CN110396683B - Insulating coating liquid for directional electrical steel sheet, and method for manufacturing directional electrical steel sheet - Google Patents
Insulating coating liquid for directional electrical steel sheet, and method for manufacturing directional electrical steel sheet Download PDFInfo
- Publication number
- CN110396683B CN110396683B CN201810371182.1A CN201810371182A CN110396683B CN 110396683 B CN110396683 B CN 110396683B CN 201810371182 A CN201810371182 A CN 201810371182A CN 110396683 B CN110396683 B CN 110396683B
- Authority
- CN
- China
- Prior art keywords
- electrical steel
- insulating coating
- directional electrical
- coating liquid
- steel sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/20—Orthophosphates containing aluminium cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—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 characterised by the process
- C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Soft Magnetic Materials (AREA)
Abstract
The invention discloses an insulating coating liquid for a directional electrical steel plate, which consists of the following components: a phosphate of at least one of Mg, Ca, Al and Zn; colloidal silicon dioxide; a compound of at least one of Ti, Mo, W and V; boric acid; at least one of silica powder, alumina powder and magnesia powder. The invention also discloses a directional electrical steel plate which comprises a substrate and an insulating coating, wherein the insulating coating is formed by coating the insulating coating liquid on the substrate. The invention also discloses a manufacturing method of the directional electrical steel plate, which comprises the following steps: coating insulating coating liquid on the surface of the substrate, and then performing sintering treatment, wherein the plate temperature in the sintering treatment is 800-950 ℃.
Description
Technical Field
The present invention relates to an insulating coating liquid and a steel sheet and a method for manufacturing the same, and more particularly, to an insulating coating liquid and a method for manufacturing an electrical steel sheet.
Background
The directional electrical steel sheet is a steel sheet having a {110} <001> texture, which has a silicon content ranging from 2.8 wt.% to 3.5 wt.% and is obtained by a cold rolling and heat treatment process, and has magnetic properties in a rolling direction significantly superior to those in a transverse direction. The directional electrical steel sheet is mainly applied to transformer core materials, and the directional electrical steel material with low iron loss and low hysteresis expansion can reduce the energy loss and the noise level of a transformer. The core loss value and the hysteresis elongation value of the directional electrical steel sheet can be reduced by applying proper tensile stress to the directional electrical steel sheet.
In the prior art, the chromium-containing insulating coating not only has good insulativity, but also can generate tensile stress to the steel plate due to different thermal expansion coefficients of the coating and the steel plate in the heat treatment process, thereby reducing the iron loss and hysteresis expansion of the steel plate. However, the coating liquid contains chromium compounds, so that waste liquid generated in the production contains a large amount of hexavalent chromium which is harmful to the environment, and the environment is seriously polluted.
Chinese patent publication No. CN101790599A, published as 7/28/2010, entitled "insulating coating treatment liquid for grain-oriented electrical steel sheet and method for producing grain-oriented electrical steel sheet having insulating coating" discloses a chromium-free insulating coating treatment liquid for grain-oriented electrical steel sheet containing at least one of phosphates of Mg, Ca, Ba, Sr, Zn, Al and Mn, and a chelate of colloidal silica and titanium.
Chinese patent publication No. CN101223300A, published as 2008/7/16, entitled "grain-oriented electrical steel sheet having insulating coating film not containing chromium and insulating coating film thereof" discloses an insulating coating film for grain-oriented electrical steel sheet not containing chromium, which mainly contains phosphate, colloidal silica, and a colloidal substance of hydroxide of Fe, Ni, Co, Cu, Sr, Mo having a particle size of 15nm or less.
Chinese patent publication No. CN102119239A, published as 7/6/2011 entitled "chromium-free coating agent for oriented electrical steel sheet, method for preparing same, electrical steel sheet using same, and method for preparing same" discloses a chromium-free coating agent for oriented electrical steel sheet, which contains phosphate, colloidal silica, and hematite silica sol.
