WO2024002261A1 - 涂料、具有该涂料形成的涂层的取向硅钢板及其制造方法 - Google Patents

涂料、具有该涂料形成的涂层的取向硅钢板及其制造方法 Download PDF

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WO2024002261A1
WO2024002261A1 PCT/CN2023/103987 CN2023103987W WO2024002261A1 WO 2024002261 A1 WO2024002261 A1 WO 2024002261A1 CN 2023103987 W CN2023103987 W CN 2023103987W WO 2024002261 A1 WO2024002261 A1 WO 2024002261A1
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coating
silicon steel
oriented silicon
steel plate
phosphate
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PCT/CN2023/103987
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English (en)
French (fr)
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吉亚明
杨勇杰
李国保
吴美洪
凌晨
赵自鹏
马长松
郭建国
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宝山钢铁股份有限公司
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Publication of WO2024002261A1 publication Critical patent/WO2024002261A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C23C22/24—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 hexavalent chromium compounds
    • C23C22/33—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 hexavalent chromium compounds containing also phosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe

Definitions

  • the present invention relates to the field of steel plate coatings, and in particular to coatings used for surface coating of oriented silicon steel, oriented silicon steel plates with the surface coating and manufacturing methods thereof.
  • Grain-oriented silicon steel plate refers to a steel plate with a silicon content in the range of 2.8wt.%-3.5wt.% and is obtained by cold rolling and heat treatment processes with ⁇ 110 ⁇ 001> texture. Its magnetic properties along the rolling direction are obvious. Better than transverse magnetic properties.
  • Oriented silicon steel plates are mainly used as transformer core materials. In order to reduce the energy loss and noise level of transformers, oriented silicon steel plates are preferred to have low iron loss and low noise. It is currently known that the iron loss value and hysteresis value of the oriented silicon steel plate can be reduced by applying appropriate tensile stress to the oriented silicon steel plate.
  • chromium-containing coatings are usually applied to the surface of oriented silicon steel plates to solve the above problems.
  • the chromium-containing coatings not only have good insulation properties, but also have different thermal expansion coefficients between the coatings and the steel plates during the heat treatment process.
  • the steel plate generates tensile stress, which can reduce the iron loss and hysteresis value of the steel plate.
  • the coating liquid used for this coating contains hexavalent chromium, the waste liquid generated during its production contains a large amount of environmentally harmful hexavalent chromium, which will seriously pollute the environment.
  • chromium-free coatings for grain-oriented silicon steel.
  • grain-oriented silicon steel using chromium-free coatings usually suffers from significant decreases in moisture absorption resistance and insufficient tension application. Therefore, chromium-free coatings are rarely used or even cannot be used.
  • a chromium-free insulation coating treatment liquid for oriented electromagnetic steel sheets which contains at least one of Mg, Ca, Ba, Sr, Zn, Al and Mn phosphates, and a chelate of colloidal silica and titanium. It can provide improved adhesion and coating tension. However, chelates tend to decompose during heat treatment to produce carbon, which will adversely affect the coating's tension.
  • the publication number is "CN101223300A” and the publication date is July 16, 2008.
  • the Chinese patent document titled "Oriented Electrical Steel Plate with Chromium-Free Insulating Film and Its Insulating Film Agent” discloses a chromium-free orientation Insulating coating agent for electromagnetic steel plates, its main components are phosphate, colloidal silica and Fe, Ni, Co, Inorganic compounds of Cu, Sr, Mo, such as hydroxides, oxides, carbonates, silicates or molybdates.
  • hydroxide colloid is not stable in the phosphate solution system, and its ability to fix free phosphate groups is not sufficient, which easily reduces the moisture absorption resistance and anti-sticking properties of the oriented silicon steel plate.
  • the publication number is "CN102119239A”, the publication date is July 6, 2011, and the name is "Chromium-free coating agent for oriented electrical steel plate, preparation method thereof, electrical steel plate using the coating agent and preparation method of the steel plate "The Chinese patent document discloses a chromium-free coating agent for oriented silicon steel plates.
  • the coating agent contains phosphate, colloidal silica and hematite silica sol.
  • hematite silica sol is difficult to exist stably in the phosphate system, and its preparation is difficult, making it difficult to achieve industrial production.
  • the coating does not contain chromium and can remain stable during heat treatment, and also has good coatability.
  • the surface coating of the oriented steel plate obtained by this coating has good moisture absorption resistance, corrosion resistance, heat resistance and anti-sticking properties, and can also provide sufficient tension effect to further reduce the iron loss and hysteresis of the oriented silicon steel. Telescopic.
  • the object of the present invention is to provide a coating for the surface coating of oriented silicon steel.
  • the coating does not contain chromium, and while protecting the environment, it can provide the oriented silicon steel with good moisture absorption resistance, tension resistance, corrosion resistance, and resistance to corrosion.
  • the thermal and anti-stick coating further reduces the iron loss and hysteresis of grain-oriented silicon steel.
  • the inventors of the present invention have unexpectedly discovered after intensive research that by using at least one vanadate selected from the group consisting of Ce, Mn, Co, Cu, and Fe in combination with a phosphate in the coating, it can be used in the coating.
