CN113248947A - Chromium-free inorganic insulating paint capable of modifying surface of oriented silicon steel and preparation method thereof - Google Patents
Chromium-free inorganic insulating paint capable of modifying surface of oriented silicon steel and preparation method thereof Download PDFInfo
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Abstract
The invention provides a chromium-free inorganic insulating coating capable of modifying the surface of oriented silicon steel and a preparation method thereof, wherein the coating comprises the following components in parts by weight: 40-70 parts of phosphorus-silica sol, 25 parts of titanium modified thickener pre-sol, 0.2-1 part of foam inhibitor, 0.05-0.2 part of flatting agent and 3.8-34.75 parts of deionized water. The preparation method of the coating comprises the following steps: firstly, preparing phosphorus-silica sol and titanium modified thickener pre-sol; then adding the foam inhibitor into the phosphorus-silica sol and uniformly stirring; adding deionized water and stirring uniformly; slowly adding titanium modified thickener pre-sol in several times and stirring uniformly; finally, adding the leveling agent and stirring uniformly. The chromium-free inorganic insulating coating prepared by the invention can modify the surface defects of the oriented silicon steel, such as defects, crystal exposure and the like; the insulating coating formed on the surface of the oriented silicon steel has good adhesion and heat resistance; the raw materials adopted by the coating are pollution-free environment-friendly materials, so that the environmental hazard caused by the chromium-containing insulating coating is solved.
Description
Technical Field
The invention belongs to the technical field of coatings, and relates to a chromium-free inorganic insulating coating and a preparation method thereof.
Background
Oriented silicon steel is a soft magnetic functional material, is mainly used as an iron core of a motor and a transformer, and is one of important materials in the fields of electromechanics, energy sources, military industry and the like. The most prominent characteristics of the oriented silicon steel are that crystal grains are distributed in regular orientation and have a sandwich structure on the surface, and the structure comprises a silicon steel base layer and magnesium silicate (MgSiO)3) The bottom layer and the insulating coating. MgSiO3The bottom layer is made by decarburization annealing of a magnesium oxide (MgO) barrier layer. The isolating layer reacts with silicon on the surface of the steel strip at the high temperature of 1000 ℃ to form glassy MgSiO3A bottom layer. MgSiO3The primer layer prevents adhesion between steel strips during recrystallization annealing and improves insulation, corrosion resistance and magnetic properties of the oriented silicon steel. Although the bottom layer has certain insulating property and corrosion resistance, the bottom layer can not meet the use requirement in practical use, so MgSiO is also needed3The bottom layer is coated with an insulating coating. The insulating coating is required to have improved electrical resistance and good adhesion, heat resistance and corrosion resistance. MgSiO3The quality of the bottom layer and the quality of the insulating coating both affect the overall performance of the oriented silicon steel. When the chemical components of the raw materials have defects, the MgO coating solution is not uniformly distributed with MgSiO3Quality defects will occur at the bottom layer, resulting in a steel stripNon-uniform color and the formation of point, strip, and band-shaped open crystals, thereby affecting the properties of the final silicon steel product. The insulating coatings currently used in practice are chromium-containing coatings containing chromates, particularly hexavalent chromium, which, although excellent in performance, are harmful to the first-line contacter. The waste silicon steel is difficult to recover, and when the waste silicon steel is not reasonably recovered, the chromium-containing coating can also harm the ecological environment.
The research of the current oriented silicon steel insulating paint mainly lies in the research and development of chromium-free insulating paint, but although the problem of chromium harm is solved to a certain extent, the comprehensive performance of the insulating coating formed by the oriented silicon steel insulating paint is poor, because the current chromium-free insulating paint is mainly divided into three types, namely organic paint, semi-inorganic paint and inorganic paint. The organic coating and the semi-inorganic coating have good insulating property due to the organic components, but the organic components have poor heat resistance, and are burnt out after high-temperature annealing in a rolling process, so that the formed coating has poor corrosion resistance and cannot reach an ideal insulating property. Although the coating formed by the inorganic coating has good heat resistance and is suitable for the existing rolling process, the existing chromium-free inorganic coating has the problems of poor adhesion, poor corrosion resistance compared with the chromium-containing coating and the like, and cannot replace the chromium-containing coating.
