CN113278311A - Chromium-free inorganic insulating coating for oriented silicon steel and preparation method thereof - Google Patents
Chromium-free inorganic insulating coating for oriented silicon steel and preparation method thereof Download PDFInfo
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- CN113278311A CN113278311A CN202110591803.9A CN202110591803A CN113278311A CN 113278311 A CN113278311 A CN 113278311A CN 202110591803 A CN202110591803 A CN 202110591803A CN 113278311 A CN113278311 A CN 113278311A
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- 238000000576 coating method Methods 0.000 title claims abstract description 97
- 239000011248 coating agent Substances 0.000 title claims abstract description 89
- 229910000976 Electrical steel Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 58
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000002518 antifoaming agent Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000003973 paint Substances 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- -1 silicon alkoxide Chemical class 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 17
- 230000007797 corrosion Effects 0.000 abstract description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052804 chromium Inorganic materials 0.000 abstract description 11
- 239000011651 chromium Substances 0.000 abstract description 11
- 230000032683 aging Effects 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000391 magnesium silicate Substances 0.000 description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 description 4
- 235000019792 magnesium silicate Nutrition 0.000 description 4
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 230000007935 neutral effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- VYQRBKCKQCRYEE-UHFFFAOYSA-N ctk1a7239 Chemical compound C12=CC=CC=C2N2CC=CC3=NC=CC1=C32 VYQRBKCKQCRYEE-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C—CHEMISTRY; METALLURGY
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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Abstract
The invention belongs to the technical field of coatings, and particularly discloses a chromium-free inorganic insulating coating for oriented silicon steel, which comprises the following raw materials in parts by weight: 10-50 parts of small-particle silica sol, 10-50 parts of large-particle silica sol, 5-50 parts of aluminum dihydrogen phosphate solution, 0.1-10 parts of auxiliary agent and 10-100 parts of water. The invention also provides a preparation method of the chromium-free inorganic insulating coating for the oriented silicon steel, which comprises the steps of uniformly mixing the small-particle silica sol and the large-particle silica sol into silica sol mixed solution, and adding water to obtain mixed silica sol water solution; and sequentially adding aluminum dihydrogen phosphate and the auxiliary agent into the mixture, and continuously stirring the mixture until the mixture is uniform to obtain the chromium-free inorganic insulating coating for the oriented silicon steel. The chromium-free inorganic insulating coating provided by the invention is suitable for oriented silicon steel, so that the oriented silicon steel is environment-friendly and harmless and has corrosion resistance and aging resistance equivalent to those of chromium-containing oriented silicon steel, thereby realizing the green industry of the oriented silicon steel and greatly improving the comprehensive performance of the oriented silicon steel.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a chromium-free inorganic insulating coating for oriented silicon steel and a preparation method thereof.
Background
The oriented silicon steel is an iron-silicon soft magnetic alloy, has excellent performances of high magnetic induction and low iron loss, is mainly used for manufacturing iron cores of motors and transformers, and is one of main functional materials for supporting the electromechanical industry and energy development. The final links in the oriented silicon steel production process are coating of the insulating coating and high-temperature annealing. The insulating coating generated by the step can improve the resistance of the oriented silicon steel, thereby reducing the eddy current loss generated by the oriented silicon steel in use and ensuring good adhesiveness, heat resistance and corrosion resistance. In the current production, most of insulating coatings used for oriented silicon steel contain chromate, particularly hexavalent chromium, which can not only cause harm to the contacters in the production link, but also harm human health when the waste silicon steel is not reasonably recycled, but also pollute the environment and seriously damage ecology.
In order to solve the problem of environmental pollution of the chromium-containing insulating coating, research on the chromium-free insulating coating of the oriented silicon steel begins to emerge, and although the problem of chromium harm is relieved to a certain extent, the comprehensive performance of the insulating coating formed by the chromium-free insulating coating is poor. The current chromium-free insulating coatings are mainly divided into three types, namely organic coatings, semi-inorganic coatings and inorganic coatings. The organic coating and the semi-inorganic coating have good insulating property because of containing organic components, but in practical production application, the organic components have poor heat resistance, burn loss occurs after high-temperature annealing, the corrosion resistance of the coating is poor, and the insulating property cannot reach an ideal state. Although 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.
Disclosure of Invention
Aiming at the problems of chromium-containing harm, poor corrosion resistance of a chromium-free insulating coating, poor adhesion and the like of the existing insulating coating of the oriented silicon steel, the invention provides a chromium-free inorganic insulating coating for the oriented silicon steel and a preparation method thereof, so as to at least solve the problems.