  • the vanadate and the phosphate in the phosphate form insoluble matter, thereby fixing the phosphate and applying tension to the oriented silicon steel, thus forming a layer on the surface of the oriented silicon steel with good moisture absorption resistance, tension, and Corrosion resistance, heat resistance and anti-stick coating, thus obtaining grain-oriented silicon steel with good iron loss and hysteresis.
  • the invention provides a coating for surface coating of oriented silicon steel, wherein the coating includes:
  • the coating does not contain Cr.
  • colloidal silica is used as a filler in the present invention to form a ceramic layer with a lower thermal expansion coefficient after heat treatment, thereby providing tension to the coating and beneficial To improve coating performance.
  • colloidal silica generally refers to a water dispersion system of nanoscale silica having silanol groups.
  • Ce, Mn, Co, Cu, Fe and V in vanadate can form insoluble phosphate compounds with the phosphate radicals in phosphate, thereby fixing phosphate radicals on the oriented silicon steel and preventing free phosphate radicals from remaining.
  • it improves the moisture absorption resistance, tension, corrosion resistance and anti-sticking properties of the coating.
  • the present invention has no special limitation on vanadate, as long as it can form insoluble vanadium phosphate with phosphate radicals.
  • vanadate may be orthovanadate, pyrovanadate or metavanadate.
  • the vanadate is orthovanadate (VO 4 3- ), pyrovanadate (V 2 O 7 4- ) and/or metavanadate ( VO 3 - ).
  • the coating contains: 25-50% phosphate, 25-50% colloidal silica and 10-50% vanadate in terms of mass percentage.
  • the phosphate is at least one selected from the group consisting of Mg, Al, Ca, Zn, and Mn.
  • the phosphate is magnesium dihydrogen phosphate, aluminum dihydrogen phosphate, calcium dihydrogen phosphate, zinc dihydrogen phosphate and manganese dihydrogen phosphate.
  • the mass ratio of the colloidal silica to the phosphate is 0.5-1.5, preferably 1.0-1.5. Good coating properties can be obtained within this range, which is beneficial to improving the coating properties of the coating of the present invention. Cloth performance.
  • the mass ratio of the vanadate to the phosphate is 0.2-2.0, preferably 0.2-1.5, more preferably 0.2-1.0, more preferably 0.2-0.5.
  • vanadate such as orthovanadate, pyrovanadate and metavanadate
  • the coating can be significantly improved.
  • the mass ratio of vanadate to phosphate is greater than 2.0, the tension and corrosion resistance of the coating will be reduced. Therefore, in the coating for oriented silicon steel plates of the present invention, vanadium The mass ratio of acid salt to phosphate is limited to 0.2-2.0.
  • the coating used for the surface coating of oriented silicon steel also contains boric acid.
  • boric acid By adding boric acid to the coating, the sintering density, tension and heat resistance of the coating can be further improved.
  • the content of the boric acid is 0.02-0.2 parts by mass relative to 100 parts by mass of the colloidal silica.
  • Adding an appropriate amount of boric acid can further improve the sintering density, tension and heat resistance of the coating.
  • the mass ratio of boric acid to colloidal silica exceeds 0.2, the tension effect, heat resistance, and corrosion resistance will decrease. Therefore, in the coating of the present invention, the mass ratio of boric acid to colloidal silica is limited. In the range of 0.02-0.2.
  • the particle size of the colloidal silica is 5-50 nm.
  • the particle size of colloidal silica it is beneficial to form a dense ceramic layer after heat treatment and obtain better tension effect and coating surface morphology.
  • the present invention also provides a oriented silicon steel plate.
  • the oriented silicon steel plate includes a substrate and a coating formed on the surface of the substrate. The coating is formed from the aforementioned coating.
  • the oriented silicon steel plate of the present invention forms a coating layer of the above paint on its surface, The tensile stress exerted by the coating on the oriented silicon steel plate is used to reduce the iron loss value and hysteresis value of the oriented silicon steel plate, making it suitable for transformer core materials and effectively reducing the energy loss and noise level of the transformer.
  • the phosphates in the coating form a network or chain structure.
  • the coating contains vanadium phosphate.
  • the dry film amount of the coating on one side is 2-10g/m 2 . If the dry film content on one side of the coating is less than 2g/m 2 , the coating will not be able to provide sufficient tension; if the dry film content on one side of the coating is higher than 10g/m 2 , the amount of coating is too much, causing heat treatment The thickness of the final coating is uneven, which can easily lead to a reduction in the lamination coefficient of the steel plate.
  • the substrate of the oriented silicon steel of the present invention is not particularly limited, and oriented silicon steel substrates commonly used in the field can be used.
  • oriented silicon steel substrates commonly used in the field can be used.
  • a oriented silicon steel substrate with a Si element content of 2-4 wt% can be used.
  • the thickness of the substrate is 0.18-0.35mm.
  • the oriented silicon steel plate also has a magnesium silicate bottom layer, which is formed by the reaction of a release agent (usually MgO) and silicon oxide (SiO 2 ) on the surface of the steel plate under high-temperature annealing conditions (for example, 1200°C).
  • a release agent usually MgO
  • silicon oxide SiO 2
  • the magnesium oxide bottom layer is located between the substrate of the oriented silicon steel plate and the coating, thereby increasing the adhesion of the coating to the steel plate.
  • the coating of the oriented silicon steel plate has a tension of 7.1 ⁇ 10.5Mpa and a phosphorus dissolution content lower than 75 ⁇ g/ 150cm2 .
  • the present invention also provides a method for manufacturing a oriented silicon steel plate.
  • the surface of the oriented silicon steel plate has a coating formed by the above-mentioned coating.
  • the method includes the following steps:
