liquid is prepared, can replace part of the chromic anhydride, and can prevent the stickiness phenomenon of the water-soluble oriented silicon steel insulating coating liquid. Therefore, the coating composite liquid provided by the embodiment of the application can improve the environmental protection property of the chromium-containing phosphate insulating coating.
As an implementation mode of the embodiment of the invention, the weight ratio of the phosphate, the silica sol, the chromic anhydride, the manganese salt and the water is (20-35): (25-40): (1-6): (0.5-5): (14-53.5).
In the application, the functions of controlling the relationship between the use amounts of the phosphate, the molybdate, the silica sol, the rare earth additive and the water are to prevent the self reaction of the oriented silicon steel insulating coating liquid and ensure the transparency and the timeliness of the oriented silicon steel insulating coating liquid (the timeliness is the stability between the preparation of the coating liquid and the coating). After the oriented silicon steel insulating coating liquid is prepared, the raw materials interact with each other to stabilize the oriented silicon steel insulating coating liquid, for example, silica sol needs phosphate to be fully dissolved, and chromic acid and manganese salt are added to stabilize the interconversion of phosphate ions.
As an embodiment of the present invention, the phosphate is at least one of aluminum phosphate, magnesium phosphate, zinc phosphate, calcium phosphate, strontium phosphate, cobalt phosphate, and nickel phosphate.
In the application, phosphate is used as a film forming main body, so that the adhesion of the insulating coating to the silicon steel is better, the adhesion degree of the insulating layer and a magnesium silicate bottom layer can be improved, a disordered solidified body is easy to obtain, and the stress and the strain are easier to absorb so as to improve the performance of the coating.
In this application, phosphate is as the binder, along with the temperature rise, can make insulating coating and oriented silicon steel base member combine inseparabler, is favorable to improving the adhesion of oriented silicon steel insulating coating.
As an implementation manner of the embodiment of the present invention, the molybdate is one or two of ammonium molybdate, ammonium molybdate tetrahydrate and magnesium molybdate.
As an embodiment of the present invention, the silica sol has a pH of 7 to 10 and SiO 2 20 to 40 weight percent of Na 2 The content of O is less than or equal to 0.3wt percent and the grain diameter is 5 to 20nm.
In this application, siO in silica sol 2 Content represents silica sol purity, na 2 O is an impurity element thereof, na 2 The high content of O results in the colloidal composition being affected. The pH value of the silica sol is controlled to ensure that phosphate is fully dissolved, and the average particle size of the silica sol is controlled to ensure that water vapor is fully released and grid structure points are formed in the coating, drying and film forming processes.
In a second aspect, an embodiment of the present application provides a method for preparing the oriented silicon steel insulating coating solution, where the method includes:
preparing a phosphate solution;
adding chromic anhydride into the phosphate solution to obtain a first mixed solution;
adding manganese salt into the mixed solution I to obtain a mixed solution II;
and adding silica sol into the second mixed solution to obtain the oriented silicon steel insulating coating solution.
In this application, to mixed solution one in add molybdate solution can make liquid become the acidity, later add silicasol solution again and can make the silicasol dissolve completely, finally configure into water-soluble orientation silicon steel insulating coating liquid, can avoid dissolving inadequately, partial component is appeared, can avoid the silicasol to take place the phase transition simultaneously, and the coating liquid is not clear, and then influences the performance of coating.
In the application, deionized water is neutral, phosphate and chromic anhydride are added to enable the slurry to become acidic, then manganese salt is added to enable the slurry to be fully dissolved, finally silica sol is added to enable the slurry to be completely dissolved, finally water-soluble oriented silicon steel insulating coating liquid is prepared, and incomplete dissolution and partial component separation can be avoided.
In a third aspect, embodiments of the present application provide an insulating coating formed from the oriented silicon steel insulating coating liquid of the first aspect.
In this application, this insulating coating is formed by the oriented silicon steel insulating coating liquid of the first aspect, not only satisfies good heat resistance, adhesion and insulating nature, and resistant hygroscopicity and corrosion resistance have obtained the promotion moreover. The insulating coating has low cost and simple preparation process, and is easy to realize industrialization.
In a fourth aspect, embodiments of the present application provide a method for preparing the insulating coating according to the third aspect, where the method for preparing the insulating coating includes:
covering the surface of the steel body with the oriented silicon steel insulating coating liquid, drying at 350-450 ℃ for 25-35 s, and then preserving heat at 780-820 ℃ for 25-35 s to obtain the insulating coating.
In this application, can coat the oriented silicon steel surface with the oriented silicon steel insulating coating liquid of preparation, prepare insulating coating through stoving and high temperature curing, simple process, easily operation need not to use magnetron sputtering equipment, easily industrial production.
In a fifth aspect, embodiments of the present application provide an oriented silicon steel including an oriented silicon steel substrate and an insulating coating attached to at least a portion of a surface of the oriented silicon steel substrate;
the insulating coating is the insulating coating of the third aspect.