However, there are still many problems in the current research on the insulating coating liquid for directional electrical steel sheets, for example, the insulating coating liquid contains chelate compounds in its components, which are easily decomposed to generate carbon during heat treatment, and adversely affect the tension of the coating layer. In another example, the composition contains a hydroxide colloid which is unstable in a phosphate solution system and has insufficient ability to fix free phosphate. For another example, the components contain hematite silica sol, which is difficult to prepare, difficult to stably exist in a phosphate system and difficult to realize industrial production.
Accordingly, it is desired to obtain an insulating coating liquid for directional electrical steel sheets, which contains no chromium, satisfies industrial production requirements in terms of stability and coatability of the coating liquid, and provides an insulating coating on the surface of a steel sheet with excellent moisture absorption resistance, corrosion resistance, heat resistance, tensile effect and anti-sticking property when used for directional electrical steel sheets.
Disclosure of Invention
An object of the present invention is to provide an insulating coating liquid for directional electrical steel sheets, which contains no chromium and can impart excellent moisture absorption resistance, corrosion resistance, heat resistance, tensile strength and anti-sticking property to an insulating coating layer on the surface of a directional electrical steel sheet when used for the directional electrical steel sheet. The insulating coating liquid can meet the requirements of industrial production in the aspects of coating liquid stability and coating property.
In order to achieve the above object, the present invention provides an insulating coating liquid for directional electrical steel sheets, which is composed of the following components:
a phosphate of at least one of Mg, Ca, Al and Zn;
colloidal silicon dioxide;
a compound of at least one of Ti, Mo, W and V;
boric acid;
at least one of silica powder, alumina powder and magnesia powder.
In the technical scheme, the phosphate can form a phosphate coating with a net-shaped or chain-shaped structure on the surface of the steel plate through heat treatment. The colloidal silica is a filler, is beneficial to improving the coating property of the insulating coating liquid, and can provide tension for the insulating coating. The insulating coating liquid for directional electrical steel sheets according to the present invention contains at least one compound of Ti, Mo, W, and V in order to fix phosphate radicals. In the heat treatment process, Ti, Mo, W and V can form insoluble substances with phosphate radicals, so that the effects of fixing the phosphate radicals and improving the moisture absorption resistance of the insulating coating are achieved. The addition of boric acid can improve the tension effect and heat resistance, and can also reduce the addition amount of compounds of Ti, Mo, W and V. In addition, the boric acid has a lower melting point, can promote the sintering compactness of the insulating coating and improve the heat resistance of the insulating coating. The addition of at least one of the silicon dioxide powder, the aluminum oxide powder and the magnesium oxide powder can increase the roughness of the surface of the insulating coating, thereby improving the anti-sticking property of the insulating coating.
Further, in the insulating coating liquid for a directional electrical steel sheet according to the present invention, a mass ratio of the colloidal silica to the phosphate is 0.5 to 1.5.
Further, in the insulating coating liquid for a directional electrical steel sheet according to the present invention, a mass ratio of the compound of at least one of Ti, Mo, W and V to the phosphate is 0.02 to 0.2.
In the aspect of the present invention, the moisture absorption resistance of the insulating coating layer can be significantly improved when the mass ratio of the compound of at least one of Ti, Mo, W, and V to the phosphate is 0.02 or more, but the tensile strength and corrosion resistance of the insulating coating layer are reduced when the mass ratio of the compound of at least one of Ti, Mo, W, and V to the phosphate is more than 0.2, and therefore, the insulating coating liquid for a directional electrical steel sheet according to the present invention limits the mass ratio of the compound of at least one of Ti, Mo, W, and V to the phosphate to 0.02 to 0.2.
Further, in the insulating coating liquid for directional electrical steel sheets according to the present invention, the mass ratio of boric acid to colloidal silica is 0.02 to 0.2.