The invention patent with the publication number of CN101928490B proposes a chromium-free insulating paint and application thereof, which comprises 1)100 parts by mass of metal dihydrogen phosphate; 2)10-100 parts by mass of resin, selected from one or more of polyvinyl acetate, polyacrylate, styrene-acrylic acid copolymer resin and epoxy resin; 3)1-40 parts by mass of soluble metal organic acid salt, selected from one or more of lactate, acetate, gluconate and citrate; 4)110-10000 parts by mass of water; 5) optionally, < 40 parts by mass of an organic solvent. Through the implementation of the invention, the chromium-free insulating coating with excellent performance can be obtained, so that the chromium-containing coating can be replaced, the requirement of environmental protection is met, and the chromium-free insulating coating can be used for non-oriented silicon steel. The invention patent with the publication number of CN102079923B proposes an environment-friendly chromium-free insulating paint, which comprises the following components: 100 parts by mass of metal dihydrogen phosphate; 10-200 parts by mass of one or more of vinyl acetate, acrylic acid, styrene-acrylic acid copolymer or phenolic resin; 1-40 parts by mass of one or more of zirconium acetate, zirconium nitrate zirconium chloride, zirconium oxychloride, zirconium n-propoxide and zirconium n-butoxide; 200 portions and 5000 portions of pure water. The insulating coating obtained by the coating disclosed by the invention shows good corrosion resistance, adhesion and heat resistance, and the replacement of chromium compounds is successfully realized, so that the environment friendliness in the production process is realized, and the chromium-free insulating coating can be used for non-oriented silicon steel. The chromium-free insulating coating for the oriented silicon steel has the characteristics of excellent adhesiveness, corrosion resistance and insulativity, but is not an inorganic material and does not have the function of repairing crystal exposure and other defects on the surface of the oriented silicon steel.
The invention patent with the granted publication number of CN106243791B provides a high-covering-property insulating coating for oriented silicon steel, which consists of 1.5 to 7 percent of inorganic salt colorant, 1.5 to 6 percent of chromic anhydride, 30 to 50 percent of dihydric phosphate aqueous solution, 30 to 50 percent of silica sol and 8 to 35 percent of deionized water in percentage by mass, wherein the sum of the mass percentages is 100 percent, and the coating is coated on the oriented silicon steel and then needs to be coated on N2Or baking, sintering and curing under the protective atmosphere of Ar and the like. The coating prepared by the insulating coating disclosed by the invention is deep and uniform in color, has good covering property, can effectively cover surface patterns, color differences and defects generated in the preparation process of the oriented silicon steel, improves the appearance quality, has good corrosion resistance, insulativity, adhesiveness and high temperature resistance, can reduce the iron loss value of the oriented silicon steel, and is not sticky after being placed in a room-temperature environment for a long time. However, the coating contains chromium, which is not environment-friendly, and the coating conditions of the coating are strict, so that the coating is not suitable for popularization and application.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a chromium-free inorganic insulating paint capable of modifying the surface of oriented silicon steel and a preparation method thereof.
A chromium-free inorganic insulating paint capable of modifying the surface of oriented silicon steel comprises the following components in parts by weight: 40-70 parts of phosphorus-silica sol, 25 parts of titanium modified thickener pre-sol, 0.2-1 part of foam inhibitor, 0.05-0.2 part of flatting agent and 3.8-34.75 parts of deionized water; the phosphorus-silica sol is obtained by mixing small-particle silica sol, large-particle silica sol and aluminum dihydrogen phosphate solution in a mass ratio of 15-25:15-25: 10-20; the titanium modified thickener pre-sol is obtained by mixing titanium dioxide, a thickener and deionized water according to the mass ratio of 0.2-2:2-6: 92-97.8.
The content of silicon dioxide in the large-particle silica sol is 25-35 wt%, and the particle size of the silicon dioxide is 15-30 nm; the content of silicon dioxide in the small-particle silica sol is 25-35 wt%, and the particle size of the silicon dioxide is 5-10 nm; the content of phosphorus pentoxide in the aluminum dihydrogen phosphate solution is 32-34%, and the content of aluminum oxide in the aluminum dihydrogen phosphate solution is 7.5-8.5%.
The thickening agent is at least one of sodium bentonite, sodium carbonate modified bentonite and cellulose modified bentonite.
The foam inhibitor is one or a mixture of more of organic silicon alkoxy alkane and mineral oil materials.
A preparation method of a chromium-free inorganic insulating coating capable of modifying the surface of oriented silicon steel comprises the following steps:
1) preparing phosphorus-silica sol;
2) preparing titanium modified thickener pre-sol;
3) adding a foam inhibitor into the phosphorus-silica sol and uniformly stirring;
4) adding deionized water into the mixed solution obtained in the step 3) and uniformly stirring;
5) slowly adding titanium modified thickener pre-sol into the mixed solution obtained in the step 4) in multiple times and uniformly stirring;
6) adding a leveling agent into the mixed solution obtained in the step 5) and uniformly stirring.
In the step 1), the preparation method of the phosphorus-silica sol comprises the following steps: adding aluminum dihydrogen phosphate solution into small-particle silica sol at 20-80 deg.C under stirring at 50-100r/min, stirring until the mixed solution is clear, adding large-particle silica sol, stirring, and stirring for 10 min.
In the step 2), the preparation method of the titanium modified thickener pre-sol comprises the following steps: sieving the thickening agent by a 200-mesh sieve, adding deionized water into the sieved thickening agent under the temperature condition of 20-80 ℃ and the stirring condition of 200-500r/min, stirring until the mixed solution is uniform and has no particles, adding titanium dioxide into the mixed solution, stirring uniformly, and grinding and stirring for 20-40min by using a high-speed ball mill disperser.