  • step 2) sintering is performed under the condition that the substrate surface temperature is 800-900°C, and the sintering time is more than 20 seconds. If the temperature is lower than 800°C, the steel plate will not be flat enough, and the tension effect imparted by the coating to the steel plate will not be significant; if the temperature is higher than 900°C, the silica in the coating will easily crystallize, resulting in a dense coating. Sexual and tension effects are reduced.
  • the coating is applied on the substrate of the oriented silicon steel plate in the form of a solution in water.
  • the manufacturing method satisfies at least one of the following:
  • the coating is coated on the substrate with a single-sided dry film amount of 2-10g/ m2 ;
  • the manufacturing method also includes forming a magnesium silicate layer between the substrate and the coating.
  • the coating of the present invention and the oriented silicon steel plate with the coating formed by the coating have the following beneficial effects:
  • the coating of the present invention does not contain harmful metal element chromium, causes little pollution to the surrounding environment, and has good environmental benefits:
  • the coating of the present invention has good stability and coating properties, and can realize industrial production and use;
  • the surface coating of the oriented silicon steel plate according to the present invention has good moisture absorption resistance, tension, corrosion resistance, heat resistance and anti-sticking properties, and can further reduce the iron loss and hysteresis of the oriented silicon steel.
  • the coatings used for the surface coating of oriented silicon steel in Examples 1-28 and Comparative Examples 1-6 of the present invention are prepared by the following method: according to the formula listed in Table 1, directly mix the phosphate solution and colloidal silica, and then Optionally, boric acid is added as a solid reagent (no boric acid was added in Example 28), stir thoroughly to completely dissolve the boric acid, and then add vanadate powder to the solution in the form of high-speed dispersion or ultrasonic dispersion to form a coating.
  • Table 1 lists the mass percentage (wt%) of each component and the particle size of colloidal silica in the coatings of Examples 1-28 and Comparative Examples 1-6. Among them, the amount of vanadate in Comparative Examples 1-6 does not meet the requirement of the present invention that the mass ratio of vanadate to phosphate is 0.2-2.0.
  • Example 1 The coatings of Examples 1-28 and Comparative Examples 1-6 were coated on the substrate of the oriented silicon steel plate, and each oriented silicon steel plate with the coating formed by the coating was obtained through the following steps (the key technical parameters are listed in Table 2), wherein the substrate of the oriented silicon steel plate contains the following chemical elements in mass percentage: C: 0.046%, Si: 3.32%, S: 0.006%, soluble Al: 0.027%, N: 0.006%, Mn: 0.012% , the balance is Fe and other unavoidable impurities:
  • the cold-rolled plate is continuously nitrided in a moist ammonia-filled nitrogen and hydrogen protective atmosphere.
  • Coating tension ⁇ With the rolling direction as the length direction, cut the oriented silicon steel plate into a sample plate with a length of 300mm ⁇ a width of 30mm, then remove the coating, bend the sample plate to test its warpage, and calculate it by the following formula The tension of the coating ⁇ .
  • Hygroscopic resistance Boil the oriented silicon steel plate in pure water at 100°C, and then quantitatively analyze the phosphorus content dissolved in the coating per unit area, in ⁇ g/150cm 2 .
  • Heat resistance Test the degree of tension deterioration and insulation deterioration of the surface coating of the oriented silicon steel plate after stress relief annealing treatment.
  • the process conditions of the stress relief annealing treatment are at 850°C and 100% N 2 Keep warm in gas for 4 hours.
  • the four grades for evaluating heat resistance are: excellent (reduction in tension and insulation ⁇ 20%), good (20% ⁇ reduction in tension and insulation ⁇ 30%), medium (30% ⁇ reduction in tension and insulation ⁇ 40%) )) and poor (tension and insulation reduced by ⁇ 40%).
  • Corrosion resistance The corrosion resistance of the coating is evaluated through a salt spray test.
  • the salt spray test solution is a 5% NaCl solution, the test temperature is 35°C, and the test time is 10 hours.
  • the four grades for evaluating corrosion resistance are: excellent (corrosion area ⁇ 5%), good (5% ⁇ rust area ⁇ 10%), medium (10% ⁇ rust area ⁇ 30%) and poor (corrosion area ⁇ 30%) ).
  • Anti-sticking property Stack oriented silicon steel plates of the same size together, and apply a pressure of 80kg/ cm2 on the vertical surface of the stacked oriented silicon steel plates. Then heat treat at 850°C for 4 hours in N2 gas with a dew point of 10°C, and evaluate the anti-sticking property of the coating by testing the average value of the peeling force F between each oriented silicon steel plate. The smaller the peeling force, the better the anti-sticking property. The better the film performance.
  • the four grades for evaluating anti-sticking properties are: excellent (F ⁇ 100g/m 2 ), good (100 ⁇ F ⁇ 250g/m 2 ), medium (250 ⁇ F ⁇ 500g/m 2 ) and poor (F ⁇ 500g /m 2 ).
  • the coating of the oriented silicon steel plate in Examples 1-28 of the present invention has excellent tension effect (tension range 7.1-10.5MPa), hygroscopicity resistance (phosphorus dissolution content ⁇ 75 ⁇ g/150cm 2 ), and Excellent heat resistance, corrosion resistance and anti-stick properties.
  • the coating of the oriented silicon steel plate of Comparative Examples 1-6 cannot meet all the properties of Examples 1-28 at the same time. Specifically, when the vanadate content is too small, although the tension coating has a tension that meets the requirements, its The higher dissolution amount of phosphorus indicates its poor resistance to hygroscopicity. When the vanadate content is too much, although the phosphate is fixed in the coating through the excess vanadate, the coating tension cannot meet the requirements of the present invention, nor can the excellent heat resistance, corrosion resistance and excellent properties required by the present invention be ensured. Anti-sticking properties.