The invention provides a chromium-free inorganic insulating coating for oriented silicon steel, which comprises the following raw materials in parts by weight: 10-50 parts of small-particle silica sol, 10-50 parts of large-particle silica sol, 5-50 parts of aluminum dihydrogen phosphate solution, 0.1-10 parts of auxiliary agent and 10-100 parts of water; SiO in the small-particle silica sol225-35 wt% of SiO2The granularity is 5-10 nm; SiO in the large-particle silica sol225-35 wt% of SiO2The particle size is 15-30 nm.
Preferably, the small particle silica sol is SiO2The content is 30 +/-1 wt% and SiO2The granularity is 7-9 nm; SiO in the large-particle silica sol2The content is 30 +/-1 wt% and SiO2The particle size is 18-22 nm.
Preferably, the chromium-free inorganic insulating paint for oriented silicon steel comprises the following raw materials in parts by weight: 15-25 parts of small-particle silica sol, 15-25 parts of large-particle silica sol, 10-20 parts of aluminum dihydrogen phosphate solution, 0.1-1 part of auxiliary agent and 29-59.9 parts of water.
Preferably, the content of the phosphorus pentoxide in the aluminum dihydrogen phosphate solution is 32-34%, and the content of the aluminum oxide in the aluminum dihydrogen phosphate solution is 7.5-8.5%.
Preferably, the auxiliary agent is a mixture of a leveling agent and an antifoaming agent, and more preferably the mass ratio of the leveling agent to the antifoaming agent is 1: (40-50) a mixture of a leveling agent and an antifoaming agent.
Preferably, the leveling agent is Byketol-WS, Byketol-OK or Byketol-S, and more preferably Byketol-WS.
Preferably, the defoaming agent is one or a mixture of several of organic silicon alkoxide defoaming agents and mineral oil defoaming agents, and more preferably YCK-625.
The invention also provides a preparation method of the chromium-free inorganic insulating coating for the oriented silicon steel, which comprises the following steps:
(1) adding large-particle silica sol into the small-particle silica sol, and uniformly mixing to form silica sol mixed solution;
(2) adding water into the silica sol mixed solution obtained in the step (1) at the temperature of 20-80 ℃ and under the stirring condition of 60-500r/min (preferably at the temperature of 50 ℃ and under the stirring condition of 300 r/min), and uniformly stirring to obtain a mixed silica sol aqueous solution;
(3) adding aluminum dihydrogen phosphate into the mixed silica sol aqueous solution obtained in the step (2) under the stirring conditions of 20-80 ℃ and 60-500r/min (preferably under the stirring conditions of 50 ℃ and 300 r/min), and uniformly stirring to obtain a mixed solution;
(4) and (3) under the stirring conditions of 20-80 ℃ and 60-500r/min (preferably under the stirring conditions of 50 ℃ and 300 r/min), adding an auxiliary agent into the mixed solution in the step (3) and continuously stirring until the mixed solution is uniform to obtain the chromium-free inorganic insulating coating for the oriented silicon steel.
The chromium-free inorganic insulating coating of the oriented silicon steel provided by the invention adopts aluminum dihydrogen phosphate and large-particle silica sol as main film forming substances, so that the environment friendliness of chromium-free is ensured, and meanwhile, excellent insulating property can be provided; the added small-particle silica sol is filled into a film forming gap, so that the corrosion resistance of the coating is further improved; the addition of the auxiliary agent can improve the coating performance of the coating.
Through the matching and synergistic effect of the components, the invention realizes the chromium-free of the oriented silicon steel insulating coating, the prepared coating has good adhesive force and heat resistance, and has corrosion resistance equivalent to that of the chromium-containing insulating coating, thereby greatly improving the comprehensive performance of the oriented silicon steel and prolonging the service life of the oriented silicon steel.
The invention has the following beneficial technical effects:
(1) the chromium-free inorganic insulating coating has good adhesive force and insulating property;
(2) the raw materials adopted by the chromium-free inorganic insulating paint are pollution-free environment-friendly materials, so that the environmental hazard caused by the chromium-containing insulating paint is avoided;
(3) when the chromium-free inorganic insulating paint is applied, the preparation is simple, no special process requirements exist, and the chromium-free inorganic insulating paint can replace the existing chromium-containing insulating paint process;
(4) when the chromium-free inorganic insulating coating is applied to the oriented silicon steel, the current oriented silicon steel rolling process is not required to be changed, the debugging cost is low, and the popularization is easy.
Drawings
FIG. 1 is an SEM image of the oriented silicon steel substrate used in example 1.