In the step 3), the temperature condition is 20-80 ℃, the stirring speed is 60-150r/min, and the stirring time is 5-10 min; in the step 4), the stirring time is 5-10 min; in the step 5), the stirring speed is 100-150r/min, and the stirring time is 5-30 min; in the step 6), stirring is carried out uniformly at a stirring speed of 60-150r/min and then continuously stirring is carried out for 30 min.
The chromium-free inorganic insulating coating with the function of modifying the surface of the oriented silicon steel adopts aluminium dihydrogen phosphate and large-particle silica sol to replace chromic anhydride or chromate in the traditional insulating coating as a main film forming substance, so that the environment-friendly effect of chromium-free is ensured, and meanwhile, excellent insulating property can be provided; the added small-particle silica sol and titanium dioxide can modify the crystal defect; the addition of the thickening agent and the flatting agent can improve the coating performance of the coating; the addition of the foam inhibitor enables the coating to meet various coating operation conditions.
According to the invention, through the matching and synergistic effect of the components, the non-chromium environment-friendly oriented silicon steel insulating coating is realized, the corrosion resistance of the insulating coating and the defects of crystal exposure bright spots and the like of the oriented silicon steel are improved, so that the oriented silicon steel has the characteristic of non-chromium environment-friendly, the appearance defects of crystal exposure and the like can be modified, the comprehensive performance of the oriented silicon steel is improved, and the service life of the oriented silicon steel is prolonged.
The chromium-free inorganic insulating coating prepared by the invention can modify the surface defects of the oriented silicon steel, such as defects, crystal exposure and the like; the insulating coating formed on the surface of the oriented silicon steel has good adhesion and heat resistance; the raw materials adopted by the coating are pollution-free environment-friendly materials, so that the environmental hazard caused by the chromium-containing insulating coating is solved; the chromium-free inorganic insulating coating can be applied to oriented silicon steel prepared by the existing rolling process, the application method is simple and has no special requirements, the existing chromium-containing insulating coating process can be completely replaced, the debugging cost is low, and the popularization is easy.
Drawings
Fig. 1 is an electron microscope image of an oriented silicon steel sheet without a coating layer.
Fig. 2 is an electron microscope picture of an oriented silicon steel sheet containing a chromium-free inorganic insulating coating.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
A chromium-free inorganic insulating paint with a function of modifying the surface of oriented silicon steel comprises the following components in parts by weight: 40-70 parts of phosphorus-silica sol, 25 parts of titanium modified thickener pre-sol, 0.2-1 part of foam inhibitor, 0.05-0.2 part of flatting agent and 3.8-34.75 parts of deionized water. The phosphorus-silica sol is prepared from small-particle silica sol, large-particle silica sol and aluminum dihydrogen phosphate solution in a mass ratio of 15-25:15-25: 10-20.
The content of silicon dioxide in the large-particle silica sol is 25-35 wt%, and the particle size of the silicon dioxide is 15-30 nm.
The content of silicon dioxide in the small-particle silica sol is 25-35 wt%, and the particle size of the silicon dioxide is 5-10 nm.
The large-particle silica sol adopted by the embodiment has large particles and high viscosity, can improve the adhesiveness of the coating, the small-particle silica sol has small particle size, can improve the compactness of the formed film, and can simultaneously improve the adhesiveness and the corrosion resistance of the formed film by combining the large-particle silica sol and the small-particle silica sol. If the content of the silicon dioxide in the silica sol exceeds the proper range, nano silicon dioxide particles are easy to agglomerate, the stability of the insulating coating is damaged, and when the content of the silicon dioxide does not reach the proper range, the silica sol component under the original adding amount can not realize the established effect, so that the comprehensive performance of the formed film is directly influenced. Similarly, if the addition amount of the silica sol exceeds the proper range, the actual content of the nano-silica in the insulating coating also exceeds the proper range, so that the nano-silica is promoted to be locally agglomerated in the insulating coating, the non-uniformity of the components of the insulating coating is caused, and the stability, the modification capability and the corrosion resistance of the insulating coating are influenced. When the addition amount of the silica sol is not within a proper range, the adhesive force, corrosion resistance and the like of the coating are directly weakened, and the expected effect cannot be achieved.
The content of phosphorus pentoxide and aluminum oxide in the aluminum dihydrogen phosphate solution is 32-34% and 7.5-8.5%.
The aluminum dihydrogen phosphate is used as a film forming agent and a high-temperature binder, so that the coating has good adhesive force and heat resistance, and the tension of the coating is improved and higher than that of a magnesium silicate bottom layer after the aluminum dihydrogen phosphate is added, thereby being beneficial to refining a surface magnetic domain and reducing the iron loss of the oriented silicon steel.
The titanium modified thickener pre-sol is prepared from titanium dioxide, a thickener and deionized water according to the mass ratio of 0.2-2:2-6: 92-97.8.
The thickener is at least one of sodium bentonite, sodium carbonate modified bentonite and cellulose modified bentonite.