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Abstract

本发明涉及用于取向硅钢表面涂层的涂料，所述涂料包含：磷酸盐；胶体二氧化硅；选自Ce、Mn、Co、Cu或Fe的钒酸盐中的至少一种；以及所述涂料不含Cr。本发明还涉及具有表面涂层的取向硅钢，所述表面涂层由上述涂料形成。本发明还涉及制备具有由上述涂料形成的表面涂层的取向硅钢的方法。本发明的涂料不含铬，其在保护环境的同时，由该涂料形成的涂层仍可提供足够的耐吸湿性并向取向硅钢板施加足够的张力，进一步降低取向硅钢的铁损和磁滞伸缩，获得优质的变压器铁芯材料。

Description

涂料、具有该涂料形成的涂层的取向硅钢板及其制造方法 技术领域
本发明涉及钢板涂层领域，尤其涉及用于取向硅钢表面涂层的涂料、具有该表面涂层的取向硅钢板及其制造方法。
背景技术
取向硅钢板是指硅含量在2.8wt.％-3.5wt.％范围之间，并采用冷轧和热处理工艺获得的具有{110}<001>织构的钢板，其沿轧向的磁性能明显优于横向的磁性能。取向硅钢板主要应用于变压器铁芯材料，为了降低变压器的能量损耗和噪音水平，优选取向硅钢板具有低铁损和低噪声。目前已知通过对取向硅钢板施加适当的拉应力可以降低取向硅钢板的铁损值和磁滞伸缩值。
现有技术中，通常在取向硅钢板表面施加含铬涂层来解决上述问题，含铬涂层不但具有良好的绝缘性，而且在热处理过程中由于涂层与钢板热膨胀系数不同，涂层会对钢板产生拉应力，从而可以降低钢板的铁损和磁滞伸缩值。然而，由于该涂层所使用的涂液中含有六价铬，其生产中产生的废液含有大量对环境有害的六价铬，这将严重污染环境。
随着近年来对环境保护关注度的提高，对不含铬、铅等有害物质的产品的需求提高，对于取向硅钢也希望开发无铬(不含铬)的涂层。然而，使用无铬涂层的取向硅钢通常存在耐吸湿性的显著下降、张力施加不足的问题，因此无铬涂层的使用场景较少，甚至无法采用。
公开号为“CN101790599A”，公开日为2010年7月28日，名称为“方向性电磁钢板用绝缘覆膜处理液以及具有绝缘覆膜的方向性电磁钢板的制造方法”的中国专利文献公开了一种方向性电磁钢板用无铬绝缘覆膜处理液，其包含Mg、Ca、Ba、Sr、Zn、Al及Mn的磷酸盐中至少一种，以及胶体二氧化硅和钛的螯合物。其可提供改善的粘着性和涂层张力，然而螯合物在热处理过程中容易分解产生碳，会对涂层的张力产生不利的影响。
公开号为“CN101223300A”，公开日为2008年7月16日，名称为“具有不含铬的绝缘皮膜的取向电磁钢板及其绝缘皮膜剂”的中国专利文献公开了一种不含铬的取向电磁钢板用绝缘皮膜剂，其主要成分为磷酸盐、胶体二氧化硅和粒径为15nm以下的Fe、Ni、Co、 Cu、Sr、Mo的无机化合物，例如氢氧化物、氧化物、碳酸盐、硅酸盐或钼酸盐。然而氢氧化物胶体在磷酸盐溶液体系中并不稳定，固定游离磷酸根的能力也不够充分，容易降低取向硅钢板的耐吸湿性和抗粘片性。
公开号为“CN102119239A”，公开日为2011年7月6日，名称为“用于取向电工钢板的无铬涂布剂、其制备方法、使用该涂布剂的电工钢板及该钢板的制备方法”的中国专利文献公开了一种用于取向硅钢板的无铬涂布剂，该涂布剂包含磷酸盐、胶体二氧化硅和赤铁矿硅溶胶。然而赤铁矿硅溶胶在磷酸盐体系中难以稳定存在，且制备较为困难，难以实现工业化生产。
基于上述问题，希望获得一种满足工业化生产要求的用于取向硅钢板的涂料，该涂料不含铬并且在热处理过程中可保持稳定，还具有良好的可涂覆性。通过此种涂料获得的取向钢板表面涂层具有良好的耐吸湿性、耐腐蚀性、耐热性和抗粘片性，同时还可提供足够的张力效果以进一步降低取向硅钢的铁损和磁滞伸缩。
发明内容
本发明的目的在于提供一种用于取向硅钢表面涂层的涂料，该涂料不含铬，其在保护环境的同时，可为取向硅钢提供具有良好的耐吸湿性、张力、耐腐蚀性、耐热性和抗粘片性的涂层，由此进一步降低取向硅钢的铁损和磁滞伸缩。
为实现以上目的，本发明人潜心研究后意外地发现，通过在涂料中将选自Ce、Mn、Co、Cu、Fe的钒酸盐中的至少一种与磷酸盐组合使用，可以在涂料的热处理过程中使该钒酸盐与磷酸盐中的磷酸根形成不溶物，从而起到固定磷酸根的作用并向取向硅钢施加张力，由此在取向硅钢表面上形成具有良好耐吸湿性、张力、耐腐蚀性、耐热性和抗粘片性的涂层，由此获得具有良好铁损和磁滞伸缩的取向硅钢。
本发明提供一种用于取向硅钢表面涂层的涂料，其中所述涂料包含：
磷酸盐；
胶体二氧化硅；
选自Ce、Mn、Co、Cu或Fe的钒酸盐中的至少一种；
所述涂料不含Cr。
上述涂料在涂覆取向硅钢板后，涂料需经热处理形成涂层，其中磷酸盐在经热处理之后可以在钢板表面形成具有网状或链状结构的磷酸盐涂层。胶体二氧化硅在本发明中作为填充物，在热处理之后形成具有较低热膨胀系数的陶瓷层，从而为涂层提供张力，并有利 于改善涂料的涂布性能。本发明中，“胶体二氧化硅”通常是指纳米级二氧化硅的水分散体系，具有硅烷醇基团。热处理过程中，钒酸盐中的Ce、Mn、Co、Cu、Fe及V均能与磷酸盐中的磷酸根形成不溶的磷酸盐化合物，从而在取向硅钢上固定磷酸根，防止游离磷酸根残留在涂层中，由此提高涂层的耐吸湿性、张力、耐蚀性和抗粘片性等。