FIG. 2 is an SEM image of the surface of an oriented silicon steel substrate coated with the chromium-free inorganic insulating coating prepared in example 1, and then cured and sintered to form a chromium-free inorganic insulating coating.
Fig. 3 is a plate surface topography of an oriented silicon steel sheet coated with the chromium-free inorganic insulating coating of example 1 after 8 hours of continuous spraying in a neutral salt spray resistance test.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Furthermore, in the following description, descriptions of well-known technologies are omitted so as to avoid unnecessarily obscuring the concepts of the present invention.
In the following examples:
the mass ratio of the used auxiliary agents is 1: (40-50) a mixture of a leveling agent and a defoaming agent, wherein the leveling agent is Byketol-WS, and the defoaming agent is YCK-625.
The content of phosphorus pentoxide and aluminum oxide in the aluminum dihydrogen phosphate solution is 32-34 wt%, and the content of aluminum oxide is 7.5-8.5 wt%.
SiO in the used small-particle silica sol2The content is 30 +/-1 wt% and SiO2The particle size is 7-9 nm.
SiO in the large-particle silica sol2The content is 30 +/-1 wt% and SiO2The particle size is 18-22 nm.
The large-particle silica sol and the small-particle silica sol adopted in the invention are both dispersion liquid of nano-scale silica in water, and because the difference of particle sizes plays different roles in the coating, the combination of the large-particle silica sol and the small-particle silica sol can improve the adhesion and the corrosion resistance of the formed film. If the content of silicon dioxide in the silica sol is too high, the silica sol becomes unstable, nano silicon dioxide particles are agglomerated, and the stability of the insulating coating is reduced. In addition, if the addition amount of the silica sol exceeds the proper range, the content of the nano-silica in the insulating coating is increased along with the increase of the content of the silica sol, and the content of the nano-silica exceeds the proper range, so that the nano-silica is locally agglomerated in the insulating coating, the components of the insulating coating are unevenly distributed, the stability of the insulating coating is affected, the timeliness of the insulating coating in exerting the anti-corrosion capability is reduced, and the anti-corrosion capability of the insulating coating is weakened.
The tension formed after the aluminum dihydrogen phosphate is added is higher than that of a magnesium silicate bottom layer on the oriented silicon steel, the tension can thin the magnetic domain on the surface of the oriented silicon steel, the saturation magnetic induction is increased, the iron loss of the oriented silicon steel is reduced, the comprehensive performance of the coating is improved, and meanwhile, the aluminum dihydrogen phosphate can effectively improve the adhesiveness of the coating as a high-temperature binder.
In order to ensure that the insulating coating is free from foaming and sagging during preparation and use and the surface is smooth and flat after sintering, the invention also uses auxiliary agents such as a leveling agent, a defoaming agent and the like, and the addition of the auxiliary agents is beneficial to the smoothness and the flatness of the surface of the insulating coating, so that the comprehensive performance of the silicon steel is further improved. However, the addition of the auxiliary agent is excessive, the cost is increased, the performance is not improved much, and the addition of the auxiliary agent can reduce the ratio of the main components and reduce the effect of the effective components.
When the preparation temperature is lower than 20 ℃, the molecular motion is reduced, the dissolution of inorganic salts is very slow, the preparation is not facilitated, and the additional long-time stirring can cause demulsification of the defoaming agent and increase the cost. When the preparation temperature is higher than 80 ℃, although the dissolution speed of the inorganic salt is accelerated and the preparation of the insulating coating can be accelerated, the preparation of the insulating coating fails due to the phenomena of coating stability loss, flocculation and the like caused by overhigh temperature, so the preparation process of the insulating coating needs to be carried out under the condition of 20-80 ℃. In a similar way, when the stirring speed is lower than 60r/min, the mixing efficiency is low, the stirring time can be prolonged, but when the rotating speed is higher than 500r/min, air can be introduced into a coating system in the stirring process, so that the stability of a product is reduced, the coating of the coating is not facilitated, and in addition, the stirring speed is higher than a proper speed, so that the demulsification of the defoaming agent is lost, the foam inhibition and defoaming capability is lost, and the use of the coating is not facilitated.
Example 1
A chromium-free inorganic insulating coating for oriented silicon steel comprises the following raw materials in parts by weight: 20 parts of small-particle silica sol, 15 parts of large-particle silica sol, 20 parts of aluminum dihydrogen phosphate solution, 0.1 part of auxiliary agent and 44.9 parts of deionized water, wherein the auxiliary agent comprises 0.02 part of flatting agent and 0.08 part of defoaming agent.