In the solution of the present invention, the addition of boric acid is advantageous for improving the tensile effect and heat resistance of the insulating coating, but when the mass ratio of boric acid to colloidal silica exceeds 0.2, the tensile effect, heat resistance, and corrosion resistance are reduced, and thus the insulating coating liquid for directional electrical steel sheets according to the present invention limits the mass ratio of boric acid to colloidal silica to 0.02 to 0.2.
Further, in the insulating coating liquid for a directional electrical steel sheet according to the present invention, a mass ratio of at least one of the silica powder, the alumina powder and the magnesia powder to the colloidal silica is 0.02 to 0.2.
Further, in the insulating coating liquid for a directional electrical steel sheet according to the present invention, the silica powder, the alumina powder or the magnesia powder has a particle size of 5 to 50 nm.
Further, in the insulating coating liquid for directional electrical steel sheets according to the present invention, the colloidal silica has a size of 5 to 50 nm.
In the technical scheme of the invention, the size of the colloidal silica is controlled to be 5-50nm in order to achieve better tension effect and surface characteristic.
Further, in the insulating coating liquid for directional electrical steel sheet according to the present invention, when the Ti compound is contained, the Ti compound is selected from the group consisting of: at least one of titanium sulfate, titanium oxide, titanium citrate and titanium oxalate; when a compound of Mo is contained, the compound of Mo is selected from: at least one of molybdenum trioxide, ammonium molybdate, sodium molybdate and molybdenum oxide; when a compound of V is present, the compound of V is selected from: at least one of vanadium oxide, vanadium sulfate, ammonium vanadate, magnesium vanadate and calcium vanadate; when a compound of W is contained, the compound of W is selected from: tungsten oxide, sodium tungstate, ammonium tungstate.
Further, in the insulating coating liquid for directional electrical steel sheet according to the present invention, the phosphate of at least one of Mg, Ca, Al and Zn is selected from: at least one of magnesium dihydrogen phosphate, calcium dihydrogen phosphate, aluminum dihydrogen phosphate and zinc dihydrogen phosphate.
Accordingly, another object of the present invention is to provide a directional electrical steel sheet coated with the above-described insulating coating liquid for a directional electrical steel sheet, so that the insulating coating layer on the surface of the steel sheet has good moisture absorption resistance, corrosion resistance, heat resistance, tensile effect, and anti-sticking property.
In order to achieve the above object, the present invention provides a directional electrical steel sheet including a substrate and an insulating coating layer, wherein the insulating coating layer is formed by coating the insulating coating liquid for a directional electrical steel sheet according to the present invention on the substrate.
Further, in the directional electrical steel sheet according to the present invention, the insulating coating layer has a dry film amount of 2 to 10g/m on one side2。
Further, in the directional electrical steel sheet according to the present invention, the thickness of the substrate is 0.15 to 0.5mm, the content of Si element in the substrate is 2 to 4 wt%, and the surface of the substrate has no magnesium silicate underlayer or a magnesium silicate underlayer.
Accordingly, it is still another object of the present invention to provide a method for manufacturing the above-mentioned directional electrical steel sheet, by which the insulating coating layer on the surface of the directional electrical steel sheet manufactured has good moisture absorption resistance, corrosion resistance, heat resistance, tension effect and anti-sticking property.
In order to achieve the above object, the present invention provides a method for manufacturing a directional electrical steel sheet, comprising the steps of: coating insulating coating liquid on the surface of the substrate, and then performing sintering treatment, wherein the plate temperature in the sintering treatment is 800-950 ℃.
Compared with the prior art, the insulating coating liquid for the directional electrical steel sheet, the directional electrical steel sheet and the manufacturing method thereof have the following beneficial effects:
(1) the insulating coating liquid for the directional electrical steel plate does not contain harmful metallic element chromium, has small pollution to the surrounding environment and good environmental protection benefit.
(2) The insulating coating liquid for the directional electrical steel plate has good stability and coating property, and can realize industrial production and use.