In the application, the insulating coating takes phosphate solution as a base material, has the advantages of suitability for high-speed welding, high surface hardness, good insulativity and heat resistance and the like, improves the wettability, the leveling property and the stability of the insulating coating liquid by chromic anhydride, and is favorable for improving the appearance of the insulating coating. And the inorganic insulating coating has small thermal expansion coefficient and larger tensile stress generated after sintering.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer.
Example 1:
an insulating coating, comprising the steps of:
(1) Selecting raw materials: according to 30g of zinc phosphate and 33g of silica sol (pH 8, siO) 2 30wt% of Na 2 Selecting raw materials with the O content of 0.2wt% and the particle size of 15nm, 4g of chromic anhydride (the purity is over 99.5 wt%), 3g of potassium permanganate (the purity is over 99.5 wt%) and 30g of water for standby;
(2) Preparing oriented silicon steel insulating coating liquid:
preparing a phosphate solution;
adding chromic anhydride into the phosphate solution to obtain a first mixed solution;
adding manganese salt into the mixed solution I to obtain a mixed solution II;
and adding silica sol into the second mixed solution to obtain the oriented silicon steel insulating coating solution.
(3) Preparing an insulating coating: covering the oriented silicon steel insulating coating liquid on the surface of the oriented silicon steel, drying at 380 ℃ for 30s, and then preserving heat at 800 ℃ for 30s to obtain the insulating coating.
Example 2:
an insulating coating, comprising the steps of:
(1) Selecting raw materials: according to 20g of zinc phosphate and 40g of silica sol (pH 7, siO) 2 20wt% of Na 2 Selecting raw materials with the O content of 0.3wt% and the particle size of 5nm, 6g of chromic anhydride (the purity is over 99.5 wt%), 5g of potassium permanganate (the purity is over 99.5 wt%) and 29g of water for standby;
(2) Preparing oriented silicon steel insulating coating liquid:
preparing a phosphate solution;
adding chromic anhydride into the phosphate solution to obtain a first mixed solution;
adding manganese salt into the mixed solution I to obtain a mixed solution II;
and adding silica sol into the second mixed solution to obtain the oriented silicon steel insulating coating solution.
(3) Preparing an insulating coating: covering the oriented silicon steel insulating coating liquid on the surface of the oriented silicon steel, drying at 380 ℃ for 30s, and then preserving heat at 800 ℃ for 30s to obtain the insulating coating.
Example 3:
an insulating coating, comprising the steps of:
(1) Selecting raw materials: according to 35g of zinc phosphate and 25g of silica sol (pH 10, siO) 2 40wt% of Na 2 Selecting raw materials with the O content of 0.2wt% and the particle size of 20nm, 1g of chromic anhydride (the purity is over 99.5 wt%), 0.5g of potassium permanganate (the purity is over 99.5 wt%) and 38.5g of water for standby application;
(2) Preparing oriented silicon steel insulating coating liquid:
preparing a phosphate solution;
adding chromic anhydride into the phosphate solution to obtain a first mixed solution;
adding manganese salt into the mixed solution I to obtain a mixed solution II;
and adding silica sol into the second mixed solution to obtain the oriented silicon steel insulating coating solution.
(3) Preparing an insulating coating: preparing an insulating coating: covering the oriented silicon steel surface with the oriented silicon steel insulating coating liquid, drying at 400 ℃ for 30s, and then preserving heat at 800 ℃ for 30s to obtain the insulating coating.
Example 4:
an insulating coating, comprising the steps of:
(1) Selecting raw materials: according to 30g of zinc phosphate and 33g of silica sol (pH 8, siO) 2 30wt% of Na 2 Selecting raw materials with the O content of 0.2wt% and the particle size of 15nm, 4g of chromic anhydride (the purity is over 99.5 wt%), 3g of potassium permanganate (the purity is over 99.5 wt%) and 30g of water for standby;
(2) Preparing oriented silicon steel insulating coating liquid:
preparing a phosphate solution;
adding chromic anhydride into the phosphate solution to obtain a first mixed solution;
adding manganese salt into the mixed solution I to obtain a mixed solution II;
and adding silica sol into the second mixed solution to obtain the oriented silicon steel insulating coating solution.
(3) Preparing an insulating coating: covering the oriented silicon steel insulating coating liquid on the surface of the oriented silicon steel, drying at 350 ℃ for 35s, and then preserving heat at 780 ℃ for 25s to obtain the insulating coating.
Example 5:
an insulating coating, comprising the steps of:
(1) Selecting raw materials: according to 30g of zinc phosphate and 33g of silica sol (pH 8, siO) 2 30wt% of Na 2 Selecting raw materials with the O content of 0.2wt%, the particle size of 15nm, 4g of chromic anhydride (the purity is over 99.5 wt%), 3g of potassium permanganate (the purity is over 99.5 wt%) and 30g of water for later use;
(2) Preparing oriented silicon steel insulating coating liquid:
preparing a phosphate solution;
adding chromic anhydride into the phosphate solution to obtain a first mixed solution;
adding manganese salt into the mixed solution I to obtain a mixed solution II;
and adding silica sol into the second mixed solution to obtain the oriented silicon steel insulating coating solution.