The specific preparation method of the chromium-free inorganic insulating coating for oriented silicon steel comprises the following steps:
(1) adding large-particle silica sol into the small-particle silica sol, and uniformly mixing to form silica sol mixed solution;
(2) adding deionized water into the silica sol mixed solution obtained in the step (1) at the rotating speed of 300r/min and the temperature of 50 ℃, uniformly stirring, then adding an aluminum dihydrogen phosphate solution into the mixture, and uniformly stirring to obtain a mixed solution;
(3) and (3) adding an auxiliary agent into the mixed solution obtained in the step (2) at the rotating speed of 300r/min and the temperature of 50 ℃, and continuously stirring for 30min until the mixture is uniformly mixed to obtain the chromium-free inorganic insulating coating for the oriented silicon steel.
Example 2
A chromium-free inorganic insulating coating for oriented silicon steel comprises the following raw materials in parts by weight: 25 parts of small-particle silica sol, 20 parts of large-particle silica sol, 10 parts of aluminum dihydrogen phosphate solution, 0.5 part of auxiliary agent and 44.5 parts of deionized water, wherein the auxiliary agent comprises 0.01 part of flatting agent and 0.49 part of defoaming agent.
The preparation method is the same as example 1.
Example 3
A chromium-free inorganic insulating coating for oriented silicon steel comprises the following raw materials in parts by weight: 15 parts of small-particle silica sol, 25 parts of large-particle silica sol, 15 parts of aluminum dihydrogen phosphate solution and 1 part of auxiliary agent
And 44 parts of deionized water, wherein the auxiliary agent comprises 0.02 part of flatting agent and 0.98 part of defoaming agent.
The preparation method is the same as example 1.
Example 4
A chromium-free inorganic insulating coating for oriented silicon steel comprises the following raw materials in parts by weight: 15 parts of small-particle silica sol, 15 parts of large-particle silica sol, 10 parts of aluminum dihydrogen phosphate solution, 0.5 part of auxiliary agent and 59.5 parts of deionized water, wherein the auxiliary agent comprises 0.02 part of flatting agent and 0.98 part of defoaming agent.
The preparation method is the same as example 1.
Example 5
A chromium-free inorganic insulating coating for oriented silicon steel comprises the following raw materials in parts by weight: 20 parts of small-particle silica sol, 20 parts of large-particle silica sol, 15 parts of aluminum dihydrogen phosphate solution, 0.51 part of assistant and 44.49 parts of deionized water, wherein the assistant comprises 0.01 part of flatting agent and 0.5 part of defoaming agent.
The preparation method is the same as example 1.
Example 6
A chromium-free inorganic insulating coating for oriented silicon steel comprises the following raw materials in parts by weight: 25 parts of small-particle silica sol, 25 parts of large-particle silica sol, 20 parts of aluminum dihydrogen phosphate solution and 0.1 part of auxiliary agent
And 29.9 parts of deionized water, wherein the auxiliary agent comprises 0.002 part of flatting agent and 0.098 part of defoaming agent.
The preparation method is the same as example 1.
Example 7
A chromium-free inorganic insulating coating for oriented silicon steel comprises the following raw materials in parts by weight: 20 parts of small-particle silica sol, 15 parts of large-particle silica sol, 15 parts of aluminum dihydrogen phosphate solution, 1 part of auxiliary agent and 49 parts of deionized water, wherein the auxiliary agent comprises 0.02 part of flatting agent and 0.98 part of defoaming agent.
The preparation method is the same as example 1.
Example 8
A chromium-free inorganic insulating coating for oriented silicon steel comprises the following raw materials in parts by weight: 25 parts of small-particle silica sol, 20 parts of large-particle silica sol, 20 parts of aluminum dihydrogen phosphate solution and 0.5 part of auxiliary agent
And 34.5 parts of deionized water, wherein the auxiliary agent comprises 0.01 part of flatting agent and 0.49 part of defoaming agent.
The preparation method is the same as example 1.
Example 9
A chromium-free inorganic insulating coating for oriented silicon steel comprises the following raw materials in parts by weight: 15 parts of small-particle silica sol, 25 parts of large-particle silica sol, 10 parts of aluminum dihydrogen phosphate solution, 0.1 part of assistant and 49.9 parts of deionized water, wherein the assistant comprises 0.002 part of flatting agent and 0.098 part of defoaming agent.
The preparation method is the same as example 1.