The titanium dioxide used in the titanium modified thickener pre-sol can physically modify the crystal defect and simultaneously improve the hydrophobic property of the coating, prevent water molecules from penetrating through the coating to corrode a substrate, improve the corrosion resistance of the coating, and have small addition amount of the titanium dioxide and cannot play an effective modifying role. Because titanium dioxide is powder and the water solubility is not high, when the addition amount of the titanium dioxide is too high, the titanium dioxide can be separated from a uniform and stable system of titanium modified nano silica sol along with time, and sedimentation is generated, so that the stability of the coating is not facilitated, the content of effective titanium dioxide in the coating can be reduced, and the comprehensive performance of the coating is damaged.
The thickening agent adopted in the titanium modified thickening agent pre-sol has excellent adsorption performance and cation exchange capacity, so that the stability of the coating can be improved, the viscosity of the coating can also be improved, and the construction and coating are facilitated. When the content of the thickener is too low, the coating is easy to layer, the viscosity is low, the thickness cannot meet the construction requirement during coating, but the viscosity is too high due to the excessive addition of the thickener, foams are easy to generate during production, and meanwhile, the sagging phenomenon is easy to generate during coating, so that the comprehensive performance of the coating is damaged.
The leveling agent is BYKETOL-WS.
The foam inhibitor is one or a mixture of more of organic silicon alkyl alkane and mineral oil.
In the coating film forming process, the phenomena of foam, sagging and the like can influence the coating effect of the coating and further influence the film forming performance, and in order to inhibit the occurrence of the phenomena of foam and sagging and improve the apparent appearance of the formed film, the leveling agent and the foam inhibitor are used to ensure the smoothness and the flatness of the formed film. In addition, the addition of the foam inhibitor can enable the coating to adapt to various coating operation conditions, and is beneficial to the popularization of the coating. However, when the addition amount of the auxiliary agent is too much, the performance is not improved much, but the cost is greatly improved, the ratio of the main components is relatively reduced, and the film forming performance is reduced to a certain extent.
A preparation method of a chromium-free inorganic insulating paint with a function of modifying the surface of oriented silicon steel comprises the following steps:
adding aluminum dihydrogen phosphate solution into small-particle silica sol at 20-80 deg.C under stirring at 50-100r/min, stirring until the mixed solution is clear, adding large-particle silica sol, stirring well, and continuously stirring for 10min to obtain phosphorus-silica sol;
sieving the thickening agent by a 200-mesh sieve, adding deionized water into the thickening agent under the temperature condition of 20-80 ℃ and the stirring condition of 200 plus 500r/min, stirring until the mixed solution is uniform and has no particles, adding titanium dioxide into the mixed solution, stirring uniformly, and grinding and stirring for 30min by using a high-speed ball-milling dispersing instrument to prepare titanium modified thickening agent pre-sol;
adding the foam inhibitor into the phosphorus-silica sol at the temperature of 20-80 ℃ and under the stirring condition of 60-150r/min, and stirring for 5-10 minutes until the mixture is uniformly mixed;
adding deionized water into the mixed solution, and stirring for 5-10min until the mixture is uniformly mixed;
keeping the stirring condition of 100-;
adding the flatting agent, stirring uniformly under the stirring condition of 60-150r/min, and continuously stirring for 30 min.
When the preparation temperature is lower than 20 ℃, the stirring and dissolving time is prolonged, which not only increases the preparation cost, but also can cause the demulsification of the foam inhibitor, so that the foam inhibitor loses the effect. When the preparation temperature is higher than 80 ℃, the preparation time is greatly reduced, but the stability of the titanium modified nano silica sol is influenced by overhigh temperature, and the phenomena of local agglomeration, flocculation and the like occur, so that the preparation of the insulating coating fails. Similarly, in different steps, when the stirring speed is lower than the recommended speed, the stirring time is prolonged, the production cost is increased, and meanwhile, the emulsified foam inhibitor in the formula is easy to break emulsion under long-time stirring, and the effects of inhibiting and eliminating foam are lost. When the rotating speed is higher than the recommended rotating speed, the foam inhibitor can be quickly broken and lose effect, a large amount of air can be introduced into a coating system in the high-speed stirring process, and additionally generated foam reduces the stability of a product and is not beneficial to coating of the coating.
The coating is used for coating the surface of the oriented silicon steel sheet with the crystal exposure bright points on the surface.
According to GB/T10125-2012 salt spray test of artificial atmosphere corrosion test, the corrosion resistance of the coated oriented silicon steel sheet is detected, and the corrosion area of the chromium-free inorganic insulating coating is measured after the chromium-free inorganic insulating coating is tested for 8 hours under the conditions of 5% NaCl aqueous solution and periodic spraying at 35 +/-0.5 ℃ so as to show whether the obtained chromium-free inorganic insulating coating has the corrosion resistance equivalent to that of the chromium-containing insulating coating.
The adhesion and insulation of the chromium-free inorganic insulating coating are tested according to GB/T2522-2007 test method for the insulation resistance and the coating adhesion of the surface of electrical steel sheets (strips).
The magnetic properties of the oriented silicon steel sheet are measured according to GB/T13789-2008 'method for measuring the magnetic properties of electrical steel sheet (strip) by using single-sheet tester'.