本发明对钒酸盐没有特别限制，只需其能与磷酸根形成不溶的磷酸钒即可，钒酸盐的实例可为正钒酸盐、焦钒酸盐或偏钒酸盐。优选地，所述钒酸盐为Ce、Mn、Co、Cu或Fe的正钒酸盐(VO4 3-)、焦钒酸盐(V2O7 4-)和/或偏钒酸盐(VO3 -)。
优选地，所述涂料以质量百分比计包含：25～50％的磷酸盐，25-50％的胶体二氧化硅以及10～50％的钒酸盐。
优选地，所述磷酸盐为选自Mg、Al、Ca、Zn、及Mn的磷酸盐中的至少一种。
优选地，所述磷酸盐为磷酸二氢镁、磷酸二氢铝、磷酸二氢钙、磷酸二氢锌和磷酸二氢锰。
优选地，所述胶体二氧化硅与所述磷酸盐的质量比为0.5-1.5，优选1.0～1.5，在此范围内可获得良好的涂覆性，有利于改善本发明所述的涂料的涂布性能。
优选地，所述钒酸盐与所述磷酸盐的质量比为0.2-2.0，优选0.2～1.5，进一步优选0.2-1.0，更优选0.2-0.5。
在本发明所述的技术方案中，钒酸盐(例如正钒酸盐、焦钒酸盐和偏钒酸盐)中的至少一种与磷酸盐的质量比在0.2以上时，可以显著改善涂层的耐吸湿性，但当钒酸盐与磷酸盐的质量比大于2.0时，会导致涂层的张力和耐蚀性降低，因此，本发明所述的用于取向硅钢板的涂料中，钒酸盐与磷酸盐的质量比限定在0.2-2.0。
优选地，所述用于取向硅钢表面涂层的涂料还包含硼酸，通过在涂料中添加硼酸，可进一步改善涂层的烧结致密性、张力和耐热性。
优选地，相对于100质量份所述胶体二氧化硅，所述硼酸的含量为0.02-0.2质量份。
添加适量的硼酸可以进一步改善涂层的烧结致密性、张力和耐热性。然而，当硼酸与胶体二氧化硅的质量比超过0.2时，会导致张力效果、耐热性、耐蚀性下降，因此，本发明所述的涂料中，硼酸与胶体二氧化硅的质量比限定在0.02-0.2范围内。
优选地，所述胶体二氧化硅的粒径为5-50nm。通过调整胶体二氧化硅的粒径，有利于在热处理后形成致密的陶瓷层，获得更好的张力效果和涂层表面形貌。
本发明还提供了一种取向硅钢板，所述取向硅钢板包括基板和在所述基板表面形成的涂层，所述涂层由前述涂料形成。本发明的取向硅钢板通过在其表面形成上述涂料的涂层， 利用该涂层在取向硅钢板上施加的拉应力，降低了取向硅钢板的铁损值和磁滞伸缩值，使其适用于变压器铁芯材料，并且有效降低变压器的能量损耗和噪音水平。
优选地，所述涂层中的磷酸盐形成网状或链状结构。
优选地，所述涂层包含磷酸钒。
优选地，在本发明所述的取向硅钢板中，所述涂层的单面干膜量为2-10g/m2。如果涂层的单面干膜量低于2g/m2，涂层将无法提供足够的张力；如果涂层的单面干膜量高于10g/m2，则涂料的量过多，使得热处理后的涂层厚度不均，容易导致钢板的叠片系数降低。
本发明的取向硅钢的基板没有特别限定，可以使用本领域中常用的取向硅钢基板，例如可使用Si元素含量为2-4wt％的取向硅钢基板。
优选地，所述基板的厚度为0.18-0.35mm。
优选地，所述取向硅钢板还具有硅酸镁底层，其由隔离剂(通常为MgO)与钢板表面的氧化硅(SiO2)在高温退火条件下(例如1200℃)反应形成，所述硅酸镁底层位于所述取向硅钢板的基板和所述涂层之间，从而增加涂层在钢板上的附着力。
优选地，取向硅钢板的涂层具有7.1～10.5Mpa的张力，低于75μg/150cm2的磷溶出含量。
本发明还提供了一种取向硅钢板的制造方法，所述取向硅钢板的表面具有由上述涂料形成的涂层，所述方法包括以下步骤：
1)在取向硅钢板的基板上涂覆上述涂料，在基板表面形成涂层；以及
2)进行烧结。
优选地，在步骤2)中，在基板表面温度为800-900℃的条件下进行烧结，烧结时间为20秒以上。如果该温度低于800℃，则钢板不够平整，且涂层对钢板赋予的张力效果不显著；如果该温度高于900℃，涂层中的二氧化硅则容易晶化，会导致涂层致密性和张力效果下降。
优选地，所述涂料以在水中的溶液形式涂敷在取向硅钢板的基板上。
优选地，所述制造方法满足如下中的一个以上：
所述涂料以2-10g/m2的单面干膜量涂覆在基板上；
所述制造方法还包括在基板与涂层之间形成硅酸镁层。
本发明所述的涂料以及具有由该涂料形成的涂层的取向硅钢板与现有技术相比，具有如下有益效果：
(1)本发明所述涂料不含有害金属元素铬，对周边环境所产生的污染小，环保效益好：
(2)本发明所述的涂料具有良好的稳定性和涂敷性，可以实现工业化生产和使用；以及
(3)本发明所述的取向硅钢板表面涂层具有良好的耐吸湿性、张力、耐腐蚀性、耐热性和抗粘片性，可进一步降低取向硅钢的铁损和磁滞伸缩。
具体实施方式
以下通过实施例对本发明的内容进行更具体的说明，以使本发明的内容更加清楚和便于理解。但需要说明的是，以下公开的实施例只是本发明的具体实施方式的例举，本发明并不局限于这些实施例。
1.用于取向硅钢表面涂层的涂料的制备
本发明的实施例1-28和比较例1-6的用于取向硅钢表面涂层的涂料通过以下方法制备：根据表1列出的配方，将磷酸盐溶液和胶体二氧化硅直接混合，之后可选地将硼酸以固体试剂形式加入(实施例28未加入硼酸)，充分搅拌使硼酸完全溶解，然后将钒酸盐粉末以高速分散或者超声分散的形式加入溶液，形成涂料。
表1列出了实施例1-28和比较例1-6的涂料中各组分质量百分比(wt％)及胶体二氧化硅的粒径。其中，比较例1-6中的钒酸盐的量均不符合本发明的钒酸盐与磷酸盐的质量比为0.2-2.0的要求。
表1