And (3) according to GB/T10125-2012 salt spray test for artificial atmosphere corrosion test, performing corrosion resistance detection on the coated oriented silicon steel. The obtained chromium-free insulating paint is tested for adhesion and interlaminar resistance according to GB/T2522-2017 test method for insulating resistance and adhesion of coating of electrical steel strips (sheets).
Table 1 coating performance test results
Note: the area of corrosion is the area measured after 8 hours of continuous salt spray. The apparent morphology is as follows: the surface of the coating after curing is uniform and compact, and the coating covers well.
The detection result shows that the corrosion area of the obtained chromium-free insulating coating is less than 1% after 8 hours of testing under the conditions of 5% NaCl aqueous solution and periodic spraying at 35 +/-0.5 ℃, and the obtained chromium-free insulating coating has corrosion resistance equivalent to that of the chromium-containing insulating coating. The chromium-free insulating coating obtained by the invention has good binding force and excellent insulating property with the oriented silicon steel.
Fig. 1 is a morphological image of an oriented silicon steel substrate taken after being enlarged by 10000 times under a scanning electron microscope. It can be found that magnesium silicate particles on the board surface are agglomerated and stacked to form a magnesium silicate bottom layer, but the defects on the board surface are more, the agglomerated and stacked magnesium silicate is not uniform, the stacking density is small, the height is low, pits are formed, and even cracks are formed.
FIG. 2 is a morphological image of an oriented silicon steel substrate coated with the chromium-free inorganic insulating coating prepared in example 1, which is cured and sintered to form a chromium-free inorganic insulating coating, and which is photographed after being magnified by 50000 times under a scanning electron microscope. It has been found that despite the presence of the ravines, the ravines are molten coatings and are denser than uncoated board surfaces, thus providing good corrosion resistance.
Fig. 3 is a plate surface topography of the oriented silicon steel sheet coated with the chromium-free inorganic insulating coating of example 1 after 8 hours of continuous spraying in neutral salt spray resistance test, and it can be found that the plate surface has no corrosion and is equivalent to a commercial chromium-containing coating.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (6)
1. A chromium-free inorganic insulating coating for oriented silicon steel is characterized in that: the chromium-free inorganic insulating paint for the oriented silicon steel comprises the following raw materials in parts by weight: 10-50 parts of small-particle silica sol, 10-50 parts of large-particle silica sol, 5-50 parts of aluminum dihydrogen phosphate solution, 0.1-10 parts of auxiliary agent and 10-100 parts of water; SiO in the small-particle silica sol225-35 wt% of SiO2The granularity is 5-10 nm; SiO in the large-particle silica sol225-35 wt% of SiO2The particle size is 15-30 nm.
2. The chromium-free inorganic insulating coating for oriented silicon steel according to claim 1, wherein: the chromium-free inorganic insulating paint for the oriented silicon steel comprises the following raw materials in parts by weight: 15-25 parts of small-particle silica sol, 15-25 parts of large-particle silica sol, 10-20 parts of aluminum dihydrogen phosphate solution, 0.1-1 part of auxiliary agent and 29-59.9 parts of water.
3. The chromium-free inorganic insulating coating for oriented silicon steel according to claim 1, wherein: 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%.
4. The chromium-free inorganic insulating coating for oriented silicon steel according to claim 1, wherein: the auxiliary agent is a mixture of a leveling agent and a defoaming agent.
5. The chromium-free inorganic insulating coating for oriented silicon steel according to claim 4, wherein: the leveling agent is Byketol-WS, Byketol-OK or Byketol-S, and the defoaming agent is one or a mixture of several of organic silicon alkoxide defoaming agents and mineral oil defoaming agents.
6. A method for preparing the chromium-free inorganic insulating coating for oriented silicon steel of any one of claims 1 to 5, wherein: the preparation method comprises the following steps:
(1) adding large-particle silica sol into the small-particle silica sol, and uniformly mixing to form silica sol mixed solution;
(2) adding water into the silica sol mixed solution obtained in the step (1) at the temperature of 20-80 ℃ and under the stirring condition of 60-500r/min, and uniformly stirring to obtain a mixed silica sol aqueous solution;
(3) adding aluminum dihydrogen phosphate into the mixed silica sol aqueous solution obtained in the step (2) at the temperature of 20-80 ℃ and under the stirring condition of 60-500r/min, and uniformly stirring to obtain a mixed solution;
(4) and (3) adding an auxiliary agent into the mixed solution obtained in the step (3) under the stirring conditions of 20-80 ℃ and 60-500r/min, and continuously stirring until the mixture is uniform to obtain the chromium-free inorganic insulating coating for the oriented silicon steel.
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