Example 1
A chromium-free inorganic insulating coating I comprising: 400g of phosphorus-silica sol, 250g of titanium modified thickener pre-sol, 0.5g of flatting agent, 2g of foam inhibitor and 347.5g of deionized water.
The phosphorus-silica sol contained 150g of small-particle silica sol, 150g of large-particle silica sol and 100g of aluminum dihydrogen phosphate solution.
The titanium modified thickener pre-sol contains 0.5g of titanium dioxide, 5g of thickener and 244.5g of deionized water. The thickening agent is sodium bentonite.
The leveling agent is BYKETOL-WS. The foam inhibitor is an organic silicon alkoxy alkane compound.
Adding aluminum dihydrogen phosphate solution into the small-particle silica sol at 50 ℃ under the stirring condition of 50r/min, stirring until the mixed solution is clear, adding the large-particle silica sol, stirring uniformly, and continuously stirring for 10min to obtain phosphorus-silica sol;
sieving the thickening agent with a 200-mesh sieve, adding deionized water into the thickening agent under the conditions of 50 ℃ and 300r/min of stirring, stirring until the mixed solution is uniform and has no particles, adding titanium dioxide into the mixed solution, stirring uniformly, and grinding and stirring for 20min by using a high-speed ball-milling dispersing instrument to prepare titanium modified thickening agent pre-sol;
adding a foam inhibitor into the phosphorus-silica sol at the temperature of 50 ℃ and under the stirring condition of 60r/min, and stirring for 10 minutes until the mixture is uniformly mixed;
adding deionized water into the mixed solution, and stirring for 10min until the mixture is uniformly mixed;
keeping the stirring condition of 100r/min, slowly adding titanium modified thickener pre-sol in several times, and stirring for 20min until the mixture is uniformly mixed;
and adding a leveling agent, stirring uniformly under the stirring condition of 60r/min, and continuously stirring for 30min to prepare the chromium-free inorganic insulating coating I.
Example 2
The chromium-free inorganic insulating coating II comprises: 550g of phosphorus-silica sol, 250g of titanium modified thickener pre-sol, 1g of flatting agent, 5g of foam inhibitor and 194g of deionized water.
The phosphorus-silica sol contains 200g of small-particle silica sol, 200g of large-particle silica sol and 150g of aluminum dihydrogen phosphate solution.
The titanium modified thickener pre-sol contains 1g of titanium dioxide, 10g of thickener and 239g of deionized water. The thickening agent is sodium carbonate modified bentonite.
The leveling agent is BYKETOL-WS. The foam inhibitor is a mineral oil compound.
Adding aluminum dihydrogen phosphate solution into the small-particle silica sol at 80 ℃ under the stirring condition of 100r/min, stirring until the mixed solution is clear, adding the large-particle silica sol, stirring uniformly, and continuously stirring for 10min to obtain phosphorus-silica sol;
sieving the thickening agent with a 200-mesh sieve, adding deionized water into the thickening agent under the temperature condition of 60 ℃ and the stirring condition of 200r/min, stirring until the mixed solution is uniform and has no particles, adding titanium dioxide into the mixed solution, stirring uniformly, and grinding and stirring for 30min by using a high-speed ball-milling dispersing instrument to prepare titanium modified thickening agent pre-sol;
adding a foam inhibitor into the phosphorus-silica sol at the temperature of 80 ℃ and under the stirring condition of 100r/min, and stirring for 10 minutes until the mixture is uniformly mixed;
adding deionized water into the mixed solution, and stirring for 10min until the mixture is uniformly mixed;
keeping the stirring condition of 120r/min, slowly adding titanium modified thickener pre-sol in several times, and stirring for 30min until the mixture is uniformly mixed;
and adding a leveling agent, stirring uniformly under the stirring condition of 100r/min, and continuously stirring for 30min to prepare the chromium-free inorganic insulating coating II.
Example 3
A chromium-free inorganic insulating coating III comprising: 700g of phosphorus-silica sol, 250g of titanium modified thickener pre-sol, 2g of flatting agent, 10g of foam inhibitor and 380g of deionized water.
The phosphorus-silica sol contains 250g of small-particle silica sol, 250g of large-particle silica sol and 200g of aluminum dihydrogen phosphate solution.
The titanium modified thickener pre-sol contains 5g of titanium dioxide, 15g of thickener and 230g of deionized water. The thickening agent is cellulose modified bentonite.
The leveling agent is BYKETOL-WS. The foam inhibitor is a mixture of organic silicon alkoxy alkane compounds and mineral oil compounds in a mass ratio of 1: 1.