2.具有表面涂层的取向硅钢板的制造
将实施例1-28和比较例1-6的涂料涂覆在取向硅钢板的基板上，并通过以下步骤获得具有由所述涂料形成的涂层的各取向硅钢板(关键的技术参数列于表2)，其中，取向硅钢板的基板以质量百分比计包含如下化学元素：C：0.046％，Si：3.32％，S：0.006％，可溶性Al：0.027％，N：0.006％，Mn：0.012％，余量为Fe和其他不可避免的杂质：
(1)按照上述各化学元素的质量百分比进行冶炼铸造，得到钢坯。
(2)将钢坯在1150℃下加热后，热轧成2.8mm厚的热轧板。
(3)热轧板经酸洗并冷轧成0.18-0.35mm厚的冷轧板。
(4)冷轧板经过脱碳退火处理后，在湿润的通氨气的氮气和氢气保护气氛中进行连续渗氮处理。
(5)在渗氮处理后的钢板上涂布以氧化镁为主的隔离剂。
(6)卷取钢板，之后在干燥的保护性气氛(如氮气和氢气的混合气)中进行二次再结晶退火，退火温度为1200℃，保温20小时,得到表面覆盖硅酸镁底层的具有高斯织构的基板。
(7)在基板的表面涂敷本发明的如上所述的涂料。
(8)在800-900℃条件下烧结20s以上，得到具有表面涂层的取向硅钢板，表面涂层的单面干膜涂敷量为2-10g/m2。
实施例1-28和比较例1-6的取向硅钢板的制造方法的关键工艺参数如表2所示。
表2

3.具有表面涂层的取向硅钢板的性能评价
对本发明的实施例1-28和比较例1-6的取向硅钢板进行性能测试，包括测试其涂层张力、耐吸湿性、耐热性、耐蚀性和抗粘片性，测试方法具体如下：
(1)涂层张力σ：以轧制方向为长度方向，将取向硅钢板剪为长300mm×宽30mm的样板，然后去除涂层，弯曲样板以测试其翘曲量，并通过以下公式计算得出涂层的张力σ。
上式中，σ表示涂层张力，其单位可以为MPa；E表示钢板杨氏模量，其单位可以为GPa；t表示钢板的厚度，其单位可以为mm；H表示翘曲量，其单位可以为mm；L表示钢板的长度，其单位可以为mm。
(2)耐吸湿性：将取向硅钢板在100℃纯水中煮沸，然后定量分析单位面积涂层中溶出的磷含量，单位为μg/150cm2。
(3)耐热性：测试取向硅钢板经消除应力退火处理后表面涂层的张力劣化程度和绝缘性劣化程度，其中，消除应力退火处理的工艺条件是在850℃下，在100％N2气体中保温4h。评价耐热性的4个等级为：优(张力和绝缘性降低<20％)、良(20％≤张力和绝缘性降低<30％)、中(30％≤张力和绝缘性降低<40％))和差(张力和绝缘性降低≥40％)。
(4)耐蚀性：通过盐雾试验评估涂层的耐蚀性，盐雾试验溶液为5％NaCl溶液，测试温度为35℃，测试时间为10h。评价耐蚀性的4个等级为：优(锈蚀面积<5％)、良(5％≤锈蚀面积<10％)、中(10％≤锈蚀面积<30％)和差(锈蚀面积≥30％)。
(5)抗粘片性：将相同尺寸的取向硅钢钢板叠放在一起，对叠放的取向硅钢板垂直板面施加80kg/cm2的压力。然后在露点为10℃的N2气体中在850℃下热处理4h，通过测试每片取向硅钢板之间的剥离力F的均值来评价涂层的抗粘片性，剥离力越小，抗粘片性能越好。评价抗粘片性的4个等级为：优(F<100g/m2)、良(100≤F<250g/m2)、中(250≤F<500g/m2)和差(F≥500g/m2)。
根据上述方法获得的实施例1-28及比较例1-6的取向硅钢板的测试结果如表3所示。
表3

由表3可以看出，本发明实施例1-28的取向硅钢板的涂层具有优异的张力效果(张力范围7.1～10.5MPa)、耐吸湿性(磷溶出含量<75μg/150cm2)，以及优良的耐热性、耐蚀性和抗粘片性能。
而比较例1-6的取向硅钢板的涂层则无法同时满足实施例1-28的各项性能，具体地，当钒酸盐含量过少时，虽然张力涂层具有满足要求的张力，但其磷溶出量较高，说明其耐吸湿性较差。当钒酸盐含量过多时，虽然磷酸根通过过量的钒酸盐固定于涂料中，但其涂层张力无法满足本发明的要求，也无法确保本发明要求的优异耐热性、耐蚀性和抗粘片性。
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术人员无需创造性劳动就可以根据本发明的构思作出各种修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。
此外，本案中各技术特征的组合方式并不限本案权利要求中所记载的组合方式或是具体实施例所记载的组合方式，本案记载的所有技术特征可以以任何方式进行自由组合或结合，除非相互之间产生矛盾。

Claims (14)

  1. 用于取向硅钢表面涂层的涂料，其中所述涂料包含：
    磷酸盐，优选地，所述磷酸盐为选自Mg、Al、Ca、Zn、及Mn的磷酸盐中的至少一种，更优选地，所述磷酸盐为磷酸二氢镁、磷酸二氢铝、磷酸二氢钙、磷酸二氢锌和/或磷酸二氢锰；
    胶体二氧化硅；
    选自Ce、Mn、Co、Cu或Fe的钒酸盐中的至少一种，优选地，所述钒酸盐为Ce、Mn、Co、Cu或Fe的正钒酸盐、焦钒酸盐和/或偏钒酸盐；
    其中所述涂料不含Cr。
  2. 根据权利要求1所述的涂料，其中，所述涂料以质量百分比计包含25～50％的磷酸盐，25-50％的胶体二氧化硅以及10～50％的钒酸盐。
  3. 根据权利要求1所述的涂料，其中，所述胶体二氧化硅与所述磷酸盐的质量比为0.5-1.5，优选1.0～1.5。
  4. 根据权利要求1所述的涂料，其中，所述钒酸盐与所述磷酸盐的质量比为0.2-2.0，优选0.2～1.0。
  5. 根据权利要求1所述的涂料，其中，所述涂料还包含：
    硼酸，其中相对于100质量份的所述胶体二氧化硅，所述硼酸的含量为0.02-0.2质量份。
  6. 根据权利要求1所述的涂料，其中，所述胶体二氧化硅的粒径为5-50nm。
  7. 取向硅钢板，所述取向硅钢板具有基板和在所述基板表面形成的涂层，所述涂层使用权利要求1-6中任一项所述的涂料形成。
  8. 根据权利要求7所述的取向硅钢板，其中，所述涂层中的磷酸盐形成网状或链状结构。
  9. 根据权利要求7所述的取向硅钢板，其中，所述涂层包含磷酸钒。
  10. 根据权利要求7所述的取向硅钢板，其中，所述涂层的单面干膜量为2-10g/m2。
  11. 根据权利要求7所述的取向硅钢板，其中，所述取向硅钢板还具有硅酸镁层，所 述硅酸镁层位于所述取向硅钢板的基板和所述涂层之间。
  12. 根据权利要求7所述的取向硅钢板，其中，所述取向硅钢板的涂层具有7.1～10.5Mpa的张力，低于75μg/150cm2的磷溶出含量。
  13. 取向硅钢板的制造方法，所述方法包括以下步骤：1)在取向硅钢板的基板上涂覆权利要求1至6中任一项中所述的涂料；以及
    2)进行烧结，在所述取向硅钢板的基板表面上形成涂层，在烧结过程中，基板表面温度为800-900℃，烧结时间为20秒以上。
  14. 根据权利要求13所述的制造方法，其中，所述制造方法满足如下中的一个以上：
    所述涂料以2-10g/m2的单面干膜量涂覆在基板上；
    所述制造方法还包括在基板与涂层之间形成硅酸镁层。
PCT/CN2023/103987 2022-06-29 2023-06-29 涂料、具有该涂料形成的涂层的取向硅钢板及其制造方法 WO2024002261A1 (zh)

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US3930905A (en) * 1972-10-26 1976-01-06 Allmanna Svenska Elektriska Aktiebolaget Method of manufacturing an object of silicon steel
CN101509131A (zh) * 2008-02-15 2009-08-19 宝山钢铁股份有限公司 耐蚀耐指纹的表面处理剂及其制备法和不锈钢板上使用方法
CN106243791A (zh) * 2016-09-13 2016-12-21 福州大学 一种用于取向硅钢的高遮盖性绝缘涂料
CN108026648A (zh) * 2016-04-26 2018-05-11 日涂工业涂料有限公司 表面处理钢材
CN108866529A (zh) * 2018-09-15 2018-11-23 马鞍山钢铁股份有限公司 一种耐蚀性和耐高温性优良的环保钝化镀铝硅钢板及生产方法
CN114106593A (zh) * 2020-08-31 2022-03-01 宝山钢铁股份有限公司 一种用于取向硅钢表面涂层的涂料、取向硅钢板及其制造方法

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CN101509131A (zh) * 2008-02-15 2009-08-19 宝山钢铁股份有限公司 耐蚀耐指纹的表面处理剂及其制备法和不锈钢板上使用方法
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