(3) The insulating coating on the surface of the directional electrical steel plate has good tension effect, moisture absorption resistance, corrosion resistance, heat resistance and anti-sticking performance.
Detailed Description
The insulating coating liquid for directional electrical steel sheets and the method for manufacturing the same according to the present invention will be further explained and illustrated with reference to specific examples, but the explanation and the illustration should not be construed as an undue limitation on the technical solution of the present invention.
Examples 1 to 21 and comparative examples 1 to 9
Tables 1 to 1 and tables 1 to 2 show the mass percentages (wt%) of the components and the sizes of some of the components in the insulating coating liquids for directional electrical steel sheets of examples 1 to 21 and comparative examples 1 to 9.
Table 1-1.
Tables 1-2.
It should be noted that, when the insulating coating liquids for directional electrical steel sheets of examples 1 to 21 and comparative examples 1 to 9 were prepared, the phosphate solution and the colloidal silica were directly mixed, ammonium molybdate and boric acid were added in the form of solid agents and required to be completely dissolved, and the silica powder was added in the form of high-speed dispersion or ultrasonic dispersion.
The insulating coating liquids for directional electrical steel sheets of examples 1 to 21 and comparative examples 1 to 9 were coated on steel sheets to manufacture directional electrical steel sheets having billets in which the chemical elements are uniformly mixed in mass percent: c: 0.042%, Si: 2.65%, S: 0.006%, Als: 0.028%, N: 0.006%, Mn: 0.010% and the balance of Fe and other inevitable impurities.
The directional electrical steel sheets of examples 1 to 21 and comparative examples 1 to 9 were manufactured using the following steps (specific process parameters are listed in table 2):
(1) and smelting and casting according to the mass percent of the chemical elements to obtain the billet.
(2) The slab was heated at 1150 ℃ and then hot-rolled into a hot-rolled sheet having a thickness of 2.8 mm.
(3) The hot-rolled sheet was pickled and cold-rolled to a cold-rolled sheet of 0.23mm thickness.
(4) After decarburization annealing treatment, continuous nitriding treatment is carried out on the cold-rolled sheet in the atmosphere of wet ammonia-introduced nitrogen and hydrogen protection.
(5) The nitrided steel sheet is coated with a release agent mainly composed of magnesium oxide.
(6) And (3) performing secondary recrystallization annealing in a dry nitrogen and hydrogen protective atmosphere after coiling, wherein the annealing temperature is 1200 ℃, and the temperature is kept for 20 hours to obtain a substrate with a Gaussian texture, the surface of which is covered with a magnesium silicate bottom layer, and the thickness of the substrate is 0.15-0.5 mm.
(7) An insulating coating liquid is applied to the surface of the substrate.
(8) Sintering at 800-950 deg.C for 5-100s to obtain directional electrical steel sheet with insulating coating having single dry film coating amount of 2-10g/m2。
TABLE 2 detailed procedures of the manufacturing methods of the directional electrical steel sheets of examples 1 to 21 and comparative examples 1 to 9
Parameter(s)
The performance of the insulative coating was tested by the following method, and the test results are listed in table 3.
(1) Insulating coating tension σ: the directional electrical steel sheet was cut into a 300mm x 30mm wide sample plate with the rolling direction as the longitudinal direction, and then the single-sided insulating coating was removed. The amount of bending of the sample was measured and the tension σ of the single-sided insulating coating was calculated by the following equation.
Wherein, σ: tension (kg/mm) of insulating coating2)
E: young's modulus (kg/mm)2)
V: poisson's ratio of 0.3
H: deflection (mm)
L: effective length (mm)
t: thickness (mm)
(2) Moisture absorption resistance: boiling the directional electrical steel sheet in pure water at 100 deg.C, and quantitatively analyzing the content of phosphorus dissolved out in the insulating coating per unit area, in units of μ g/150cm2。
(3) Heat resistance: testing the tension degradation degree and the insulation degradation degree of the insulation coating after the stress relief annealing treatment of the directional electrical steel plate, wherein the process condition of the stress relief annealing treatment is that the temperature is 850 ℃ and the temperature is 100% N2Keeping the temperature in the air for 4 hours. The 4 grades for evaluating heat resistance were: excellence (reduction in tension and insulation)<20 percent), good (the tension is less than or equal to 20 percent and the insulativity is reduced<30 percent), medium (30 percent or less of tension and insulation reduction<40%)) and poor (a decrease in tension and insulation of 40% or more).