(3) Preparing an insulating coating: covering the oriented silicon steel surface with the oriented silicon steel insulating coating liquid, drying at 450 ℃ for 25s, and then preserving heat at 800 ℃ for 35s to obtain the insulating coating.
Comparative example 1:
the raw materials in example 1 were changed to: 30g of zinc phosphate and 33g of silica sol (pH 8, siO) 2 30wt% of Na 2 O content of 0.2wt%, particle diameter of 15 nm), chromic anhydride 4g (purity over 99.5 wt%), water 30g, and the rest is the same as example 1.
Comparative example 2:
the raw materials in example 1 were changed to: 30g of zinc phosphate and 33g of silica sol (pH 8, siO) 2 30wt% of Na 2 O content of 0.2wt%, particle diameter of 15 nm), chromic anhydride of 0.5g (purity over 99.5 wt%), water of 30g, and the rest is the same as example 1.
The coating performance test of the oriented silicon steel with the insulating coating on the surface obtained in the examples and the comparative examples is performed, and the results are shown in table 1.
TABLE 1 Performance of Environment-friendly insulating coating for oriented silicon steel
| Examples of the invention | Appearance of the product | Adhesion Property | Moisture absorption resistance | Corrosion resistance |
| Example 1 | Smooth and compact | Superior food | Superior food | Superior food |
| Example 2 | Smooth and compact | Superior food | Superior food | Superior food |
| Example 3 | Smooth and compact | Youyou (an instant noodle) | Superior food | Superior food |
| Example 4 | Smooth and compact | Superior food | Superior food | Superior food |
| Example 5 | Smooth and compact | Superior food | Superior food | Superior food |
| Comparative example 1 | Unevenness of the surface | In general | In general terms | In |
| Comparison ofExample | ||||
| 2 | Unevenness of the surface | Difference between | Difference between | Difference (D) |
As can be seen from table 1, the absence of the manganese salt or the reduction of the addition amount of chromic anhydride without the addition of manganese salt in comparative examples 1 and 2 significantly affects the appearance, adhesion, moisture absorption resistance, and corrosion resistance of the insulating coating. The appearance, moisture absorption resistance and corrosion resistance of the insulating coating are significantly improved by using manganese salt instead of reduced chromic anhydride in examples 1, 2, 3, 4 and 5.
In summary, the embodiment of the application provides an oriented silicon steel insulating coating liquid, the coating composite liquid comprises five components of phosphate, silica sol, chromic anhydride, manganese salt and water, the manganese salt is adopted to partially replace the chromic anhydride, the consumption of the chromic anhydride is reduced, the environment is protected, and the prepared insulating coating is excellent in performance. Therefore, the coating composite liquid provided by the embodiment of the application ensures that the insulating coating has good heat resistance, adhesion and insulativity, and improves the moisture absorption resistance and the corrosion resistance.
It is understood that the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value and that such ranges or values are to be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. In addition, the term "and/or" appearing herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B, may mean: a exists alone, A and B exist simultaneously, and B exists alone.
The above description is merely illustrative of particular embodiments of the invention that enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The oriented silicon steel insulating coating liquid is characterized by comprising the following components: phosphate, silica sol, chromic anhydride, manganese salt and water.
2. The insulating coating solution for oriented silicon steel according to claim 1, wherein the weight ratio of the phosphate to the silica sol to the chromic anhydride to the manganese salt to the water is (20-35): (25-40): (1-6): (0.5-5): (14-53.5).
3. The oriented silicon steel insulating coating liquid of claim 1, wherein the phosphate is at least one of aluminum phosphate, magnesium phosphate, zinc phosphate, calcium phosphate, strontium phosphate, cobalt phosphate, and nickel phosphate.
4. The insulating coating solution for oriented silicon steel as claimed in claim 1, wherein the silica sol has a pH valueIs 7 to 10 of SiO 2 20-40 wt% of Na 2 The content of O is less than or equal to 0.3wt percent and the grain diameter is 5 to 20nm.
5. The method for preparing the oriented silicon steel insulation coating liquid according to any one of claims 1 to 4, wherein the method comprises the following steps:
preparing a phosphate solution;
adding chromic anhydride into the phosphate solution to obtain a first mixed solution;
adding manganese salt into the mixed solution I to obtain a mixed solution II;
and adding silica sol into the second mixed solution to obtain the oriented silicon steel insulating coating solution.
6. An insulating coating formed from the insulating coating liquid for oriented silicon steel according to any one of claims 1 to 4.
7. A method for preparing the insulating coating according to claim 6, characterized in that it comprises:
covering the surface of the steel body with the oriented silicon steel insulating coating liquid, drying at 350-450 ℃ for 25-35 s, and then preserving heat at 780-820 ℃ for 25-35 s to obtain the insulating coating.
8. The oriented silicon steel is characterized by comprising an oriented silicon steel substrate and an insulating coating attached to at least part of the surface of the oriented silicon steel substrate;
the insulating coating is the insulating coating of claim 6.
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2022
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