Adding aluminum dihydrogen phosphate solution into the small-particle silica sol at the temperature of 20 ℃ and under the stirring condition of 100r/min, stirring until the mixed solution is clear, adding the large-particle silica sol, stirring uniformly, and continuously stirring for 10min to obtain phosphorus-silica sol;
sieving the thickening agent with a 200-mesh sieve, adding deionized water into the thickening agent under the temperature condition of 20 ℃ and the stirring condition of 500r/min, stirring until the mixed solution is uniform and has no particles, adding titanium dioxide into the mixed solution, stirring uniformly, and grinding and stirring for 40min by using a high-speed ball-milling dispersing instrument to prepare titanium modified thickening agent pre-sol;
adding a foam inhibitor into the phosphorus-silica sol at the temperature of 20 ℃ and under the stirring condition of 150r/min, and stirring for 10 minutes until the mixture is uniformly mixed;
adding deionized water into the mixed solution, and stirring for 5min until the mixture is uniformly mixed;
keeping the stirring condition of 150r/min, slowly adding titanium modified thickener pre-sol in several times, and stirring for 5min until the mixture is uniformly mixed;
and adding a leveling agent, stirring uniformly under the stirring condition of 150r/min, and continuously stirring for 30min to prepare the chromium-free inorganic insulating coating III.
Example 4
A chromium-free inorganic insulating paint IV comprising: 500g of phosphorus-silica sol, 250g of titanium modified thickener pre-sol, 1.5g of flatting agent, 8g of foam inhibitor and 240.5g of deionized water.
The phosphorus-silica sol contained 150g of small-particle silica sol, 200g of large-particle silica sol and 150g of aluminum dihydrogen phosphate solution.
The titanium modified thickener pre-sol contains 2g of titanium dioxide, 6g of thickener and 242g of deionized water. The thickening agent is a mixture of sodium bentonite, sodium carbonate modified bentonite and cellulose modified bentonite in a mass ratio of 2:2: 1.
The leveling agent is BYKETOL-WS. The foam inhibitor is a mixture of organic silicon alkoxy alkane compounds and mineral oil compounds in a mass ratio of 3: 1.
The preparation method of the chromium-free inorganic insulating paint IV is the same as that of example 2.
Example 5
A chromium-free inorganic insulating paint V comprising: 550g of phosphorus-silica sol, 250g of titanium modified thickener pre-sol, 0.8g of flatting agent, 3.5g of foam inhibitor and 195.7g of deionized water.
The phosphorus-silica sol contains 200g of small-particle silica sol, 250g of large-particle silica sol and 100g of aluminum dihydrogen phosphate solution.
The titanium modified thickener pre-sol contains 2.5g of titanium dioxide, 8g of thickener and 239.5g of deionized water. The thickening agent is a mixture of sodium carbonate modified bentonite and cellulose modified bentonite with the mass ratio of 1: 1.
The leveling agent is BYKETOL-WS. The foam inhibitor is a mixture of organic silicon alkoxy alkane compounds and mineral oil compounds in a mass ratio of 1: 4.
Adding aluminum dihydrogen phosphate solution into the small-particle silica sol at 80 ℃ under the stirring condition of 100r/min, stirring until the mixed solution is clear, adding the large-particle silica sol, stirring uniformly, and continuously stirring for 10min to obtain phosphorus-silica sol;
sieving the thickening agent with a 200-mesh sieve, adding deionized water into the thickening agent under the conditions of 80 ℃ and 500r/min of stirring, stirring until the mixed solution is uniform and has no particles, adding titanium dioxide into the mixed solution, stirring uniformly, and grinding and stirring for 40min by using a high-speed ball-milling dispersing instrument to prepare titanium modified thickening agent pre-sol;
adding a foam inhibitor into the phosphorus-silica sol at the temperature of 80 ℃ and under the stirring condition of 150r/min, and stirring for 10 minutes until the mixture is uniformly mixed;
adding deionized water into the mixed solution, and stirring for 10min until the mixture is uniformly mixed;
keeping the stirring condition of 150r/min, slowly adding titanium modified thickener pre-sol in several times, and stirring for 30min until the mixture is uniformly mixed;
and adding a leveling agent, stirring uniformly under the stirring condition of 150r/min, and continuously stirring for 30min to prepare the chromium-free inorganic insulating coating V.
Example 6
Chromium-free inorganic insulating coating VI, comprising: 600g of phosphorus-silica sol, 250g of titanium modified thickener pre-sol, 1.7g of flatting agent, 7g of foam inhibitor and 141.3g of deionized water.
The phosphorus-silica sol contains 250g of small-particle silica sol, 150g of large-particle silica sol and 200g of aluminum dihydrogen phosphate solution.
The titanium modified thickener pre-sol contains 4g of titanium dioxide, 7.5g of thickener and 238.5g of deionized water. The thickening agent is a mixture of sodium bentonite and cellulose modified bentonite with the mass ratio of 2: 3.
The leveling agent is BYKETOL-WS. The foam inhibitor is an organic silicon alkoxy alkane compound.
The preparation method of the chromium-free inorganic insulating coating VI is the same as that of example 5.
Example 7
A chromium-free inorganic insulating coating VII comprising: 600g of phosphorus-silica sol, 250g of titanium modified thickener pre-sol, 1.8g of flatting agent, 1g of foam inhibitor and 138.2g of deionized water.