(4) Corrosion resistance: the corrosion resistance of the insulating coating is evaluated by a salt spray test, wherein the salt spray test solution is a 5% NaCl solution, the test temperature is 35 ℃, and the test time is 10 hours. The 4 grades evaluated for corrosion resistance were: excellent (the corrosion area is less than 5 percent), good (the corrosion area is more than or equal to 5 percent and less than 10 percent), medium (the corrosion area is more than or equal to 10 percent and less than 30 percent) and poor (the corrosion area is more than or equal to 30 percent).
(5) Anti-blocking property: stacking the same size directional electrical steel plates together, and aligning the stacked directional electrical steel plates with the vertical plate surfaceApplying 80kg/cm2The pressure of (a). The insulation coating was then heat-treated at 850 deg.c for 4 hours in nitrogen having a dew point of 10 deg.c, and the anti-blocking property of the insulation coating was evaluated by measuring the mean value of the peeling force F between each directional electrical steel sheet, the smaller the peeling force, the better the anti-blocking property. The 4 grades evaluated for blocking resistance were: you (F)<100g/m2) Good (100 ≤ F)<250g/m2) Where (250. ltoreq. F)<500g/m2) The sum and difference (F is more than or equal to 500 g/m)2)。
Table 3.
As can be seen from table 3, the insulating coatings of the directional electrical steel sheets according to examples 1 to 21 of the present invention have good tensile effect, moisture absorption resistance, heat resistance, corrosion resistance and anti-sticking property.
The insulating coatings of the directional electrical steel sheets of comparative examples 1 to 9 did not have good tensile effect, moisture absorption resistance, heat resistance, corrosion resistance and anti-sticking property.
It should be noted that the prior art in the protection scope of the present invention is not limited to the examples given in the present application, and all the prior art which is not inconsistent with the technical scheme of the present invention, including but not limited to the prior patent documents, the prior publications and the like, can be included in the protection scope of the present invention.
In addition, the combination of the features in the present application is not limited to the combination described in the claims of the present application or the combination described in the embodiments, and all the features described in the present application may be freely combined or combined in any manner unless contradictory to each other.
It should also be noted that the above-mentioned embodiments are only specific embodiments of the present invention. It is apparent that the present invention is not limited to the above embodiments and similar changes or modifications can be easily made by those skilled in the art from the disclosure of the present invention and shall fall within the scope of the present invention.
Claims (11)
1. An insulating coating liquid for directional electrical steel sheets, characterized in that it consists of the following components: a phosphate of at least one of Mg, Ca, Al and Zn;
colloidal silicon dioxide;
a compound of at least one of Ti, Mo, W and V;
boric acid;
at least one of silica powder and alumina powder;
wherein the mass ratio of at least one of the silica powder and the alumina powder to the colloidal silica is 0.02 to 0.2, and the particle size of the silica powder or the alumina powder is 5 to 50 nm.
2. The insulating coating liquid for directional electrical steel sheets according to claim 1, wherein the mass ratio of the colloidal silica to the phosphate is 0.5 to 1.5.
3. The insulating coating liquid for directional electrical steel sheets according to claim 1, wherein the mass ratio of the compound of at least one of Ti, Mo, W and V to the phosphate is 0.02 to 0.2.
4. The insulating coating liquid for directional electrical steel sheets according to claim 1, wherein the mass ratio of the boric acid to the colloidal silica is 0.02 to 0.2.
5. The insulating coating liquid for directional electrical steel sheets according to claim 1, wherein the colloidal silica has a size of 5 to 50 nm.
6. The insulating coating liquid for directional electrical steel sheets as set forth in claim 1, wherein when the Ti compound is contained, the Ti compound is selected from the group consisting of: at least one of titanium sulfate, titanium oxide, titanium citrate and titanium oxalate; when a compound of Mo is contained, the compound of Mo is selected from: at least one of molybdenum trioxide, ammonium molybdate, sodium molybdate and molybdenum oxide; when a compound of V is present, the compound of V is selected from: at least one of vanadium oxide, vanadium sulfate, ammonium vanadate, magnesium vanadate and calcium vanadate; when a compound of W is contained, the compound of W is selected from: tungsten oxide, sodium tungstate, ammonium tungstate.
7. The insulating coating liquid for directional electrical steel sheets as set forth in claim 1, wherein the phosphate of at least one of Mg, Ca, Al and Zn is selected from the group consisting of: at least one of magnesium dihydrogen phosphate, calcium dihydrogen phosphate, aluminum dihydrogen phosphate and zinc dihydrogen phosphate.
8. A directional electrical steel sheet comprising a substrate and an insulating coating layer, wherein the insulating coating layer is formed by coating the insulating coating liquid according to any one of claims 1 to 7 on the substrate.
9. A directional electrical steel sheet according to claim 8, wherein the insulative coating layer has a dry film amount of 2 to 10g/m on one side2。
10. A directional electrical steel sheet according to claim 8, wherein the thickness of the substrate is 0.15 to 0.5mm, the content of Si element in the substrate is 2 to 4 wt%, and the surface of the substrate has no magnesium silicate primer layer or has a magnesium silicate primer layer.
11. The method of manufacturing a directional electrical steel sheet as set forth in any one of claims 8 to 10, comprising the steps of: coating insulating coating liquid on the surface of the substrate, and then performing sintering treatment, wherein the plate temperature in the sintering treatment is 800-950 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810371182.1A CN110396683B (en) | 2018-04-24 | 2018-04-24 | Insulating coating liquid for directional electrical steel sheet, and method for manufacturing directional electrical steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810371182.1A CN110396683B (en) | 2018-04-24 | 2018-04-24 | Insulating coating liquid for directional electrical steel sheet, and method for manufacturing directional electrical steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110396683A CN110396683A (en) | 2019-11-01 |
| CN110396683B true CN110396683B (en) | 2021-01-12 |
Family
ID=68320122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810371182.1A Active CN110396683B (en) | 2018-04-24 | 2018-04-24 | Insulating coating liquid for directional electrical steel sheet, and method for manufacturing directional electrical steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110396683B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171609A (en) * | 2020-01-22 | 2020-05-19 | 上海迪升防腐新材料科技有限公司 | Environment-friendly insulating masking liquid and preparation method and application thereof |
| CN111793421B (en) * | 2020-07-22 | 2022-06-10 | 武汉迪赛环保新材料股份有限公司 | Environment-friendly chromium-free insulating coating liquid for surface treatment of oriented silicon steel and preparation method and application thereof |
| CN114381584B (en) * | 2020-10-22 | 2024-03-08 | 宝山钢铁股份有限公司 | Insulating coating liquid for oriented silicon steel surface, oriented silicon steel plate and manufacturing method thereof |
| CN112831200A (en) * | 2020-12-30 | 2021-05-25 | 南京宝淳新材料科技有限公司 | Coating for chromium-free oriented electromagnetic steel sheet, preparation method thereof and preparation method of chromium-free oriented electromagnetic steel sheet with coating |
| CN113248947A (en) * | 2021-05-21 | 2021-08-13 | 武汉科技大学 | Chromium-free inorganic insulating paint capable of modifying surface of oriented silicon steel and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101596446B1 (en) * | 2014-08-07 | 2016-03-07 | 주식회사 포스코 | Pre-coating composition for forsterite film-eliminated grain oriented electrical steels, grain oriented electrical steels manufactured by using the same, and method for manufacturing the same grain oriented electrical steels |