The phosphorus-silica sol contains 150g of small-particle silica sol, 250g of large-particle silica sol and 200g of aluminum dihydrogen phosphate solution.
The titanium modified thickener pre-sol contains 3g of titanium dioxide, 12g of thickener and 235g of deionized water. The thickening agent is sodium bentonite.
The leveling agent is BYKETOL-WS. The foam inhibitor is a mineral oil compound.
The chromium-free inorganic insulating paint VII was prepared in the same manner as in example 2.
Example 8
A chromium-free inorganic insulating coating VIII comprising: 500g of phosphorus-silica sol, 250g of titanium modified thickener pre-sol, 2g of flatting agent, 6g of foam inhibitor and 242g of deionized water.
The phosphorus-silica sol contained 200g of small-particle silica sol, 150g of large-particle silica sol and 150g of aluminum dihydrogen phosphate solution.
The titanium modified thickener pre-sol contains 2.5g of titanium dioxide, 11g of thickener and 236.5g of deionized water. The thickening agent is sodium carbonate modified bentonite.
The leveling agent is BYKETOL-WS. The foam inhibitor is a mineral oil compound.
The chromium-free inorganic insulating paint VIII was prepared in the same manner as in example 5.
Example 9
A chromium-free inorganic insulating coating IX comprising: 550g of phosphorus-silica sol, 250g of titanium modified thickener pre-sol, 1g of flatting agent, 5g of foam inhibitor and 194g of deionized water.
The phosphorus-silica sol contains 250g of small-particle silica sol, 200g of large-particle silica sol and 100g of aluminum dihydrogen phosphate solution.
The titanium modified thickener pre-sol contains 1g of titanium dioxide, 14g of thickener and 235g of deionized water. The thickening agent is sodium carbonate modified bentonite.
The leveling agent is BYKETOL-WS. The foam inhibitor is an organic silicon alkoxy alkane compound.
The chromium-free inorganic insulating coating IX was prepared in the same manner as in example 2.
Example 10
A chromium-free inorganic insulating coating material X comprising: 550g of phosphorus-silica sol, 250g of titanium modified thickener pre-sol, 0.6g of flatting agent, 8.5g of foam inhibitor and 190.9g of deionized water.
The phosphorus-silica sol contains 250g of small-particle silica sol, 200g of large-particle silica sol and 150g of aluminum dihydrogen phosphate solution.
The titanium modified thickener pre-sol contains 4.5g of titanium dioxide, 13.5g of thickener and 235g of deionized water. The thickening agent is sodium bentonite.
The leveling agent is BYKETOL-WS. The foam inhibitor is a mineral oil compound.
The chromium-free inorganic insulating paint X was prepared in the same manner as in example 5.
The chromium-free inorganic insulating coatings prepared in examples 1 to 10 were coated on the same batch of grain-exposed grain-bright oriented silicon steel sheets, which were tested by the above-described test method, and the test results are shown in table 1.
Fig. 1 is an electron microscope image of an oriented silicon steel sheet without a coating, the magnification is 10000 times, the surface of the oriented silicon steel sheet has a morphology defect of an exposed crystal bright point, it can be known from fig. 1 that a magnesium silicate bottom layer of the oriented silicon steel sheet is loose, gaps among particles are many, the oriented silicon steel sheet is in a loose particle bulk structure, a plurality of pits are also present on the surface of the oriented silicon steel sheet, the morphology characteristics of particle accumulation inside and outside the pits are different, and the bottom surface of the pit is flat. The element content of the surface of the oriented silicon steel sheet is analyzed, the analysis result is shown in table 2, the iron element content at the bottom of the pit with the crystal bright point exposed is the highest, the mass percent of the iron element reaches more than 90 percent and is the main component of the iron element, and the mass percent of the magnesium element, the silicon element and the oxygen element is very small; the normal surface of the oriented silicon steel sheet is in a state that the contents of iron element, magnesium element, silicon element and oxygen element are relatively balanced, which shows that the exposed crystal bright spot defect can directly expose the substrate of the oriented silicon steel sheet and seriously damage the performance of the oriented silicon steel sheet. The chromium-free inorganic insulating coating is used for coating the surface of the oriented silicon steel sheet with the exposed crystal bright spots, so that a coating is formed on the surface of the oriented silicon steel sheet, fig. 2 is an electron microscopic picture of the oriented silicon steel sheet containing the chromium-free inorganic insulating coating, the magnification is 10000 times, the surface of the coating of the oriented silicon steel sheet is flat and compact, and is not a loose granular bulk structure, no pit or substrate is exposed, and the exposed crystal bright spots are successfully covered by the coating.
According to the test result, after the chromium-free inorganic insulating coating of the oriented silicon steel sheet is tested for 8 hours under the conditions of 5% NaCl aqueous solution and 35 +/-0.5 ℃ periodic spraying, the exposed crystal bright spots of the oriented silicon steel sheet are successfully covered by the coating, so that the oriented silicon steel sheet has excellent salt spray resistance, the corrosion area of the oriented silicon steel sheet is less than 1%, and the oriented silicon steel sheet coated with the chromium-free inorganic insulating coating has excellent corrosion resistance and corrosion resistance equivalent to that of the chromium-containing insulating coating; in addition, through the tests of adhesiveness, insulativity and magnetic property, the chromium-free inorganic insulating coating has good bonding force with the oriented silicon steel sheet, the chromium-free inorganic insulating coating has excellent insulativity, and the oriented silicon steel sheet containing the chromium-free inorganic insulating coating has good magnetic property.
In conclusion, the chromium-free inorganic insulating coating prepared by the technical scheme has excellent performance and is particularly suitable for being applied to oriented silicon steel sheets with morphological defects.
Table 1 coating performance test results
Note: the area of corrosion is the area measured after 8 hours of continuous salt spray.
TABLE 2 analysis results of elemental contents on the surface of grain-oriented silicon steel sheet
| Element(s) | Normal surface | Pit bottom with crystal bright spots |
| O | 17.02 | 2.51 |
| Mg | 24.44 | 1.44 |
| Si | 14.00 | 3.45 |
| Fe | 44.54 | 92.60 |
Claims (8)
1. A chromium-free inorganic insulating paint capable of modifying the surface of oriented silicon steel is characterized by comprising the following components in parts by weight: 40-70 parts of phosphorus-silica sol, 25 parts of titanium modified thickener pre-sol, 0.2-1 part of foam inhibitor, 0.05-0.2 part of flatting agent and 3.8-34.75 parts of deionized water; the phosphorus-silica sol is obtained by mixing small-particle silica sol, large-particle silica sol and aluminum dihydrogen phosphate solution in a mass ratio of 15-25:15-25: 10-20; the titanium modified thickener pre-sol is obtained by mixing titanium dioxide, a thickener and deionized water according to the mass ratio of 0.2-2:2-6: 92-97.8.
2. The chromium-free inorganic insulating coating capable of modifying the surface of oriented silicon steel according to claim 1, wherein the silica content in the large-particle silica sol is 25-35 wt%, and the particle size of the silica is 15-30 nm; the content of silicon dioxide in the small-particle silica sol is 25-35 wt%, and the particle size of the silicon dioxide is 5-10 nm; the content of phosphorus pentoxide in the aluminum dihydrogen phosphate solution is 32-34 wt%, and the content of aluminum oxide in the aluminum dihydrogen phosphate solution is 7.5-8.5 wt%.
3. The chromium-free inorganic insulating paint capable of modifying the surface of oriented silicon steel as claimed in claim 1, wherein the thickener is at least one of sodium bentonite, sodium carbonate modified bentonite and cellulose modified bentonite.
4. The chromium-free inorganic insulating coating capable of modifying the surface of oriented silicon steel according to claim 1, wherein the foam inhibitor is one or a mixture of organic silicon alkoxide and mineral oil materials.
5. The method for preparing chromium-free inorganic insulating paint capable of modifying the surface of oriented silicon steel according to any one of claims 1 to 4, comprising the following steps:
1) preparing phosphorus-silica sol;
2) preparing titanium modified thickener pre-sol;
3) adding a foam inhibitor into the phosphorus-silica sol and uniformly stirring;
4) adding deionized water into the mixed solution obtained in the step 3) and uniformly stirring;
5) slowly adding titanium modified thickener pre-sol into the mixed solution obtained in the step 4) in multiple times and uniformly stirring;
6) adding a leveling agent into the mixed solution obtained in the step 5) and uniformly stirring.
6. The method for preparing the chromium-free inorganic insulating coating capable of modifying the surface of the oriented silicon steel according to claim 5, wherein the method comprises the following steps: in the step 1), the preparation method of the phosphorus-silica sol comprises the following steps: adding aluminum dihydrogen phosphate solution into small-particle silica sol at 20-80 deg.C under stirring at 50-100r/min, stirring until the mixed solution is clear, adding large-particle silica sol, stirring, and stirring for 10 min.
7. The method for preparing the chromium-free inorganic insulating coating capable of modifying the surface of the oriented silicon steel according to claim 5, wherein the method comprises the following steps: in the step 2), the preparation method of the titanium modified thickener pre-sol comprises the following steps: sieving the thickening agent by a 200-mesh sieve, adding deionized water into the sieved thickening agent under the temperature condition of 20-80 ℃ and the stirring condition of 200-500r/min, stirring until the mixed solution is uniform and has no particles, adding titanium dioxide into the mixed solution, stirring uniformly, and grinding and stirring for 20-40min by using a high-speed ball mill disperser.
8. The method for preparing the chromium-free inorganic insulating coating capable of modifying the surface of the oriented silicon steel according to claim 5, wherein the method comprises the following steps: in the step 3), the temperature condition is 20-80 ℃, the stirring speed is 60-150r/min, and the stirring time is 5-10 min; in the step 4), the stirring time is 5-10 min; in the step 5), the stirring speed is 100-150r/min, and the stirring time is 5-30 min; in the step 6), the stirring speed is 60-150r/min, and the stirring is continued for 30min after the uniform stirring.
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