| CN107190252B (en) * | 2017-06-13 | 2018-04-03 | 武汉圆融科技有限责任公司 | A kind of chrome-free insulating coating composition and preparation method thereof and directional silicon steel |
-
2018
- 2018-04-24 CN CN201810371182.1A patent/CN110396683B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110396683A (en) | 2019-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110396683B (en) | Insulating coating liquid for directional electrical steel sheet, and method for manufacturing directional electrical steel sheet | |
| EP2182091B1 (en) | Insulating film treating liquid for grain oriented electromagnetic steel plate, and process for producing grain oriented electromagnetic steel plate with insulating film | |
| JP5181571B2 (en) | Chromium-free insulating coating solution for grain-oriented electrical steel sheet and method for producing grain-oriented electrical steel sheet with insulation film | |
| JP4700691B2 (en) | Grain-oriented electrical steel sheet having an insulating coating containing no chromium and its insulating coating agent | |
| JP4695722B2 (en) | Oriented electrical steel sheet and manufacturing method thereof | |
| CN108026645B (en) | Grain-oriented electromagnetic steel sheet and method for producing grain-oriented electromagnetic steel sheet | |
| JP5063902B2 (en) | Oriented electrical steel sheet and method for treating insulating film | |
| EP3255640B1 (en) | Method for predicting transformer noise property | |
| JP2009057591A (en) | Treatment liquid for forming chromium-free insulation film on grain-oriented electromagnetic steel sheet, and method for manufacturing grain-oriented electromagnetic steel sheet provided with insulation film | |
| JP6682888B2 (en) | Insulating coating agent for grain-oriented electrical steel sheet, grain-oriented electrical steel sheet, and method for treating grain-oriented electrical steel sheet | |
| KR20200021999A (en) | Directional electronic steel sheet | |
| RU2698234C1 (en) | Sheet from textured electrical steel having a chromium-free insulating coating creating a tension, and methods of making such a steel sheet | |
| JP6558325B2 (en) | Treatment liquid for forming chromium-free tension coating, grain-oriented electrical steel sheet with chromium-free tension film, method for producing grain-oriented electrical steel sheet with chromium-free tension film, and core for transformer | |
| JP2008266743A (en) | Grain oriented electrical steel sheet, and method for producing the same | |
| KR101286248B1 (en) | Coating solution for forming an insulation film on grain-oriented electrical steel sheet, method for manufacturing said coating solution, and method for forming an insulation film on grain-oriented electrical steel sheet by using the same | |
| JP2005200705A (en) | Grain oriented silicon steel sheet having insulating film containing no chromium, and insulating film agent therefor | |
| JP3564079B2 (en) | Insulating coating agent and method for producing non-oriented electrical steel sheet with excellent weldability using the same | |
| JP2012158800A (en) | Grain oriented electromagnetic steel sheet with chromeless stress coating | |
| CN114106593B (en) | Paint for oriented silicon steel surface coating, oriented silicon steel plate and manufacturing method thereof | |
| JP2019137874A (en) | Oriented electrical steel sheet and manufacturing method thereof | |
| CN112831200A (en) | Coating for chromium-free oriented electromagnetic steel sheet, preparation method thereof and preparation method of chromium-free oriented electromagnetic steel sheet with coating | |
| JP4321181B2 (en) | Method for forming an overcoat insulating film containing no chromium | |
| EP3904557A1 (en) | Grain-oriented electrical steel sheet and method for manufacturing same | |
| CN117343557A (en) | Paint, oriented silicon steel sheet having coating layer formed from the paint, and method for manufacturing the oriented silicon steel sheet | |
| JP7222450B1 (en) | Method for manufacturing electrical steel sheet with pretreatment liquid and insulation coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |